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TOPICS ON

PHASE BEHAVIOR AND FLOW

OF PETROLEUM RESERVOIR FLUIDS

Curtis H. Whitson

The University of Trondheim

Norwegian Institute of Technology

Departments of Petroleum and Chemical Engineering

1983
1983
$n$
-H
TOPICS ON
TOPICS ON PHASE
PHASE BEHAVIOR
BEHAVIOR AND
AND FLOW
FLOW
OF PETROLEUM
OF PETROLEUM RESERVOIR
RESERVOIR FLUIDS
FLUIDS

Submitted by
Submitted by
Curtis H.
Curtis H. Whitson
Whitson

to

The University of
of Trondheim
Norwegian Institute ofof Technology
Departments of Petroleum
and Chemical Engineering

as fulfillment
as of
fulfillment of
requirements for the degree
degree
doctor
doctor of the technical sciences
of the technical sciences

August
August 1983
1983
iI

DEDICATION
DEDICPJIQN

G.kLd +(-% (Lbc.


i11i

FOREWORO
FOREWORD

This thesis gives a review of independent


research performed during the period 1978 to 1983. It
started in August, 1978 when i arrived in Trondheim, Norway
at the Norwegian Institute of Technology (NTH). Without
certain inspiration from M.B. Standing at Stanford
lJniversity
University during my four-year
fouryear undergraduate studies (1974
to 1978), the arrival at NTH would probably never have been
realized.
My first professional contact in Norway was with !2l.0. GlasgJ
Glas
who headed the fluids (PVT) laboratory at SINTEF (the
research organization affiliated with NTH). He promptly put
me to work repairing a vacuum pU"ll,
pump, the first of numerous
jobs i had while working in the PVT laboratory. Without
regret, it should be noted that none of the experimental
work completed during this first year was of any merit. The
experience did, however, give me insight into the importance
of high quality experimental data and the difficulty in its
measurement. Glas deserves special thanks for allowing me
Glas~
this opportunity.

Several collegues at NTH deserve credit for inspiring my


work in fluid flow. Professor T. van Golf-Racht
GolfRacht was
particularly patient and allowed me to develop the
engineering skills i was supposed to have learned as an
undergraduate. He introduced me to the dynamics of
reservoir engineering and particularly the importance of
understanding fluid flow in porous media; his liberal use of
Muskat's examples and approach to reservoir engineering
Muskats
stimulated my interest in the area of fluid flow in porous
media. Most of all he let me discover reservoir engineering
on my own.

spending the first two


After spending two years at NTH as a teachers
teacher's
assistant and
and guest lecturer, i spent three years
years (1980 to
1983) as aa research fellow for Rogaland Regional
1983) as Regional College
College
(RDH). were provided by NAVF, the
Funds were the Norwegian general
council" The fellowship gave me the time and
research council.
projects and continue those which had
freedom to develop new projects
Trondheim. It
started in Trondheim. It also introduced me to an active
program in chemical analysis of
experimental program of petroleum
petroleum
fluids: the Oil and Gas Gas Laboratory
Laboratory at
at Rogaland Research
headed by Tor Austad
Institute (RRI), headed Austad and
and Olav
Olav Vikane.
Golan and
Michael Golan and later (through
(through his introduction), Mike
Mike
Fetkovich and Raj Raghavan provided
Fetkovich provided important
important insight
insight into
into
practical problems of flow in porous media.
practical media. Discussions
Discussions with
with
these three led toto several
several papers onon the same
same subject
subject (A.7
(A.7
to A.9). Somewhat of an exception was
to was the
the paper TwoPhase
Two-Phase
iii
111

Pressure Test Analysis,


na1ysis, which stemmed from work my first
year at RDH with coauthors Arild B~e and Svein Skaeveland.
Prild Be
B(lle
Be was responsible for the theoretical developments and i
performed all numerical calculations.

Throughout the three-year


threeyear fellowship it was a pleasure to
work wi th Leif
with Lei f Larsen at RRI. We enjoyed numerous
discussions about the more theoretical aspects of pressure
transient testing, a subject on which Larsen has made
considerable contributions during the short period he has
worked in the field.
One year spent at IKU (Continental Shelf Institute) in
Trondheim (1982) provided the catalyst for my work with
equation-of-state
equationofstate development and application. Discussions
with Vilgeir Dalen and Rasmus Risnes were particularly
helpful. More recently it has been my pleasure to work
with Haakon Norvik on implementation of the generalized
cubic equation of state proposed in this study, as well as
learning about the methods of numerical solution used to
solve multicomponent VLE calculations.
The following organizations have been central in providing
services such as computing, travel, financial support,
and access to experimental data:
Norwegian Institute of Technology (NTH)
Rogaland Regional College (RDH)
Norwegian General Research Council (NAVF)
(NPNF)
Rogaland Research Institute (RF)
(RE)
Continental Shelf Institute (IKu)
(IKU)
Norwegian Petroleum Directorate (NPD/OD)
AGIP A/S
Norsk PGIP b\/S
Phillips Petroleum Company
Without
without their help the research would not have been
possible.

It is a pleasure to recognize those who have made the thesis


worth finishing: Grete, m & d, Pokey, grandpa, Andreas,
m&d, Pndreas,
Lucille, Barth, and Josef Faust. As
Is far as Craig and frying
pan go, yall provided the laughs when they were most
dAkke ha!
welcome. Takk ska dkke
TOPICS ON PHASE BEHAVIOR AND
ANO FLOW
OF PETROLEUM RESERVOIR FLUIDS

CONTENTS

DEDICATION iI

FOREWORD iiii

INTRODUCTION .................. 1

SUtJMARY
SUMMARY 22

Chapter 11 66
vi
V REVIEW AND DEVELOPMENT OF CUBIC EQUATIONS OF STATE

1.1 What is a Cubic Equation of State?


State 66
1.2 A
A Short Review of
of Cubic Equations 99
1.3 Redlich/Kwong Modifications 10
1.4 Peng/Robinson Equation 12
1.5 Usdin!McAuliffe
Usdin/McAuliffe Equation 14
1.6 Comparison of Three Cubic Equations 15
1.7 Proposed Equation-of-State
EquationofState Modifications 28
Nomenclature ...................... 45

Chapter 22 .............................................. 47
CHARACTERIZING PETROLEUM FRACTIONS
CHARACTERIZING

2.1 Introduction to the Problem 47


2.2 Proposed Molar Distribution Model...............
Model 48
2.3 Estimating Specific Gravity and Boiling Point 64
2.4 Traditional Critical-Property
CriticalProperty Estimation 66
2.5 Equation-of-State CriticalProperty
EquationofState Critical-Property Estimation..
Estimation 68
2.6 Equation-of-State Predictions Using Proposed
EquationofState
Critical-Property
CriticalProperty Estimation 99
Nomenclature ............ 106

Chapter 33 107
. . . . . . . . . . . . . . . . . 107

FLOW IN POROUS MEDIA


3.1 Introduction to Fluid Flow in Porous Media 107
107
3.2 Corey/Burdine Relative Permeability Model 113
3.3 Constant-Rate
ConstantRate Well Testing Under Conditions
of Two-Phase,
TwoPhase, Gas-Oil
GasOil Flow 121
3.4 Determining Deliverability by Multirate Testing 125
125
3.5 Constant-Pressure
ConstantPressure Dimensionless Rate Solution
During Depletion ............. 128
3.6 Partial Penetration Effects on Fluid Flow 134
134
Nomenclature ...................... 137
REFERENCES 140
.

Appendix A
P1 ...................... A.1-1
P1.1-i

PUBLISHED/UNPUBLISHED
PUBLISHEDAJNPUBLISHED TECHNICAL PAPERS

A.l
P1.1 Glas~,~.
Glas, and Whitson, C.H.:
0.
The Accuracy of PVT Parameters Calculated From
Computer Flash Separation at Pressures Less Than
1,000 psia A.1-1
A.2
P1.2 Whitson, C.H.:
Characterizing Hydrocarbon Plus Fractions A.2-1
A.2-i

A.3
P1.3 Whitson, C.H. and Torp, S.B.:
5.6.:
Evaluating Constant-Volume
ConstantVolume Depletion Data A.3-1
A.3-i

A.4
P1.4 Whitson, C.H.:
Effect of Physical Properties Estimation of
Equation-of-State
EquationofState Predictions A.4-1

A.S
P1.5 Whitson, C.H.:
A
A Family of Cubic Equations of State A.5-1
A.5-i

- A.6
P1.6 Austad, T., Hvidsten, J.,
J., Norvik, H. Whitson, C.H.:
Practical Aspects of Characterizing Petroleum
Flui ds ............ A.
Fluids 6-1
A.6-1

A.7
P1.7 B~e,
Be, A., Skjaeveland, S.M., and Whitson, C.H.:
Two-Phase
TwoPhase Pressure Test Analysis A.7-1

A.a
P1.8 Whitson, C.H.:
Reservoir Well Performance and Predicting
Deliverability .... A.8-1
A.8-i

A.9
P1.9 Whitson, C.H.:
Discussion of Constant-Rate
ConstantRate Decline During
Depletion A.9-1

Appendix B
B B.1-1
B.1-i

EXPERIMENTAL DATA FOR SEVERAL PETROLEUM RESERVOIR FLUIDS


B.l
B.1 Hoffman/Crump/Hocott Fluids B.1-1
B.2
6.2 Standing/Katz Recombined Mixtures B.2-1
B.3 Eilerts Fluids ............ 8.3-1
B.3-1
B.4 Jacoby Recombined Mixtures B.4-1
B.S
B.5 aIds/Sage/Lacey
Olds/Sage/Lacey Recombined Mixtures B.5-1
INTRODUCTION

this is the short and long of it - W. Shakespeare

Two subjects have been considered in this thesis.


The first, phase behavior of petroleum reservoir fluids,
covers cubic equations ofof state and characterization of
petroleum fractions. The second, fluid flow in porous
media, reviews a hodgepodge of new and historical ideas
ranging from two-phase
twophase flow to partial penetration effects.
Combined, the two subjects represent a type of dipole
moment - the product of two topics with dissimilar nature

of equal importance.

A
P1 good introduction should review the pertinent literature
associated with the subject being discussed. This has been
delegated to individual chapters. References are given at
the end of the thesis but have been separated into two
lists, reflecting the two general subjects of the thesis.
AP1 review of what has been done is given in the Summary
Surrnary
section, once again separated in two.
Several papers, some published and some not, have resulted
during the past five years. They should be considered on
their own merit. The three chapters of the thesis do not,
in general, repeat material found in the papers. Instead
they provide new work, together with elaboration and
criticism of the old. Mere repetition of the papers would
lend the thesis to Frank Dobies
Dobie's definition as a
"transference
transference of bones from one graveyard to another."
another.
Hopefully this has been avoided.
If
it i were to suggest a way of getting through the thesis
with minimum pain and effort, it would be to first read the
Summary section, then the first sections of each chapter
introductions) , next to the papers, and finally the main
(introductions),
C
text in Chapters 1, 2, and ahd 3. Obv ious ly the choice is
Obviously
up to you. Whether burdened wi th the reading or made by
with
choice, i hope you enjoy the remainder.

Style Note:
The unorthodox practice of combining multiple authors into
(/) instead of hyphen C-)
a combined form using slash C/) ()
tries to circumvent confusion resulting from the increasing
use of two surnames combined by a hyphen. Hopefully this
will not detract from readability.
22

SUMMARY:
SUMMPiRY: Chapters 1
1 and 2
2

(1) It is doubtful that any cubic equation ofof state can


accurately predict phase behavior of petroleum reservoir
fluids over the full range of pressure, temperature and
composition normally encountered between the outer boundary
of a reservoir and the final pre-processing
preprocessing stage of
production.
(2) The description of the h~avy
heavy fractions is very
important to the predictive capabilities of cubic equations
of state and should be given serious consideration. However,
it does not appear that even the best characterization will
guarantee that cubic equations can be used as an accurate
predictive tool.

(3) Having attempted to properly define the properties of


individual components in a mixture, the engineer should be
prepared to make adjustments based on experimental data. A
practical approach should involve initial adjustment of
properties for the heaviest petroleum fraction - e.g., the

boiling point and molecular weight of distillation residue.


If this does not result in the desired match of experimental
PVT data, manipulation of petroleum-fraction
petroleumfraction critical
properties or EQS
EOS constants can be tried, though not
necessarily limited to the heaviest fraction.
(4) Before characterizing a petroleum reservoir fluid with
an equation of state the engineer should define why the
calculations are being performed. If high accuracy is
required - e.g.,
minimum miscibility determination-
determination

experimental data should be obtained in the pressure-,


pressure,
temperature-, and composition range of interest.
Considerable effort should be given gi ven to heptanes-plus
heptanesplus
characterization.
(5) Development in cubic equations of state should
concentrate on improving volumetric predictions, and
particularly liquid density estimation. Several attempts
have been made in this study to improve existing equations
and develop new ones with the goal of improving liquid
densi ty estimation. The first suggestion is a modification
density modi fication
of the three-constant
threeconstant Usdin!McAuliffe
Usdin/McIuliffe EOS.
EQS. Saturated liquid
densi ties are fit by including a second correction factor
densities
for EQS
EOS constants; the functional form of this correction
factor is simple and arid does not introduce addi tional
additional
correlating parameters. The next development is a family of
cubic equations based on the four-constant
fourconstant Martin equation.
The speci fication
specification of cri tical compressibility and a
critical
numerical constant simplifies the general equation to almost
any two-or
twoor three-constant
threeconstant EOS
EQS of interest. By minimizing
33

the absolute
the absolute error
error of
of saturated
saturated liquid an optimal
liquid densities, an optimal
EOS has
EQS has been
been proposed;
proposed; for compounds
compounds similar to hexane
similar to hexane and
and
heptane the
heptane the new
new EQS
EOS simplifies to the
simplifies to the PR
PR EQS.
EOS.
(6) PA probabilistic
(6) probabilistic model
model has
has been
been proposed
proposed for describing
describing
the relation
the relation between
between molar
molar quantity
quantity and molecular
and molecular weight
weight of
of
petroleum fractions - i.e.,
petroleum i.e., molar distribution.
distribution. In the
In
absense of
absense of distillation oror chromatographic data,
data, the
the model
model
can be
can be used
used to
to generate
generate aa molar distribution based on
based on the
the
average molecular
average molecular weight
weight of
of the
the petroleumfraction
petroleum-fraction mixture.
If aa partial
If partial analysis isis available,
available, the model
model can
can be
be used to
to
extrapolate or
extrapolate or split
split the heaviest fraction, having
having first
data for the
matched data the lighter fractions. The The model
model has
has been
been
improved by
improved by introducing
introducing the concept of of cumulative
cumulative normalized
normalized
quantities.

(7) PA method based on the Watson


Watson characterization
characterization factor
is proposed for estimating petroleumfraction
petroleum-fraction specific
gravities and boiling points. The necessary data include
molecular weight of each fraction, and
molar quantity and molecular
specific gravity of the total petroleumfraction
average specific petroleum-fraction
mixture. The
mixture. The method is
is simple
simple to
to use
use and
and can
can be
be solved
solved
and error). Despite
explicity (without trial and Despite its
its approximate
nature, the method appears to have advantages over over other
other
methods presently
methods presently available. Estimations based only on
Estimations
weights (which themselves may be estimated
molecular weights estimated or
or
calculated) can only
only be approximate, and none of of the
presently available methods will give accurate estimates of
specific gravities and boiling points.
(8) IA new method for calculating critical properties and
(8)
acentric factor of petroleum fractions based on an EQS EOS
appear to give promising improvements in both volumetric and
phase behavior predictions. The method requires only molar
volume (ratio of molecular weight to specific gravity) and
boiling point. The acentric factor relation is empirical,
though it accounts for non-paraffinicity
nonparaffinicity via the Watson
characterization factor and simplifies to an accurate
relation for paraffins and aromatics. Simply stated, the
method matches input molar volume and boiling point with the
EOS
EQS by adjusting critical pressure and critical temperature.
Tables of EOS-based
EQSbased critical properties are given for the
Peng/Robinson and Soave/Redlich/Kwong equations.
(9) A method is suggested for calculating the so-called
socalled
black-oil PVT properties of gas condensates and volatile
blackoil
oils based on constant-volume
constantvolume depletion data. The modified
gas/oil ratios and formation volume factors form the basis
for modified black-oil
blackoil numerical simulators which have been
shown to have, for certain reservoir processes, comparable
accuracy with multicomponent compositional models.
44

SUMMARY:
SUMMIRY: Chapter 3
3

(1) Probably the most difficult engineering task facing


the multiphase flow problem in porous media is determination
of
of accurate (average) relative permeability relations
applicable to fluid flow at reservoir conditions. This
leads to the second most difficult task of finding the
correct physical/mathematical definition ofof the relevent
saturation relation.
(2) Given the uncertainties associated with the definition
of realistic relative permeabilities, complicated
mathematical solutions of the saturation/pressure relation
for gas/oil flow are probably of questionable merit. More
emphasis should be placed on a practical engineering
solution to the estimation of twophase
two-phase fluid flow. The
Evinger/Muskat pseudopressure function provides a reasonable
balance between accuracy and arid simplicity. For many
applications, the pressure-squared
pressuresquared method suggested by
Fetkov ich prov
Fetkovich ides a solid engineering approach for
provides
analyzing multirate and drawdown!buildup
drawdown/buildup test data.

(3) Based on results of numerical simulations for


solution-gas
solutiongas drive depletion, Vogel develops a simple
expression for the relation between oil rate and well flowing
weilfiowing
pressure. The empirical form of Vogel's
Vogels relation has been
generalized and interpreted in terms of the pressure
function proposed by Evinger and Muskat. Having defined the
linear form of the pressure function, insight has been
gained into alternative and modified inflow performance
relations. In particular, it is found that the Standing
method for correcting the Vogel relation for nonzero skins
has severe limitations for stimulated wells.
(4) A method is proposed for generalizing the analysis of
multirate tests. It is based on the observations made by
Fetkovich from analyzing over 40 multi rate tests on oil
multirate
wells. AP type curve is given for analyzing multirate data;
this type curve shows that the common interpretation of aa
linear log-log
loglog deliverability plot is only approximate over
a limited range of drawdown. Examples show the use of the
type curve and method of analysis for gas and oilwells.
55

(5) The
(5) The theoretical considerations
considerations ofof constantpressure
constant-pressure
depletion have been considered. Different
production during depletion Different
suggestions in
suggestions in the literature
literature about
about the proper
proper means of
normalizing analytical dimensionless rate are discussed. The
is best approximated using the first
exponential decline is
root ofof the Bessel function expression
expression resulting from
solution of the differential equation
solution equation describing flow under
under
constant-pressure conditions.
constantpressure The practical problem with
Bessel functions to
determining this root and calculating Bessel
of the exponential
determine the constants of exponential rate expression
compared the various empirical and
are unfortunate. Having compared
semi-analytical methods of normalizing the dimensionless
semianalytical
rate solution, aa suggestion is made as to which relation
compromise between
offers the best compromise between accuracy and simplicity.
simplicity.
partial penetration
(6) The solution to the partial penetration problem
problem
proposed by Brons and Marting uses aa numerical solution to
Nisle's approximate analytical solution.
Nisles Despite their
claim that the key function, G( b) , must be sol
C(b), ved
solved
numerically, it is shown that an exact analytical expression
is found in the original Muskat solution, and that its form
can be solved directly, without the need of a computing
device. While Brons and Martings
Marting's suggest that the Muskat
solution (and their expression using G(b))
0(b)) is only valid for
'large'
large dimensionless heights, it is shown that the
corresponding total thicknesses is 25 feet (7.5 m) or less.
This means that for all practical purposes the original
Muskat solution can be used to estimate partial penetration
skin.
66

Chapter 11
REVIEW AND DEVELOPMENT OF CUBIC EQUATIONS OF STATE

in memory of J.J. Martin

1.1 WHAT IS A
A CUBIC EQUATION OF STATE?

What is a cubic equation of state? It is an equation


relating pressure, temperature, composition and volume.
Slightly oversimplified, we can write a general form of the
cubic equation as

V3 +
3 22 +
+ aV
aV bV +
+ bV c
+ C =0
= (1.1)

Constants a, band
b and c are defined by pressure, temperature,
composition and the amount (moles) of fluid. Since the
equation is cubic in volume, there may be one, two (seldom)
or three real solutions which satisfy the speci fied
specified
conditions. Which volume should be choosen if there are,
say, three volumes? In practice the largest volume is
defined as vapor and the smallest volume as liquid; if a
third volume exists between these two then it is merely
ignored. If only one volume satisfies the equation then
there is obviously no problem in choosing the correct
solution. Negative volumes may result at large
supercritical temperatures (e.g., nitrogen at 4006 psia and
163.5 FF using the Peng/Robinson EOS),
EOS) , in which case the
negative root is ignored.
Why choose a cubic form? The answer lies in the behavior of
of
real fluids. Consider water for a moment. At room
conditions water behaves as a liquid and has a density of
approximately 11 g/cc. When water is heated its density
decreases, though only slightly (mass remains constant while
volume increases)
increases). However, once 100 C
0C is reached the
water becomes aa vapor (steam) and its density changes
abruptly, becoming several orders of magnitude lower. At
0c we can actually say that water has two densities -
100 C

the saturated vapor density (steam) and saturated liquid


density (heated water). To correctly predict this abrupt
change in density (i.e., volume, assuming a constant mass),
the cubic equation chooses the larger volume solution to
describe steam, and the smaller volume solution to describe
heated water.
77

Cubic equations are usually expressed in terms of of the


compressibility factor, Z, which is defined by the real gas
law: ZZ =
= pV/NRT, where pp == pressure, V=
V = volume, N =
N = moles,
T = absolute
T temperature, and R =
R = the universal gas
constant. The general form of any cubic equation of state
can now be wrhtten,

Z3
3 +
Z 22 +
+ eZ
eZ + fZ
fZ +
+ g
g = 00
= (1.2)

where constants e, f and g g are defined by p, T, and


composition. Considering only pure compounds, constants e,
f and gg can be expressed for one of the more popular cubic
equations of state - the Peng/Robinson (PR) equation,

= B-11
ee=B
ff =A -
= 22
38
3B - 28
2B ........................ (1.3)

g = B + 62 PB

where
)pc)
O.45724O(p/T
/
2 (Tc ................ ((1.4a)
1.4a)
B =
B = 0.07780(p/T)(T c/Pc) (1.4b)
0.07780(p/T)(Tc/pc)

and
IQ == 1+(O.37464+1.54226w0.26992w
1+(0.37464+1.54226w-0.26992W2)(1~)
)
2 (1vTE) (1.4c) ..

The expressions for PA and BB result by forcing the two van


der Waals criteria that the first and second derivatives of
pressure with respect to volume (at the critical
temperature) equal zero. Constants 0.45724 and 0.07780 are
usually designated a~a and ~b,
b, respectively, and are only
approximate, rounded here to five significant digits. The
term a is an empirical correction factor dependent of the
compound (e.g., acentric factor, or another correlating
parameter) and reduced temperature, T r It is found by
Tr.
matching experimental vapor pressures along the
vapor-pressure
vaporpressure curve and fitting the results with the
equation form (Eq. 1.4c) first suggested by Soave in his
modification of the Redlich/Kwong equation.
8

To calculate volume of of a pure compound, first specify


component properties w, Pc
Pc, and T c. Calculate a from Eq.
Tc.
1.4c, then constants AA and 8B from Eqs. 1.4a and 1.4b,
from which constants e, f and g g are found from Eq. 1.3. The
cubic equation (Eq. 1.2) is solved for Z. Analogous to our
previous discussion of multiple.-volume
multiple-volume roots, the largest
Z-factor is assumed to represent vapor and the smallest
Zfactor
Z-factor
Zfactor is assumed to represent liquid; no choice is posed
if only one Z-factor
Zfactor root exists. Given Z, volume is found
from ZNRT/p. Density is merely NM/vNM/V or pM/ZRT, where MM is
molecular weight.

An example calculation is given for methane, which has


w=O. 0115, Pc=4.
properties w=0.0115, 604

4
Pc 604 MPa, and T
O
9c=190..
Tc=l
58 58 K. The
boiling point of methane at atmospheric pressure (0.10132
MPa) is 111.
111.66 K
K (T r=O. 58558). From these data, a=1.
(Tr=0.58558). 0921,
a=1.0921,
A=0.03205, 8=0.002924,
B=0.002924, e=-0.99708,
e=0.99708, f=0.02617, and
g=-0.00008510
g0.0000851. Solving the cubic equation gives Z=0.0038,
Z=O. 0038 ,
0.0231, and 0.9702, the smallest root being designated as
the liquid factor and the largest root as the vapor factor.
Corresponding liquid and vapor densities are 0.461 and
0.001806 g/cc, respectively.

The procedure for finding volume and density is essentially


the same for mixtures. Given composition, the terms AA and B
B
are calculated using appropriate mixing rules. If the
mixture exists in the single-phase
singlephase region, the procedure can
be applied directly to the mixture composition. If the
mixture splits into two phases, then the procedure is
performed for each phase; this requires, however, the
composition of each phase. Vapor/liquid equilibria (VLE)
calculations necessary for determining phase compositions
are more complicated and will not be reviewed here.
Several points deserve mention. First, the PR EOS is an
example of aa two-constant
twoconstant cubic equation. The two constants
are AA and 8, B, as defined by Eqs. 1.4 Second, the critical
properties (as well as acentric factor and molecular weight)
reqI,Jired
required for each component in a mixture are not
well-defined
welldefined properties for petroleum fractions. They are
usually di fficult to estimate, and it may be found that
difficult
different correlations give considerably different results.
Another observation about two-constant
twoconstant equations is that
constant AA usually dictates VLE and vapor density
predictions, whereas 8B usually dictates liquid density
prediction. Consequently, Tc has more influence on VLE and
vapor density predictions than pc. Pc Also, a second
correction factor the so-called
socalled binary interaction
parameter - is often used to correct VLE deficiencies for

mixtures of compounds with unlike properties. 8inary


Binary
coefficients are also applied to constant A.
9

1.2 A
A Short Review of Cubic Equations

Professor Joseph J. Martin from the University of Michigan


summarizes the problem resulting from an overabunance of
cubic equations of state (EOS) by quoting from none other
than Snow White:
white: "Mirror,
Mirror, mirror on the wall, who's
whos the
fairest of them all?"
all? Despite Martins
Martin's claim to have
developed the 'fairest'
fairest cubic equation, it is probably safe
to say that all equations have inherent limitations and that
no single equation performs better than all others.
van der Waals proposed the first cubic EOS in 1873. Since
then, the evolution of cubic equations has resulted in new
forms such as those proposed by Redlich/Kwong (RK), Martin,
Peng/Robinson (PR), and Usdin/McAuliffe
Usdin!McAuliffe (UM), only to name a
few. Several alternative forms of these equations have been
suggested, but the RK equation has certainly been the most
popular basis for modification.
AA recent trend (Martin, Abbott, Usdin!McAuliffe,
Usdin/McAuliffe,
Schmidt/Wenzel, etc.) has been to propose generalized cubic
equations which can be simplified to more popular/familiar
forms. Most investigators agree that no single equation, no
matter how complicated (three, four, or five constants), can
accurately predict volumetric and phase behavior of pure
compounds or mixtures over a large range of conditions
and composition.
Description of pressure/volume/temperature (PVT) behavior of
petroleum reservoir fluids has formed the basis for
developments given in papers A.2 to A.5. A.S. Saturation
pressures, densities and twophase
two-phase VLE are the properties
which have received most attention. Emphasis has also been
gi ven to application of EOSs
given EOS' s at conditions of pressure
and temperature found in the reservoir, production tubulars,
Low-temperature
surface separators and transportation lines. Lowtemperature
conditions found in refineries and gas-stripping
gasstripping plants have
not been considered.

Most petroluem engineering applications of cubic equations


rely on a modification of the RK EOS EQS or PengRobinsons
Peng-Robinson' s
original equation. Numerous variants of the RK equation have
found acceptance. Soave's
Soaves modification (SRK) is the
simplest and most widely used. Unfortunately it yields poor
liquid densities. In an attempt to improve volumetric
predictions, Zudkevitch and Joffe (ZJRK) propose a method in
which both EQS
EOS constants (a and b) are corrected by
temperature functions. Several months after the original
publication, Joffe, Schroeder and Zudkevitch proposed a
slight modification of the original procedure. Others, such
as Yarborough and Gray, base their own modifications on the
10
10

ideas of
ideas of Zudkevitch,
Zudkevitch, Joffe
Joffe and
and Schroeder.
Schroeder. The
The acronym
acronym ZJRK
ZJRK
is used
is used for
for all
all modifications
modifications based
based on
on the
the original
original work
work by
by
Zudkevitch and
Zudkevitch and Joffe.
Joffe.
The PR
The PR EQS
EOS isis comparable
comparable toto the
the SRK
SRK equation
equation in in simplicity
simplicity
and form.
and Peng and
Peng and Robinson
Robinson report
report that
that their
their equation
equation
predicts liquid
predicts liquid densities
densities better
better than
than the
the SRK
SRK EQS
EOS (though
(though
they are
they are usually inferior to
usually inferior to ZJRK
ZJRK EQSEOS predictions).
predictions). P1A
distinct advantage
distinct advantage of of the PR PR and and SRKSRK equations
equations is is
reproducibility; simple temperaturedependent
reproducibility; temperature-dependent expressions
expressions
used to
are used to express
express the correction to EQS EOS constant
constant A.A. The
The
ZJRK equations
ZJRK equations rely on on tables
tables or complex
or complex best-fit equations
bestfit equations
non-linear correction
to represent highly nonlinear correction terms
terms for EQSEOS
constants 1
P and B.
constants A and B.

AA promising
promising three constant
constant EQSEOS was proposed almost
simultaneously by
by Usdin/McP1uliffe
Usdin!McAuliffe (UM) and Fuller.
Fuller. Although
Although
the equation has not received wide acceptance, it exhibits
exhibits
several qualities which make it an attractive alternative.
Martin shares his admiration of the equation by equating Ht
in accuracy to his own best
'best' equation (his claim that
translation in volume is simpler than defining a
componentdependent critical compressibility factor seems
component-dependent
debatable).
P1A new concept to cubic equations of state was proposed by
Martin in 1979: translation in volume. The application
given by Martin is essentially to ease the comparison of his
proposed generalized EOS EQS with previously published
equations. It also shows similarites/differences in simple
volumetric predictions by various equations. In an
independent study, Peneloux et ale al. uses the idea of
translation in volume to improve volumetric capabilities of
the Soave RK EOS.EQS. Peneloux, et al.'s
al.s most important
observation is that traditional VLE calculations based on
component fugacity ratios are not affected by translation in
volume. They do not discuss, however, the potential effect
which results when using fugacities directly - e.g., with

the Peng/Robinson method for predicting semi-solid


semisolid phase
equilibr ia)
equilibria).

1.3 Redlich/Kwong Modifications


A
P1 newcomer
newcomer introduced to the RK EOS EQS may
may be
intrigued
intrigued byby the
the simplicity,
simplicity, accuracy andand mathematical
mathematical
pleasure which results from deriving its thermodynamic
thermodynamic
properties. This has lead to inumerable
inumerable attempts toto better,
better,
extend and in
in some cases, bastardize, the original equation.

There
There are
are certainly hundreds if not
hundreds if not thousands
thousands of
of technical
technical
papers,
papers, theses,
theses, and
ano compendiums
compendiums written
written about
about the
the RK
RK EOS.
EQS.
11

With the advent of advanced numerical computers, this craze


developed into what Abbott
Pbbott coined the Redlich/Kwong decade
(1967-1977). Abbott
(19671977). P
b
1 bott claims that the remarkable sucess of
of the
EOS results from its excellent prediction of the second
RK EQS
viral coefficient (securing good performance at low
densities) and reliable predictions at high densities in the
supercritical region. This latter observation results from
the compromise fit of densities in the near-critical
nearcritical region;
all pure components are required by the RK EQSEOS to have a
critical compressibility factor of 1/3. This value is
reasonable for liqhter hydrocarbons but is less satisfactory
for heavier compounds.

Soave/Redlich/Kwong (SRK)
Several attempts have been made to improve vapor-pressure
vaporpressure
(i.e., VLE) predictions by introducing a correction term for
EOS
EQS constant P.A. Soave uses vapor pressures directly to
determine the functional relation for the correction factor.
The SRK EOS
EQS appears to be the most accepted modification
proposed to date. Still, it overestimates liquid volumes of
petroleum mixtures.
The present use of the SRK EOS
EQS results from historical and
practical reasons. It offers an excellent predictive tool
for systems requiring accurate predictions of VLE and vapor
properties. It
It should be used with caution, however, when
liquid volumes are important for the engineering
application.

Zudkevitch/Joffe/Redlich/Kwong
Zudkevitch/Joffe/Redlich/Kwong (ZJRK)

Zudkevitch and Joffe propose a novel procedure for


improving the volumetric predictions of the RK EQSEOS without
sacrificing VLE capabilities of the original equation. Their
method suggests that the same EOS
EQS constants, P1A and B, be
used for both the liquid and vapor phases, yet that they be
corrected as a function of temperature to match saturated
liquid densities and fugacities. They show that errors in
vapor fugacities and fugacity ratios (i.e., K-values)
Kvalues) remain
unaffected for all practical purposes. They do not comment
on the effect of their procedure on vapor densities.
Only
Qnly six months after the original ZJRK modification, Joffe,
Schroeder and Zudkevitch proposed an alternative method
(similar to one previously used for a modified BWR EOS) EQS)
whereby liquid fugacity was dropped and vapor pressure used
directly. That is, constants AA and B B are determined by
matching the RK EQS
EOS to saturated liquid densities and vapor
12

pressures at subcritical temperatures. The procedure for


determining A
I and BB is trial and error. The authors claim
this procedure only can be used below the critical
temperature. Haman, et ale
al. show, however, that a single
procedure can, in fact, be used for subcritical and critical
temperatures (based on suggestions by Kato, et al.).

The Joffe/Schroeder/Zudkevitch procedure, which is little


more than a twist on the original Zudkevitch/Joffe proposal,
also is given the acronym ZJRK. To my knowledge, no one uses
the original procedure and the acronym should not,
therefore, cause confusion.
The ZJRK approach has been used to determine constants PA and
B
B for pure paraffins (Haman, et al.) and petroleum fractions
(Yarborough and Gray). Unfortunately, the resulting
temperature functions are very complex, being represented by
higher-order
higherorder polynomials or cubic splines; the behavior of
these functions is highly nonlinear near the critical point.
Also, there does not appear to be one set of correlations
PJso,
accepted by the industry, thereby making it difficult to
reproduce results. Gray suggests that the ZJRK procedure be
performed each time the EOS
EQS is used. He claims that it is
not necessary to know critical properties of petroleum
fractions to use the procedure.
In review, two Relich/Kwong modifications - Z3RK
ZJRK and SRK -

seem to have received the most interest in application to


petroleum reservoir fluids. The Soave equation is preferred
because of its simplicity and overall accuracy. Its primary
disadvantage is poor volumetric predictions. The
Zudkevitch/Joffe
Zudkevitch/3offe equation is surprisingly accurate for both
liquid and vapor property estimation; its main disadvantage
is the complexity of functions used to represent
temperature-dependent correction factors for EOS
temperaturedependent EQS constants.

1.4 Peng/Robinson (PR)


In 1975, Peng and Robinson proposed a two-constant
twoconstant
equation which created great expectations for ftr improved
liquid density predictions. The equation does not produce
inferior VLE compared with the RK equations. also, Also, the
relation used to describe the temperature-dependent
temperaturedependent
correction factor for EOS
EQS PA (Eq. 1.4c)
l.4c) is nearly identical
to the Soave correlation.
The largest improvement offered by the PR equation is a
universal critical compressibility factor of
0.307401. -somewhat
Q.3Q7401... somewhat lower than the RK
RI< value of 1/3 and
arid
closer to experimental values of heavier hydrocarbons. The
13

difference between PR and SRK liquid volumetric predictions


can be substantial, though in many cases the errors in oil
densi ties are unacceptable from both equations. There is
densities
evidence that the PR equation underpredicts saturation
pressure of reservoir fluids and that considerable
adjustments of binary interaction coefficients are required
to match measured VLE data ere
(re Katz and Firoozabadi).

Availability
Pvailability and considerable publicity have given the PR
equation an obvious advantage in recent years. Peng and
Robinson certainly make their equation well known by
documenting how it can be applied to petroleum and
non-hydroocarbon systems.
nonhydroocarbon They also have presented
numerical solutions to difficult problems near the critical
region, as well as proposing novel methods for predicting
multiphase and semi-solid
semisolid phase behavior. In addition to
their own efforts, the PR EOS
EQS has almost become chic to use
for research applications. By virtue of the interest which
industry has bestowed upon Peng and Robinson's
Robinsons efforts, it
almost seems obligatory to choose the PR over the SRK
equation.
To my knowledge, no effort has been made to improve the PR
EOS using the ZJRK technique. Neither has the use of volume
EQS
translation been suggested. It is not obvious why either Of
of
the two methods might not be sucessful in improving the
original PR EQS.
EOS.
In review, the PR EQSEOS is a popular, simple and relatively
accurate alternative to RK equations. But it is just that -

an al ternati ve - and not really a replacement. One


alternative Qne good
reason for using the PR EOSEQS is that there presently exists
extensive sets of binary interaction coefficients for
important hydrocarbon/non-hydrocarbon
hydrocarbon/nonhydrocarbon systems. In
particular, recent experimental work with carbon dioxide has
almost exclusively been fit by the PR EQS
EOS using interaction
parameters. Considering the practical importance of C02 2 to
CQ
petroleum reservoirs, the PR EOS
EQS will certainly continue as
an important tool in describing fluid behavior of complex
hydrocarbon mixtures.
14
14

1.5 Usdin/Mculi
1.5 Usdin!McAuliffe (UM)
ffe (UM)

In 1976,
In 1976, Usdin
Usdin and
and McP
McAuU
u
1 ffe presented
liffe presented aa threeconst
three-constant
ant
cubic EQS
cubic EOS which
which isis claimed
claimed to
to improve
improve liquid
liquid density
density
predictions while
predictions while retaining
retaining VLE accuracy and simplicity
simplicity of
of
RK equations.
RK equations. By
By specifying
specifying critical
critical compressibil
compressibility
ity factor
each component,
for each component, Usdin
Usdin and
and McPuliffe
McAuliffe show
show that
that their
their
equation gives
equation gives greater
greater flexibility, while
while reducing to
reducing to more
more
common forms such
common such asas the ideal
ideal gas
gas law,
law, van der Waals
Waals'
equation or
equation or the RK equation.
equation. (Fuller presented
presented the same EQS
EOS
in an independent studty some six months after after Usdin and
McAuliffe. )
Mc/uliffe.)

Usdin and McPuliffe


McAuliffe do not suggest that measured critical
critical
compressibility
compressibil ity factor be used to define EOS
EQS constants.
Instead they propose aa method where Zc is defined by
matching predicted liquid density of aa component at aa given
temperature with its experimental value; e.g., liquid
temperature
density at standard temperature, usually expressed relative
to water as specific gravity.
The temperature-dependent
temperaturedependent correction factor for EOS
EQS A
I is
determined in the same manner as proposed by Soave. Usdin
and McAuli ffe give, however, aa slightly more complicated
McPuliffe
expression for temperature dependence. They do not indicate
if the simpler form proposed by Soave is sufficient (though
VLE comparisons presented by Usdin and McPuliffe
McAuliffe suggest
that little is gained by using the more complicated
expression)
expression). Also,
Piso, results are not presented for phase
behavior at supercritical temperatures.
temperatures.

The method proposed by Fuller for adjusting UM EOS


EQS constants
to match vapor pressures and saturated liquid densities is
similar to the ZJRK method. In fact the same procedure has
been performed in this study without knowledge of the work
by Fuller, and not surprisingly gives similar results.
An
Pn important difference between the ZJRK and Fuller methods
is that EOS
EQS constant's
constants variation with temperature is smooth
and easily described using the UM EOS EQS (Fuller's
(Fullers choice).
This results because critical compressibility
compressibility factor is
specified by the UM EOS EQS and represents a much better
estimate if not exact experimental value of Ze.
Zc.

In my opinion, the UM EOS


EQS provides one of
of the most practical
al ternati ves to
alternatives to RK and PR equations
equations without complicating
thermodynamic
thermodynamic predictions. Apparently
pparently the improvement
improvement in
in
liquid densities has not given sufficient
sufficient reason
reason to make the
the
UM alternative widely accepted.
15
15

1.6 Comparison of Three Cubic Equations


In this section a comparison is given between the
predicti ve capabili
predictive ties of the Peng/Robinson and two
capabilities
modifications of the Redlich/Kwong equations. The reservoir
fluids used to make the compar ison are those presented by
comparison
Standing and Katz. The reason for this choice is that the
Standing/Katz data, though somewhat limited in number, form
the basis for two of the most widely used density
correlations found in the petroleum industry. The
Standing/Katz reV1S1on
revision of the corresponding states
compressibility factor chart is recognized as the industry
standard from which all empirical and EOS-based
EQSbased correlations
are compared. The liquid density correlation is somewhat
limi ted in the range of temperature but has proven to be
limited
both accurate and easy to use,
use. Of upmost importance is that
both density correlations resulting from the Standing/Katz
data are predictive
predicti ve i. e. , no adjustment of model
i.e.,
parameters is necessary.
The SRK and ZJRKZ3RK equations are chosen to represent the
Redlich/Kwong family. Tables of correction terms used by
the ZJRK EOSEQS have been read from Yarborough's
Yarboroughs figures
IKU).
(Hustad, IKtJJ. Critical properties of the petroleum
fractions were estimated from correlations (Cavett and
Edmister). Complete description of the reservoir fluid
mixtures and their properties are given in Appendix B. The
Cavett/Edmister property estimations for petroleum fractions
are found in Table 1.1.

TABLE 1.1 - Estimated Critical Properties and Acentric


Factor for Petroleum Fractions of the


Standing/Katz Mixtures using Empirical
Correlations of Cavett and Edmister.

Cavett Edmister

Critical . Critical
Pressure Temperature Acentric
Fraction (MPa) (K) Factor

Fl 3.164 522.7 0.3044


F2 2.630 616.3 0.4358
F3 2.127 690.5 0.5365
F4 1.692 754.9 0.6280
F5 1.442 808.9 0.7000
F6 1.268 857.5 0.7736
F7 1.136 933.0 1.1360
16
16

Table 1.2
Table gives EQS
1.2 gives EOS predictions ofof saturation
saturation pressures
pressures and
and
vapor/liquid densities. Standing and Katz
Standing Katz do
do not
not report
experimental saturation pressures,
experimental pressures, although
although they
they note that
that
all systems should
all should be
be above their critical
critical temperature, and
pressures should
therefore the saturation pressures should all be
be dew
dew points.
points.
fact it is
In fact is seen
seen from Table 1.2 PR and SRK equations
1.2 that PR
bubble points for systems C,
predict bubble C, GG and
and H;
H; the
the ZJRK EQS
EOS
Predicted
correctly predicts dew points for all systems. Predicted
saturation densities, though not not representing the same
pressures, give
saturation pressures, gi ve the general
general qualitative trend
that ZJRK densities are greater than PR densities which are
greater than SRK densities.

It is unfortunate
It unfortunate that Standing
Standing and Katz do not report dew
point pressures for their systems. Vapor/liquid equilibria
data which are reported, however, indicate minimum
minimum values of
dew point pressures. These are listed in Table 1.2. In
nearly all cases, the PR and
arid SRK equations underpredict the
minimum saturation pressures considerably (true dew points
are probably from 55 to 15 Wa IFa greater than the minimum
values listed)
listed). The ZJRK EOSEQS always predhcts dew point
pressures above the minimum pressures indicated.

Table 1.3 reports experimental and predicted vapor phase


densi ties; it also gives PR and SRK values obtained after
densities;
adjustment of the methane-C7+
methane_C-,+ binary interaction parameters
to fit the ZJRK dew point for system A at 322.039 K;
binaries are 0.0819 and 0.0702 for the PR and SRK equations,
respectively. Also
Plso reported in Table 1.3 are predicted
vapor densities using the Standing/Katz Z-factor
Zfactor correlation
(these values were given in the original work).
Qualitatively, the PR and ZJRK equations perform best,
though in general all equations underpredict vapor
densities.
Table 1.4 reports similar results to Table 1.3 but for
liquid phase densities. Also
P1so reported in Table 1.4 are
predicted liquid densities using the Standing/Katz method
based on pseudo-liquid
pseudoliquid densities of methane and ethane and
temperature/pressure correction charts. Quali tati vely, EOS
Qualitatively, EQS
predictions of liquid densities are poor, although the PR
and ZJRK equations perform better than the SRK equation. PR
generally underpredicts, while ZJRK overpredicts; SRK
always underpredicts.
Tables 1.5 and 1.6 present results for experimental and
predicted properties of the heptanes-plus
heptanesplus fraction,
including molecular weight and specific gravity. Predictions
are not bad in general, although they show considerable
scatter. Heptanes-plus
Heptanesplus properties are not easily determined
experimentally, which may explain partly the observed
scatter.
17
17

Table 1.7
Table 1.7 compares
compares experimental and
and EQS
EOS liquid volumes in
in
two-phase region. It is
the twophase is somewhat
somewhat difficult to make an
objective comparison sincesince saturation
saturation pressure of of the
experimental systems
experimental systems is
is unknown, and itit can
can be expected that
had the EQSEOS been
been first matched
matched to the saturation pressure
pressure
it would
that it would better
better predict VLE.
Tables 1.8a to 1.8d
Tables predicted
1.8d compare experimental and predicted
(K-values) for the Standing/katz
equilibrium constants (Kvalues) Standing/Katz
Predictions range from poor
mixtures. Predictions poor to good, but they are
generally far from desired engineering accuracy. As might
be expected
be expected from the previous
previous discussion of saturation
predictions, the ZJRK equation gives
pressure predictions, gi ves better
bet ter
heavy-component Kvalues.
estimation of heavycomponent K-values.
comparison provide
Results of this comparison provide an excellent statement of
the problem with which we are dealing: cubic equations of
state are seldom predictive tools which can be used, without
adjustment, to describe the phase and volumetric behavior of
petroleum reservoir mixtures. The three equations used in
the comparison certainly indicate large variation in phase
behavior prediction, the same indication given in paper A.4.
This observation is less valid if critical properties of
the petroleum fractions are consistent with the EOS
EQS itself,
a topic considered in the next chapter.
TABLE 1.2
TABLE 1.2 - COMPARIS
-
COMPARISON OF PREDICTED
ON OF PREDICTED AND
AND MEASURED
MEASURED SATURATIO
SATURATION PRESSURES AND
N PRESSURES AND SATURATE
SATURATED DENSITIES FOR
D DENSITIES FOR
THE STANDING/KATZ
THE STANDING/KATZ MIXTURES.
MIXTURES .

Saturation
Satura Property
tion Proper tlj

Uapor Densit
DenSityij (gm/cc)
(g_/CC) LiqUid Densit
Liquid Densityy (gm/cc)
(gm/cc)
Pre ure
Pressu ("Pa)
re (MPa) Uapor

Sample
Temperrature
Tempe
(K)
ature
--------------------------------------
EXp. cc PR SRK

ZJ'RK
ZJRK
----------------------------
PR
PR SRK
SRK ZJRK
ZJ'RK
-----------------------------
--

PR
PR SRK
SRK
ZJRK
ZJRK
Sample

AA
(K)
-----------

322.039
9
322.03
-------- -------- -------- -------- -------- -------- -------- -------- -------- --------
Exp.

>) 56.7
56.7
PR

36.639
36.639
SRK

39.753
39.753 61.618
61.679 0.4005
0.4005 0.3744
0.3744 0.4413
0.4413 0.4972
0.4972 0.4603
0.4603
0.8674
0.8674
3)d (0.4i98 )d (0.628 i)d (0.556
(0.6281)d 5)d
(0.5565)d
(61.678)d
(61.67 (61.678)d
8)d (61.67 8)d (0.4623)d
(0.462 (0.4198)d
0.3595 0.5063 0.5653 0.8384
BB 394.261
394.261 >) 42.7
42.7 40.088
40.088 44.223
44.223 53.779
53.779 0.3162
0.3162 0.3267
0.3267 0.3595 0.5063 0.5653 0.9394
0.5082 0.4766 0.4363 0.6249
CC 322.039
322.03 9 >) 36.7
36.7 31.422a
31.422 a 33.312a
33.3i2a 49.125 0.3724 0.3506 0.5082 0.4766 0.4363 0.6249
0.3905 0.5103 0.4780 0.9494
D
0 322.039
322.039 >) 29.8
29.8 30.520
30.520 32.684
32.694 46.742 0.3599
0.3599 0.3370 0.3905 0.5103 0.4790 0.9494
0.4999 0.4488 0.8134
E
E 322.039
322.039 >) 29.9
28.9 42.180
42.180 46.244 76.117
76.117 0.4286 0.4005 0.4790
0.4790 0.4889 0.4488 0.8134
0.6052
F'F 394.261 )> 38.1 0.4292
0.4292 0.4128
0.4128 0.3806
0.3806 0.6052
394.261 38.1 35. 693b
35.693b 38.426b
38,425b 46.146 0.4128 0.3806 0.6776
274.817 0.5559 0.5178
0.5178 0.4688
0.4688 0.6776
G
0 274.917 )> 34.3
34.3 25.404a
25.404a 27. 127a
27.127 a 52.840
52.840 0.3563 0.3422 0.5559 0.6656
282.594 )> 35.5 0.5477
0.5477 0.5110
0.5110 0.4634
0.4634 0.6656 OJ
H
H 292.594 35.5 26.588.
26.598a 28.318a
28.319a 51.766 0.3586 0.3433

aa Predicted indicates aa de. point.


dew pOint.
Predicted saturation
saturation pressure
pressure is
is aa bubble
bubble point.
point. Experi.ental
Experimental indicates
formulation are given instead.
are given
bb Convergence SakerLuks formulation
the Baker-Luks
Convergence not
not achieved. Critical
Critical pOint
point properties
properties calculated
calculated using
achieved. using the instead.
F'or critical temper ature is 389.517
LOS. critic.l temper.ture is 389.~17 K. K.
For the
the PR
PR E06,
LOS, critical
Critical temperature
temperature is is 382.825
382.925 KI Ki for the
the SRK
SRK EOS,
in this table and corresp ond to
cC ExperImental listed
are listed in this table and correspond to
Lxperimentai saturation
saturation pressure.
pressures were
were not
not reported. "inimum
Minimum values
reported. values are
pressure in most c.ses
in most be at least
Will be
cases will
the hIghest two-phase equilibrium
the highest twophase equilib rium pressure
pressu re reportedl
reporte d; true
true satur.tion
saturat ion pressure at le.st
should be
systems should
all systems their critical
above their
be above
5-15 HPa higher than the value reported. Standing
515 tlPa higher than the value reported. Standing andand Katz
Katz note
note that
that all critical
temperature .nd therefore .11 s.tur.tion
temperature and therefore all saturat ion pre.sure
pressu res hould
should be
be de.
dew points.
points.
EOS.
predict
pressure predicted
point pressure ed by the ZJRK
dd Values
Values Inin parentheses
parentheses results
results after
after having
having matched
matched thethe retrograde
retrograde de. dew pOint by the ZJRK PR EOS.
d to 0.0819 .nd for the
0.0702 for
and 0.0702
Interaction coefficients between .ethane
Interaction coefficients between methane and
and .11
all C7+
C7+ fr.ctions
fractio ns were
were adjusted
adjuste to 0.0919 the PR
and
and SRK
SRK equations.
equations. respectively.
respectively.
TABLE
TABLE 1.3
1.3 - COMPARISON
COMPARISON OF
- OF PREDICTED
PREDICTED AND MEASURED VAPOR DENSITIES FOR THE
STANDING/KATZ
STANDING/KATZ MIXTURES.

Equilibrium Condition.
Equilibriu. Conditions
Equilibriu. Vapor
Vapor Pha.e
Phase Den.ity
Density (g./cc)
(gm/cc)

Run No.
Run No.
Pressure
Pressure
(MPa)
UIPa)
Temperature
Te.perature
(K)
(K)
------------------------------------------------
Exp.
Exp. PR
PR SRK
SRX ZJRK
ZJRK SK
9K b

A-S
A-S 6.882
6.882 322.039
322.039 0.056
0.056 0.0551
0.0551 0.0534 0.0543
0.0543 0.0561
(0.0550)c (0.0533)c
(0.0533)c
A-4 and
A-4 41
and 41 .. 11.011
11.011 322.039 0.097
0.097 0.0951
0.0951 0.0906
0.0906 0.0929 0.0981
0.0981
(0.0946)c (0.0902)c
Ai
A-1 21.919
21.919 322.039 0.224
0.22" 0.2151 0.1983 0.2053 0.2308
(0.2079)c (0.1936)c
A2 and
A-2 and 21
21 . . 36.268 322.039
322.039 0.340
0.3"0 0.3911 0.3267
0.326? 0.3127 0.3333
(0.3199)c
C0.3199)c (0.2931)c
A-3 56.570 322.039 0.404
0.40" a a 0."169
0.4169 0.4038
(0."324)c
(0.4324)c (0.3934)c

8-3
8-3 11.562 394.261 0.091 0.0830 0.0793 0.0816 None 1.0
81
8-1 20.061 394.261 0.154
0.15" 0.1504
0.150" 0.1403 0.1463 0.1530
8-2
8-2 42.668 394.261 None a 0.3014 0.2947 None
NOne

C2 and
C-2 and 21
21 . 6.951 322.039 0.056 0.0561 0.0544 0.0554 0.0530
Ci
C-l . 19.820
19.820 322.039 0.203 0.1987 0.01839 0.1937 0.2035
C3 and
C-3 31 .
and 31 . . 36.681 322.039
322.039 0.400 aa aa 0.3703 0.4087

F-I
1'"-1 21.960
21.960 394.261 0,192
0.192 0.1857
0.1857 0.1707
0.1707 0.1817 0.2051
0.2051
F2 29.751 394.261 0.277 0.2689
0.2689 0.2388 0.2537 0.2772
1'"-2
F3
1'"-3
29.751
38.128 394.261
394.261 0.349 ..
a 0.3500 0.3326 0.3"62
0.3462

61
G-l 13.996
13.996 274.817 0.176 0.1674 0.1568 0.1595 None
None
6-2
G-2 24.028
24.028 274.817 0.383 0.3305 0.2971 0.3008
0.3008 0.3878
0.3878
63
G-3 34.267
34.267 274,817
274.817 0.463
0.463 aa aa 0.3969
0.3969 0.4593
0.4583

H-4
H-4 12.514
12.514 282.594
282.594 0.140
0.140 0.1357
0.1357 0.1279
0.1279 0.1302
0.1302 None
None
H2
H-2 21.063
21.063 282.594
282.594 0.296
0.296 0.2663
0.2663 0.2443
0.2443 0.2515
0.2515 None
None
H-3
H-3 35.508
35.508 282.594
282.594 0.474
0.47" aa aa 0.3989
0.3989 None
None

D1
D-l 29.799
29.799 322.039
322.039 0.327
0.327 0.3481
0.3481 0.3052
0.3052 0.3017
0.3017 0.3237
0.3237

E1
E-l 28.942
28.942 322.039
322.039 0.261
0.261 0.2581
0.2581 0.23 ....
0.2344 0.2376
0.2376 0.2612
0.2612

aa Pressure
Pressure higher
higher than
than predicted
predicted saturation to be
assumed to
pressure, assumed
saturation pressures be aa liquid.
liqUid.
bII Calculated
Calculated values
values reported
reported by
by Standing
Standing and
and Katz using natural
Katz using compressibility charts:
gas compressibility
natural gas charts.
cc Values
Ualues in
in parentheses
parentheses result
result after
after having
having matched
matched the retrograde dew
the retrograde pressure predicted
point pressure
dew point predicted
by the
by the ZJRI<
ZJRK tOg.
EOS. Interaction coefficients
Interaction between methane
coefficients between and all
.ethane and C7+ fractions
all C7+ were adjusted
fractions were adjusted
to 0.0819
to 0.0819 and 0.0702 for
and 0.0702 the PR
for the and SRK
PR and equations. respectively.
SRK equations, respectively.
TABLE
TABLE 1.4 - COMPARISON OF PREDICTED AND MEASURED LIQUID DENSITIES FOR THE
-

STANDING/KATZ MIXTURES.

Equilibrium Condition.
Equilibriu. Conditions
Equilibriu.
Equilibrium LiqUid
Liquid Ph Density (ga/cc)
Phase (gmcc)
Pressure
Pr.ssur. T p.r.ture
Temperature
Run No. (liPa)
("P.) (K)
(t() EXP,
Exp. PR SRI<
SRK ZJRK SK
SK b

A5
A-5 6.882 322,039
322.039 0.726 0.7112 0.6352 0.787"
0.7874 None
(0.7228)c (0.6"35)c
(0.6435)c
A4 And
A-4 and 41
.. 11.011 322.039 0.702 0.6809 0.609"
0.6094 0.7601 0.709
(0.7021)c (0.62"6)c
(0.6246)c
A-i
A-l 21.919 322.039 0.696 0.6203 0.5622 0.7495 0.722
(0.6757)c (0.6007)c
A2 and 21 ..
A-2 ., 36.268 322.039
322. 039 0.745 0.5059 ... 98..
00.4964 0.7865 None
NOnC
(0.6637)c (0.5905)c
A3
A-3 56.570 322 039
322.039
0.814 0.4549.
0.4549a 0.4130a 0.8568 0.811
(0.6"04)c
(0.6404)c (0.568")c
(0.56B4)c

83
B-3 11.562 394.261 None 0.7027 0.6274 0.8077 None N
8i
B-1 0.700
o
20.061 394.261 0.697 0.6635 0.59 ....
0.5944 0.7823
82
B-2 42.668 394.261 Hone
None 0.3372A
0.3372a 0.5171 0.8152 None
C2 and 21 . .
C-2 6.951 322. 039
322.039 0.711
0.711 0.7025 0.6271 0.7690
0.7690 0.713
Ci
C-l 19.820 322.039
322.039 0.652 0.6052 0.5 .. 7 ..
0.5474 0.6968 0.649
C3 and
C-3 And 31
31 36.681
36.681 322. 039
322.039 0.712 0.4926a
0."926a 00.4450a
..... 50. 0.6747 0.708

Fi
1'"-1 21.960 394.261
394.261 0.654 0.5983
0.5983 0.5409 0.6932 0.668
F2
1'"-2 29.751 394.261
394.261 0.657
0,657 0.5396 ... 99 ..
00.4994 0.6725 0.664
F3
1'"-3 38.128
38.128 394.261 0.677 0.4100.
0.4100a 0.4089 0.6506 0.681
0.681
394.261 0."089
0i
G-l 13. 996
13.996 274.817
274. 817 0.665 0.6377 0.5742
0,5742 0.7262 Non.
None
02
G-2 24.028 274. 817
274.817 0.679 0.5387
0.5387 0.5023 0.7108 0.676
03
G-3 34.267
34.267 274. 817
274.817 0.766 0.5388a
0.5398a 0.4839a
0.4839a 0.7125 0.756
H4
H-4 12.514
12.514 282.594 0.682 0.6542 0.5873
0,5873 0.7326
0.7326 None
H2
H-2 21.063
21.063 282.594
282,594 0.659 0.5789
0.5789 0.5293 0.7055
0.7055 None
H3
H-3 35.508
35.508 282.594
282.594 0.752
0.752 0.5329.
0.5329a 0.4790a
0.47905 0.7037
0.7037 None
None

D-l 29.799
29.799 322.039
322.039 0.731
0.731 0.5164
0.516" 0.4880
0.4880 0.7411
0.7411 0.713
0.713

E1
E-l 28.942
28.942 322.039
322.039 0.753
0.753 0.6372
0.6372 0.5829
0.5829 0.825"
0.8254 0.736
0.736

aa Pressure
Pressure higher
higher than
than predicted
predicted saturation
saturation pressurel
pressure, assumed
assumed to
to bebe aa liquid.
liquid.
bb Calculated
Calculated values
v.lues reported
reported by
by Standing
St.nding and
.nd Katz
Katz using app.rent density
using apparent density method.
.ethod.
Cc Values
Values in
in parentheses
parentheses result
result after
after having
having matched the retrograde
mAtched the retrograde dew pOint pressure
de. point pressure
predicted
predicted by
by the
the ZJRK
ZJRK EOS.
EOS. Interaction
Inter.ction coefficients
coefficient. between
between methane
.eth.ne and all C7+
and all C7+
fractions
fractions were
were adjusted
AdjUsted to
to 0.0819
0.0819 and
and 0.0702
0.0702 for
for the
the PR
PR and
and SRI( equ.tions, respectively.
SRK equations respectively.
TABLE 1.5
TABLE 1.5 - COMPARISON
COMPARISON OF
- OF PREDICTED
PREDICTED AND
AND MEASURED
MEASURED HEPTANES-PLUS
HEPTANES-PLUS MOLECULAR
MOLECULAR WEIGHTS
WEIGHTS FOR
FOR THE
THE STANDING/KATZ
STANDING/KATZ
MIXTURES.
MIXTURES.

Hept&ne.-plu.
Heptanesplus "olecul&r
Molecular Weight
Weight
Equilibrium Condition.
Equilibriu. Conditions
Vapor Ph
VApor .. e
Phase Liquid
Liquid Pha ..
Phase
Pressure
Pres.ure Temperature
Te.per&ture
Run
Run No.
No. (MPa)
("p&) (K)
00 Exp.
Exp. PR
PR Exp. PR SRK ZJRK
SRK
SRK Z1RK
ZIRK Exp. PR SRK ZJRK
AS
A-5 6.882
6.882 322. 039
322.039 t10.Oa
110 . 0. 96.76 192.69 193.33
96.76 96.48
96.48 96.43
96.43 162.0b
162. Ob 193.13
193.13 192.69 193.33
(96.59)d
(96.59)d (96.35)d
(96. 35)d <192.81)d
(192.81)8 <192.46)d
(192.46)d
A4 ind
A-4 and 41
41 " 11.011
11.011 322.039 110. Oa 195.53
-
322.039 110.0& 98.54
96.54 98.02 97.82
97.82 196.0
196.0 195.25
195.25 194.50
194.50 195.53
(98.05)d
(98. 05)d (97.67)d
(97. 67)d <194.60)d
(194. 60)8 <194.03)d
(194.03)8
A-i
A-l 21.919
21.919 322. 039
322.039 127.0 209.55 215.59
127.0 111. 34
111.34 108.88
108.98 106.75
106.75 240.0
240.0 211.30
211.30 209. 55 215.59
<106.40)d
(106.40)cl (105.50)d
(105. 50)8 (207.84)d
(207.84)8 (206.97)11
(206. 97)8
A2 ind
A-2 and 21
21 . 36.268
36.268 322. 039
322.039 131.0 191.49 226.46 232.76 259.19
131.0 191.49 157.39
157.39 129.06
129.06 279.0
279.0 226.46 232.76 259. 19
<127.37)d
(i2?.37)d <125.82)d
(125.92)d (231.77)d (230.86)11
(230.86)8
A-3 56.570 322.039
322.039 144.0 cC cC 173.05 356.0 cC cC 324.78
324.78
(171.42)d
(171.42)8 (170.96)d
(170.96)d (253.58)11
(253.58)8 (251.94)11
(251 94)8

3-3
B-3 11.562 394.261 None
Non. 105.82 104.70
104.70 104.84
104.84 Non.
None 228.05
228.05 225.35 228.74
229.74
225.35
Bi
8-1 20.061
20.061 394.261 115.Oa
115.0& 114.80 112.03 111.88 231.0 240.86 235.84
235.84 243.22
243.22 N
32
8-2 42.668
42.668 394.261
394.261 None
Nan. c 176.78
176.78 153.08 None cc 277.57
277.57 318.15
318.15

C2
C-2 and 21
ind 21 6.951
6.951 322.039
322.039 i00.Oa
100.0& 96.53 96 . 29
96.29 96.24 186.0 186.85
186.05 186.65
186.65 186 . 95
186.95
Ci
C-l ...... 19.820
19.820 322.039
322.039 113.0 105.90
105.90 104.39
104.39 103.17
103.17 186.0
186.0 191. 77
191.77 191. 34
191.34 194.26
194.26
C3
C-3 and 31
ind 31 . 36.681
36.681 322.039
322.039 151.0 cC cC 134.04 240.0 c cc 218.94
210.94
Fi
r-l 21.960
21.960 394.261 130.0
130.0 114.66 111. 79
111.79 111.38 216.0 210.74 208.56
206.56 214.95
214.95
F2
f"-2 29. 751
29.751 394.261 139.0
139.0 135.04 127.30
127.30 124.17 256 .0
256.0 213.86
213.86 212 . 59
212.59 227.30
227.30
F3
r-3 38.120
38.128 394.261
394.261 157.0 c 172.33
172.33 146.77 290.0 c
C 196.14
196.14 239.87
239.87
G-i
G-l 13.996
13.996 274.817
274.817 Non.
None 99.20 98.59 97.65 None 186.28
186.28 186.16
186.16 186.67
196.67
02
G-2 24.028
24.028 274.817 128.0
128.0 124.82
124.82 119.70
119.70 108.52
108.52 215.0 186.83
186.03 188.84
108.84 198.08
198.08
03
G-3 34.267
34.267 274.817
274.817 145.0
145.0 c c 127.45
127.45 315.0
315.0 cC c
C 213.52
213.52

H-4
H-4 12.514
12.514 282.594
282.594 None
Non. 97.92
97.92 97.46
97.46 96.95
96.95 None
None 185.56
185.56 185.41
185.41 185.73
185.73
H2
H-2 21.063
21.063 292.594
282.594 None
None 110.64
110.64 108.43
108.43 104.02
104.02 None
None 188.74
188.74 199.12
189.12 193.10
193.10
H-3
H-3 35.508
35.508 282.594
282.594 None
Non. c cc 130.16
130.16 Non.
None cc cc 214.70
214.70

Dl_
D-1 29.799
29.799 322.039
322.039 123.0
123.0 148.45
148.45 136.12
136.12 120.65
120.65 268.0
268.0 213.63
213.63 214.00
214.00 242.35
242.35

E-l 28.942
28.942 322.039
322.039 130.0
130.0 128.26
128.26 122.11
122.11 114.75
114.75 242.0
242.0 240.14
240.14 237.99
237.99 245.68
245.68

ai Estimated
Estimited b
by Standing
StAnding and
ind Katz.
Katz.
bb Molecular
Moleculir weight
weight for
for pentanespl us reported
pent&nes-plu. r.ported byby Standing
StAnding and
And Katz.
Katz.
cc Pressure
Pressure higher
higher than
than predicted
predict.d saturation
sAturAtion pressure.
pr sur
TABLE 1.6
TABLE 1.6 - COMPARISON
COMPARISON OF
OF PREDICTED
PREDICTED AND
AND MEASURED
MEASURED HEPTANES-PLUS
HEPTANES-PLUS SPECIFIC

SPECIFIC GRAVITIES
GRAVITIES FOR
FOR THE
THE STANDING/KATZ
STANDING/KATZ
MIXTURES
MIXTURES..

H.ptan
Heptan -plu.
espi ul Sp.cific
Specific Gravity
Gravity
Equilibrium Condition.
Equilibriu. Condition
Vapor Pha
Phase Liquid
Liquid Ph e
Phase
Pressu
Pr re
ur. TTempe ratur
p.r.tur.
Run No (PIPa) (K)
Run No. C"Pa) . CK) Exp.
Exp. PR
PR SRK
SRI( ZlRK
Z3R)( Exp.
Exp. PR
PR SRK Z.JRK
A-5 6.88! 322.039
A-5 6.882 322.039 0.742a
0.742. 0.7106
0.7106 0.7099
0.7099 0.7098
0.7098 None
None 0.8441
0.8441 0.8437
0.8437 0.84"2
0.8442
A-4 and 41 .. CO.7102)c (0.7096)c
(0.7096)c CO.8438)c
(0.9430)C (0.8435)c
(0.8435)c
A-4 ~nd 41 . 11.011
11.011 322.039
322.039 0.742a
0.742a 0.7149 0.7137
0.7137 0.7132 0.850 0.8458 0.8452 0.8460
0.71"9 0.713! 0.850 0.8458 0.8452 0.8460
(0.7137)c CO.7128)c
(0.7128)c (0.8"53)c
(0.8453)c (0.8448)c
co.8448)c
Ai 21.919 322.039
A-t 21.919 322.039 0.775
0.775 0.7415
0.7"15 0.7369
0.7369 0.7328
0.7329 0.863
0.863 0.8580
0.8580 0.8567
0.8567 0.8609
0.8609
A! and 21 .. (0.7320)c (0.7302)c
(0.730!)c (0.8555)c
(0.8555)c (0.8548)c
(0.8548)c
A-2 .nd 21 ., 36.268
36.268 322.039
322.039 0.788
0.788 0.8338
0.8338 0.8085
0.9085 0.7708
0.7708 0.904 0.869" 0.8732 0.8876
0.904 0.8694 0.8732 0.8876
(0.7665)c
(0.7685)c (0.7661)c
(0.7661)c (0.8719)c
(O.8719)c (0.8713)c
(0.8713)c
A-3 56.570
56.570 322.039 0.802 0.8253 0.9191
322.039 0.802 bb bb 0.8253 0.95"
0.954 bb bb 0.9191
(0.8!38)c (0.8233)c
(0.8238)c (0.8!33)c (0.8858)c (0.8849)c
(0.8858)c (0.9849)c
03 11.562 394.261 N
8-3 11.562 394.261 None
Non. 0.7311 0.7289 0.7292 None 0.8690
0.8690 0.8673
0.9673 0.869"
0.8694 N
8-1 20.061 394.261
394.261 O.753a
0.753. 0.7479
0.7"79 0.7430
0.7"30 0.7428 0.870
0.070 0.8769
0.8769 0.8738 0.8781
B! 0.8738 0.6781
8-2 42.668
42.668 394.261
394.261 None
Non. b 0.8292
0.9292 0.8029 None bb 0.8985 0.9154
None 0.8985 0.9154
C-! and 21 6.951 322.039
C-2 .nd 21 ., 6.951 322.039 o.725a
0.725a 0.7100 0.7094
0.709" 0.7093 0.836 0.8388
0.8388 0.8386
0,8386 0.8389
0.6389
Ci 19.820 322.039
C-l . 19.820 322.039 0.750 0.7309 0.7278
0.7276 0.7253 0.84"
0.844 0.8429
0.8429 0.8426
0.8426 0.8450
0.8450
C-a and 31 35.681 322.039
C-3 .nd 31 36.681 322.039 0.800
0.800 b b 0.7783 0.881 b
b bb 0.8638
0.8638
F-i 21.960 394.26 1 0.8605
1'"-1 21.960 394.261 0.768 0.7476
0.7"76 0.7424
0.7"24 0.7"17
0.7417 0.862 0.8576
0.8576 0.8560
0.8560 0.6605
F-! 29.751 394.26 0.8592 0.8691
1'"-2 29.751 394.2611 0,791
0.791 0.7800
0.7800 0.7685
0.7685 0.7635
0.7635 0.888
0.888 0.860>
0.860? 0.8592 0.8691
F3 38.128 394.26 1 0.808 0.8469 0.8776
1'"-3 38.128 394.261 0.808 b 0.8250
0.8250 0.7955
0.7955 0.912
0.912 bb 0.8469 0.8776
6-1 13.996 274.81 7 0.8382 0.8386
0-1 13.996 274.817 None
Han. 0.7164
0.7164 0.7150
0.7150 0.7128
0.7128 None
None 0.8383
0.6383 0.8382 0.8386
6-! 24.028 274.81 7 0.765 0.8388 0.8405 0.8481
0-2 2".028 274.817 0.765 0.7647
0.76"7 0.7562
0.7562 0.7361
0.7361 0.863
0.863 0.8388 0.8405 0.8481
G-3 34.267 274.81 7 0.8599
0-3 34.267 274.817 0.792
0.792 bb bb 0.7685
0.7685 0.903
0.903 bb bb 0.8599
H4 12.514 282.59 4 0.8377 0.8375 0.8378
H-4 12.51" 282.59" None
Non. 0.7134
0.713" 0.7123
0.7123 0.7111
0.7111 None
None 0.8377 0.8375 0.8378
H! 21.063 282.59 4 Non. 0.8404 0.8407 0.8441
H-2 21.063 282.594 None
Non. 0.7401
0.7401 0.7359
0.7359 0.7271
0.7271 None 0.8404 0.0407 0.8441
H3 35.508 292.59 4 Non. 0.8608
H-3 35.508 282.59" Non.
Non. bb bb 0.7726
0.7726 None bb bb 0.8608

D-l 29.799
29.799 322.03
322.0399 0.788
0.788 0.7994
0.7994 0.7826
0.7826 0.7584
0.7584 0.893
0.893 0.8621
0.8621 0.8621
0.8621 0.8796
0.8796

E-l 28.94!
28.942 322.03
322.0399 0.771
0.771 0.7693
0.7693 0.7597
0.7597 0.7474
0.7474 0.877
0.877 0.8761
0.8761 0.8747
0.9747 0.8790
0.8790
a Estimated by Standing and Katz.
b
Estim.ted by St.nding .nd K.tz.
Pressure higher than predicted saturation pressure.
C
b Pressure higher than predicted .aturltion pr ure.
Values in parentheses result acter having matched the retrogr
c V,lu.s In p.r.nth result .ft.r h.vlng .atched the retrograde dew point
ade dew point pressu
pr ure predicted
re predict by the
ed by the ZJRI<
Z.JRK EDS.
EOS.
Interaction coefficients between methane and all C7+ fractio
Inter~ction coefficients b.t en .ethln. and all C7+ frictions .ere adjuste
ns were adJu.t.dd toto 0.0819
0.0819 and
and 0.0702
0.0702 For
for the
the PP
PR
and SRK equations, respectively.
,nd SRK equ.tions. respectively.
TABLE 1.7 - COMPARISON
COMPARISON OF PREDICTED AND MEASURED LIQUID VOLUMES FOR
-

THE STANDING/KATZ
STANDING/KATZ MIXTURES.
MIXTURES.

Equilibrlu.
Equilibrium Condition.
Conditions
Liquid UGlu - P.rc.nt
Volume Total
of Tot.1
Percent of

Run No.
Pr ur.
Pressure
("Pa)
(MPa)
Temperature
T p.r.tur.
(I()
(K)
--------------------------------------
Exp. PR SRI(
SRK ZJRI(
ZIRK

A-5
A-S 6.882 322.039 3.0 5.37
5.31 5.75 4.57
(S.18)c (S.59)c
(5.59)c
A-4 and 41 .. 11.011
11.011 322.039
322.039 9.3 9.58 10.10
10.10 7.91
(B.96)c C9.58)c
(9.58)c
A-1
AI 21.919 322.039 15.6 19.28 19.63
19.63 13.23
13.23
U6.38)c U1.2S)c
(17.25)c
A-2
A2 and 21 .. 36.268 322.039 21.0 6.53 19.48
19.48 11.76
11.76
U8.22)c U9.19)c
(19.19)0
A-3
A3 56.570 322.039 19.1
19.1 O.OOb
0.OOb O.OOb
0.OOb 3.12
(8.59)c (9.35)c
(9.35)0
N)
N
B-3
8-3 11.562 394.261 None
Non. 4.75 5.15 3.95 W
B-1
8i. 20.061 394.261 B.7
8.7 8.24 8.92 6.54
42.66B
42.668 394.261 Non.
None O.OOb
0.OOb 4.06 5.16
B-2
82

C-a and 21
C-2 6.951 322.039 11.2
11.2 11.44
11.44 12.18 9.88
C-l
C-I .. 19.820 322.039 33.0 40.58 40.58 29.92
C-3 and 31 .. 36.681
36.681 322.039
322.039 25.0 100.00b
L00.OOb 100.OOb
100.00b 32.31
32.31

r-l
F-i 21.960 394.261 22.6 24.29 25.29 18.95
r-2
Fa 29.751 394.261
394.261 22.8
22.9 32.66 33.60
33.60 21.80
r-3
F3 38.128
39.128 394.261 19.0 O.OOb
0.OOb 41.69 19.59

13.996 214.817
274.81? 34.2 41.44 41.40
41.40 30.52
30.52
G-1
6-1 13.996
24.028 274.811
274.817 29.0 84.86
84.86 74.89
14.89 39.42
G-2
6-2
G-3
6-3 34.267
34.267 274.811
274.817 13.3a 100.00b
100.OOb 100.OOb
100.00b 36.59

H-4 12.514
12.514 282.594 2B.5
28.5 33.04 33.54 25.72
282.594 41.0 62.12 59.0B
59.08 37.84
37.B4
H-2
H-? 21.063
21.063
H-3
H-3 35.508
35.508 282.594
282.594 8.9
B.9 100.00b
100.OOb 100.00b
100.OOb 35.76

322.039 2.4 4.34


4.34 9.61 6.15
6.15
D-1 29.799 322.039

28.942
28.942 322.039
322.039 18.0
18.0 24.79
24.79 24.91
24.97 16.00
16.00
E-l
E1

aa Evidence of
of third pha
phase par.tion r.port.d
separation Standing .nd
reported by St.ndlng Katz.
and K.tZ.
b Pressure high.r
nigher than predict.d
predicted satur.tlon pressure.
saturation pr.ssur
cc Values retrograde d.w
the r.trogr.d. pressure
point pressure
dew paint
Values in
in p.r.nth re.ult
parentheses result aft.r
after h.ving
having .atch.d
matched the
predicted by the ZJRI( EOS. Int.r.ctlonn
Interactiofln coefficients
co.fflcl.nts between
b.t en methane
than and
nd all
.11 C7+
C7+
predicted y the ZJRK LOS.
fractions w.r dJust.d to 0.0819 .nd
and 0.0702
0.0702 for the
the PR
PR and SRI<
SRI( equations,
.quatlons, respectively.
respectively.
fractions were adjusted to
TABLE 1.8a - COMPARISON
COMPARISON OF PREDICTED AND MEASURED K-VALUES FOR THE STANDING/KATZ
- STANDING/KATZ MIXTURE A.

Eqwilibriua
Equilibrium Condition.
Conditions
Equilibriua
Equilibrium Con.tant
Constant
Pre ure
Pressure
(Wa)
("Pa)
'eaperature
Temper atur.
(K)
--------------------------------------------------------------------
Cl C2 C3 n-C4
nC4 C5'.
C5s n-C6
nC6 C7+

A-5
AS
Run No.
No,

6.882 322.039
-------- -------- -------- -------- -------- -------- --------
Ci

Exp. : 12
4.12 0.97 0.547 00.450
50

PR : 33.4886
888 1.0334 00.4331
331 0.1826 0.0864 0.0370 0.0101
PRb: ((4.2713)
2713) (1.0251) (0.4259) (0.1780) (0.0837) (0.0328) (0.0089)
(0.0089>
SRK : 3.5631 1.09.1
1.0941 00.4559
559 0.2025 0.0887
0.0687 0.0377 0.0092
SRKb: ((4.1925)
1925) (1.0884) (0.4502) (0.1986) (0.0864) (0.0342) (0.0083)
ZJRK : 22.7
4.2247 1.2327 00.4847
847 0.2167 0.093.
0.0934 0.0389 0.0091

A-4
A4 and 41 . . 11.011
11.011. 322.099
322.039
Exp. :
EXp. 3.09 0.72 0.388 0.192 0.093 0.065 0.036
PR : 2.383.
2.3834 0.8649 00.4250
250 0.2101 0.1149 0.0581 0.0166
PRb: (2.90.6)
(2.9046> (0.8542) (0.4131) (0.2010) (0.1085) (0.0473)
(0,0473) (0.0134)
SRK : 2.4276 0.9045 0.4392 0.2252 0.1142 0.0575 0.0148 N
(0.0125) ~
SRKb: (2.U4.)
(2.8444) (0.8975) (0 300)
(0.4300) (0.2178)
(0.2176) (0.1090) (0.0490)
ZJRK
ZJRI( : 2.8639 1.0141 0.4608 0.2369 0.1177 0.0579 0.0141

A-l
Ai 21.919 322.099
322.039
EXp.
Exp. : 2.02 0.703 0.479 0.323 0.242 0.171 0.095
PR : 1.4816 0.8484
0.9484 0.5863 0.4071 0.3012 0.2145 0.0734
PRb: (1.8246) (0.8252) (0.5445) (0.3612) (0.2575) (0.1388) (0.0433)
SRK : 1.5130 0.8739 0.5935 0.4166 0.2888 0.2095 0.0642
SRKb: (1.7850)
(1.7950) (0.8597) (0.5624) (0.3815) (0.2551) (0.1494) (0.0423)
ZJRK
ZJRI( : 1.8264
1.8264 0.9796 0.6076 0.4203 0.2800
0.2600 0.2688
0.2698 0.0492

A-2
A2 and 21 ,. 36.268 322.039
Exp. : 1.54 0.97 0.81 0.570 0.522 0.324 0.145
PR : 1.0732 0.9581 0.8923 0.8320 0.7870 0.7393 0.5338
(1.4147) (0.8746) (0.7042) (0.5692) (0.4808) (0.3038) (0.1159)
PRb: 0.3264
SRK :: 1.1373
1.1373 0.94.7
0.9447 0.8318 0.7412 0.6544 0.6024
(1.3891) (0.9044) (0.7234) (0.5910) (0.4747) (0.3329) (0.1171)
(0.1171>
SRKb:
1. 4610
1.4610 1.0138 0.7626 0.6269 0.4957 0.4229 0.1183
ZJRK :
A3
A-3 56.570 322.039
1.39 0.90 0.865 0.830 0.728 0.782 0.173
Exp. : a
PR : a a a a a a
(1.1727) (0.9300) (0.8508) (0.7799) (0.7296) (0.5536) (0.3086)
PRb:
SRK : a a a a a a a
(1.1549) (0.9500) (0.8668)
0.8669) (0.7978) (0.7252) (0.5996) (0.3253)
(0.3253>
SRKb: 0.2263
ZJRK : 1.2673 1.023.
1.0234 0.8632 0.7782 0.6784 0.6388

a Pressure higher than predicted saturation prepressure.


ure.
bb Value. point pres.ure b the
predicted by
pressure predicted EOS.
ZJRK EOS.
Ua)ues in
ir parenthe.e.
parentheses re.ult
result after
after having .atched
matched the
thC retrograde de.
dw paint the ZJRK
Interaction adjsted to and 0.0702
0.0819 and
to 0.0819 0.0702 for the PR
for the
Interaction coefficients
coeficAents bet n .ethane
between methane and all C7+
C74 fractions .ere
were adJsted PR
and SRK
SRI( equations,
eQuations, respectively.
TABLE 1.8b - COMPARISON OF PREDICTED AND MEASURED K-VALUES FOR THE STANDING/KATZ
-

MIXTURES BAND
B AND C.

quiiibriu.
Equi1ibrum Conditions
----------------------
Pressure Te.perature
quiIibrum
Equilibriu. Constant
Run No. ("Pa)
(MPa)
Te.peratur,
(K)
(I() --------------------------------------------------------------------
Cl
Ci C2 C3 nC4
n-C4 CSs
C5's nCS
n-C6 C7+
---------------
8-3
3-3 ........ ----------
11.562 ----------
394.261
-------- -------- -------- -------- -------- -------- --------
Exp.
xp. : None None None None None None None
PR 2.7906 1.2973 0.7525 0.4383 0.2750 0.1641 0.0362
SRK : 2.8293
2.9293 1.3396
1.3396 0.7749 0.4682 0.2774 0.1659 0.0338
Z.JRK
ZJRK : 3.2580 1.4601
1.4601 0.8519 0.4834 0.2922 0.1735 0.0322

8-1
8i ........
EXp.
20.061 394.261
0.320 0.255 0.069
xp. 2.10 1.11
1.11 0.83 0.483
PR : 1.8228 1.0472 0.7142 0.4889 0.3549 0.2490 0.0656 N
SRK : 0.7239 0.3468 0.2450 0.0594 (ii
1.8540 1.0723 0.5051 U1
Z.JRK
Z3RK : 2.1339 1.1722 0.7961 0.5179
0.5178 0.3602 0.2521 0.0527

8-2
92 ........ 42.668 394.261
None None
Exp. None None None None None
PR a a a a a a a
SRK 1.1607
1.1607 0.9770 0.8672 0.7784 0.6928 0.6364 0.3158
0.:3158
Z.JRK
ZJRK : 1. 4016
1.4016 1.0480
1.0480 0.8849 0.7107 0.6030 0.5314 0.1517

C-2 and 21 .. 6.951 322.039


Exp. : 4.18 1.10 0.520 0.187 0.0695 0.0354 0.005
PR 3.4434 1.0266 0.4322 0.1831 0.0878 0.0375 0.0110
SRK : 3.5151 1.0845 0.4543 0.2023 0.0900 0.0382 0.0101
Z.JRK
Z3R)< 4.1220 1.2122
1.2122 0.4906
0.4806 0.2153 0.0945 0.0393 0.0101

C-l
CI ........
Exp. :
19.820 322.039
0.620 0.356 0.276 0.169
0.168 0.069
1.83
1.83 0.86
PR : 11.5422
. 5422 0.8439
0.8439 0.5635
0.5635 00.3781
. 3781 0.2724
0.2724 0.1866 0.0719
0.0719
SRK : 1.5718
1.5718 0.8695 0.5711 0.3977
0.3877 0.2625 0.1823 0.0633
0.0633
Z.JRK
Z3RK : 1. 8313
1.8313 0.9629
0.9629 0.5884 0.3974 0.2623 0.1769 0.0553
0.0553

C-3
C-3 and 3131 . .. 36.681
36.681 322.039
322.039
Exp. : 1.42
1.42 0.98
0.98 0.92
0.92 0.86
0.86 0.78 0.70
0.70 0.218
0.218
PR 1\ a a a aa a a
SRK : aa aa a a aa aa aa
Z.JRK
ZJRK :: 1.2905
1.2905 1.0178
1.0178 0.8452 0.7445
0.7445 0.6409 0.5786
0.5786 0.2706

aa Pressure
Pressure higher than predicted saturation
saturation pres.ure.
pressure.
TABLE 1.8c
1 .8c - COMPARISON OF PREDICTED AND MEASURED K-VALUES FOR THE STANDING/KATZ
-

MIXTURES F
F AND G.

Equillbriu.
Equlflbrlu. Condition.
CondItions
----------------------
Pre ure T..p,r
Pressure T p.ratur.
ature
Equilibrium
Equllibrlu. Constant
--------------------------------------------------------------------
Run Ho.
No. ("Pa)
(PIPa) (K) (IC) Cl C2 C3 nC4
n-C4 C5'.
C5s nC6
n-C6 C7+
---------------
F'-1
F_-i ........ ----------
21.960 ----------
394.261

---.----- -------- -------- -------- -------- -------- --------
EXp.
Exp. 1.89 1.20 0.658
0.655 0.520 0.314 0.346 0.141
0.141
PR : 1.6135 1.0271 0.7539 0.5551 0.4302 0.3229
0.3229 0.1247
SRI< : 1.6469
1.6469 1.0488
1.0485 0.7594 0.5646 0.4164 0.3133 0.1108
ZJRK
ZJRI( : 1.8421 1.1262
2.1262 0.8200 0.5738 0.4251
0.4281 0.3194
0.3194 0.1012

F"-2
F-2 ........ 29.751 394.261
Exp. : 1.57 0.98
0.96 0.60
0.80 0.654 0.561 0.414 0.201
PR : 1.2805 0.9829 0.8308 0.7003 0.6089 0.5204 0.2714
SRI< : 1.3242 1.0017 0.8232 0.6881 0.5714 0.4863 0.2247 (3
N
cm
0\
ZJRI< : 1.4996 1.0717 0.8708 0.6796 0.5598 0.4680 0.1772

F'-3
F-3 ........ 38.128
38. 128 394.261
0,248
Exp. 1.36
1.36 1.09
1.09 0.87 0.77 0.75 0.77 0.248
PR
SRI< :
a
1.1052
1,1052
a
0.9964
a
0.9596
a
0.9273
a
0.9945
0.8945
a
0.8694
0.8694
a
0.7287
ZJRI<
ZJRK : 1.2830 1.0428 0.9224 0.7895 0.7027 0.6379
0.6378 0.3095

0-1
6-1 ........ 13.996 274.817
274.917
None None None
EXp. Han.
None Nan.
None None
Hone None
Homr Han. Han. Han.
PR 1. 6371
1.6371 0.6499 0.3494
0.3494 0.1892 0.1142 0.0630 0.0208
SRI< : 1.6694
1.6694 0.6801 0.3592
0.3592 0.1990 0.1111
0.1111 0.0626 0.0183
ZJRI<
ZJRI( : 2.0528 0.7013 0.3664
0.3664 0.1926 0.1024
0.1024 0. 04i
0.0~41 0.0146
0.0146

0-2
62 ........ 24.028
24.028 274.817
274.917
0.585 0.528 0.422 0.217
0.217
EXp.
Exp. : 1.44
1.44 0.96
0.96 0.79
PR : 1.1781
1.1781 0.8602 0.7065 0.5823 0.5004 0.4187
0.4187 0.2325
SRI< : 1.2132
1.2132 0.8736 0.6970
0.6970 0.5667
0.5667 0.4591
0.4591 0.3918
0.3918 0.1887
0.1887
ZJRI<
ZJRI< : 1.5377
1.5377 0.8792 0.6557
0.6557 0.4878
0.4878 0.3584
0.3584 0.2809
0.2809 0.0944
0.0944

0-3
6-3 ........ 34.267 274.817
274.817
0.71 0.655
0.655 0.289
0.289
EXp.
Exp. 1.35
1.35 0.96 0.86
0.86 0.80
PR aa a aa a aa aa aa
SRI< :
ZJRK ::
ZJRI<

a
1.3211
1.3211
aa
0.9509
0.9509
a
0.8156
0.8156
a
0.6977
0.6977
aa
0.5952
0.5852
aa
0.5280
a
0.2248
0.2248

a Pressure
Pressure high.r
higher than pr.dicted
predicted saturation pressure.
saturation pr ur
TABLE 1.8d
TABLE 1.8d - COMPARISON
COMPARISON OF
- OF PREDICTED
PREDICTED AND
AND MEASURED
MEASURED K-VALUES
K-VALUES FOR
FOR THE
THE STANDING/KATZ
STANDING/KATZ
MIXTURES H, D, AND
MIXTURES H, 0, AND E.
E.

EqutItbru. Condition.
Equilibriue Condt1ons
Equilibriu.
qu11IbrIuM Con.tant
Constant
Pressure
Pre ure fl.per ature
Te.perature
Run Ho.
Run No. (MPa)
("Pa) (K) Cl
Cl C2
CE C3
C3 n-C4 C5. n-C6 C7+
nC4 C5s nCE C7+
H4
H-4 12. 514
12.514 202.594
282.594
Exp.
Exp. Hone
None None None
None Hone
None None
None Hone
None None
None
PR 1.8288
1.8288 0.6521 0.3224 0.1605 0.0899 0.0454
0.0454 0.0144
0.0144
SRK 1.8650
1.8650 0.6824 0.3314
0.3314 0.1697
0.1697 0.0876
0.0876 0.0448
0.0440 0.0126
0.0126
ZJRK:
Z.JRK 2.2672 0.6946 0.3440 0.1691
0.1691 0.0842
0.0842 0.0408
0.0408 0.0108
0.0108
H2
H-Z 21.063
21.063 282.594
282.594
xp.
Exp. Hone
None Hone
None None Hone
None Hone
None Hone
None Hone
None
PR 1.3176 0.7978 0.5778 0.4204 0.3261 0.2422 0.1060 N
1. 3176 0.2422 0.1060 I-)
"'-J
SRK 1.3469 0.8236 0.5850
0.5950 0.4272 0.3115 0.2382
0.2382 0.0927
0.0927
Z3RK:
Z.JRK 1.6572
1.6572 0.8319 0.5795 0.3988
0.3998 0.2725 0.1947
0.1947 0.0618
0.0618
H3
H-3 35.500
35.508 282.594
Exp.
Exp. Hone
None None Hone
None None Hone
None Hone
None Hone
None

a
PR
SRK a
a a
a
aa
aa
a
a
a a
a a
aa
Z3RK:
ZJRK 1.3008
1.3008 0.9508
0.9508 0.8300 0.7186
0.7186 0.6104
0.6104 0.5540
0.5540 0.2466
0.2466
01
D-l 29.799
29.799 322.039
322.039
Exp.
Exp. 1.58
1.58 1.04
1.04 0.78
0.78 0.575 0.605
0.605 0.332
0.332 0.147
0.147
PR 1.1360
1.1360 0.9417
0.9417 0.8356
0.8356 0.7430
0.7430 0.6760
0.6760 0.6019
0.6079 0.3877
0.3877
SRK 1.1811
1.1811 0.9458
0.9458 0.8109
0.8109 0.7045
0.7045 0.6085
0.6085 0.5442
0.5442 0.2958
0.2959
ZJRK
ZJRK 1.4934
1.4934 1.0231
1.0231 0.7623
0.7623 0.6179
0.6179 0.4850
0.4850 0.4037
0.4037 0.1302
0.1302
Ei
E-l 28.942
28.942 322.039
322.039
xP.
EXp. 1.72
1.72 0.94
0.94 0.712
0.712 0.500
0.500 0.357
0.357 0.Z96
0.296 0.073
0.073
PR 1.3290
1.3290 0.8558
0.0558 0.6439
0.6439 0.4865
0.4865 0.3874
0.3874 0.2999
0.2999 0.0984
0.0984
SRK 1.3652
1.3652 0.8758
0.8758 0.6445
0.6445 0.4885
0.4885 0.3625
0.3625 0.2891
0.2891 0.0812
0.0812
ZJRK:
Z.JRK 1.7114
1.7114 0.9892
0.9892 0.6500
0.6500 0.4793
0.4793 0.3360
0.3360 0.2554
0.2554 0.0516
0.0516
a Pressure
Pressure higher
higher than
than predicted
predicted saturation
saturation pressure.
pre ure.
28
28

1.1.7
.7 Proposed EQS
Proposed EOS Modifications
Modifications
Several methods
Several methods for
for improving
improving EQS
EOS predictions
predictions of
of petroleum
petroleum
reservoir fluids
reservoir fluids have
have been
been proposed
proposed during this
during this study.
study.
Although they
IU.though have not
they have not necessarily
necessarily proven
proven to
to be
be major
major
improvements, or
improvements, or even
even original,
original, their
their presentation
presentation reviews
reviews
some important
some important aspects
aspects of
of EQS
EOS development.
development.
The twoterm,
The two-term, fourconstant
four-constant generalized
generalized EQS EOS proposed
proposed by
by
Martin is
Martin is given
given in paper A.S. Several new aspects of
in paper P.5. Several new aspects of his
his
equation have been
been developed
developed inin this
this work:
work: the
the fugacity and
and
Z-explicit
Zexplicit expressions
expressions are
are formulated;
formulated; equations
equations for
for
calculating EQS
EOS constants
constants are
are proposed.
proposed. Two Two new equations
equations
are proposed:
proposed: aa modified
modified UMUM EQS
EOS and
and an
an extended
extended PRPR EQS.
EOS.
The modified
modified UM
UM EQS
EOS is
is developed
developed using
using aa method
method similar
similar to
the ZJRK procedure. b\s As mentioned
mentioned in the
the previous section,
section,
this work
work resembles
resembles Fullers.
FUller's. is presented
What is presented here,
however, was completed without knowledge of the former and
also appears to be simpler and more conduci ve to
conducive
petroleum-engineering applications. Details of the proposed
petroleumengineering
modification can bebe found in paper A.S.
P.5.

The present discussion will consider the description of


several cubic equations in terms of the proposed EOS
EQS family.
The Z-explicit
Zexplicit form of the general Martin equation is,

Z3
3 +
z + Z2{-3B
{3B +
2
Z + (C+D-l)}
(C+Dl)J

+ 22 - 2B(C+D-l)
Z{3B
Z{3B 2B(CDl) +
+ (A+CD-C-D)}
(P+CDcD)}

+
+ 33 +
{_B
{B + B2(C+D-l)
(C--Dl) - B(A+CD-C-D)
2
B B(PCDC-D) - CD}
- = 0Q
=

... (1.5)

where EOS
EQS constants are given by

2T2 2 ...................
A = ap/R
P = T
2
ap/R = aS2
= 2 a Pr/Tr
cxapr/Tr (1.6a)
(l.6a)

B
B = bp/RT
bp/RT = a S2bPr/Tr ....................
SQbPr/Tr (1.6b)
C = cp/RT
C = cp/RT = cPr/Tr ....................
= ~SlcPr/Tr (1.6c)
0D = dp/RT
= d.p/RT = 1S
= S2 dPr/Tr ....................
QdPr/Tr (1.6d)
29

where PrP/Pc
Pr=P/Pc and T r= TIT c. Parameters a, a
TrT/Tc. S,, ~,, and 15iS are
correction terms to the EOSEQS constants S"2
a , S"2b,
a b c S"2 c , and S"2d,
d,
respectively. The corrections are usually applied to ensure
accurate VLE, and perhaps liquid volumetric predictions.
They are temperature dependent and commonly rely on acentric
factor to correlate variation in temperature dependence for
compounds of varying species.
Numerical constants S"2a,
a S"2b,
2 b, S"2 c ' and S"2d
c d must be determined,
typically using the critical constraints of van der Waals:
(ap/aV)=(a
p
(ap/aV)=(a
)
2 =Q
/aV 2p/av 2)=0 at critical temperature, Tc.
Tc. These two
cons taints are only sufficient to define two of the EQS
constaints EOS
constants, with two more constraints remaining to be
specified. An intuitive choice might be to choose critical
compressibility factor, Zc'Z, for each compoud. Martin and Hou
show that the combination of van der Waals criteria and
specification of Zc Zc is equivalent to solving the cubic
equation (V-Vcr~=O,
(VVc)=O, or its equivalent (Z-ZC)3=0.
=O.
3
(ZZ) Imposing
this relation on the general Martin equation results in,

Zc
3 = b
3 + (1. 7a)
(1.7a)

3Zc
2 =
2 3S"2b 2 - 2S"2b(S"2 +S"2d-1) + (S"2
3Zc = ccd + (ac2dc42d)
2
b(
22
)
1 a+S"2cS"2d-S"2c-S"2d) (1.7b)
.. (l.7b)

-Zc
3 =
3 -~b3 +
Zc 3 + S"2b2(S"2c+S"2d-1)
= b (c+Qd...1) - S"2b(S"2a+S"2cS"2d-S"2c-S"2d)
2
b

-SlcSld
cd .... (1.7c)

What can be seen from Eq. 1.7 is that two groups, S"2 d
c
2c+S"2d and
S"2cS"2d, are present. If If one more condition is imposed then
values of all constants can be determined. Speci fy ing
Specifying
another thermodynamic criterion might be considered, but is
should be chosen with care. Consider, for example, the
universal sum-chart o=O.62, suggested by Martin
sumchart value, a=0.62,
(where a=Zc-aZ/apr
a=ZcZ/apr at Pr=O
0
Pr and Tr=l).
Tr1). It can be shown that
the fourth criterion becomes,

Zc = 0b
= b - Sla
a + a
0 (1.8)
30
30

and EOS constants are given by


and

0b 3 ++ Qb
(0b
2(3-3Z ) ++ b(3Zc
Ob(3ZC
-
2
2-6ZC+2)
6Zc+2)
3
b 2 33zc) c
+ (-ZC3+3Zc2-2ZC+l-cr)
+ 2
+
3
(Zc
2 3Zc == 00 (1.9a)
Zc+10) (1.9a)
Oa =b
=nb + Ga
+ ZC
- Z

.............................. (1.9b)

Oc 2 ++ 0c(-u-l)
2c(_u_1) ++ Ww == 00 (1.9c)
(1.9c)
2
c

= w/2 .................................... (1.9d)


(1.9d)

where

uu =
= 3%
3Qj - 3Z,
3ZC
0
(1.lOa)

3
Z + 3
2Qb 2
3Zc2b
2
32Ij(Z_Q) ((l.lOb)
1.lOb)

The largest root of Eq. 1.9a is chosen for 0b,


b and either of
2
the roots in Eq. 1.9c can be chosen, the second root being
equal to 0d.
Martin reports the PR EOS gives cr=0.68684.
o=O.68684. Recalling that Zc
for the PR EOS
EQS is 0.307401. ; solving Eqs. 1.9a
0.307401...; l.9a and 1.9b
gives Ob=0.07780
b=
2

0778 and 0a=0.45723.
45723
0
a=
From Eqs. 1.10, u=-0.6888
u=0.6888
and w=0.0121, yielding 0c=0.26565
c=O.
2
26565 or 0.045548 and
Od=0.045548
045548

0
d= or 0.26565. Using
using the sum-chart
sumchart criterion
results in a symetric relation between constants 0c c and &d,
0d,
(2~2)xO.0778=0.0945548 and
as shown by this example; note, (2./2)xO.0778=0.0945548
(2~2)xO.0778=0.26565.
(2+/2)x0.O778=0.26565.

Theoretically we have defined a four-constant


fourconstant EOS
EQS using
purely thermodynamic criteria. Practically, however, the
true (experimental) values of ZC Zc and cr
a will not give the
best equation. In fact, purely mathematical constraints
must be respected, thereby limiting the range of values of cra
for a given Zc.Zc. Observation shows that for all Zc Zc of
interest, constants (3-3ZC)
(33Z) and (3ZC2-6ZC+2)
_6Zct2) are positive
2
(3Zc
(see Table 1.9). Since Ob b represents a key parameter in the
2
cubic EOS
EQS and its value should be close to 1/10 for the
resulting equation to yield reasonable high densities
(Abbott),
(Pbbott), the last constant in Eq. 1.9a must be less than
zero. For this to be so, cra must be larger than the values
listed in the last column of Table 1.9, where the value is
dependent on ZC.
Zc. Interestingly, the original van der Waals
EOS
EQS yields cr=0.62,
o=O.62, an observation overseen by Martin.
31
31

TABLE 1.9
TABLE 1.9 - LIMITATIONS
LIMITATIONS OF THE
THE EOS
EOS MODEL
MODEL USING MARTINS
MARTIN'S
SUM-CHART AS
SUMCHART AS AA CRITERIA
CRITERIA FOR
FOR DEFINING
DEFINING EOS
EOS
CONSTANTS
CONSTANTS

Limiting
Limiting
a(J
=
+
3
_Zc3Zc2
-Zc'+3Zc
2
2
Z
Zc (3-3Zc)
(33Z) (3Zc
6
2 -6Zc+2)
Zc+2)
(3Zc -2Zc+1
Zc+l
2

0.250
0.250 2.250
2.250 0.687500
0.687500 0.671875
0.671875
0.275 2.175
2.175 0.576875 0.656078
0.656078
0.300
0.300 2.100
2.100 0.470000 0.643000
0.325
0.325 2.025
2.025 0.366875
0.366875 0.632547
1/3 2.000 0.333333
0.333333 0.629630
0.629630
0.35 1.950
1.950 0.267500
0.267500 0.624625
0.624625
0.375 1.875
1.875 0.171875 0.619141

This excercise exhibits the limitations


limitations and danger in
forcing too many and too rigid thermodynamic criteria for
the general fourconstant
four-constant EQS.
EOS. AA practical review of
popular cubic equations suggests two workable approaches.
They both require, however, the use of van der Waals
critical criteria - i.e.,
i.e., critical
critical temperature
temperature and critical
pressure are EQSEOS variables defining the nature of aa
compound. Thereafter the methods differ as summarized
below:
Set Zc
Z at a constant, universal value for all compounds
and define, somewhat empirically, the relation between
constant S7.c
c (or dJ
2 Qd) and Qb. Examples would be the PR EOSEQS
where Zc=0.307401.
=Q.3O74O1...
0
Z and Qc=(2-12)Qb;
2c=(2v2)c2b; or the RK EOS
EQS where
Z1/3 and Qc~b.
Zc=1/3 c=b
Allow Z Zc to vary for each component, thereby fully
utilizing the critical criteria (Z-Zc)
=O
3
(ZZcJ'=0 at T c , Pc.
Tc, Pc Once
again, an arbitrary relation is specified between nc
2 (or
dJ and~.
Qd) and c2b. Examples would be the Usdin!McAuliffe EOS
Usdin/McAuliffe EQS where
cb and Ze;
Qc~b Zc is specified or given as a function of W; w; or
the Schmidt/Wenzel EOS EQS which relates Q cc
2 and Qb
b differently
for each compound, dependent on w (as is Zc). Zr).

With these points in mind, the development of a new family


of cubic equations is suggested. It is only one of many
possibilities, as can be inferred from the discussion above.
It offers, however, a means of generalizing most of the
popular cubic equations and studying the behavior of
different equations in more general terms.
32
32

The proposed
The proposed family
family starts
starts fromfrom the
the general
general fourconstant
four-constant
Martin EQS,
Martin EOS, and
and applies
applies the full
the full critical criteria
critical criteria forfor each
each
component, allowing
component, allowing the specification of Zc different than
the specification of Z different than
measured experimental
measured experimentally. ly. The relation between
The between EQS
EOS constant
constant
ilc (or
c ild) and
(or d) and bilb is
is directly
directly proportional
proportional - i.e.,
i.e., cb
ilc=Ailb,
where AA is
where is aa numerical
numerical constant
constant which
which is
is not
not necessarily
necessarily the the
same value
same value for all all compounds.
compounds. It merely
It merely allows
allows thethe
definition of aa specific EQS. EOS. The
The proposed
proposed family of of cubic
cubic
equations is now presented
presented in in terms of of other
other well
well known
known
EOS's.
EQSs. The ob jecti
objective ve is
is to relate
relate the
the old
old equations
equations in
terms of the parameters Zc Zc and A. A. The correction
correction factors
for EQS
EOS constants
constants are also given, given, resulting in in complete
complete
definition of of the particular
particular equation.

Redlich/Kwong
A 11
A= =
Zc
Zc = 1/3
=

Soave modification
modification::
la(Tr,wJ
i/a(Tr,w) =
= 1 + m(1~)
1 + m(i../TE)

m =
m = 0.480 + 1.S74w
Q.48Q + 22
l.574u. - 0.176w
0.176w

Pen9IBobinson
Peng/obinson

A
A = 22/
= -12 (or 2-+V2)
2+v)

Zc
Zc = 0.307401
=
la(Tr,w) =
= 1 + m(1~)
1 + m(1vT)

m =
m = 0.37464 + 22
+ 1.54226w - 0.26992w
0.26992w
33

Martin, p=RT/(v-b)-a/(v+c-b)2;
p=RT/(vb)a/(v+cb) c=d
;
2

A
A == 0.125/(Zc-0.25)
0.125/(ZcO.25)

Kubic modification:

Zc
Z =
= 0.291 - 0.083'00'
0.083w (modified Pitzer)
-

a(Tr,oo)
a(Tr,w) = a
= aO + a1oo'
+ cz
w
1

aO =
= 0.l5l4Tr +
-0.1514T 0.7895 +
+ 0.7895 + 0.3314/T 0.029/Tr 2
0.3314/Trr ++ 2
0.029/Tr
+ 0.0015/T
7
0.0015/Tr
7
+ r
a1 =
= -0.237Tr-0.7846/Tr+1.0026/Tr2+0.019/Tr7
+0.019/Tr
2
_0.237Tr_0.7846/Tr+1.0026/Tr
7

8 =
=11

~(Tr,oo')=o(Tr,oo')=(0.043yo+0.0713oo'yl)/(nc-nb)
(Tr,w)(Tr,w)=(0.043+0.0713wy)/(cQb)

yO == 4.275051 - 8.878889/T
8.878889/Trr ++ 8.508932/T
2
8.508932/Tr
2

r
- 3.481408/T
3
3.481408/Tr

3
0.576312/Tr~
r ++ 0.576312/Tr
4

yl == 12.856404 - 34.744125/Tr
34.744125/Tr ++ 37.433095/T
2
37.433095/Tr 2

r
- 18.059421/T
3
18.059421/Tr

3
3.514050/Tr~
r ++ 3.514050/Tr
4

00' = 0.000756 ++ 0.9098400


= 0.90984w ++ 2
0.16226w 33
0.1622600 2 ++ 0.1454900
0.14549w

Usdin!McAuliffe
Usdin/McIuli ffe

A=1
A 1 =
la(Tr,oo)
vct(Tr,w) =
= 1 m(1~)
1 ++ m(1i/TE)

m
m =
= 0.48049 ++ 4.Sl6wZ
4.516wZc ++ {0.67713(oo-0.35)-0.02}(T
0 r -0.7)
{0.67713(w_0.35)_0.02}(Tr0.7)
Tr sO.7
for TrO.
7

m
m =
= 0.48049 + 4.516wZc - {0.67713(oo-0.35)-0.02}xO.4
+ 4.516wZ {0.67713(w0.35J-.0.02}xO.4

Tr sO.3
for TrO.3
3
m
m =
= 0.48049 +
+ 4.516wZc
4.5l6wZc ++ {37.7846wZc
{37.7846wZc ++ 0.78662}(T
3 r -0.7)2
0.78662}(Tr0.7)
2
for 0.7<T
<Trl.O
7
O. r S1.0

Usdin and McAuliffe


McPuliffe suggest extrapolation at Tr>1
Tr>l by
matching the slope at Tr=l
Tr=1 from the preceeding
expression. No equation is given, but the following
satisfies their criteria of extrapolation,
34
34

=
mm = 0.48049
0.48049 ++ 4.51iZc
4.516wZC ++ (37.7846wZc
(37.7846wZC3+0.78662)x
4
3 0.78662)x
(0.69-0.6/T r ) for
(0.690.6/Tr) for Tr>l
Tr>1

Usdin and
Usdin and McP
McAuliffe
u
1 liffe do do not
not suggest
suggest experimental
experimental values
values
of Z
of Zc be
be used.
used. Instead, they give best-fit values
Instead, they give bestfit values
obtained by
obtained by matching
matching specific
specific gravity
gravity (i.e.,
(i.e., density
density at
at
standard conditions). Pn An extrapolation
extrapolation for heavy
heavy
petroleum fractions is
petroleum is given
given by
by the
the bestfit
best-fit equation,
equation,

Zc
Z = 0.3328
= 0.3328 - O.O42lw
0.0421w

modification:
Fuller modification:
The Fuller EQS
The EOS is equivalent to the
the UM
UM EQS
EOS when both
both are
expressed
expressed in their simplest form (without EOS constant
EQS constant
correction factors). The equation form given by Fuller
is unnecessarily complicated, as is easily seen when
trying to make the necessary simplifications to equate
it with the UM EOS. Also,
Plso, the correlating variable for
EOS
EQS constant ~ is parachor
parachor instead of acentric factor,
an unfortunate choice (and probably without real physical
justification). The Fuller relations are therefore
not included, and in its place are the equations
developed in the present study
study.

Proposed modification:
Zc
Zc = 0.291
= - O.oew
0.08w (Pitzer)

la(Tr,wJ
Va(Tr,w) = 11 + m(1-T
=
r)
m(lTr)
+

m =
m = 0.46089 + 22
+ 1.2032w - 0.3454ew
0.34548w -

S== 1
+ (S*_1){2/(1+e8(T r -1))_1}
1 +

S* = 1.4891
= 1.4891 +
+ 0.92175w
0.92175(i) + 22
+ 0.40116w
0.40116w (Tr~1)
(Trl)

S* = 11 (Tr>1)
(T>l)

~ =S
6 = 11 ++ (~b/~d)(S-1)
(b/cd)(s)
35

Schmidt/Wenzel
Schrnidt/Wenzel (modified by Wenzel/Moorwood/Baumgartner)
wenzel/Moorwood/Baumgartner)

=
AA = 3(1+w)/2 {/(9(1+w)2_8)}/2
{V(9(1+wJ8).}/2

Zc = {3(1+w8 c )}_1
{3(1+wSc)}
=

where 8c is the smallest root of the cubic equation:


38c 2 ++ 38
(6w+1)8 c 3 + c
2 1 == 0
3c - 1 0

la(Tr,w)
vcL(Tr,) = 11 ++ m(1/T)
= m(1~) for Trl TrS1
a(Tr,w)
a(Tr,w) = 11 - (O.4774+1.328u)lfl(Tr)
(0.4774+1.328w)ln(Tr )

for Tr>1
Tr>l

m =
m = mO
m for wSO.4
w0.4

m =
m m1 for w~0.55
= m w0.55

= m1 ((w-0.4)/0.15)
mm = m((w0.4)/0.15) + m((0.55w)/0.15)
+ mO((0.55-w)/0.15) for 0.4<w<0.55
mO = k
m kO
= + (1/70)(5T
+ 2 r -3kO-1)2
(l/70)(5Tr...3k4)

m1 = k
m kO
= ++2
0.71(T r -0.779)2
0.71(Tr0.779J

kO
k = 0.465
= + 0.528w 2 for w0.3671
+ 1.347w - 2
0.528w

wSO.3671
kO
k = 0.5361
= + 0.9593w for w>0.3671
+

would be interesting to know what happens physically


at acentric factors of 0.3671, 0.4, and 0.55!(?)
36

Peneloux/Rauzy/Freze

A =
A = 1
1 - 0.40768(0.29441-Z

ra )/Qb,RK
0.40768(0.29441_Zra)/2b,RK

Zc =
= {1- Qb,RK(1-A)}/3
{lQb,RK(lA)}/3

la(Tr,w)
Vo(Tr,w) = 11 ++ m(1~)
= m(i-./T) (Soave)
m =
m = 0.480 + 22
+ 1.574w - 0.176w
0.176w

where Qb
b RKRK =
= 0.08664 is the original RK EOS constant
...

and Zra
Zra Is
s the Rackett compressibility factor used to
predict saturated liquid densities (see Table 22 in
paper I.5).
A.5).
The table below shows AA and Zc
Zc for several values of
the Rackett variable, indicating only a slight
modification of the original RK EOS for a rather large
variation in Zra.
Zra.

Zra A Zc

0.28 0.9322 0.3314


0.29 0.9792 0.3327
0.30 1.0263 0.3341
0.31 1.0734 0.3355
0.32 1.1204 0.3368
0.33 1.1675 0.3382

The suggested procedure for calculating Zra


Zra for PNA
PNP
fractions based on the Robinson/Peng correlations is
of questionable merit. Refer to Paper A.4
P.4 for a
discussion of PNA
PNP densities.
37

Coats
ml
1
m = AA-I1
=

m2
2
m =
= 2
2 - AA - (1-3Z


c )/nb
(13Zc)/2b

Values of ml
1 and m2
m 2 for the RK and PR equations are,
m
respectively, m
ml=O
=
1 =l, and ml=1~2
0 and m2=1,
2
m =l+i/2 and m2=1~2.
1
m =1/2.
2
m
If the Coats EOS becomes popular because of its use by
commercial users then the relations above give a simple
means of calculating constants m
ml and m2
1 2 where
m
one physical parameter is used (Zc).
(Zc).

Having already considered the sum-chart


sumchart as a thermodynamic
parameter, it is interesting to consider its relation to Z Zc
and A. PsAs shown in paper A. 5, the minimum value of (Ja is
A.5,
0.67188. This occurs for combinations of Z and AA Zc
corresponding to the Martin EOS, E05, p=RT/(v-b)-a/(v+c-b)2,
,
2
p=RT/(vb)a/(v+cb)
which corresponds to nc=nd.
cd Unfortunately the component
fugacity relation derived in paper A.5
P.5 for the four-constant
fourconstant
Martin EOS assumes ncjnd.
f2c92d. The relation which must be used
instead is found in the literature (e.g., Kubic),

In(f/p)
ln(f/p) =
= -In(Z-B)
ln(Z-B) + B/(Z-B) - 2A/(Z+C-B)
+ B/(ZB) 21\/(Z+CB)

+ A(C-B)/(Z+C-B)2
+ 2
(CB)/(z+CB) .................... (1.11)

In(fi/xiP)
ln(f/xp) = = -In(Z-B)
ln(ZB) ++ B/(ZB)
Bi/(Z-B)
- 2
2 LXjAij/(Z+C-B) +
+ A(Ci-Bi)/(Z+C-B)2

(1.12)

and also applies to the Kubic modification of


of the original
Martin three-constant
threeconstant EOS.

As an extension of the family of cubic EOS'


P
s
1 EOSss proposed in
this paper, a study was made to find the optimal values of of A
A
and Zc
Zc for several paraffins which minimized the absolute
average error, E(A,ZC)'
E(A,Zc), of saturated vapor and liquid
densities, after having first fit the EOS
EQS to vapor pressure
data using correction factor a. Results are shown in
Figs. 1.1 to 1.3. Two values of AA have been chosen: A=lA=1 and
A=2-12
/
1 2,, corresponding to the RK and PR EOSs
A=2- EOS's when Zc=1/3
Zc=1/3 and
Zc=0.307401
ZcO.3O74O1..., , repsectively. Calculations were performed
at Tr
Tr from 0.4 to 0.96 at intervals of 0.02 using the
38
38

Lee/Kesler correlation
Lee/Kesler correlation for
for vapor
vapor pressure.
pressure. If vapor
If vapor
pressure from
pressure from the
the Lee/Kesler
Lee/Kesler correlation
correlation was
was less
less than
than 0.1
0.1
psia then
psia then the
the particular
particular Tr
Tr point
point was
was not
not included.
included.
Fig. 1.1
Fig. shows the
1.1 shows the error
error function,
function, Esv,
Esv' for
for saturated
saturated vapors
vapors
as aa function
as function of le. Normal
of Z. Normal paraffins
paraffins methane,
methane, butane,
butane,
octane, and
octane, and dodecane
dodecane are
are considered.
considered. The The first
first observation
observation
is that
is that the
the minimum
minimum Esv
Esv is
is approximatel
approximately the same
y the same for
for all
all
compounds, about
compounds, about 0.3%.
0.3%. In fact, the
In the error
error isis not
not large
large
(less than
(less than 3%) all values
3%) for all values of le in
of Zc in the
the range 0.24 to
range 0.24 to
Interestingly,, minima
0.40. Interestingly
0.40. minima occur
occur at
at about
about the
the same le for
same Zc for
both A=1
both A=l and A=2~2, though
and X=2/2, though somewhat
somewhat lower
lower for
for x1.
A=l.
Approximate values
Approximate values of
of the
the minima
minima are
are given
given in
in Table
Table 1.10.
1.10.
Figs. 1.2
Figs. 1.2 and
and 1.3 show the
1.3 show the error
error function, , Esl'
5
E 1 forfor
saturated liquids
saturated liquids as
as aa function of le. Once
of Zc. Once again,
again, normal
normal
paraffins methane,
paraffins methane, butane,
butane, octane,
octane, andand dodecane
dodecane areare
considered. Fig.
considered. Fig. 1.2
1.2 gives
gives results for X=l,
A=l, and
and Fig.
Fig. 1.3
1.3
gives results for A=2V2.
gives A=2-1'2. The minima for E 5 1 are
Esl are
approximately
approximatel y the same for all compounds. However, the
minimum for A=1
minimum A=l is slightly
slightly higher than
than for X=2/2
A=2-v'2 (about
(about
versus 1.75%, respectively)
2.75% versus
2.75% respectively),, and minimum errors
decrease slightly for heavier compounds.
decrease

TABLE 1.10 - VALUES OF CRITICAL COMPRESSIBILITY FACTORS


MINIMIZING SATURATED VAPOR AND LIQUID


A =
DENSITIES FOR VALUES OF A 2v2
1 AND 2-1'2
= 1

Critical Compressibility
Compressibility Factors
Mimimizing Absolute Average Error
Normal Vapor Liquid Liquid
Paraffin A=l, 2-12
2/ A=l
A1 A=2-12
X2v

methane 0.336 0.330 0.321


butane 0.312 0.322 0.312
octane 0.289
0.289 0.314 0.304
dodecane
dodecane 0.274 0.309
0.309 0.298
0.298
39

~
I0
10

~ In
II!
A =1
-
z
>
>
U,
III
N
N
A = 2-ff

---
Lu
Z L1J
C)
0
I>
1 ->
cz:
:> VI
l- N
00
N

L1J Z
OLi]
C L1J
C
C)
LU
L1J
c.!: 0::
cz: 0
0:: 0..
L1JCZ:

LD
ID

:>:>
cz:
UJUJ
cC)
L1J L1J C
IF
1-1- ~
cz:
::l
-J
-10::
0=
O::l
VIl-
a::. cz:
cz: VI


ID
U,
o0
-~r---,.------r-=-:"""--'-";;::i=---- MIN IMUM
C

0.26
0.26 0.28
0.28 O.!O
0.50 0.!2
3.52 0.34
O.!'" 0.56 O.!B
0.38 0 ....0
0.40

COMPRESSIBILITY FACTOR, Z
CRITICAL COMPRESSIBILITY Zc

Fig. 1.1 - Calculated Error


- Error in Saturated Vapor Density of
of Four
Four Normal
Normal
Paraffins as aa Function of
of EOS Critical
Critical Compressibility
Values of EQS-Defining
Factor for Two Values EOS-Defining Constant
Constant A.
40

0
50

A=
25
20
16

,....
,
ABSOLUTE AVERAGE DEVIATION IN SATURATED LIQUID DENSITY, Ei

VI
LU
..
-
>-
~
10

t I)
z:
LU
C

--
C
ID
6

; ::)
0-
....J MINIMUM
C
LU
~
00

~ 0.10

C
.1
0.!8 0.!8

C
(N
a)
0.52
(N
3

0.2-t 0.28
(N
N

C
0

O.~
0

0.26
0

0
(N
N
0
0
N
3

;::)
~

CRITICAL COMPRESSIBILITY FACTOR, Zc FI


cm
1-4

-I
0
-I

1]
(1,

xi
Cl,
xi
0

r
cm

-4
-1
cm
xi

-o
cm

rn

tI)

-z: n

--z:
50

o , ,
"" ,, ,,
\ \ \
\\ \ \
~
\\
\\
\\
\
\
\
\
\
\ "
"
I
I ,
I
\\ \ \ I, , I
> \\ \ \ " I I
LU
C
\1
II
1\
\ \
,
I'
I
I
I
I
I A = 2-'1/2
26

\1 \ \ , I I I
LU 1\ \ \ " I I
\1 \ \ " , ,
~ II 1\ , I I I
\1 I' , I I ,
~ I I '
'I \'
I
"
"
,
I ,
I
LU I' ,\ II I I
>
I'
II 1\
\\ " , ,
20

II I I

LU
I'" I:"
\\ \ \ I I " :
~ \\ \ \ /," I
;::)
....J \ \ , \ I I : "
II \ I II I ,
o
tI) \\ \ I " / :
46

a:I \ \ ,,\ ,',', I


,
\
,
I
\\ \ II,'
,
, 'I
I I ' I " , I

\\ \ \ //,/,/
\\ \\ I,' I I
I' 1\,'1,':
10

I" ' "\ ,I I I " I


\\ \'/./ I,'
\ \ \,' I ' ,
\ \ ,,', I ,
,,\ \' 'J : '
I' \' I,
ID ,,\ l,,' \ ', "
6

I
I I , \' ,,' :

\ , \,'
'I
1,
, \
\.'" ,
"
\
"
,'\
\,
/ '\
\. ,
I',
> ....
I
MINIMUM
aD

0.50 0.52 0.56 O.!B


0
(N

0.2-t 0.28
(N
3

0
a)

.1
N

0
(N

(N
0

0
0

0."0
(N
N
0

0.26
N
0
3

a)
N

CRITICAL COMPRESSIBILITY FACTOR, Zc


-I

0
-.4
cm
m

xi
c-fl
(1

-H
r
xi
r

C-,

-o
0
C-,

cm
-I

Figs . 1.2 and 1.3 - Calculated Error in Saturated Liquid Density of Four
-fl
rfrt
5 0
a
ct. a

_.

Orfr
-

--a

LOC/Dc*
n -s r

m n rn

mcn
z cm

-h c a
Di w
a
-9

rI

-S
0
C
(DO
(15
>- cm o
In c-fr CD

0
00
z-s
00

3 00
5

0cm-S
tnDiDi

rt_5
fl

1]O
C tr c
.c Ifl DJ
to
LI,

0D0

I, I
-s.
00.

Normal Paraffins as a Function of EOS Critical Compressibility


a.
-H-h
_5 1

i,
o -a.

(1)
0
9
Din
J Di
c

0
t
c
3

Factor for Two Values of EOS-Defining Constant A.


o
o
Cl,

-b
-a.
o

CD
Di
-s

D
O

z
CD

I
41

0
N,
10

~ ID DODECANE
.......
- ..
N
N
z:
U,
III
z:
---
Lu L.LJ
0
F->
I-
~I-
>- 2CN
>Vl
uJ
L.LJ
cDLU
z:
L.LJ
Q
Q A
Lu
UJ
<.!l
~;;
Q

c:r
-
LD
ID
A 1/3
Lucy
L.LJ
>- B 0.425
~-I
Lu
L.LJ Q C
$!
C 1/2
I-
I-Lu L.LJ
=>
DI I- D 2 - ff
c5~
(/)D
Vl => E 3/4
III I-
~~
Vl LD
ID
F

0.24
0.2" 0.26
0.26 0.28
0.28 0.50
0.30 0.52
0.52 0.54 0.56
0.38 0.58
0.38 O ..a
0 .*0

Cor~PRESSIBILITY FACTOR, ZZc


CRITICAL COMPRESSIBILITY
C

Fig. 1.4 - Calculated Error in Saturated Liquid Density of Dodecane


-

as aa Function of LOS
EOS Critical Compressibility Factor for
Six Values of EOS-Defining
EOS-Defining Constant A
A.
42
42

Since minimum
mlnlmum errors
errors dodo not appear to bebe strongly
strongly dependent
on the compound,
on compound, the
the effect of AA on minimum
minimum error
error is studied
studied
by using dodecane
by dodecane only. b\lso,
Also, only
only the saturated
saturated liquid
liquid
density error is is considered.
considered. This
This seems
seems reasonable since the
vapor density
vapor densi ty predictions
predictions are less sensitive
sensitive to Zc
to AA and Z.
Fig. 1.4
1.4 shows the E Esl
5 several
1 function for dodecane using several
values ofof AA (1/3,
(1/3, 0.425, 1/2, 2~2, 3/4,
1/2, 212, 3/4, and 1).
1). It
It is seen
seen
that the minima
that minima occur
occur at decreasing values of Zc Zc and that no
improvement occurs at AA values lower than approximately 2~2
approximately 212
(Esr::1. 75%). There is probably nothing
l.75%).
51
(E nothing magical about this
value of A, but it is chosen to develop aa new threeconstant
three-constant
EOS qui te similar, but
quite but less complicated than the
Schmidt/Wenzel EOS.

Zc for
involves correlating optimal values of Zc
The first task involves
A=2-12 as aa function of acentric factor. The relation is
A=2v2
simple and quite accurate,

Zc
Zc = 0.3208 - 0.0415u)
0.041Sw (1.13)

which yields the PR EOS if w=0.3229 (somewhat between


normal hexane and normal heptane).
Next, the correction function, a, is correlated as
a function of temperature and acentric factor. The Soave
form for a is used,

ra = 11 + m(1vT)
= +m(l...!T;) (1.14)

where m
m is a smooth function of acentric factor, as shown in
Fig. 1.5,

m =
m = 0.40841 + 22
+ 1.44989w - 0.2537Ow
0.25370w

(1.15)

What really has been done by utilizing the empirical


criteria of minimized saturated liquid density error is best
illustrated in Fig. 1.6. The error between calculated and
experimental saturated liquid compressibility factors has
43
43

been plotted
been plotted as as aa function ofof reduced
reduced temperature
temperature for normal
normal
butane (same
butane (same figure as as given
given by
by Peng
Peng and
and Robinson).
Robinson). TheThe new
new
equation is
equation is compared
compared with
with the original
original PR
PR and SRK
SRK equations.
equations.
The important factor is
The is that the shape
shape of
of all
all curves
curves is
is the
the
same (also
same (also exhibited
exhibited byby the
the Schmidt/Wenzel
Schmidt/Wenzel EOS).
EOS). The The new
new
equation results in aa shift so so that the total absolute error
is minimized. vapor) densities in
To predict liquid (and vapor)
near-critical region requires that correction factor B
the nearcritical
(and possibly ~ and 6)
(and possibly and correlated
5) be used and correlated asas aa function
of reduced
of reduced temperature
temperature and acentric factor, along the the lines
lines
proposed for the modified Usdin/Mculiffe
proposed Usdin!McAuliffe EOS.
EOS.
44
N

q
.-
E

:::IE:
0::
L.U
I-
F

-.
c.!J
(!3
Zc:o
F C
1-0
e(
-J
PENG/ROBINSON
EQUATION (+)
uJ
L.U
0::
0::
ocD
UC-)

CD
C

1-
C
0.0 O.
0.1i 0.2 0.5 0."
0.4 0.5 0.6
ACENTRIC FACTOR, ww

Fig. 1.5 - Relation Between Correlating Parameter m


m and Acentric
Factor for the Proposed EOS.
2r------.-------r------~----~~----~------~
C
N

.. N-BUTANE
--
>- CD
I-ID
F-
VI
CJ)
Z
L.U
(JJ
C

-
C

-
5
cD.5!
= C

-J
-
C
J

L.U
SRK EOS
lF
-
e(
51DCD
I
l-
e(
VI
C,,

-
Z

Z
C
PROPOSED EOS (A = 2-'1'2)
~ r-----~~--~======::::::::====~~~~----~~------------i
-
F 0
e(

:::-
I-u
L.U
c PR EOS
~
CD L-______~========~======~=L== ______ _L________~______~

0."
0.1 0.5 0.6 0.1 0.8 0.9 i.O
1 .0

REDUCED TEMPERATURE, Tr
Tr

Fig. 1.6 -- Error in Saturated Liquid Density of Normal Butane for


Three Equations of State.
45

NOMENCLATURE
NOMENCLPJURE

a,b,c,d,e,f,g =
= constants in the general forms of the
cubic EOS
EQS

A,B,C,D
P,B,C,D =
= EOS
EQS constants

Aij,Bi,Ci,Di
,C,Dj. =
1
Ajj,B = EOS
EQS constants for component i

f =
= fugacity
fugacity

f/p =
= fugacity coefficient of a pure component

fi/xiP
fi/xip =
= fugacity coefficient of
of component i in a
mixture
k,k1 =
kO,k = correlating parameters in the Schmidt/Wenzel
EOS
EQS for parameter m
m

K
K =
= Watson (Universal Oil Products)
characterization factor =
= Tb(OR)1/3/
Tb(0R)1/3/y
y

m
m =
= correlating parameter in the Soave-type
Soavetype
correction factor expression for a, usually
made a polynomial function of w
w

m,m1 =
mO,m = limiting values for m
m in the Schmidt/Wenzel
EOS
EQS

ml,ffi2
,
1
m
2 m =
= defining parameters in the Coats
modification of Martin's
Martins four-constant
fourconstant EOS
EQS

M
M =
= molecular weight (mass)

N = number of
N = of moles

pp =
= absolute pressure

Pr
Pr =
= reduced pressure, =p/Pc
=p/pc

Pc
Pc =
= critical pressure, absolute units

R
R =
= universal gas constant

T
T =
= absolute temperature

TC
Tc =
= critical temperature, absolute units

Tr = reduced temperature, =T/Tc


=T/Tc
46

u,w =
= expressions used for defining EOS
EQS constants
using van der Waals critical criteria
vV == volume
Z
Z = compressibility factor, =pV/NRT

Zc
c =
7 = critical compressibility factor

Zra
Zra =
= Rackett critical compressibility factor
used in a correlation for estimating
saturated liquid densities of pure
compounds

a,B,~,6 = correction factors for EOS


= EQS constants
1
aO,a
,cx =
0
a
1 = correlating parameters in the Kubic
three-constant
modification of the Martin threeconstant
EOS
EQS for correction factor a
ct

yO,yl
1 =
Yo, = correlating parameters in the Kubic
modification of the Martin three-constant
threeconstant
EOS
EQS for correction factors ~ and 6S

B* == limiting value of the correction factor B in


the proposed modification of the tJsdin/
Usdin/
McAuliffe
Mculiffe EOS
EQS (termed 'cold
cold temperature
beta limit by Fuller)

Bc =
= defining parameter for expressing the
Schmidt/Wenzel EOS
EQS in terms of the proposed
proposeo
family of equations
A == proportionality constant between EOS
A EQS
constants ~c
c and ~,
b defining the proposed
family of cubic equations
pp =
= density

cra =
= sum-chart
sumchart (proposed by Martin)
=
= Zc - aZiaPr
aZ/apr at Pr=O
0 and Tr=l
Pr= Trtl

w = acentric factor,
= -log(Pv/Pc)-l.O
log(p/p)l.Q at Tr =O.7
TrQ.7
,
w
w =
= corrected acentric factor used by the Kubic
modification of the Martin threeconstant
three-constant
EOS
EQS

~a,~b,~c,~d =
= numerical constants defining EOS
EQS costants
47

Chapter 2
CHARACTERIZING
CHIRACTERI ZING PETROLEUM FRACTIONS

as easy as an Okie sayin 'ae


ae e tronder ae'
ae

2.1 Introduction to the Problem


This chapter reviews and updates work performed on
characterization of petroleum fractions. In the present
discussion a petroleum fraction is considered any mixture of
hydrocarbons with more than six carbon atoms. The petroleum
industry usually refers to the entire mixture of such
compounds as heptanes-plus,
heptanesplus, C7+.
+. Depending on the method of
7
C
chemical analysis, several compounds with six carbon atoms
(e.g., benzene) may be found in the heptanes-plus
heptanesplus fraction.

The characterization of petroleum fractions may consist of


different procedures for different engineering purposes.
This study considers characterization as the following:

Description of the relation between molar quantity


(mole fraction) and molecular weight, hereafter
referred to as molar distribution,

Measurement or estimation of specific gravity and


normal or average boiling point,

Estimation of critical pressure, critical temperature,


and acentric factor.

Other properties are either difficult or expensive to obtain


(e.g., paraffin/naphthene/aromatic
paraffin/naphthene/aromatic content, PNA)
PNP) or are
seldom available to the petroleum engineer (e.g., viscosity,
refractive index, cloud point).
point).
Mole fraction has the obvious function of
the of defining
defining
composition. Molecular weights are needed to convert from
molar quantities calculated by an EOS,
quantities EDS, to measured
such as density. Engineers seldom work
volumetric properties such
case of petroleum
in terms of molar quantities, and in the case
economics may dictate the choice to quantify
liquids, economics quantify in
barrels instead of kgmoles.
barrels kg-moles.
Speci fic gravity and
Specific and boiling
boiling point
point are the two mostmost common
common
used for defining
physical properties used defining petroleum
petroleum fractions.
This was
This was true even in
in the
the early
early 1930s,
1930's, and
and led
led to
to the first
characterization schemes
characterization schemes byby Smith,
Smith, Watson,
Watson, and
and coworkers.
From aa practical
From practical point
point ofof view,
view, these
these two
two properties
properties are
are
48
48

easily determined
easily determined from
from distillation
distillation experiments
experiments and
and
thermodynamically represent
thermodynamically represent two
two important
important states:
states: vapor
vapor
pressure and undersaturated
pressure and undersaturated liquid.
liquid.
Critical pressure
Critical pressure and
and temperature
temperature are
are required
required byby nearly
nearly all
all
cubic equations
cubic equations of
of state.
state. They
They are
are chosen
chosen toto define
define the
the EQS
EOS
constants, e.g.,
constants, e. g., aSla and
and b
Slb, using
using van
van der
der Waals
Waals criteria.
criteria.
Acentric factor
centric factor is is usually
usually included
included in in anan EQS
EOS as
as aa
correlating parameter
correlating parameter toto ensure
ensure good
good VLE
VUE predictions.
predictions.
Traditionally, molar
Traditionally, molar distribution,
distribution, specific
specific gravity,
gravity, and
and
boiling point
boiling point result
result from hightemperature
high-temperature distillation
data. Critical
data. Critical properties
properties and
and acentric factor are
are estimated
estimated
by empirical
by empirical correlations
correlations using specific
specific gravity
gravity and
and boiling
boiling
point as correlating
point correlating parameters. Most of the work in in this
this
been made
study has been made to help estimate the properties of
petroleum fractions when distillation data are not
petroleum
available. ---

Proposed Molar Distribution Model


2.2 Proposed

The relation between molar quantity (mole fraction) and


molecular weight has earlier been defined as molar
distribution. It is somewhat misleading actually, because
there is not a direct relation between molecular weight and
mole fraction of individual petroleum fractions. For
example, plotting mole fraction versus molecular weight will
not result in aa single curve if petroleum fractions
represent single-carbon-number
singlecarbonnumber (SCN) groups in the one case,
and lO-percent
10percent volume cuts in the other. If the same data
are plotted as cumulative mole fraction versus cumulative
average molecular weight, a single curve results. The
cumulative distribution curve is unique. The remaining
problem is how to define the cumulative distribution
mathematically.
Paper A.2 presents the mathematical model for describing
molar distribution. Some of the original applications have
been replaced by more practical ones. An n example is the
method used to match experimental data. The original
procedures rely on the use of limited molecular weight
boundaries and SCN description. This has been discarded for
a more general and easy-to-apply
easytoapply method described below. It
should be kept in mind that the concept of describing molar
describing molar
distribution with a probabilistic model model is foreign
foreign toto most
petroleum and chemical engineers. Al though i don't claim
petroleum chemical engineers. although i dont
originality, there has been no stimulus
stimulus from the literature
in conceiving the original model or later modifications
presented in this chapter.
49

Instead of
Instead of repeating
repeating the probability model
model in
in this
this section,
it
it is
is recommended
recommended that
that paper A.2 be
be read
read before
before continuing
with this
with this discussion.
The idea
The idea of using
using cumulative quanti ties to
cumulative quantities to describe
describe molar
molar
distribution resulted from aa long-time
distribution resulted longtime frustration over how how
to present
to present the
the probability
probability model
model in aa consise, easy-to-apply
easytoapply
form.
form. The solution comes
The comes in terms
terms of of two
two cumulative,
normalized quantities.
normalized quantities. The first ofof these
these is
is defined as
as
cumulative normalized mole fraction, Xi,
normalized mole Xj,

i N
Xi
Xj =
= .I
z Xj / Z Xj
Xj I.I Xj (2.1)
J=n
j=n J=n
j=n

The second quantity will be referred to as cumulative


normalized molecular weight
normalized molecular weight variable, Qi,
variable, Qj,

ii ii
{IxM/Ix}-n
{Z xM /Z x 1 }
j=n J J j=n J

j=n
= ............... (2.2)
Mn+ - nn
-

where
where Xj
Xj = mole
mole fraction
= fraction of fraction
fraction ij
Mj
M = molecular
molecular weight
= of fraction j
weight of
Mn+
Mn+ = Cn+ average molecular
= Cn+ molecular weight
iin = parameter in the
= parameter the distribution
distribution model
representing thethe minimum
minimum molecular
molecular
weight found
weight found inin the
the Cn+
Cn+ mixture
j = n,n+l, .,N
= n,n+1,.. ,N
Average molecular weight
1verage molecular weight of
of the total mixture,
mixture, Mn+, can be
Mn+,
expressed as

N
N N
N
Mn+
Mn+ =
= .I xjMj / Xj
xJ.M I.I Xj (2.3)
J=n
j=n J=n
j=n

and Mn+
Mn+ should
should always be
be measured
measured experimentally.
experimentally.
Eq. 2.2
2.2 can be
be solved for
for average molecular
molecular weight
weight of a
fraction i, Mi,
Mi, in
in the
the Cn+ mixture,
Cn+

_______J
50
50

1
M = + (Mn+_fl)(XiQi_Xi fQ )/(X.X.
1
i
.... (2.4)

a isis the model


model parameter
parameter defining
defining the
the form of of the
distribution function.
distribution For a=l
For a=l the
the distribution
distribution is
is
exponential; for a<l the
a<l the distribution is is accelerated
a>l the distribution
exponential; for a>l distribution is leftskewed.
left-skewed. J2s
As
a-, becomes
a~, the distribution becomes normal, folded n.
at ri.

Based on
Based on these
these definitions, values
values ofof Xj
Xi and GJi have
and Qj have been
been
calculated andand are given in
are given in Table 2.1.
2.1. Fig. 2.1 presents
2.1 presents
same quantities
the same quantities graphically. In In fact, Fig.
Fig. 2.1 can be be
used to fit experimental molar distribution data without the
use of a computer. The method
method is, unfortunately, trial and
best-fit is by eye. However, it
error, and the bestfit it greatly
simpli fies the model
simplifies model and allows the engineer to apply it it
probability theory,
without knowledge of probability theory, gamma functions,
tunctions,
etc.

Instead of presenting aa stepbystep


step-by-step procedure, an example
calculation is used to show the use of Table 2.1.
calculation 2.1. Consiaer
Consider
aa heptanesplus
heptanes-plus fraction with average molecular weight of
198.7. Suppose detailed compositional data are not
available from distillation or chromatographic analysis. IfIf
we want to split the fraction into four groups with, say,
mole fractions, x xi, 0.3, 0.3, 0.2, and 0.2, then the
,
1
probability model can be used to calculate molecular
weights. With no other information, model parameters a and
nr are set equal to 1.0 and 92.0 (1476),
(147-6), respectively.
XFl
XF
1 = 0.3
= 0.3
XFl
XF =
= 0.3
QFl
1
QF =
= 0.16776 (Table 2.1)

MFI
1 =
MF = 92+0.16776(198.7-92)
92+0.16776(198.792)
=
= 109.90

xF2
2 = 0.3
XF
XF2
2 =
XF = 0.3+0.3
0.30.3 =
= 0.6

QF2
2
QF =
= 0.38914 (Table 2.1)
Mf2
2 =
MF = 92 +
+ (198.7-92)(0.6xO.38914-0.3xO.16776)/(0.6-0.3)
(198.792)(0.6x0.389140.3x0.16776)/(0.6-0.3)
=
= 157.14
51

xF3
3
XE = 0.2
= 0.2
XF3
3
XE = 0.3+0.3+0.2 = 0.8
= =

QF3
3
QF = 0.59764 (Table 2.1)
MF3
MF = 92 ++ (198.7-92)(0.8xO.59764-0.6xO.38914)/(0.8-0.6)
= (198.792)(0.8x0.597640.6x0.38914)/(O.80.6)
= 222.51
=

xF4
4
XE = 0.2
= 0.2

XF4
4
XE =
= 0.3+0.3+0.2+0.2 =
0.30.30.2+0.2 = 1.0
QF4 =
= 1.0 (by definition)

MF4
4
ME = 92 ++ (198.7-92)(1.0xl.0-0.8xO.59764)/(1.0-0.8)
= (198.7-92)(l.Oxl.00.8x0.59764)/(l.0-O.8)
=
= 370.43

Check M7+
7
M = 0.3xl09.90
0.3x109.90 +
+ (0.6-0.3)x157.14
(0.60.3)x157.14
+
+ (0.8-0.6)x222.51
(0.80.6)x222.51 ++ (1.0-0.8)x370.43
(1.00.8)x370.43
=
= 198.70 V
I

If distillation
If data or chromatographic analysis is
available then the molar distribution can be fit to the
present model. The suggested procedure can be solved either
graphically or with a a programmable iterative routine. It
It
uses the normalized cumulative quantities, X Xi and Qi,
Qj, and
does not consider molecular weight boundaries for each
fraction in the mixture. This greatly simplifies the
A.2. The
matching procedure from what is proposed in paper Pi.2.
cumulati ve concept also allows aa more accurate description
cumulative descr iption
and extrapolation of experimental data.

An outline
An outline is given
gi ven below to describe the matching
matching
procedure. It -Le.,
It assumes mole fractions are available i.e.,
molecular weights have been measured and used to convert
weight fractions. If only chromatographic analysis is
and generalized SCN molecular weights are not
available and
distillation studies
defined from previous distillation studies of similar
mixtures, then
mixtures, then only weight fractions cancan be considered. AA
modification ofof the
the piocedure
procedure below
below is
is necessary in
in this
this
situation.
situation.
52
52

1. Tabulate
1. Tabulate mole
mole fractions
fractions and
and molecular
molecular weights
weights of
of groups
groups
making up
making up the
the petroleum
petroleum fraction
fraction mixture.
mixture.

2. Calculate
2. Calculate normalized mole fractions,
normalized mole fractions, Xj,
Xi, using
using Eq.
Eq. 2.1
2.1
3. Calculate
3. Calculate cumulative
cumulative molecular
molecular weight
weight for
for each
each group
group by
by
summing xjMj up to i and dividing by the sum of Xj.
summing up to i and dividing by the sum of xj.

Assume several
4. Assume several values
values of
of model
model parameter
parameter n. Considering
1. Considering
a C
a Cn+
n + mixture then
then n
ri values
values might
might range
range from 14n-20 to
14n20 to
14 n, but
14n, but no
no physical
physical meaning
meaning should
should be
be given
given rinand its
and its
numerical value
numerical value has
has no
no limit
limit (except
(except that
that it
it must
must be
be less
less
than Mn+).
than Mn+).
For each r,
5. For n, calculate normalized molecular
molecular weights, Qi,
Qj,
2.2 .
using Eq. 2.2.

6. Plot
6. Qi versus Xj
Plot Qj Xi on
on Fig. 2.1
2.1 for each value of
of ii.
n.
Determine by
Determine by eye
eye or
or aa bestfit
best-fit minimization the optimal
optimal
value of a and n.

last group in the mixture is not to be split then


7. If the last
calculations are finished, though you might ask why the
match was made in the first place.
8. To split the last group requires choosing mole fractions
of each subgroup. Thereafter, calculate the corresponding
values of Xi
Xj and enter either Fig. 2.1 or, preferably,
pref.erably, Table
2.1 to find values of Qi
Q at the optimal a.

9. Calculate molecular weights of the subgroups using


Eq. 2.4.

Table 2.2 illustrates the matching procedure using molar


distribution data given by Hoffman, et al. for a reservoir
oil. Fig. 2.2 shows the plot of Qi
Q versus Xi
Xj for values of n
r
equal to 65, 70, 75, and 80. A A best fit of 72.5 was chosen,
corresponding to a=2.5. Fig. 2.3 shows the model fit for
(a,n)=(2.5,72.5).
(a,n)=(2.5,72.5J. To check the goodness of the match in a
physically meaningful way requires that mole fraction (which
is common to both the exper imental data and the model) be
experimental
plotted versus molecular weight. Calculated and
experimental molecular weights, Mi,
Mi, are shown in Table 2.2
and plotted in Fig. 2.4 versus mole fraction, xi.
xj. The match
is quite satisfactory, particularly when we consider its
bimodal shape.
53
53

-
0C

0. 6 0.5
0. 7
0. 8
0. 9
Ja
-r-
0- eD
.. C
I.&J
0 1
-J
...J 1.4
-
c::a
cC 1.6
0:::
cC 1. 8
:::-
F
l-
=

-
xcL3 CO
(!l CD

I.&J 0
:3
0:::
cC
...J
=
=:J
C)
U
I.&J
-J
...J
C)
0
~

0
....
-
I.&J 0
N
...J
cC
~
c:::
0
Z

-
I.&J
:::-
N
l-
cC 0

...J
=
=:J
~
=:J
C-)
U

C
0.2 0.4 0.6 0.8 1.0

CUMULATIVE NORMALIZED
CUMULATIVE NORMALIZED MOLE
MOLE FRACTION,
FRACTION, X.Xi

Fig.
Fig . 2.1
2.1 - Probabilistic
Probabilistic Model
Model for
for Molar
Molar Distribution
Distribution Expressed
Expressed in
in
Cumulative
Cumulative Quantities
Quantities.
54
54

TABLE 2.1
TABLE 2.1 - MOLAR
- MOLAR DISTRIBUTION
DISTRIBUTION MODEL
MODEL EXPRESSED
EXPRESSED IN
IN CUMULATIVE
CUMULATIVE QUANTITIES
QUANTITIES.
CUmulative Normalized
CLu1u1ative Nonnalized Molecular Height, Qi,
M:>lecular Weight, Qi, for Specified aex
fur Specified

xi
Xi 0.3
0.3 0.4
0.4 0.5
0.5 0.6
0.6 0.7
0.7 0.8
0.8 0.9
0.9 1.0
1.0
0.02
0.02 0.00000
0.00000 0.00003
0.00003 0.00021
0.00021 0.00076
0.00076 0.00192
0.00192 0.00383
0.00383 0.00655 0.01007
0.00655 0.01007
0.04
0.04 0.00001
0.00001 0.00017
0.00017 0.00084
0.00084 0.00243
0.00243 0.00518
0.00518 0.00915
0.00915 0.01423
0.01423 0.02027
0.02027
0.06
0.06 0.00005
0.00005 0.00047
0.00047 0.00189
0.00189 0.00478
0.00478 0.00927
0.00927 0.01524
0.01524 0.02245 0.03062
0.02245 0.03062
0.08
0.08 0.00012
0.00012 0.00096
0.000% 0.00336
0.00336 0.00773
0.00773 0.01403
0.01403 0.02193
0.02193 0.03108 0.04111
0.03108 0.04111

0.10
0.10 0.00025
0.00025 0.00168
0.00168 0.00525
0.00525 0.01124
0.01124 0.01936
0.01936 0.02913
0.02913 0.04006
0.04006 0.05176
0.05176
0.12
0.12 0.00046
0.00046 0.00265
0.00265 0.00757
0.00757 0.01527
0.01527 0.02521
0.02521 0.03676
0.03676 0.04936
0.04936 0.06256
0.06256
0.14
0.14 0.00076
0.00076 0.00389
0.00389 0.01033
0.01033 0.01980
0.01980 0.03154
0.03154 0.04480
0.04480 0.05895
0.05895 0.07352
0.07352
0.16
0.16 0.00119
0.00119 0.00544
0.00544 0.01351
0.01351 0.02481
0.02481 0.03834
0.03834 0.05323
0.05323 0.06882
0.06882 0.08464
0.08464
0.18
0.18 0.00177
0.00177 0.00731
0.00731 0.01714
0.01714 0.03029
0.03029 0.04557
0.04557 0.06202
0.06202 0.07897
0.07897 0.09595
0.09595

0.20
0.20 0.00251
0.00251 0.00953
0.00953 0.02121
0.02121 0.03623
0.03623 0.05323
0.05323 0.07117
0.07117 0.08938
0.08938 0.10743
0.10743
0.22
0.22 0.00345
0.00345 0.01211
0.01211 0.02574
0.02574 0.04264
0.04264 0.06130
0.06130 0.00067
0.08067 0.10007
0.10007 0.11909
0.11909
0.24
0.24 0.00462
0.00462 0.01508
0.01508 0.03072
0.03072 0.04951
0.04951 0.06979
0.06979 0.09051
0.09051 0.11102
0.11102 0.13095
0.13095
0.26
0.26 0.00604
0.00604 0.01846
0.01846 0.03617
0.03617 0.05683
0.05683 0.07869
0.07869 0.10069
0.10069 0.12224
0.12224 0.14301
0.14301
0.28
0.28 0.00774
0.00774 0.02226
0.02226 0.04210
0.04210 0.06461
0.06461 0.08799
0.08799 0.11122
0.11122 0.13374
0.13374 0.15528
0.15528

0.30
0.30 0.00975
0.00975 0.02652
0.02652 0.04852
0.04852 0.07285
0.07285 0.09770
0.09770 0.12209
0.12209 0.14551
0.14551 0.16776
0.16776
0.32
0.32 0.01210
0.01210 0.03125
0.03125 0.05543
0.05543 0.08156
0.08156 0.10783
0.10783 0.13331
0.13331 0.15757
0.15757 0.18047
0.10047
0.34
0.34 0.01484
0.01484 0.03647
0.03647 0.06286
0.06286 0.09074
0.09074 0.11837
0.11837 0.14488
0.14488 0.16993
0.16993 0.19341
0.19341
0.36
0.36 0.01798
0.01798 0.04222 0.07081 0.10041
0.10041 0.12933
0.12933 0.15681 0.18258
0.18258 0.20660
0.20660
0.38
0.38 0.02158
0.02158 0.04850 0.07930
0.07930 0.11057
0.11057 0.14073
0.14073 0.16912
0.16912 0.19555
0.19555 0.22005
0.22005

0.40
0.40 0.02566 0.05536 0.08835
0.08835 0.12124
0.12124 0.15257 0.18180 0.20883 0.23376
0.23376
0.42 0.03027 0.06282 0.09797 0.13243 0.16486 0.19487 0.22245 0.24776
0.24776
0.44 0.03546 0.07090 0.10819 0.14414 0.17762 0.20834 0.23642 0.26205
0.46 0.04125 0.07964 0.11903 0.15641 0.19086 0.22224 0.25074 0.27665
0.48 0.04772 0.08907 0.13050 0.16925 0.20460 0.23657 0.26544 0.29158
0.29158

0.50
0.50 0.05490 0.09924 0.14265 0.18269 0.21886 0.25135 0.28054 0.30685
0.52 0.06285 0.11016 0.15550 0.19674 0.23366 0.26660 0.29605 0.32249
0.54
0.54 0.07163 0.12190 0.16908 0.21144 0.24903 0.28235 0.31200 0.33851
0.56 0.08131 0.13450 0.18342 0.22682 0.26499 0.29862 0.32841 0.35494
0.58 0.09195 0.14001
0.14801 0.19858 0.24290 0.28157 0.31544 0.34530 0.37181

0.60 0.10364 0.16249 0.21459 0.25974 0.29882 0.33285 0.36272 0.38914


0.62
0.62 0.11646 0.17799 0.23151 0.27737 0.31676 0.35087 0.38068 0.40696
0.64 0.13051 0.19460 0.24940
0.24940 0.29584 0.33545 0.36956 0.39924 0.42532
0.66 0.14588 0.21240 0.26832 0.31522 0.35493 0.38895 0.41843 0.44425
0.68
0.68 0.16271
0.16271 0.23147 0.28834 0.33557 0.37526 0.40909 0.43830 0.46380
0.46300
0.70
0.70 0.18113
0.18113 0.25191
0.25191 0.30956
0.30956 0.35695
0.35695 0.39651
0.39651 0.43006
0.43006 0.45891
0.45891 0.48401
0.72
0.72 0.20129
0.20129 0.27386
0.27386 0.33207
0.33207 0.37946 0.41876
0.41876 0.45192
0.45192 0.48032
0.40032 0.50496
0.50496
0.74
0.74 0.22337
0.22337 0.29746
0.29746 0.35599
0.35599 0.40320
0.40320 0.44209
0.44209 0.47474 0.50260
0.50260 0.52670
0.52670
0.76
0.76 0.24759
0.24759 0.32285
0.32285 0.38146
0.38146 0.42829 0.46661 0.49863
0.49863 0.52586 0.54933
0.54933
0.78
0.78 0.27419
0.27419 0.35025
0.35025 0.40864
0.40864 0.45486
0.45486 0.49245
0.49245 0.52371
0.52371 0.55018
0.55018 0.57294
0.57294
0.80
0.80 0.30349
0.30349 0.37989
0.37989 0.43772
0.43772 0.48310
0.48310 0.51976
0.51976 0.55010
0.55010 0.57570
0.57570 0.59764
0.59764
0.82
0.82 0.33583
0.33583 0.41206
0.41206 0.46896
0.46896 0.51320
0.51320 0.54872
0.54872 0.57798
0.57798 0.60257
0.60257 0.62358
0.62358
0.84
0.84 0.37170
0.37170 0.44712
0.44712 0.50265
0.50265 0.54544
0.54544 0.57957
0.57957 0.60755
0.60755 0.63098
0.63098 0.65094
0.65094
0.86
0.86 0.41168
0.41168 0.48555
0.48555 0.53918
0.53918 0.50014
0.58014 0.61261
0.61261 0.63909
0.63909 0.66118
0.66118 0.67993
0.67993
0.88
0.88 0.45654
0.45654 0.52794
0.52794 0.57907
0.57907 0.61775
0.61775 0.64822
0.64822 0.67294
0.67294 0.69348
0.69348 0.71087
0.71087
0.90
0.90 0.50737
0.50737 0.57516
0.57516 0.62302
0.62302 0.65889
0.65889 0.68695
0.68695 0.70960
0.70960 0.72834
0.72834 0.74416
0.74416
0.92
0.92 0.56570
0.56570 0.62841
0.62841 0.67204
0.67204 0.70442
0.70442 0.72956
0.72956 0.74976
0.74976 0.76639
0.76639 0.78037
0.78037
0.94
0.94 0.63397
0.63397 0.68961
0.68961 0.72772
0.72772 0.75571
0.75571 0.77727
0.77727 0.79449
0.79449 0.80860
0.80860 0.82042
0.82042
0.96
0.96 0.71645
0.71645 0.76211
0.76211 0.79284
0.79284 0.81514
0.81514 0.83218
0.83218 0.84569
0.84569 0.85670
0.85670 0.86588
0.86588
0.98
0.98 0.82253
0.82253 0.85323
0.85323 0.87346
0.87346 0.88793
0.88793 0.89886
0.89886 0.90745
0.90745 0.91440
0.91440 0.92016
0.92016
55
55

TABLE 21
TABLE continued
2; 1 continued
CUmulative Normalized
Cumulative Nonnalized Molecular
Molecular Weight,
Hekj'ht, Qi, Specified ca
Qi, for Specified

Xi
Xi 1.1
1.1 1.2
1.2 1.3
1.3 1.4
1.4 1.5
1.5 1.6
1.6 1.7
1.7 1.8
1.8

0.02
0.02 0.01430
0.01430 0.01917
0.01917 0.02456
0.02456 0.03040
0.03040 0.03657
0.03657 0.04302
0.04302 0.04966
0.04966 0.05645
0.05645
0.04 0.02709
0.02709 0.03452 0.04239
0.04239 0.05059
0.05059 0.05899
0.05899 0.06753
0.06753 0.07612
0.07612 0.08471
0.08471
0.06
0.06 0.03950
0.03950 0.04887
0.04887 0.05856
0.05856 0.06843
0.06843 0.07838
0.07838 0.08832
0.08832 0.09818
0.09818 0.10794
0.10794
0.08
0.08 0.05173
0.05173 0.06270
0.06270 0.07385
0.07385 0.08503
0.08503 0.09616
0.09616 0.10716
0.10716 0.11797
0.11797 0.12857
0.12857

0.10
0.10 0.06389
0.06389 0.07622
0.07622 0.08858
0.08858 0.10084
0.10084 0.11293
0.11293 0.12476
0.12476 0.13633
0.13633 0.14758
0.14758
0.12 0.07603
0.07603 0.08954
0.08954 0.10294 0.11611
0.11611 0.12899
0.12899 0.14152
0.14152 0.15368
0.15368 0.16547
0.16547
0.14
0.14 0.08819
0.08819 0.10275
0.10275 0.11704
0.11704 0.13099
0.13099 0.14454
0.14454 0.15765
0.15765 0.17031
0.17031 0.18253
0.18253
0.16 0.10040
0.10040 0.11588
0.11588 0.13097
0.13097 0.14559
0.14559 0.15971
0.15971 0.17331
0.17331 0.18639
0.18639 0.19896
0.19896
0.18 0.11268
0.11268 0.12899
0.12899 0.14477
0.14477 0.15998
0.15998 0.17460
0.17460 0.18861
0.18861 0.20204
0.20204 0.21491
0.21491

0.20
0.20 0.12505
0.12505 0.14210
0.14210 0.15850
0.15850 0.17422
0.17422 0.18926
0.18926 0.20363
0.20363 0.21736
0.21736 0.23047
0.23047
0.22
0.22 0.13752
0.13752 0.15524 0.17219
0.17219 0.18836
0.18836 0.20377
0.20377 0.21844
0.21844 0.23242
0.23242 0.24573
0.24573
0.24 0.15012
0.15012 0.16843 0.18587
0.18587 0.20243
0.20243 0.21816 0.23309
0.23309 0.24727 0.26074
0.26074
0.26
0.26 0.16285 0.18170 0.19956
0.19956 0.21647
0.21647 0.23247
0.23247 0.24762
0.24762 0.26196
0.26196 0.27556
0.27556
0.28
0.28 0.17572
0.17572 0.19505 0.21329
0.21329 0.23050
0.23050 0.24673
0.24673 0.26205
0.26205 0.27653
0.27653 0.29024
0.29024

0.30 0.18875 0.20851 0.22709 0.24455 0.26097


0.26097 0.27644
0.27644 0.29102 0.30400
0.30480
0.32 0.20196 0.22210 0.24096 0.25863 0.27522
0.27522 0.29080 0.30546
0.30546 0.31928
0.31928
0.34 0.21535 0.27278
0.23582 0.25492 0.27278 0.28949
0.28949 0.30515 0.31987 0.33371
0.33371
0.36
0.36 0.22893 0.26900 0.28700
0.24969 0.26900 0.30380
0.30380 0.31953
0.31953 0.33427 0.34812
0.34812
0.38 0.24272 0.26373 0.28321 0.30132
0.28321 0.30132 0.31819
0.31819 0.33394
0.33394 0.34869
0.34869 0.36252
0.36252

0.40 0.25674 0.27795 0.29757 0.31575 0.33266


0.33266 0.34842
0.34842 0.36314
0.36314 0.37694
0.42 0.27099 0.29237 0.31208 0.33032 0.34724
0.34724 0.36298
0.36298 0.37766
0.37766 0.39140
0.44 0.28549 0.30700 0.32678
0.32678 0.34503 0.36193
0.36193 0.37763
0.37763 0.39226 0.40592
0.46 0.30026 0.32185 0.34166 0.35991
0.35991 0.37677 0.39241 0.40695 0.42052
0.42052
0.48 0.31532 0.33696 0.35677 0.37497 0.39177 0.40732 0.42176 0.43522

0.50 0.33067 0.35232 0.37210 0.39024 0.40694 0.42238 0.43671 0.45004


0.52 0.34634 0.36797 0.38768 0.40572 0.42231 0.43762 0.45181 0.46500
0.54 0.36236 0.38393 0.40353 0.42145 0.43790 0.45306 0.46708 0.40011
0.48011
0.56 0.37874 0.40021 0.41968 0.43745 0.45373 0.46871 0.48256 0.49541
0.58 0.39551 0.41684 0.43615 0.45373 0.46981 0.48460 0.49825 0.51090

0.60 0.41270 0.43384 0.45295 0.47032 0.48619 0.50076 0.51419 0.52662


0.62 0.43033 0.45126 0.47013 0.48726 0.50288 0.51721 0.53040 0.54260
0.64 0.44845 0.46911 0.48772 0.50457 0.51992 0.53397 0.54690 0.55885
0.66 0.46708 0.48744 0.50574 0.52228 0.53733 0.55109 0.56373 0.57540
0.68 0.48628 0.50629 0.52423 0.54043 0.55515 0.56859 0.50093
0.58093 0.59230
0.70 0.50610 0.52571 0.54326 0.55908 0.57343 0.58652 0.59852 0.60958
0.72 0.52658 0.54574 0.56285 0.57825 0.59221 0.60492 0.61656 0.62728
0.74 0.54780 0.56645 0.58308 0.59802 0.61154 0.62384 0.63510 0.64544
0.76 0.56983 0.58791 0.60400 0.61844 0.63149 0.64335 0.65418 0.66413
0.78 0.59276 0.61021 0.62571 0.63960 0.65213 0.66350 0.67389 0.68341
0.80 0.61670 0.63345 0.64830 0.66158 0.67355 0.68440 0.69429 0.70336
0.82 0.64179 0.65775 0.67188 0.68450 0.69585 0.70613 0.71549 0.72406
0.84 0.66819 0.68328 0.69661 0.70849 0.71917 0.72883 0.73761 0.74565
0.86 0.69611 0.71022 0.72267 0.73374 0.74368 0.75265 0.76080 0.76825
0.88 0.72582 0.73884 0.75029 0.76047 0.76959 0.77781 0.78527 0.79207
0.90 0.75771 0.76949 0.77983 0.78900 0.79720 0.80458 0.81128 0.81737
0.92 0.79232 0.80268 0.81175 0.81978 0.82694 0.83339 0.83921 0.84452
0.94 0.83049 0.83918 0.84678 0.85349 0.85947 0.86484 0.86969 0.87409
0.96 0.87367 0.88037 0.88622 0.89136 0.89594 0.90004 0.90373 0.90708
0.98 0.92502 0.92919 0.93281 0.93599 0.93880 0.94131 0.94357 0.94562
56
56

TABLE 2.1
TABLE continued
2.1 continued
CUmulative Normalized
Cumulative Nonnalized Molecular
Ho1ecular Weight,
Height, Qi,
Qi, for
for Specified
Spec ified a
CY

Xi
Xi 1.9
1.9 2.0
2.0 2.1
2.1 2.2
2.2 2.3
2.3 2.4
2.4 2.5
2.5 2.6
2.6
0.02 0.06333
0.02 0.07027 0.07722
0.06333 0.07027 0.07722 0.08417
0.08417 0.09109
0.09109 0.09796
0.09796 0.10478
0.10478 0.11151
0.11151
0.04 0.09326 0.10174 0.11011
0.04 0.09326 0.10174 0.11011 0.11837
0.11837 0.12650
0.12650 0.13448
0.13448 0.14232
0.14232 0.15000
0.15000
0.06 0.11754 0.12697 0.13621 0.14526
0.06 0.11754 0.12697 0.13621 0.14526 0.15409
0.15409 0.16272
0.16272 0.17114
0.17114 0.17935
0.17935
0.08 0.14904 0.15889
0.13893 0.14904
0.08 0.13893 0.16848
0.15889 0.16848 0.17780
0.17780 0.18686
0.18686 0.19567
0.19567 0.20422
0.20422

0.10
0.10 0.15853
0.15853 0.16915
0.16915 0.17945 0.18944
0.17945 0.18944 0.20849
0.19911 0.20849
0.19911 0.21757
0.21757 0.22637
0.22637
0.12
0.12 0.17687
0.17687 0.18790
0.18790 0.19855
0.19855 0.20884
0.20884 0.21878 0.22839
0.21878 0.22839 0.23767
0.23767 0.24664
0.24664
0.14
0.14 0.19430
0.19430 0.20565
0.20565 0.21658 0.22710
0.21658 0.22710 0.23725 0.24702
0.23725 0.24702 0.25645
0.25645 0.26555
0.26555
0.16
0.16 0.21104
0.21104 0.22264
0.22264 0.23379 0.24450
0.23379 0.24450 0.25479 0.26470
0.25479 0.26470 0.27424
0.27424 0.28342
0.28342
0.18
0.18 0.22723
0.22723 0.23904
0.23904 0.25036 0.26121
0.25036 0.26121 0.27162 0.28162
0.27162 0.28162 0.29123
0.29123 0.30047
0.30047

0.20
0.20 0.24299
0.24299 0.25497
0.25497 0.26641
0.26641 0.27737
0.27737 0.28787
0.28787 0.29794
0.29794 0.30760
0.30760 0.31687
0.31687
0.22
0.22 0.25841
0.25841 0.27051
0.27051 0.28206
0.28206 0.29310
0.29310 0.30366
0.30366 0.31376
0.31376 0.32345
0.32345 0.33274
0.33274
0.24
0.24 0.27355
0.27355 0.28575
0.28575 0.29738
0.29738 0.30846
0.30846 0.31906
0.31906 0.32918
0.32918 0.33888
0.33888 0.34817
0.34817
0.26
0.26 0.28847
0.28847 0.30074
0.30074 0.31242
0.31242 0.32354
0.32354 0.33414
0.33414 0.34427
0.34427 0.35396
0.35396 0.36323
0.36323
0.28
0.28 0.30322 0.31553
0.31553 0.32724
0.32724 0.33837
0.33837 0.34897
0.34897 0.35909
0.35909 0.36875
0.36875 0.37799
0.37799
0.30
0.30 0.31783
0.31783 0.33017 0.34188
0.34188 0.35300
0.35300 0.36359
0.36359 0.37367
0.37367 0.38330
0.38330 0.39249
0.39249
0.32
0.32 0.33233
0.33233 0.34468
0.34468 0.35638
0.35638 0.36748
0.36748 0.37803 0.38808
0.38808 0.39765
0.39765 0.40679
0.40679
0.34
0.34 0.34677
0.34677 0.35910 0.37077
0.37077 0.38183
0.38183 0.39234
0.39234 0.40233
0.40233 0.41185
0.41185 0.42092
0.42092
0.36
0.36 0.36116 0.37346
0.37346 0.38508
0.38508 0.39610
0.39610 0.40654 0.41647
0.41647 0.42591
0.42591 0.43491
0.43491
0.38
0.38 0.37552 0.38778 0.39935
0.39935 0.41029
0.41029 0.42067
0.42067 0.43051 0.43988
0.43988 0.44880
0.44880
0.40
0.40 0.38989 0.40208 0.41358 0.42445 0.43474
0.43474 0.44450 0.45377
0.45377 0.46260
0.46260
0.42
0.42 0.40428 0.41640 0.42781 0.43858 0.44878 0.45844 0.46762
0.46762 0.47634
0.47634
0.44
0.44 0.41872 0.43074 0.44205 0.45273 0.46282 0.47237 0.48144 0.49006
0.46
0.46 0.43322 0.44513 0.45633 0.46689 0.47687 0.48630 0.49525 0.50376
0.50376
0.48
0.48 0.44780 0.45959 0.47067 0.48110 0.49095 0.50026 0.50909 0.51746
0.51746
0.50
0.50 0.46249 0.47414 0.48508 0.49538 0.50509 0.51426 0.52296 0.53120
0.52
0.52 0.47730 0.48880 0.49959 0.50974 0.51930 0.52833 0.53688 0.54499
0.54
0.54 0.49225 0.50359 0.51422 0.52420 0.53361 0.54249 0.55088 0.55884
0.55884
0.56
0.56 0.50736 0.51853 0.52898 0.53800
0.53880 0.54003
0.54803 0.55674 0.56498 0.57278
0.58
0.58 0.52266 0.53364 0.54390 0.55353 0.56259 0.57113 0.57919 0.58683
0.60
0.60 0.53817 0.54894 0.55900 0.56844 0.57730 0.58566 0.59354 0.60101
0.60101
0.62
0.62 0.55392
0.55392 0.56446
0.56446 0.57431
0.57431 0.58353 0.59220
0.59220 0.60036
0.60036 0.60805
0.60805 0.61533
0.61533
0.64
0.64 0.56992
0.56992 0.58022
0.58022 0.58984
0.58984 0.59885
0.59885 0.60730
0.60730 0.61525
0.61525 0.62275
0.62275 0.62984
0.62984
0.66
0.66 0.58621
0.58621 0.59626
0.59626 0.60564
0.60564 0.61441
0.61441 0.62263
0.62263 0.63037
0.63037 0.63766
0.63766 0.64455
0.64455
0.68
0.68 0.60283
0.60283 0.61261
0.61261 0.62172
0.62172 0.63024
0.63024 0.63823
0.63823 0.64573
0.64573 0.65280
0.65280 0.65948
0.65948
0.70
0.70 0.61980
0.61980 0.62929
0.62929 0.63813
0.63813 0.64638
0.64638 0.65411
0.65411 0.66138
0.66138 0.66822
0.66822 0.67467
0.67467
0.72
0.72 0.63717
0.63717 0.64635
0.64635 0.65489
0.65489 0.66287
0.66287 0.67033
0.67033 0.67734
0.67734 0.68394
0.68394 0.69016
0.69016
0.74
0.74 0.65499
0.65499 0.66384
0.66384 0.67207
0.67207 0.67975
0.67975 0.68693
0.68693 0.69367
0.69367 0.70000
0.70000 0.70598
0.70598
0.76
0.76 0.67331
0.67331 0.68100
0.68180 0.68970
0.68970 0.69706
0.69706 0.70394
0.70394 0.71039
0.71039 0.71646
0.71646 0.72217
0.72217
0.78
0.78 0.69219
0.69219 0.70031
0.70031 0.70784
0.70784 0.71487
0.71487 0.72143
0.72143 0.72758
0.72758 0.73336
0.73336 0.73879
0.73879
0.80
0.80 0.71170
0.71170 0.71942
0.71942 0.72657
0.72657 0.73324
0.73324 0.73946
0.73946 0.74529
0.74529 0.75076
0.75076 0.75591
0.75591
0.82
0.82 0.73194
0.73194 0.73922
0.73922 0.74597
0.74597 0.75225
0.75225 0.75811
0.75811 0.76359
0.76359 0.76874
0.76874 0.77358
0.77358
0.84
0.84 0.75303
0.75303 0.75984
0.75984 0.76615
0.76615 0.77201
0.77201 0.77748
0.77748 0.78259
0.78259 0.78739
0.78739 0.79190
0.79190
0.86
0.86 0.77509
0.77509 0.78139
0.78139 0.78722
0.78722 0.79264
0.79264 0.79769
0.79769 0.80241
0.80241 0.80683
0.80683 0.81099
0.81099
0.88
0.88 0.79832
0.79832 0.80406
0.80406 0.80938
0.80938 0.81431
0.81431 0.81891
0.81891 0.82320
0.82320 0.82722
0.82722 0.83099
0.83099
0.90
0.90 0.82296
0.82296 0.82810
0.82810 0.83285
0.83285 0.83725
0.83725 0.84134
0.84134 0.84517
0.84517 0.84874
0.84874 0.85210
0.85210
0.92
0.92 0.84937
0.84937 0.85384
0.85384 0.85795
0.85795 0.86177
0.86177 0.86531
0.86531 0.86862
0.86862 0.87171
0.87171 0.87461
0.87461
0.94
0.94 0.87812
0.87812 0.88181
0.88181 0.88521
0.88521 0.88837
0.88837 0.89129
0.89129 0.89402
0.89402 0.89657
0.89657 0.89895
0.89895
0.96
0.96 0.91013
0.91013 0.91294
0.91294 0.91551
0.91551 0.91790
0.91790 0.92011
0.92011 0.92216
0.92216 0.92408
0.92408 0.92588
0.92588
0.98
0.98 0.94748
0.94748 0.94918
0.94918 0.95074
0.95074 0.95219
0.95219 0.95353
0.95353 0.95477
0.95477 0.95592
0.95592 0.95701
0.95701
57
57

TABLE 2.1
TABLE continued
2.1 continued
CUmulative Normalized
Cumulative Nonnalized Molecular
Molecular Weight, for Specified
Qi, for
\lJeight, Qi, Specified Cl.
(l

Xi
Xi 2.7
2.7 2.8
2.8 2.9
2.9 3.0
3.0 3.1
3.1 3.2
3.2 3.3
3.3 3.4
3.4

0.02
0.02 0.11817
0.11817 0.12474
0.12474 0.13121
0.13121 0.13759
0.13759 0.14387
0.14387 0.15004
0.15004 0.15611
0.15611 0.16208
0.16208
0.04
0.04 0.15752
0.15752 0.16489
0.16489 0.17210
0.17210 0.17915
0.17915 0.18605
0.18605 0.19280
0.19280 0.19940
0.19940 0.20586
0.20586
0.06
0.06 0.18735
0.18735 0.19515
0.19515 0.20276
0.20276 0.21017
0.21017 0.21739
0.21739 0.22443
0.22443 0.23130
0.23130 0.23799
0.23799
0.08
0.08 0.21254
0.21254 0.22062
0.22062 0.22847
0.22847 0.23610
0.23610 0.24352
0.24352 0.25073
0.25073 0.25775
0.25775 0.26458
0.26458

0.10
0.10 0.23489
0.23489 0.24316
0.24316 0.25117
0.25117 0.25895
0.25895 0.26649
0.26649 0.27381
0.27381 0.28092
0.28092 0.28783
0.28783
0.12
0.12 0.25532
0.25532 0.26371
0.26371 0.27183
0.27183 0.27970
0.27970 0.28732
0.28732 0.29471
0.29471 0.30187
0.30187 0.30882
0.30882
0.14
0.14 0.27433
0.27433 0.28281
0.28281 0.29101
0.29101 0.29893
0.29893 0.30660
0.30660 0.31402
0.31402 0.32121
0.32121 0.32817
0.32817
0.16
0.16 0.29227
0.29227 0.30081
0.30081 0.30905
0.30905 0.31700
0.31700 0.32469
0.32469 0.33212
0.33212 0.33931
0.33931 0.34628
0.34628
0.18
0.18 0.30937
0.30937 0.31794
0.31794 0.32620
0.32620 0.33416
0.33416 0.34185
0.34185 0.34928
0.34928 0.35646
0.35646 0.36341
0.36341

0.20
0.20 0.32579
0.32579 0.33437
0.33437 0.34263
0.34263 0.35059
0.35059 0.35826
0.35826 0.36567
0.36567 0.37283
0.37283 0.37975
0.37975
0.22
0.22 0.34166
0.34166 0.35023
0.35023 0.35848
0.35848 0.36642
0.36642 0.37407
0.37407 0.38145
0.38145 0.38857
0.38857 0.39544
0.39544
0.24 0.35707
0.35707 0.36563
0.36563 0.37385 0.38175
0.38175 0.38937
0.38937 0.39670
0.39670 0.40378
0.40378 0.41061
0.41061
0.26
0.26 0.37211
0.37211 0.38063
0.38063 0.38881
0.38881 0.39668
0.39668 0.40424
0.40424 0.41153
0.41153 0.41855
0.41855 0.42533
0.42533
0.28 0.38683 0.39531 0.40344
0.40344 0.41125
0.41125 0.41877
0.41877 0.42600
0.42600 0.43296
0.43296 0.43967
0.43967

0.30
0.30 0.40129
0.40129 0.40971
0.40971 0.41779
0.41779 0.42554
0.42554 0.43299
0.43299 0.44016
0.44016 0.44705
0.44705 0.45370
0.45370
0.32 0.41553
0.41553 0.42389
0.42389 0.43190
0.43190 0.43959
0.43959 0.44697
0.44697 0.45406 0.46089 0.46746
0.46746
0.34 0.42959 0.43788 0.44582
0.44582 0.45343
0.45343 0.46073
0.46073 0.46775 0.47450 0.48099
0.48099
0.36 0.44350 0.45171 0.45957 0.46710
0.46710 0.47432 0.48126
0.48126 0.48792
0.48792 0.49434
0.49434
0.38 0.45730 0.46543 0.47320
0.47320 0.48064 0.48777
0.48777 0.49462
0.49462 0.50119
0.50119 0.50752
0.50752

0.40 0.47101 0.47904 0.48672 0.49407 0.50110 0.50786 0.51434 0.52058


0.52058
0.42 0.48466 0.49259 0.50016 0.50741 0.51435 0.52100 0.52739 0.53353
0.44 0.49826 0.50608 0.51355 0.52069 0.52753 0.53408
0.53408 0.54037 0.54641
0.54641
0.46 0.51184 0.51955 0.52691 0.53394 0.54066 0.54711 0.55329 0.55922
0.48 0.52543 0.53302 0.54025 0.54716 0.55378 0.56011 0.56618 0.57200
0.57200

0.50 0.53904 0.54649 0.55361 0.56040 0.56689 0.57310 0.57905 0.58477


0.58477
0.52 0.55268 0.56001 0.56699 0.57365 0.58001 0.58610 0.59194 0.59754
0.59754
0.54 0.56639 0.57357 0.58042 0.58694 0.59318 0.59914 0.60485 0.61033
0.56 0.58018 0.58721 0.59391 0.60030 0.60640 0.61223 0.61781 0.62316
0.58 0.59407 0.60095 0.60749 0.61373 0.61969 0.62538 0.63083 0.63605
0.63605

0.60 0.60808 0.61479 0.62118 0.64902


0.62727 0.63308 0.63863 0.64394 0.64902
0.62 0.62223 0.62878 0.63500 0.64093 0.64659 0.65199 0.65715 0.66210
0.64 0.63655 0.64292 0.64897 0.65474 0.66023 0.66547 0.67049 0.67529
0.66 0.65107 0.65725 0.66312 0.68863
0.66871 0.67404 0.67912 0.68398 0.68863
0.68 0.66580 0.67178 0.67747 0.70213
0.68288 0.68803 0.69294 0.69764 0.70213
0.70 0.68078 0.68656 0.69205 0.69727 0.70224 0.70698 0.71150 0.71583
0.72 0.69604 0.70161 0.70689 0.71191 0.71669 0.72125 0.72560 0.72976
0.74 0.71162 0.71697 0.72203 0.72685 0.73143 0.73579 0.73996 0.74394
0.76
0.76 0.72757 0.73268
0.73268 0.73752 0.74211 0.74648 0.75065 0.75842
0.75462 0.75842
0.78
0.78 0.74393
0.74393 0.74879
0.74879 0.75339 0.75775
0.75775 0.76191 0.76586
0.76586 0.76963 0.77324
0.80
0.80 0.76076 0.76535
0.76535 0.76970
0.76970 0.77383 0.77775 0.78148 0.78504 0.78844
0.82 0.77814
0.77814 0.78245 0.78653
0.78653 0.79040 0.79408 0.79758 0.80092 0.80410
0.84
0.84 0.79615
0.79615 0.80016
0.80016 0.80396
0.803% 0.80756
0.80756 0.81098
0.81098 0.81423
0.81423 0.81733 0.82028
0.82028
0.86
0.86 0.81490
0.81490 0.81860
0.81860 0.82209 0.82540 0.82854
0.82854 0.83153 0.83438 0.83709
0.88
0.88 0.83454
0.83454 0.83789
0.83789 0.84106
0.84106 0.84406
0.84406 0.84690 0.84961 0.85218 0.85464
0.90
0.90 0.85526
0.85526 0.85824
0.85824 0.86105
0.86105 0.86371
0.86371 0.86624
0.86624 0.86864
0.86864 0.87092
0.87092 0.87309
0.87309
0.92
0.92 0.87734
0.87734 0.87990
0.87990 0.88233
0.88233 0.88462
0.88462 0.88680
0.88680 0.88886
0.88886 0.89082
0.89082 0.89269
0.89269
0.94
0.94 0.90120
0.90120 0.90331
0.90331 0.90530
0.90530 0.90718
0.90718 0.90896
0.90896 0.91065
0.91065 0.91226
0.91226 0.91379
0.91379
0.96
0.96 0.92757
0.92757 0.92915
0.92915 0.93065
0.93065 0.93206
0.93206 0.93340
0.93340 0.93466
0.93466 0.93587
0.93587 0.93701
0.93701
0.98
0.98 0.95002
0.95802 0.95897
0.95897 0.95987
0.95987 0.96071
0.96071 0.96151
0.96151 0.96227
0.96227 0.96299
0.96299 0.96367
0.96367
58
58

TABLE 2.1
TABLE continued
2.1 continued
CUmula tive Normalized
Cumulative M:>lecular Weight,
Nonnalized Molecular Qi, for
\ieight, Qi, Specified aa.
for Specified

xi
Xi 3.5
3.5 3.6
3.6 3.7
3.7 3.8
3.8 3.9
3.9 4.0
4.0 4.1
4.1 4.2
4.2
0.02
0.02 0.16795
0.16795 0.17370
0.17370 0.17937
0.17937 0.18492
0.18492 0.19038
0.19038 0.19574
0.19574 0.20101
0.20101 0.20618
0.20618
0.04
0.04 0.21217
0.21217 0.21835
0.21835 0.22438
0.22438 0.23029
0.23029 0.23607
0.23607 0.24173
0.24173 0.24727
0.24727 0.25269
0.25269
0.06
0.06 0.24452
0.24452 0.25089
0.25089 0.25710
0.25710 0.26317
0.26317 0.26909
0.26909 0.27487
0.27487 0.28052
0.20052 0.28604
0.28604
0.08
0.08 0.27123
0.27123 0.27770
0.27770 0.28401
0.28401 0.29015
0.29015 0.29614
0.29614 0.30198
0.30198 0.30767
0.30767 0.31323
0.31323

0.10 0.29454
0.10 0.29454 0.30107
0.30107 0.30742
0.30742 0.31360 0.31962
0.31360 0.31962 0.32548
0.32548 0.33118
0.33118 0.33675
0.33675
0.12 0.31557
0.12 0.31557 0.32212
0.32212 0.32848
0.32848 0.34069
0.33467 0.34069
0.33467 0.34655
0.34655 0.35225
0.35225 0.35780
0.35700
0.14 0.33493
0.14 0.33493 0.34148
0.34148 0.34784
0.34784 0.35402 0.36002
0.35402 0.36002 0.36586
0.36586 0.37154
0.37154 0.37706
0.37706
0.16 0.35302
0.16 0.35302 0.35956
0.35956 0.36591
0.36591 0.37206 0.37804
0.37206 0.37804 0.38384
0.38384 0.38949
0.38949 0.39497
0.39497
0.18 0.37013
0.18 0.37013 0.37664
0.37664 0.38295
0.38295 0.38907 0.39501
0.38907 0.39501 0.40078
0.40078 0.40638
0.40638 0.41183
0.41183
0.20
0.20 0.38644
0.38644 0.39291
0.39291 0.40526 0.41116
0.39918 0.40526
0.39918 0.41116 0.41688 0.42243
0.41688 0.42243 0.42783
0.42783
0.22
0.22 0.40209
0.40209 0.40852
0.40852 0.41475 0.42078
0.41475 0.42078 0.42662
0.42662 0.43229 0.43779
0.43229 0.43779 0.44313
0.44313
0.24
0.24 0.41721
0.41721 0.42359
0.42359 0.43573 0.44152
0.42976 0.43573
0.42976 0.44152 0.44713 0.45257
0.44713 0.45257 0.45785
0.45785
0.26
0.26 0.43187
0.43187 0.43819
0.43819 0.44430 0.45021
0.44430 0.45021 0.45594
0.45594 0.46149 0.46687
0.46149 0.46687 0.47208
0.47208
0.28
0.28 0.44615
0.44615 0.45241
0.45241 0.46430 0.46996
0.45845 0.46430
0.45845 0.46996 0.47544 0.48076
0.47544 0.40076 0.48591
0.48591
0.30
0.30 0.46011
0.46011 0.46630
0.46630 0.47228
0.47228 0.47005
0.47805 0.48364
0.48364 0.48906
0.48906 0.49430
0.49430 0.49938
0.49938
0.32 0.47300
0.47380 0.47991 0.48581
0.48581 0.49152
0.49152 0.49704
0.49704 0.50238
0.50238 0.50755
0.50755 0.51256
0.51256
0.34
0.34 0.48725 0.49329
0.49329 0.49911
0.49911 0.50474
0.50474 0.51018
0.51018 0.51545
0.51545 0.52054
0.52054 0.52548
0.52548
0.36
0.36 0.50051
0.50051 0.50647 0.51221 0.51776
0.51776 0.52312 0.52831 0.53332
0.53332 0.53818
0.53818
0.38
0.38 0.51361
0.51361 0.51948 0.52514
0.52514 0.53061
0.53061 0.53588
0.53588 0.54099
0.54099 0.54592
0.54592 0.55070
0.55070
0.40
0.40 0.52658 0.53236 0.53793 0.54331 0.54850 0.55352 0.55837 0.56307
0.56307
0.42
0.42 0.53944 0.54512 0.55060 0.55589
0.55589 0.56099 0.56593 0.57069 0.57531
0.57531
0.44 0.55221 0.55780 0.56319 0.56838 0.57339 0.57824 0.58291 0.58744
0.46
0.46 0.56493 0.57042 0.57570 0.50000
0.58080 0.58572 0.59047 0.59506 0.59950
0.59950
0.48
0.48 0.57760 0.58299 0.58817 0.59317 0.59799 0.60264 0.60714 0.61149
0.50
0.50 0.59026 0.59554 0.60062 0.60551 0.61023 0.61479 0.61919 0.62344
0.52
0.52 0.60291 0.60808 0.61305 0.61784 0.62246 0.62691 0.63121 0.63537
0.54 0.61558 0.62064 0.62550 0.63018 0.63469 0.63903 0.64323 0.64729
0.56 0.62829 0.63323 0.63797 0.64254 0.64694 0.65118 0.65527 0.65923
0.65923
0.58
0.58 0.64106 0.64587 0.65049 0.65494 0.65923 0.66336 0.66735 0.67120
0.60
0.60 0.65390
0.65390 0.65858
0.65858 0.66308
0.66308 0.66741 0.67158 0.67560 0.67948 0.68322
0.62
0.62 0.66684 0.67139 0.67576 0.67997 0.68401 0.68792 0.69168 0.69531
0.64
0.64 0.67989
0.67989 0.68430
0.68430 0.68855
0.68855 0.69262 0.69655 0.70033
0.70033 0.70397 0.70749
0.70749
0.66
0.66 0.69308
0.69308 0.69735
0.69735 0.70146
0.70146 0.70540
0.70540 0.70920
0.70920 0.71285
0.71285 0.71638
0.71638 0.71978
0.71978
0.68
0.68 0.70644
0.70644 0.71056
0.71056 0.71452
0.71452 0.71833
0.71833 0.72199
0.72199 0.72552 0.72892
0.72892 0.73220
0.73220
0.70
0.70 0.71998
0.71998 0.72395
0.72395 0.72777
0.72777 0.73143
0.73143 0.73496
0.73496 0.73835
0.73835 0.74162
0.74162 0.74477
0.74477
0.72
0.72 0.73374
0.73374 0.73756
0.73756 0.74122
0.74122 0.74473
0.74473 0.74811
0.74811 0.75137
0.75137 0.75450
0.75450 0.75753
0.75753
0.74
0.74 0.74775
0.74775 0.75140
0.75140 0.75491
0.75491 0.75827
0.75827 0.76150
0.76150 0.76461
0.76461 0.76761
0.76761 0.77049
0.77049
0.76
0.76 0.76205
0.76205 0.76553
0.76553 0.76887
0.76887 0.77207
0.77207 0.77515
0.77515 0.77811
0.77811 0.78096
0.78096 0.78370
0.78370
0.78
0.78 0.77668
0.77668 0.77998
0.77998 0.78314
0.78314 0.78618
0.78618 0.78909
0.78909 0.79190
0.79190 0.79459
0.79459 0.79720
0.79720
0.80
0.80 0.79169
0.79169 0.79480
0.79480 0.79778
0.79778 0.80064
0.80064 0.80339
0.80339 0.80603
0.80603 0.80857
0.80857 0.81102
0.81102
0.82
0.82 0.80714
0.80714 0.81005
0.81005 0.81284
0.81284 0.81552
0.81552 0.81809
0.81809 0.82055
0.82055 0.82293
0.82293 0.82522
0.82522
0.84
0.84 0.82311
0.82311 0.82581
0.82581 0.82839
0.82839 0.83088
0.83088 0.83326
0.83326 0.83554
0.-83554 0.83774
0.83774 0.83986
0.83986
0.86
0.86 0.83968
0.83968 0.84216
0.84216 0.84453
0.84453 0.84600
0.84680 0.84898
0.84898 0.85108
0.85108 0.85310
0.85310 0.85504
0.85504
0.88
0.88 0.85698
0.85698 0.85922
0.85922 0.86136
0.86136 0.86341
0.86341 0.86538
0.86538 0.86728
0.86728 0.86909
0.86909 0.87084
0.87084
0.90
0.90 0.87517
0.87517 0.87715
0.87715 0.87904
0.87904 0.88086
0.88086 0.88260
0.88260 0.88427
0.88427 0.88588
0.88588 0.88743
0.88743
0.92
0.92 0.89447
0.89447 0.89618
0.89618 0.89780
0.89780 0.89936
0.89936 0.90086
0.90086 0.90229
0.90229 0.90367
0.90367 0.90499
0.90499
0.94
0.94 0.91525
0.91525 0.91664
0.91664 0.91797
0.91797 0.91925
0.91925 0.92047
0.92047 0.92164
0.92164 0.92276
0.92276 0.92384
0.92384
0.96
0.96 0.93810
0.93810 0.93914
0.93914 0.94013
0.94013 0.94108
0.94108 0.94200
0.94200 0.94287
0.94287 0.94370
0.94370 0.94451
0.94451
0.98
0.98 0.96432
0.96432 0.96494
0.96494 0.96553
0.96553 0.96609
0.96609 0.96664
0.96664 0.96715
0.96715 0.96765
0.96765 0.96812
0.96812
59
59

TABLE 2.1
TABLE continued
2.1 continued
CUmulative Normalized
Cumulative Nonnalized Molecular
Molecular Weight, Qi, for
Height, Qi, Spec ified cCL
for Specified

Xi
Xi 4.3
4.3 4.4
4.4 4.5
4.5 4.6
4.6 4.7
4.7 4.8
4.8 4.9
4.9 5.0
5.0

0.02
0.02 0.21126
0.21126 0.21625
0.21625 0.22114
0.22114 0.22596
0.22596 0.23068 0.23533
0.23068 0.23533 0.23989 0.24437
0.23989 0.24437
0.04
0.04 0.25799
0.25799 0.26318
0.26318 0.26828
0.26828 0.27326
0.27326 0.27815 0.28293
0.27815 0.28293 0.28763 0.29223
0.28763 0.29223
0.06
0.06 0.29143
0.29143 0.29670
0.29670 0.30186
0.30186 0.30690
0.30690 0.31183 0.31666
0.31183 0.31666 0.32138 0.32601
0.32138 0.32601
0.08
0.08 0.31865
0.31865 0.32395
0.32395 0.32912
0.32912 0.33417
0.33417 0.34394
0.33911 0.34394
0.33911 0.34866 0.35328
0.34866 0.35328

0.10
0.10 0.34217
0.34217 0.34746
0.34746 0.35263
0.35263 0.35767
0.35767 0.36259
0.36259 0.36740
0.36740 0.37210
0.37210 0.37669
0.37669
0.12
0.12 0.36321
0.36321 0.36848 0.37362
0.36848 0.37362 0.37863 0.38352
0.37863 0.38352 0.38830
0.38830 0.39296
0.39296 0.39752
0.39752
0.14
0.14 0.38244
0.38244 0.38768 0.39278
0.38768 0.39278 0.40261
0.39776 0.40261
0.39776 0.40735
0.40735 0.41197
0.41197 0.41648
0.41648
0.16
0.16 0.40031
0.40031 0.40551 0.41058
0.40551 0.41058 0.41551 0.42031
0.41551 0.42031 0.42500
0.42500 0.42958
0.42958 0.43404
0.43404
0.18
0.18 0.41712
0.41712 0.42227 0.42729
0.42227 0.42729 0.43217 0.43693
0.43217 0.43693 0.44156
0.44156 0.44609
0.44609 0.45050
0.45050

0.20
0.20 0.43307
0.43307 0.43817
0.43817 0.44313 0.44796
0.44313 0.44796 0.45266
0.45266 0.45724
0.45724 0.46171
0.46171 0.46607
0.46607
0.22
0.22 0.44832
0.44832 0.45336
0.45336 0.45826 0.46303
0.45826 0.46303 0.46768
0.46768 0.47220
0.47220 0.47661
0.47661 0.48091
0.40091
0.24
0.24 0.46298
0.46298 0.46796
0.46796 0.47200 0.47752
0.47280 0.47752 0.48210
0.48210 0.48657
0.48657 0.49091
0.49091 0.49515
0.49515
0.26
0.26 0.47715
0.47715 0.48207
0.48207 0.48685 0.49150
0.48685 0.49150 0.49602
0.49602 0.50042
0.50042 0.50471
0.50471 0.50889
0.50889
0.28
0.28 0.49091
0.49091 0.49576
0.49576 0.50048 0.50506
0.50048 0.50506 0.50952
0.50952 0.51386
0.51386 0.51808
0.51808 0.52219
0.52219

0.30 0.50431
0.50431 0.50910
0.50910 0.51375
0.51375 0.51826
0.51826 0.52265
0.52265 0.52692
0.52692 0.53108
0.53108 0.53513
0.53513
0.32 0.51742
0.51742 0.52213 0.52671
0.52671 0.53116
0.53116 0.53548
0.53548 0.53968
0.53968 0.54377
0.54377 0.54775
0.54775
0.34
0.34 0.53026
0.53026 0.53491
0.53491 0.53941
0.53941 0.54379
0.54379 0.54004
0.54804 0.55217
0.55217 0.55619
0.55619 0.56011
0.56011
0.36 0.54289 0.54746
0.54746 0.55189
0.55189 0.55619
0.55619 0.56037
0.56037 0.56443
0.56443 0.56839
0.56839 0.57223
0.38 0.55533 0.55982 0.56418
0.56418 0.56841
0.56841 0.57251 0.57650
0.57650 0.58038
0.58038 0.58416
0.58416

0.40 0.56762 0.57203 0.57631 0.50046


0.58046 0.58449 0.58840 0.59221 0.59591
0.42 0.57978 0.58410 0.58830 0.59237 0.59633 0.60017
0.60017 0.60390 0.60753
0.44 0.59182 0.59607 0.60019 0.60418 0.60805 0.61181 0.61547 0.61902
0.46 0.60379 0.60795 0.61198 0.61589 0.61969 0.62337
0.62337 0.62695 0.63043
0.48 0.61569 0.61977 0.62371 0.62754 0.63125 0.63485 0.63835 0.64175

0.50 0.62755 0.63153 0.63539 0.63913 0.64276 0.64628 0.64970 0.65302


0.52 0.63939 0.64328 0.64704 0.65070 0.65424 0.65767 0.66101 0.66425
0.66425
0.54 0.65121 0.65501 0.65869 0.66225 0.66570 0.66905 0.67230 0.67546
0.67546
0.56 0.66305 0.66675 0.67033 0.67300
0.67380 0.67716 0.68043 0.68359 0.68667
0.58 0.67492 0.67852 0.68200 0.68538 0.68865 0.69182 0.69490 0.69789

0.60 0.68684 0.69034 0.69372 0.69700 0.70017 0.70325 0.70624 0.70914


0.62 0.69882 0.70221 0.70549 0.70867 0.72044
0.71175 0.71473 0.71763 0.72044
0.64 0.71089 0.71417 0.71735 0.72042 0.72340 0.72629 0.72909 0.73180
0.73100
0.66
0.66 0.72306
0.72306 0.72623
0.72623 0.72930 0.73227 0.73515 0.73793 0.74064 0.74326
0.68
0.68 0.73536 0.73842
0.73842 0.74138 0.74424 0.74701 0.74969 0.75229 0.75482

0.70
0.70 0.74781 0.75075 0.75359
0.75359 0.75634 0.75900
0.75900 0.76158
0.76158 0.76408 0.76650
0.72 0.76044 0.76326 0.76598
0.76598 0.76861 0.77116 0.77363
0.77363 0.77602 0.77834
0.77834
0.74
0.74 0.77328
0.77328 0.77597
0.77597 0.77857
0.77857 0.78108
0.78108 0.78351 0.78587 0.78815
0.78815 0.79036
0.79036
0.76
0.76 0.78635
0.78635 0.78891
0.78891 0.79138
0.79138 0.79377 0.79608
0.79608 0.79832
0.79832 0.80049
0.80049 0.80259
0.80259
0.78
0.78 0.79970
0.79970 0.80212
0.80212 0.80446
0.80446 0.80672
0.80672 0.80891
0.80891 0.81102
0.81102 0.81307
0.81307 0.81506
0.81506
0.80
0.80 0.81337
0.81337 0.81565
0.81565 0.81785
0.81785 0.81997
0.81997 0.82203
0.82203 0.82402
0.82402 0.82594
0.82594 0.82781
0.82781
0.82
0.82 0.82742
0.82742 0.82955
0.82955 0.83160
0.83160 0.83358
0.83358 0.83550
0.83550 0.83736
0.83736 0.83915
0.83915 0.84089
0.84089
0.84
0.84 0.84190
0.84190 0.84387
0.84387 0.84577
0.84577 0.84761
0.84761 0.84938
0.84938 0.85110
0.85110 0.85276
0.85276 0.85437
0.85437
0.86
0.86 0.85690
0.85690 0.85870
0.85870 0.86044
0.86044 0.86212
0.86212 0.86375
0.86375 0.86531
0.86531 0.86683
0.86683 0.86830
0.86830
0.88
0.88 0.87253
0.87253 0.87415
0.87415 0.87572
0.87572 0.87723
0.87723 0.87869
0.87869 0.88011
0.88011 0.88147
0.88147 0.88280
0.88280
0.90
0.90 0.88891
0.88891 0.89035
0.89035 0.89173
0.89173 0.89307
0.89307 0.89436
0.89436 0.89560
0.89560 0.89681
0.89681 0.89797
0.89797
0.92
0.92 0.90626
0.90626 0.90749
0.90749 0.90867
0.90867 0.90982
0.90982 0.91092
0.91092 0.91198
0.91198 0.91302
0.91302 0.91401
0.91401
0.94
0.94 0.92488
0.92488 0.92588
0.92588 0.92684
0.92684 0.92777
0.92777 0.92867
0.92867 0.92954
0.92954 0.93038
0.93038 0.93119
0.93119
0.96
0.96 0.94528
0.94528 0.94603
0.94603 0.94674
0.94674 0.94743
0.94743 0.94810
0.94810 0.94875
0.94875 0.94937
0.94937 0.94997
0.94997
0.98
0.98 0.96858
0.96858 0.96902
0.96902 0.96945
0.96945 0.96985
0.96985 0.97025
0.97025 0.97063
0.97063 0.97100
0.97100 0.97135
0.97135
60

TABLE 2.2 - EXAMPLE


EXAMPL.E OF HOW THE MOLAR DISTRIBUTION MODEL CAN BE USED TO
FIT EXPERIMENTAL DATA: HOFFMAN, et ale
al. RESERVOIR OIL.

X.=
X
1 Calculated
x.1
X LX
1
zx LxM
1
zxM Q;
i
for n=72.5
72.5
LX;M;
zxM
1 1
No. x.
1
x ';'36.84
36.84 .;.36J4
36.84 M.
M -:-LX.
Zx ~xp.
Exp. Calc.
Caic. .;.Zx.
LX. M.
M
--L ---1.. ----1. ~ ---l..
7 2.630 0.0714 0.0714 99.0 99.0 0.2100 0.1855 95.9 95.9
8 2.340 0.0635 0.1349 110.0 104.2 0.2510 0.2518 104.3 113.7
9 2.350 0.0638 0.1987 121.0 109.6 0.2938 0.3065 111.2 125.8
10 2.240 0.0608 0.2595 132.0 114.8 0.3354 0.3536 117.1 136.5
11
11 2.412 0.0655 0.3250 145.0 120.9 0.3836 0.4012 123.1 146.9
12 2.457 0.0667 0.3917 158.0
158.0 127.2 0.4336 0.4400
0.4480 129.0 157.8
13 2.657 0.0721 0.4638 172.0
172.0 134.2
134.2 0.4888 0.4979 135.3 169.5
14
14 3.262 0.0885 0.5523 186.0 142.5 0.5546 0.5596 143.1 183.9
15 3.631 0.0986 0.6509 203.0 151.7 0.6272 0.6308 152.1
152.1 202.5
16 2.294 0.0623 0.7132 222.0 157.8 0.6759 0.6785 158.1 221.0
17 1.714 0.0465 0.7597 238.0 162.7
162.7 0.7148 0.7162 162.9 235.8
18
18 1.427 0.0387 0.7984 252.0 167.0 0.7491 0.7494 167.1 249.2
19 1.303 0.0354 0.8338 266.0 171.2 0.7824 0.7815 171.1 262.7
20 1.078
1.078 0.0293 0.8631 279.0 174.9 0.81.13
0.8113 0.0099
0.8099 174.7 276.7
21 0.871 0.0236 0.8867 290.0 178.0
178.0 0.8356 0.8343 177.8
177.8 290.2
290.2
22
22 0.715
0.715 0.0194
0.0194 0.9061 301.0
301.0 100.6
180.6 0.8565 0.8556 100.5
180.5 303.3
303.3
23 0.575
0.575 0.0156
0.0156 0.9217 315.0
315.0 182.9
182.9 0.8746
0.8746 0.8738
0.8738 182.8
182.8 315.9
315.9
24
24 0.481.
0.481 0.0131
0.0131 0.9348
0.9348 329.0
329.0 184.9
184.9 0.8907
0.8907 0.8899
0.8899 184.8
184.8 328.2
328.2
25
25 0.394
0.394 0.0107
0.0107 0.9455 343.0
343.0 186.7
186.7 0.9049
0.9049 0.9038 186.6
186.6 340.2
26 0.335
0.335 0.0091
0.0091 0.9546 357.0
357.0 188.3 0.9178 0.9163 188.1 352.0
27 0.200
0.280 0.0076 0.9622 371.0
371.0 189.8 0.9292 0.9273 189.5
189.5 363.9
28 0.250
0.250 0.0068
0.0068 0.9689 385.0
385.0 191.1 0.9400 0.9376 190.8
190.8 376.1
29
29 0.232
0.232 0.0063 0.9752 399.0
399.0 192.5
192.5 0.9507 0.9478
0.9478 192.1
192.1 389.6
389.6
30
30 0.912
0.912 0.0248
0.0248 1.0000
1.0000 444.0
444.0 198.7
198.7 1.0000
1.0000 1.0000
1.0000 198.7
198.7 458.3

36.840
36.840 1.0000
1.0000 198.7
198.7 198.7
198.7
61
61

-C
C)

--
.
n = 65
.....
0-
.. n = 70
UI
Lt.J
-J
...J
CD

- n = 75
- = 80
- n
III C
C) :lit
c::r
0 ::
c::r
::>
lF-
-
x=
-
CD
<.!'
LUI
:3
t.J

0::
co
Co
C

C)
c:C
-J
...J
=:l
C)
U
UI
Lt.J
-J
...J
0CD
~

0CD
UI
Lt.J

-
N
.-J
..J
...
1
C
C)
U

~
0::
CD
0
2!

-
UI
Lt.J
:::-
-4
I
~
...J
-j
N
N
=:l
~ C
C)

=
=:l
C)
U

C
C)

"8.0
.0 0.2 0."
0.4 0.8
0.6 0.8 4.0
i.O
Xi
CUMULATIVE NORMALIZED MOLE FRACTION, X.

Fig. 2.2 - Example Best-Fit


Best-Fit of
of Experimental
Experimental Molar
Molar Distribution
Distribution Data
Data
(Hoffman, et a].
(Hoffman, a1. Reservoir Oil)
Oil) Using the Proposed
Model with
Probabilistic Model with Four Values of
of Parameter n.
n.
62
62

Ca

-J
a
. C

=
(.3
I
bJ
coa
C
-J

C-)
-J
C

C
bJ

L2
C

LU
>.

F
-J
= N

q
C ~ __ ~~ __ ~~ __ ____ ____ ____ ____- L____
~ ~ ~ ~ ~ ____ ~ ____ ~

~.O 0.2
0.2 O.i
0.4 0.8
0.6 0.8
0.8 t.O
.i0
CUMULATI
CUMULATIVE NORMALIZED
VE NORMALIZ MOLE FRACTION
ED MOLE FRACTION,, X.
X.
1

Fig.
Fig. 2.3
2.3 - Best-Fit

Best-Fit Match
Match of
of Experimenta
Experimentall Molar
Molar Distribution
Distribution Data
Data
for the
for the Hoffman,
Hoffman, et
et al.
a1. Reservoir
Reservoir Oil
Oil Heptanes-Plu
Heptanes-P1us
s
Fraction Using
Fraction Using the
the Proposed
Proposed Probabilistic
Probabilistic Model
Model Expressed
Expressed
in Cumulative
in Cumulative Quantities.
Quantities.
63

e
C

0 IIIIIII
II I

I IT I

+
+
.
x"~ -
~. I-
X
....

.
r 0

. .- .. -e
:z:
0
.....
II
I!
....... a -
l-
uC-.,
<
IX

0C
I- DI.

u...
LJ
I.&J
.
..
-.3
-'
0
::E
Q
~
~
-
.
0C
Li-.1
I.&J
N
.....
-'
~
IX
0
:z:
~

0
I-
o0 MEASURED
+ CALCULATED
+
-. III +
-
(a=2.5,
(c=2.5, n=72.5)
.....
+ ...... .,
.

I I I I
0 ,II,,,III ,I,,IIIII.I,II,II,,

0 0 100 200 300


500 400
100 500

MOLECULAR WEIGHT, Mi
M

Fig. 2.4 - Best-Fit Match of Experimental Molar Distribution Data


-

for the Hoffman, et ale


al. Reservoir Oil Heptanes-Plus Fraction
Expressed Directly as Mole Fraction and Molecular Weight.
64
64

2.3 Estimation
2.3 Estimation of
of Specific
Specific Gravity
Gravity and
and Boiling
Boiling Point
Point
If specific
If specific gravities
gravities andand boiling
boiling points
points are notnot
available then
available then their
their values
values can
can be
be estimated.
estimated. TheThe proposed
proposed
procedure is
procedure is based
based onon the
the assumption
assumption thatthat the
the Watson
Watson
characterization factor, K,
characterization Kw, which
which by by definition
definition isis the
the
cubic-root of
cubicroot of boiling
boiling point
point (R)(OR) divided
divided byby specific
gravity: K=
gravity: Kw=3/Tb(OR)/y,
3 ./Tb(R)/y, is is constant
constant for eacheach fraction. \A
relation between
relation between molecular
molecular weight,
weight, specific gravity
specific gravity and
and
Watson Kw
Watson Kw has
has been
been developed
developed from the correlation between
correlation between
weight, specific
molecular weight, spec! fic gravity
gravity and and boiling
boiling point
point
suggested by
suggested by Riazi and Daubert,
Daubert,

Kw
Kw = 4.5579M
= 4.5579MO.15178. y-O.84573 (2.5)
84573
y
05178 (2.5)

Suppose now that onlyonly mole fractions, xj,


xi, and molecular
weights, Mi, are defined for the
the fractions making up
up aa C
C7+
+
7
mixture, e.g.,
mixture, e. g., from the molar distribution
distr ibution model or
chromatographic analysis. ssuming
chromatographic Assuming aa constant
constant Kw for each
each
specific gravity can
fraction, the specific can be
be calculated
calculated from Eq.
2.5,

Y1 -
- 66.OlO8M
= . Ol08MO.17947K

824
Kw
7947 1 W-1.18241 (2 6)
(2.6)

Kw such that the mixture specific


It is necessary to choose Kw
gravity, Y7+,
Y7+, calculated from

nn
7+M7+ // 1=1
Y7+ = xx
M
7 Z xiMi/Yi
.L
1=1
xjM/yj (2.7)

equals the measured value. It can be shown that the value


of
Of Kw necessary to meet this criterion is given by,
65
65

Kw =-- {O 16637'Y7+' 5/( x7+' M7+ )}-0.84573 (2.8)


. (2.8)

where
where
N
0
= L XiMiO.82053
S 82
=Zxj.MiW
5
O 3 (2.9)
(2.9).

i=n

summation is
The surmation is performed
performed for all fractions in in the
the
mixture. Having calculated
Having calculated Kw,
Kw, specific
specific gravity
gravity of
of each
each
fraction isis found from Eq. 2.6.2.6. Boiling
Boiling point, Tbj,
Tbi, isis
(Kw'Yi)3, found directly from the
merely (Kwyj)
,
3 the definition
definition of
of K,.
Kw'
methods are available for estimating petroleum
Other methods petroleum
fraction specific gravities, although this is the onlyonly one
which has aa simple, direct solution. For example, the
method suggested by by Yarborough is graphical (specific
carbon number); the bestfit
gravity versus carbon best-fit functions are
and require interpolation. Haaland
complex and Haaland'ss modification of
proposed procedure
the proposed procedure is
is perhaps more
more physical meaningful
meaningful
since KK varies
since varies for each
each carbon
carbon number. However,
However, neither thethe
Yarborough oror Haaland method can can be
be used
used for random
random
petroleum fractions which are not associated
petroleum associated with single
single
carbon numbers.

Continuing with the example from the previous section,


specific gravities can be calculated by noting the C C7+
+
7
specific gravity is 0.8409 (corresponding to the M7+
7 of
M
198.7). Specific gravities of the four fractions are
calculated below.

S0
50 = 0.3xl09.900.82053
= 082053
O.3xl09.90 + O.3x157.l4
+ 0.3x157.140.82053
082053

+
+ 0.2x222.510.82053
8203 +
O.2x222.5l + 0.2x370.430.82053
O.2x37O.43
82053

= 75.70441
=

Kw = (0.16637xO.8409x75.704/1.0/198.7)-0.84573
Kw (0. l6637x0.8409x75.704/l.0/l98.7
=84573

= 11.93526
=

and
and 6.0108x11.935-1.18241
8241
6.0l08xll.935 = 0.32039
= 0.32039

J
66
66

YF1
F1
= 7947
= 0.32040x109.90.17947
0.32040x109 .9

=0.74469
=0.74469
Y
F2
F2
=0.32040x157.14
=
0.17947
0.32040X157.140.17947
= 0.79404
= 0.79404
0.17947
YF3
F3
= 0.32040x222.51
= 0.32040x222.510.17947
= 0.84519
= 0.84519
YF4
F4
=0.32040x370.43
=
0.17947
0.32040x370.430.17947
= 0.92615
= 0.92615

Y7+ = 1.0x198.7
= 1.0x198.7 // (0.3x109.9/0.74469
(0.3x109.9/0 .74469 + 0.3x157.14/0
+ .79404
0.3x157.14/0.79404
+ 0.2x222.51/0
0.2x222.51/0.84519
.84519 + 0.2x370.43/0
+ 0.2x370.43/0.92617)
.92617)

= 0.8409 1I
=

Traditional Critical Property Estimation


2.4 Traditional

As noted in the introduction to this chapter, the the. main


purpose of characterizing
characterizing petroleum fractions is to arrive
at estimates of critical pressure, critical temperature, and
acentric factor. Presently, experimental determination
determination of
these properties is seldom if if ever practiced. In the 1930's
1930 s
there was considerable activity in this area, forming the
basis for graphical, and later, best-fit
bestfit correlations. Work
by Roess
Roess,, Smi th , Watson, and coworkers prov
Smith, ided the
provided
foundation, data base, and correlative techniques for
critical property estimation. Acentric factor was introduced
in 1955 by Pitzer, et a!.al. as a correlating parameter for a
corresponding
corresponding states theory. Edmister provided a simple
working relation for estimating acentric factor some three
years later. A A review of these developments and those which
which
came thereafter is given in paper A.4.
Nearly all correlations for critical properties and acentric
factor are functions of specific gravity and boiling point.
A
A few correlations (e.g., Robinson/Peng and Bergman) rely
rely on
quantification
quantification of the paraffin-naphthene-aromatic
paraffinnaphthenearomatic (PNA)
(PNA)
content of each fraction. These later correlations have
have
several practical drawbacks, the most severe
severe being
determination
determination of
of PNA content.
67
67

Critical property
Critical property correlations
correlations for
for pure
pure compounds
compounds have
have been
been
developed by
developed by several
several workers,
workers, perhaps
perhaps the
the most
most important
important
being Lydersens.
being Lydersen's. The SpencerDaubert
The Spencer-Daubert modification
modification of
of
Nokay's relation
Nokays relation isis more
more empirical
empirical than
than Lydersens
Lydersen' s group
group
contribution theory
contribution theory although
although it
it isis more
more easily
easily applied
applied by
by
practicing engineers;
practicing engineers; specific
specific gravity
gravity and
and boiling
boiling point
point are
are
used instead
used instead of
of purecompound
pure-compound group
group contribution
contribution parameters.
parameters.
The Lydersen
The Lydersen and
and Spencer/Daubert
Spencer/Daubert correlations
correlations are
are of
of limited
limited
use for petroleum
use petroleum fractions unless accurate
accurate determination
determination of
of
the chemical
the chemical nature (e.g.,
(e.g., PNA
PNA content)
content) can
can be
be made.
made.
In general
In general it
it can
can be
be stated
stated that
that petroleumfraction
petroleum-fraction critical
critical
property correlations
property correlations are empirical.
empirical. Most have
Most have been
been
developed using the basic
developed basic data measured
measured in
in the
the 1930s.
1930' s. In
In
A.4 it is
Paper 1.4 is shown how different correlations
correlations effect EQSEOS
predictions. Clearly
predictions. Clearly one
one of
of the
the main
main problems
problems facing thethe
engineer is
engineer is which
which correlations
correlations toto choose.
choose. It is reasonable
that none of the empirical
to assume that empirical correlations
correlations isis best
best
all applications.
for all applications. The conclusions given in
in Paper A.4
led to the idea of estimating critical properties based on
on
the EOS
E0S itself - the topic
of the following section.

/A short summary of the observations found in paper A.4 are


given below.
Empirical critical property correlations based on
experimental data of petroleum fractions include a wide
variety of forms including graphical, tabulated, and
best-fit
bestfit equations. The third type is commonly used by
industrial persons because it can be programmed on simple
computing machines. Unfortunately there are many forms of
best-fit
bestfit equations, including simple three-constant
threeconstant power
equations, polynomials, and complicated multiconstant
two/three-variable
two/threevariable relations. When used with an EOS,
di fferent correlations result in di
different fferent predictions of
different
VLE and volumetric properties. There does not appear to be
agreement in the industry or scientific community as to
which correlation is best-suited
bestsuited to EOS's
EQSs in general, or to
particular EOS's.
EQSs.

Several types of correlations exist for estimating


acentric factor. The Edmister relation is best known and
gi ves very good estimates for pure compounds.
gives The
Lee/Kesler equations - one for T
8 <0.8
Tr<O.
r and one for T
8 >0.8
Tr>Q.
r -

are similar to best-fit


bestfit critical property correlations.
Unfortunately the two correlations are not continuous and
are developed from two types of data. Acentric factors
estimated from the Lee/Kesler equations may be considereably
larger than Edmister estimates. This can have a noticable
effect
effect on
on volumetric predictions by
by ZJRK-type
ZJRKtype equations, and
to
to aa lesser
lesser extent
extent on
on VLE predictions.
predictions.
68
68

The
The Robinson/Peng
Robinson/Peng critical
critical property
property andand acentric
acentric factor
factor
correlJ tions are
correiitions are highly unreliable.
highly unreliable. This observation
This observation is is
detailed in
detailed in paper
paper P.4
A.4 and
and will
will not
not bebe repeated
repeated here.
here. If If
property estimations
property estimations are
are to
to be
be made
made byby aa method
method based
based onon PN
PNA
content then
content then accurate
accurate estimation
estimation of of PNP
PNA isis necessary.
necessary. This
This
can best
can best (and
(and perhaps
perhaps only)
only) be
be determined
determined using the
using the
refractive-index/density
refractiveindex/density correlations.
correlations. Other
Other methods
methods which
which
have been
been suggested
suggested rely on on aa material
material balance
balance and
and two
two data
data
such
such as
as boiling
boiling point
point and
and specific gravity.
gravity. These
These methods
methods
are susceptible to
are to small
small errors
errors in in measured
measured properties,
properties,
often resulting
often resulting inin negative
negative compositions
compositions of of one
one oror two
two of
of
the constituents. They
the three constituents. They also
also rely
rely onon description
description of of
petroleum fractions as single
petroleum single carbon
carbon numbers, aa concept
concept
which looses validity at relatively
which relatively low boiling
boiling points.
points.

2.5 EquationofState
2.5 Equation-of-State Critical Property
Property Estimation
Estimation
During the comparison of empirical critical property
During
correlations it occured that aa basic requirement of
petroleum fraction characterization should be that the EQS
EOS
prediction of specific gravity (Le.,
(i.e., liquid density at
standard conditions) and boiling point should reproduce
experimental values. It is easily shown that empirical
cr i tical property correlations do not have this property -
critical

i.e., different equations of state predict different values


of specific gravity and boiling point even though they use
the same critical properties.
The present work suggests a reasonable estimate of critical
properties can be found by fitting the EOS
EQS to experimental
values of specific gravity and boiling point for each
petroleum fraction. One of the problems in developing this
method has been definition of acentric factor, W;
w; i.e., two
properties are known - specific gravity and boiling point -

but three properties must be determined - critical pressure,


critical temperature and acentric factor (in fact, it is


the ratio of molecular weight to specific gravity, or molar
volume, and not specific gravity alone which is required).
69
69

Acentric factor
Pcentric factor isis included
included in
in the
the EQS
EOS asas aa correlating
correlating
parameter for
parameter for the
the correction
correction term
term to
to EQS
EOS constant
constant PA (a)
(S2a).
Hopefully aa good
Hopefully good estimate of tow will
estimate of will suffice
suffice since
since anan
experimental vapor
experimental vapor pressure
pressure is
is used
used to
to determine
determine critical
critical
pressure and
pressure and critical
critical temperature.
temperature. Paraffin
Paraffin acentric
acentric factor
factor
is approximatel
is approximatelyy aa linear
linear function
function ofof boiling point
boiling point (see
(see
Fig. 2.5),
Fig. 2.5), given
given by
by

uw = 0.477
= -0.477 +
+ 0.00218Tb(K)
0.00218.Tb(K) (2.10)
(2.10)

?romatic acentric factor can


Aromatic acentric can be
be approximated
approximated by
by the linear
linear
function,

ww = 0.587
= -0.587 +
+ 0.00218Tb(K)
O.Q0218Tb(K) (2.11)
(2.11)

Assuming an average Watson characterizat


assuming characterization of 12.7
ion factor of
for paraffins, and 10.0 for aromatics, the following
approximate relation for tow in terms of boiling point
and Watson Kw is,

w = -1
to = + 0.042K
_1 + O.Ow +
Kw
42 + 0.00218Tb(K)
0.00218Tb(K) (2.12)

If degrees Rankine is used for Tb instead of degrees Kelvin,


the second constant in these equati,ons
equations becomes 0.000983.
Recall the definition of Kw
Kw as Tb(R)I/3/y
-
co
CD

....
-
q NORMAL PARAFFINS
+ AROMATICS
"",
K = 10.0
" w

- , ",
N
N

CORRELATION:
"
"
"
3S
lx
0::
0c
I-
-
0C.

w =-1 +0.042.K +O.00218.T (K)
w b
~ ~ 91.127.(M/y)0.49593. Tb (K)-0.75584
,,',-'-
"",
u CO
ex:
Li
I.J....
0o
U
(_.) -.....J
......
I ,,-,-,',',' o

."
lx
0::
I-
I

,,
Z CO
Li_i
LLJ
U
(_)
0C

ex:
<

"
.... , ""
0C ,4
,4-
,+
NN

,*
0C
,,,'tbenzene
o
C
,, "
"

D 0 200 400
100 600 800 1000
NORMAL BOILING POINT, KK

Fig. 2.5 - Acentric Factor as aa Function of Normal Boiling Point for Normal Paraffins, Aromatics

and Two Values of Watson Characterization Factor Using the Proposed Acentric Factor
and Two Factor
Correlation.
Lorrelatl o,
71
71

AA problem
problem with
with using
using the
the original
original definition
definition ofof Kw
Kw is
is that
that
the resulting
the resulting critical
critical property
property correlation,
correlation, though
though based
based on
on
an EOS,
an EOS, requires
requires three
three data:
data: molar
molar volume,
volume, boiling
boiling point
point and
and
specific gravity,
specific gravity, used
used to
to define
define Kw;
Kw; Criticals =
Criticals = Criticals
Criticals
(M/y,Tb,Y). An
(M/y,Tb,y). An estimate
estimate of
of Kw
Kw based
based on
on M/y
M/y and
and Tb
Tb can
can be
be
developed from the
developed the RiaziDaubert
Riazi-Daubert correlation
correlation in an
in an analogous
analogous
manner used
manner used to
to develop
develop Eq.
Eq. 2.5,
2.5,

Kw
Kw = 49593
= 91.127(M/y)O.49593Tb(K)-O.75584
9l.l27(M/y)
75584
Tb(K) . (2.13)

If Tb
If Tb is
is given
given in
in degrees Rankine instead,
instead, constant
constant 91.127
becomes 142.1.
becomes 142.1. Now the critical property correlation based
based
on an EQS
EOS can
can be determined in
in terms of only
only M/y and Tb;
=
Criticals = Criticals (M/y,Tb).
It be shown in the following section that using Eqs.
It will be
2.12 and 2.13 is not considerably better than merely using
the paraffin relation, Eq. 2.11. Eqs. 2.12 and 2.13 are
adopted in the event that EOS
EQS predictions may be enhanced
for mixtures with relatively aromatic petroleum fractions.
Critical pressures and temperatures have been calculated for
the PR and SRK EOS's.
EQSs. They are presented in Tables 2.3 to
2.6 and Figs. 2.6 to 2.9. The ratio Tc/Tb is used instead
of Tc
Tc directly.

After the present procedure was developed it was found that


Schmidt and Wenzel had suggested that an EOS
EQS could be used
to predict critical properties. They use their own EOS
EQS (see
Chapter 1) and rely on two vapor pressure measurements and
one density measurement to determine critical pressure,
critical temperature, and acentric factor. They conclude
that the EOS
EQS predictions are accurate for a wide range ofof
pure compounds when compared with experimental data. Not
surprisingly they show that critical pressure is mostly
influenced by molar volume, while critical temperature is
mostly affected by vapor pressure. It is interesting to note
that their EOS
EQS predicts critical properties and acentric
factors better than the PR or SRK equations.
Application to petroleum fractions is not discussed by
Schmidt and Wenzel, and and the most obvious problem is
determination of the second vapor pressure data. Also, thethe
experimental determination of molecular weight for petroleum
fractions is, at best, 2 to 3 percent, and even worse for
heavy
heavy constituents. The same
same problem
problem is inherent in thethe
present method.
present Perhaps the major di fference between the
difference between the
72
72

Schmidt/Wenzel study
Schmidt/Wenzel study and
and the
the proposed
proposed procedure
procedure is
is that
that the
the
former tries
former tries to
to show
show the
the application
application of a specific EQS
of a specific EOS for
for
accurate prediction
accurate prediction ofof true
true critical
critical properties
properties and
and acentric
acentric
factor, whereas
factor, whereas the
the aim
aim ofof this
this study
study has
has been
been to
to find
find aa
method for (1) consistently
method for (1) consistently defining
defining the
the critical
critical properties
properties
of petroleum
of petroleum fractions
fractions given
given aa specific
specific EQS,
EOS, and
and (2)
(2)
improving liquid density
improving liquid density and
and VLE
VLE predictions
predictions for
for any
any EOS
EQS
chosen.
chosen.

From prelimenary
From prelimenary calculations
calculations with
with the
the proposed
proposed method
method for
for
the PR
the PR EOS,
EOS, it
it appears
appears that
that VLE
VLE predictions
predictions are
are improved
improved
considerably. Liquid
considerably. Liquid density
density (i.e.,
(i.e., volumetric)
volumetric) predictions
predictions
are
are also
also improved,
improved, though
though it
it seems
seems that
that instead
instead of
of
underestimated liquid
liquid densities,
densities, as as is
is usually
usually shown
shown by
by the
the
PR EQS
PR EOS with
with traditional
traditional critical
critical property
property correlations,
correlations, itit
now overpredicts
now overpredicts liquidliquid densities.
densities. It has
It has not
not been
been
established if
established if the
the same
same problem
problem exists
exists for the
the SRK
SRK EQS.
EOS.
73
73
PENG/ROBINSON
PENG/ROBINSON EQUATION OF
OF STATE
STATE
C

~
....

"'
c..
~

..;
Ui

""
=>
VI
VI
Ul

""c.......
0
0
10
-J

-a:
..:
u
II
-

uL)

0C
NN

200 ICC
100 800 800 1000
BOILING POINT, K
K

SOAVE/REDLICH/KWONG EQUATION OF STATE


0
LD

00

....1-

"'
c..
~

..;
Ui

"":::::.
V)
VI
(J 0
0
VI
Ui
Ul
0
10

""
c..
.....
-J
..:
C-,
~
-""
F
I-

u
C-)

0
0
N
N

200
200 400 600
800 800
800 taoo
1000
BOILING POINT,
BOILING POINT, KK

Figs. 2.6
Figs. 2.6 and
and 2.7
2.7 -- EOS-Based
EOS-Based Critical
Critical Pressure
Pressure for
for PR
PR and
and SRK
SRK EOSs
EOS's
as a Function of Boiling
as a Function of Boiling Point
Point and
and Molar
Molar Volume.
Volume.
74
PENG/ROBINSON
PENG/ROBINSON EQUATION OF STATE
STATE
CD

M/y

LD
Lfl r
.; I-
-

..c
150 .
I- ....
......u _
I-
I- --. -

to r .
.; I-
-
.400
500

-
N
"! . I I . I

200 400
100 600 aoo
800 4600
BOILING POINT, K
K

SOAVE/REDLICH/KWONG
SOAVE/REDLICH/KWONG EQUATION OF STATE
CD

ID

C-)
I

)0

200 400 600 aoo


800 1000
BOILING POINT, K
K

Critical_Temperature/Boiling Point Ratio


Figs. 2.8 and 2.9 - EOS-Based Critical-Temperature/Boiling
-

for PR and SRK EOS's


EQSs as a Function of Boiling Point
and Molar Volume.
75
75

TABLE 2.3
TABLE 2.3 - EQS-BASED
EOS-BASED CRITICAL
CRITICAL PRESSURE
PRESSURE (MPa)
(MPa) FOR
FOR THE
THE PR
PR EQS.
EOS.

PENG/ROBINSCN
PG/RDE1NS OF STATE
ECUATICN OF
0N EUITICt STATE

Boiling Point
Soiling Point Molar Vo1u
Molar Volume (Mol
(r.tol Wright/specific Gravity)
ight/Specific Gravity)
(K)
(K) (R)
(R) 100
100 105
105 110
110 115
115 120
120 125
125

270
270 486
486 3.6456
3.6456
280
280 504
504 3.6959
3.6959 3.4952
3.4952
290
290 522
522 3.7523
3.7523 3.5475 3.3630
3.5475 3.3630
300
300 540
540 3.8132
3.8132 3.6044 3.4162
3.6044 3.4162 3.2459
3.2459 3.0910
3.0910
310
310 558
558 3.8775
3.8775 3.6647 3.4729
3.6647 3.4729 3.2993
3.2993 3.1415 2.9974
3.1415 2.9974
320
320 576
576 3.9442
3.9442 3.7276 3.5323
3.7276 3.5323 3.3555
3.3555 3.1947 3.0478
3.1947 3.0478
330
330 594
594 4.0129
4.0129 3.7924 3.5937
3.7924 3.5937 3.4137
3.4137 3.2499 3.1004
3.2499 3.1004
340
340 612
612 4.0830
4.0830 3.6566 3.4734
3.8588 3.6566
3.8588 3.4734 3.3068 3.1547
3.3068 3.1547
350
350 630
630 4.1542
4.1542 3.7207 3.5345
3.9263 3.7207
3.9263 3.5345 3.3650 3.2102
3.3650 3.2102
360
360 648
648 4.2264
4.2264 3.9947 3.7858
3.9947 3.7858 3.5964
3.5964 3.4241 3.2667
3.4241 3.2667
370
370 666
666 4.2991
4.2991 4.0638 3.8515
4.0638 3.6592
3.8515 3.6592 3.4841 3.3241
3.4841 3.3241
300
3130 684
684 4.3724
4.3724 4.1335 3.9179
4.1335 3.7225
3.9179 3.7225 3.5446 3.3820
3.5446 3.3820
390
390 702
702 4.2036 3.9847
4.2036 3.9847 3.7863
3.7863 3.6056 3.4405
3.6056 3.4405
400 720
720 4.0518 3.8504
4.0518 3.8504 3.6670 3.4993
3.6670 3.4993
410 738
738 4.1192 3.9148
4.1192 3.9148 3.7287 3.5584
3.7287 3.5584
420
420 756
756 3.9795
3.9795 3.7906 3.6179
3.7906 3.6179
430
430 774
774 3.8527 3.6775
3.8527
440 792 3.7372

PENG/ROBINSCN STATE
mUATICN OF STME
PENG/PDmNSa1 EUATIC

Boiling
Soiling Point r-to1ar
Molar Volume
Voluire (Mol Wright/Specific
J4-it/Specific Gravity)

(K) (R) 130 135 140 145 1SO


150 155
320 576 2.9133
330 594 2.9634 2.8374
340 612 3.0152 2.8869 2.7685 2.6590
350 630 3.0683 2.9377 2.8173 2.7058 2.6023
360 648 3.1224 2.9896 2.8671 2.7536 2.6484 2.5505
370 666 3.1773 3.0423 2.9177 2.8023 2.6953 2.5957
300
380 684 3.2329 3.0957 2.9690 2.8517 2.7429 2.6416
390 702 3.2890 3.1495 3.0208 2.9016 2.7910 2.6881
400 720 3.3454 3.2038 3.0731 2.9520 2.8396 2.7350
410 738 3.4023 3.2585 3.1257
3.1257 3.0027 2.8886 2.7823
420 756 3.4593
3.4593 3.3134 3.1786
3.1786 3.0537 2.9378 2.8299
430 774
774 3.5166
3.5166 3.3685
3.3685 3.2317 3.1050 2.9873 2.8777
440 792 3.5741
3.5741 3.4238
3.4238 3.2850
3.2850 3.1564
3.1564 3.0369 2.9257
2.9257
450 810
810 3.6316
3.6316 3.4792 3.3384 3.2079 3.0868
3.0868 2.9739
2.9739
460 828
828 3.5348
3.5348 3.3920
3.3920 3.2596
3.2596 3.1367
3.1367 3.0222
3.0222
470
470 846
846 3.4456
3.4456 3.3114
3.3114 3.1868
3.1868 3.0707
3.0707
400
480 864
864 3.4993
3.4993 3.3633
3.3633 3.2369
3.2369 3.1192
3.1192
490
490 882
882 3.4152
3.4152 3.2871
3.2871 3.1678
3.1678
500
500 900
900 3.3374
3.3374 3.2164
3.2164
510
510 918
918 3.2651
3.2651
76
76

TABLE 2.3
TABLE 2.3 - EQS-BASED
- EOS-BASED CRITiCAL
CRITICAL PRESSURE
PRESSURE (MPa)
(MPa) FOR
FOR THE
THE PR
PR EQS.
EOS.

PENG/ROHENSaST mtJATICN OF
PEN3/ROBINSCN FUATICN OF STATE
STATE

Boiling Point
3Diling Point Molar Vo1un
Molar (Mol
Volume (Mci Wright/Specific Gravity)
ight/Specific

(K) (R)
(R) 160
160 165
165 170
170 175
175 180
180 185
185

370
370 666
666 2.5028
2.5028 2.4160
2.4160
380
380 684
684 2.5471 2.4588
2.4588 2.3761
2.3761
390
390 702
702 2.5920
2.5920 2.5023
2.5023 2.4182
2.4182 2.3393
400
400 720
720 2.6374
2.6374 2.5462
2.5462 2.4607 2.3805
2.3805 2.3050
2.3050 2.2340
410
410 738
738 2.6831 2.5904
2.5904 2.5036
2.5036 2.4221
2.4221 2.3454
2.3454 2.2732
2.2732
420
420 756
756 2.7292
2.7292 2.6350
2.6350 2.5468
2.5468 2.4640 2.3861
2.3861 2.3127
430
430 774
774 2.7755 2.6798
2.6798 2.5902
2.5902 2.5061
2.5061 2.4270 2.3525
2.3525
440
440 792
792 2.8219
2.8219 2.7249
2.7249 2.6339
2.6339 2.5485
2.5485 2.4682
2.4682 2.3925
450 810 2.8686
2.8686 2.7701
2.7701 2.6778
2.6778 2.5911
2.5911 2.5095
2.5095 2.4327
460
460 828
828 2.9154 2.8154 2.7217 2.6338 2.5510 2.4730
2.4730
470 846 2.9623 2.8609 2.7658 2.6766 2.5926 2.5135
480 864
864 3.0093
3.0093 2.9064 2.8100 2.7195 2.6343 2.5540
490 882 3.0563 2.9521
2.9521 2.8543 2.7625 2.6761 2.5947
500
500 900 3.1034
3.1034 2.9978
2.9978 2.8987 2.8056 2.7180 2.6354
2.6354
510 918
918 3.1506
3.1506 3.0435
3.0435 2.9431
2.9431 2.8487 2.7599 2.6762
2.6762
520
520 936 3.1978
3.1978 3.0893
3.0893 2.9875 2.8919 2.8018
2.8018 2.7170
530
530 954
954 3.1351
3.1351 3.0320 2.9351 2.8439 2.7579
540 972
972 3.0765 2.9783 2.8859 2.7988
2.7988
550
550 990 3.0216 2.9280 2.8397
560 1008
1008 2.9701 2.8807
570 1026
1026 2.9217
77
77

TABLE 2.3
TABLE 2.3 - EQS-BASED
- EOS-BASED CRITICAL
CRITICAL PRESSURE
PRESSURE (MPa)
(MPa) FOR
FOR THE
THE PR
PR EOS.
EOS.
PEThIG/ROBINSC EOUATICN OF
PENG/ROBINSCN EX2UATION OF STATE
STATE

Point
Boiling Point
Boiling Molar
Molar Volun (Mol
Volume (Mol weight/specific Gravity)
ict/Specific Gravity)
(K)
(K) (R)
(R) 190
190 195
195 200
200 210
210 220
220 230
230

410
410 738
738 2.2050
2.2050
420
420 756
756 2.2434
2.2434 2.1780
2.1780
430
430 774
774 2.2821
2.2821 2.2157
2.2157 2.1527
2.1527
440
440 792
792 2.3210
2.3210 2.2535
2.2535 2.1896
2.1896 2.0715
2.0715
450
450 810
810 2.3601
2.3601 2.2916
2.2916 2.2267
2.2267 2.1068
2.1068 1.9985
1.9985
460
460 828
828 2.3994
2.3994 2.3298
2.3298 2.2639
2.2639 2.1422
2.1422 2.0322
2.0322
470
470 846
846 2.4387
2.4387 2.3681
2.3681 2.3012
2.3012 2.1777
2.1777 2.0661
2.0661 1.9648
1.9648
400
480 864
864 2.4782
2.4782 2.4066
2.4066 2.3387
2.3387 2.2133
2.2133 2.1000 1.9972
1.9972
490 882
882 2.5178
2.5178 2.4451
2.4451 2.3763
2.3763 2.2490
2.2490 2.1341
2.1341 2.0298
2.0298
500
500 900 2.5574
2.5574 2.4837 2.4139 2.2849
2.2849 2.1683
2.1683 2.0624
2.0624
510
510 918
918 2.5971 2.5224
2.5224 2.4516
2.4516 2.3207 2.2025
2.2025 2.0951
2.0951
520
520 936
936 2.6369
2.6369 2.5611
2.5611 2.4893
2.4893 2.3567 2.2368
2.2368 2.1279
2.1279
530
530 954
954 2.6767
2.6767 2.5999
2.5999 2.5271 2.3926
2.3926 2.2711
2.2711 2.1607
2.1607
540
540 972
972 2.7165 2.6387 2.5650
2.5650 2.4287
2.4287 2.3054 2.1935
550 990 2.7563
2.7563 2.6775 2.6028
2.6028 2.4647 2.3398
2.3398 2.2264
560 1008 2.7962 2.7164 2.6407 2.5008 2.3743 2.2594
570 1026
1026 2.8361
2.8361 2.7552 2.6786 2.5369 2.4087 2.2923
580 1044 2.8761 2.7942 2.7166 2.5730 2.4432 2.3253
590 1062 2.8331 2.7545 2.6092 2.4777 2.3583
600 1080 2.7925 2.6453 2.5123 2.3913
610 1098
1098 2.6815 2.5468 2.4244
620 1116 2.7177 2.5813 2.4574
630 1134 2.6159 2.4905
640 1152 2.6505 2.5236
650 1170 2.5566
660 1188 2.5898

J
78
78

TABLE 2.3
TABLE 2.3 - EOS-BASED
EOS-BASED CRITICAL
CRITICAL PRESSURE
PRESSURE (MPa)
(MPa) FOR
FOR THE
THE PR
PR EOS.
EOS.
PENG/ROBINSON ECUATICN OF
PENG/ROBINSCN E)2U?iTIC OF STATE
STATE

BJiling Point
iling Point Molar Vo1urr
Molar Vo1une (Mol
(Mol Wright/specific Gravity)
ight/Specific Gravity)

(K)
(K) (R)
(R) 240
240 250
250 260
260 270
270 280
280 290
290

400
480 864
864 1.9036
1.9036
490
490 882
882 1.9347 1.8477
1.9347 1.8477
500
500 900
900 1.9659 1.8777
1.9659 1.8777
510
510 918
918 1.9972 1.9077
1.9972 1.9077 1.8254
1.8254
520
520 936
936 2.0286 1.9378
2.0286 1.9378 1.8543
1.8543 1.7774
1.7774
530
530 954
954 2.0600 1.9679
2.0600 1.9679 1.8833
1.8833 1.8053
1.8053 1.7332
1.7332
540
540 972
972 2.0915 1.9981
2.0915 1.9981 1.9123
1.9123 1.8332
1.8332 1.7601 . 1.6923
1.7601 1.6923
550
550 990
990 2.1230 2.0283
2.1230 2.0283 1.9414
1.9414 1.8612
1.8612 1.7871 1.7183
1.7871 1.7183
560
560 1008
1008 2.1546 2.0586
2.1546 2.0586 1.9704
1.9704 1.8892
1.8892 1.8140 1.7444
1.8140 1.7444
570
570 1026
1026 2.1861 2.0889
2.1861 2.0889 1.9996
1.9996 1.9172
1.9172 1.8410 1.7704
1.8410 1.7704
500
580 1044
1044 2.2177 2.1192
2.2177 2.1192 2.0287
2.0287 1.9452
1.9452 1.8681 1.7965
1.8681 1.7965
590
590 1062
1062 2.2494 2.1496
2.2494 2.1496 2.0579
2.0579 1.9733
1.9733 1.8951 1.8226
1.8951 1.8226
600
600 1000
1080 2.2810 2.1799
2.2810 2.1799 2.0871
2.0871 2.0014
2.0014 1.9222 1.8488
1.9222 1.8488
610
610 1098
1098 2.3126 2.2103
2.3126 2.2103 2.1163
2.1163 2.0295
2.0295 1.8749
1.9493 1.8749
1.9493
620
620 1116
1116 2.3443 2.2407
2.3443 2.2407 2.1455
2.1455 2.0577
2.0577 1.9764
1.9764 1.9011
630
630 1134
1134 2.3760 2.2711
2.3760 2.2711 2.1747
2.1747 2.0858
2.0858 2.0036 1.9273
2.0036 1.9273
640
640 1152
1152 2.4077 2.3016
2.4077 2.2040 2.1140 2.0307 1.9535
2.0307 1.9535
650
650 1170
1170 2.4394 2.3320 2.2332 2.1422 2.0579 1.9797
1.9797
660
660 1188
1188 2.4711 2.3625
2.4711 2.2625 2.1703 2.0851 2.0060
670 1206
1206 2.5029 2.3929 2.2918
2.2918 2.1985 2.1123 2.0322
600
680 1224
1224 2.5346 2.4234 2.3211 2.2268 2.1395 2.0585
690 1242 2.4539 2.3504 2.2550 2.1667 2.0847
700 1260 2.4844 2.3797 2.2832 2.1939 2.1110
710 1278 2.4091
24091 2.3115 2.2211 2.1373
720 1296 2.3397 2.2484 2.1636
730 1314 2.3680 2.2756 2.1899
740 1332 2.3029 2.2162
750 1350 2.3301 2.2425
760 1368 2.2689
770 1386 2.2952
79
79

TABLE 2.3
TABLE 2.3 - EOS-BASED
- EOS-BASED CRITICAL
CRITICAL PRESSURE
PRESSURE (MPa)
(MPa) FOR
FOR THE
THE PR
PR EOS.
EOS.

PmG/ROmNSCN
PENG/ROBI mUATICN OF
NSON E2UATICST OF STATh
STATE
8:liling Point
Boiling Point Molar Volurre
Molar Vo1urte (Mol
(Mol \'eight/Specific Gravity)
ight/Specific Gravity)
(K)
(K) (R)
(R) 300
300 310
310 320
320 340
340 360
360 380
300

550
550 990
990 1.6545
1.6545
560
560 1008
1008 1.6796
1.6796
570
570 1026
1026 1.7048
1.7048 1.6436
1.6436
580
580 1044
1044 1.7300
1.7300 1.6680 1.6101
1.6680 1.6101
590
590 1062
1062 1.7552
1.7552 1.6924 1.6337
1.6924 1.6337
600
600 1080
1080 1.7805
1.7805 1.7168 1.6573
1.7168 1.6573 1.5495
1.5495
610
610 1098
1098 1.8057
1.8057 1.7413 1.6810 1.5717
1.7413 1.6810 1.5717
620
620 1116
1116 1.8310
1.8310 1.7657 1.7047
1.7657 1.7047 1.5940
1.5940
630
630 1134
1134 1.8563
1.8563 1.7902 1.7284
1.7902 1.7284 1.6163
1.6163 1.5172
1.5172
640
640 1152
1152 1.8817
1.8817 1.8147 1.7521
1.8147 1.7521 1.6386
1.6386 1.5383
1.5383
650
650 1170
1170 1.9070
1.9070 1.8392 1.7759
1.8392 1.7759 1.6609
1.6609 1.5593 1.4690
1.5593 1.4690
660
660 1188
1188 1.9324
1.9324 1.8638 1.7996
1.8638 1.7996 1.6833
1.6833 1.5804 1.4889
1.5804 1.4889
670
670 1206
1206 1.9577
1.9577 1.8234 1.7056
1.8883 1.8234
1.8883 1.7056 1.6015 1.5089
1.6015 1.5089
680
680 1224
1224 1.9831
1.9831 1.9128
1 .9128 11.8472
.8472 11.7280
.7280 11.6226 .5289
.6226 11.5289
690 1242
1242 2.0085 1.9374 1.8710 1.7503
1.9374 1.8710 1.7503 1.6437 1.5489
1.6437 1.5489
700
700 1260
1260 2.0339
2.0339 1.9620 1.8948
1.9620 1.8948 1.7727
1.7727 1.6649 1.5689
1.5689
710
710 1278
1278 2.0593 1.9865
1.9865 1.9186
1.9186 1.7951
1.7951 1.6860 1.5889
1.6860 1.5889
720 1296 2.0847 1.8175
2.0111 1.9424 1.8175 1.6089
1.7071 1.6089
730
730 1314 2.1101 2.0357 1.9662 1.8399 1.6289
1.7283 1.6289
740 1332 2.1356 2.0603 1.9900 1.8624 1.7495 1.6490
750 1350 2.1610 2.0850 2.0139 1.8848 1.6690
1.7706 1.6690
760 1368 2.1865 2.1096 2.0377 1.9072 1.6891
1.7918 1.6891
770 1386 2.2119 2.1342 2.0616 1.9297 1.8130 1.7091
780 1404 2.2374 2.1589 2.0855 1.9521 1.8342 1.7292
790 1422 2.2629 2.1835 2.1094 1.9746 1.7493
1.8554 1.7493
800 1440 2.2082 2.1332 1.9971 1.7694
1.8766 1.7694
810 1458 2.1571 2.0196 1.8979 1.7895
1.8979
820 1476 2.1811 2.0421 1.8096
1.9191 1.8096
1.9191
830 1494
1494 2.0646 1.9403 1.8297
1.9403 1.8297
840
840 1512
1512 2.0871 1.9616 1.8498
1.9616 1.8498
850
850 1530
1530 2.1096 1.9829 1.8699
1.9829 1.8699
860
860 1548
1548 1.8901
2.0041 1.8901
870
870 1566
1566 2.0254 1.9102
2.0254 1.9102
880
880 1584
1584 2.0467 1.9304
2.0467 1.9304
890
890 1602
1602 1.9506
1.9506
900
900 1620
1620 1.9708
1.9708
910
910 1638
1638 1.9910
1.9910
920
920 1656
1656 2.0112
2.0112
80

TABLE 2.3 - EQS-BASED


- EOS-BASED CRITICAL PRESSURE (MPa) FOR THE PR EOS.

PENG/ROBINSCN EOUATICN OF STATE


PE7SIG/ROBINSON EUTIST

Boiling Point Molar Vo1urce


Volun (Mol Wright/Specific
ight/Specific Gravity)

(K) (R) 400 420 440 460 480 500

670 1206 1.4260


680 1224 1.4450
690 1242 1.4639 1.3875
700 1260
1260 1.4829 1.4055
710 1278
1278 1.5019 1.4236 1.3527
720 1296 1.5209 1.4417 1.3700
730 1314
1314 1.5399 1.4598
1.4598 1.3872 1.3213
740 1332 1.5589 1.4779 1.4045 1.3378
750 1350 1.5780 1.4960 1.4218 1.3543
760 1368
1368 1.5970 1.5141 1.4391 1.3708 1.3085
770 1386
1386 1.6161 1.5322 1.4564 1.3874 1.3243
780 1404 1.6351
1 .6351 11.5504
.5504 1.4737
1 .4737 1.4039 1.3402
1 .3402 1.2818
790 1422 1.6542 1.5685 1.4910 1.4204 1.3560 1.2970
800 1440 1.6733 1.5867 1.5083 1.4370 1.3719 1.3122
810 1458 1.6923 1.6048
1.6048 1.5256 1.4535
1.4535 1.3877 1.3274
820 1476 1.7114 1.6230 1.5429 1.4701 1.4036 1.3426
830 1494
1494 1.7305 1.6412 1.5603 1.4867 1.4195 1.3579
840 1512 1.7496 1.6594 1.5776 1.5033 1.4354 1.3731
850 1530 1.7688 1.6776 1.5950 1.5199 1.4513 1.3883
860 1548 1.7879 1.6958 1.6124 1.5365 1.4671 1.4036
870 1566 1.8070 1.7140 1.6297 1.5531 1.4831 1.4189
880 1584 1.8262 1.7322 1.6471 1.5697 1.4990 1.4341
890 1602 1.8453 1.7504 1.6645 1.5863 1.5149 1.4494
900 1620 1.8645 1.7687 1.6819 1.6030 1.5308 1.4647
910 1638 1.8837 1.7869 1.6993 1.6196 1.5468 1.4800
920 1656 1.9029 1.8052 1.7167 1.6363 1.5627 1.4953
930 1674 1.9220 1.8235 1.7342 1.6529 1.5787 1.5106
940 1692 1.9413 1.8418 1.7516 1.6696 1.5946 1.5259
950 1710 1.9605 1.8601 1.7691 1.6863 1.6106 1.5412
960 1728 1.8784 1.7865 1.7030 1.6266 1.5566
970 1746 1.8967 1.8040 1.7197 1.6426 1.5719
980 1764 1.9150 1.8215 1.7364 1.6586 1.5873
990 1782 1.8390 1.7531 1.6746 1.6026
1000 1800 1.8565 1.7699 1.6907 1.6180
1010 1818 1.8740 1.7866 1.7067 1.6334
1020 1836 1.8034 1.7228 1.6488
1030 1854 1.8201 1.7388 1.6642
1040 1872 1.8369 1.7549 1.6796
81
81

TABLE 2.4
TABLE 2.4 - EOS-BASED
- EOS-BASED Tc/Tb
Tc/Tb RATIO
RATIO FOR
FOR THE
THE PR
PR EOS.
EOS.

mtJATICN OF
PENG/ROBtNSCN E2UNFIC
P/RoBINsa OF STATE
STATE

Boiling Point
Boiling Point (Mol
Volume (Mol
Molar Volurr
Molar Wright/Specific Gravity)
it/Specific Gravity)

(K)
(K) (R)
(R) 100
100 105
105 110
110 115
115 120
120 125
125

270
270 486
486 1.5866
1.5866
280
280 504
504 1.5850
1.5850 1.5692
1.5692
290
290 522
522 1.5832
1.5832 1.5677
1.5677 1.5531
1.5531
300
300 540
540 1.5811
1.5811 1.5659
1.5659 1.5516
1.5516 1.5382
1.5382 1.5256
1.5256
310
310 558
558 1.5788
1.5788 1.5639
1.5639 1.5499
1.5499 1.5367
1.5367 1.5243
1.5243 1.5126
1.5126
320
320 576
576 1.5762
1.5762 1.5617
1.5617 1.5400
1.5480 1.5351
1.5351 1.5229
1.5229 1.5113
1.5113
330
330 594
594 1.5734
1.5734 1.5592
1.5592 1.5458
1.5458 1.5332
1.5332 1.5212
1.5212 1.5099
1.5099
340
340 612
612 1.5704
1.5704 1.5565
1.5565 1.5434
1.5434 1.5311
1.5311 1.5194
1.5194 1.5083
1.5083
350
350 630
630 1.5672
1.5672 1.5537
1.5537 1.5409
1.5409 1.5288
1.5288 1.5173
1.5173 1.5064
1.5064
360
360 648
648 1.5639
1.5639 1.5506
1.5506 1.5381
1.5381 1.5263
1.5263 1.5151
1.5151 1.5045
1.5045
370
370 666 1.5604
1.5604 1.5475
1.5475 1.5352
1.5352 1.5237
1.5237 1.5127
1.5127 1.5023
1.5023
300
380 684
684 1.5568
1.5568 1.5442
1.5442 1.5322
1.5322 1.5209 1.5102
1.5102 1.5000
1.5000
390
390 702
702 1.5408 1.5291
1.5291 1.5181
1.5181 1.5076
1.5076 1.4976
1.4976
400 720 1.5259 1.5151 1.5049
1.5049 1.4951
410 738 1.5226 1.5120
1.5120 1.5020 1.4925
420 756 1.5089
1.5089 1.4991
1.4991 1.4898
1.4898
430
430 774
774 1.4962
1.4962 1.4870
1.4870
440
440 792 1.4842

EOUTICtI OF STATE
PEG/ROBINSCN mtJATICN
PENG/ROBtNSCN

Ik>iling Point
Boiling VolurrE (Mol
Molar Volume it/Specific Gravity)
Wright/specific

(K) (R) 130 135 140 145 150 155

320 576 1.5004


330 594 1.4991 1.4889
340 612 1.4977 1.4877
1.4877 1.4781 1.4690
350 630 1.4961
1 .4961 1.4863
1 .4863 1.4769
1 .4769 1.4679
1 .4679 1.4594
360 648 1.4943
1 .4943 1.4847
1 .4847 1.4755
1 .4755 1.4667
1 .4667 1.4583
1 .4583 1.4502
370 666 1.4924 1.4830 1.4740 1.4653 1.4571 1.4492
300
380 684 1.4903
1 .4903 1.4811
1 .4811 1.4723
1 .4723 1.4638
1 .4638 1.4557 1.4479
1 .4479
390 702 1.4881 1.4791 1.4704 1.4621 1.4542 1.4466
400 720 1.4858 1.4770 1.4685 1.4604 1.4526 1.4451
410 738 1.4834 1.4747 1.4664 1.4585 1.4508 1.4435
420 756 1.4009
1.4809 1.4724
1.4724 1.4643
1.4643 1.4565 1.4490 1.4418
430 774 1.4783 1.4700
1.4700 1.4621
1.4621 1.4544 1.4471 1.4400
1.4400
440 792 1.4757 1.4676 1.4598 1.4523 1.4451 1.4382
450 810 1.4730 1.4650 1.4574 1.4501 1.4430
1.4430 1.4363
460 828
828 1.4625
1.4625 1.4550
1.4550 1.4478
1.4478 1.4409
1.4409 1.4343
1.4343
470 846 1.4526 1.4455
1.4455 1.4388 1.4323
1.4323
400
480 864
864 1.4501
1.4501 1.4432
1.4432 1.4366
1.4366 1.4302
1.4302
490 882
882 1.4408 1.4343
1.4343 1.4281
1.4281
sao
500 900
900 1.4321
1.4321 1.4259
1.4259
510
510 918
918 1.4238
1.4238
82
82

TABLE 2.4
TABLE 2.4 - EOS-BASED
- EOS-BASED Tc/Tb
Tc/Tb RATIO
RATIO FOR
FOR THE
THE PR
PR EQS.
EOS.

PENG/ROBINSCN E)UATION
PENG/POBINSON OF STATE
mUATICN OF STATE

Foiling Point
Boiling Point Molar VolUte (Mol
Molar Volun (Mol Wright/specific Gravity)
ight/Specific Gravity)

(K)
(K) (R)
(R) 160
160 165
165 170
170 175
175 180
180 185
185
370
370 666
666 1.4415
1.4415 1.4342
1.4342
380
380 684
684 1.4405
1.4405 1.4264
1.4333 1.4264
1.4333
390
390 702
702 1.4393
1.4393 1.4322 1.4254
1.4322 1.4254 1.4189
1.4189
400
400 720
720 1.4379
1.4379 1.4310 1.4243
1.4310 1.4243 1.4179
1.4179 1.4117 1.4057
1.4117 1.4057
410
410 738
738 1.4365
1.4365 1.4297 1.4231
1.4297 1.4168
1.4231 1.4168 1.4107 1.4048
1.4107 1.4048
420
420 756
756 1.4349
1.4349 1.4283 1.4218
1.4283 1.4218 1.4156
1.4156 1.4097 1.4039
1.4097 1.4039
430
430 774
774 1.4333
1.4333 1.4267 1.4204 1.4144
1.4267 1.4204 1.4144 1.4085 1.4028
1.4085 1.4028
440
440 792
792 1.4315
1.4315 1.4251 1.4190
1.4251 1.4190 1.4130
1.4130 1.4072 1.4016
1.4072 1.4016
450
450 810
810 1.4297
1.4297 1.4235 1.4174
1.4235 1.4174 1.4115
1.4115 1.4059 1.4004
1.4059 1.4004
460
460 828
828 1.4279
1.4279 1.4217 1.4158
1.4217 1.4158 1.4100
1.4100 1.4045 1.3991
1.4045 1.3991
470
470 846
846 1.4260
1.4260 1.4199 1.4141
1.4199 1.4141 1.4084
1.4084 1.4030 1.3977
1.4030 1.3977
480
480 864
864 1.4240
1.4240 1.4181 1.4124
1.4181 1.4124 1.4068
1.4068 1.4015 1.3963
1.4015 1.3963
490
490 882
882 1.4220
1.4220 1.4162 1.4106
1.4162 1.4106 1.4051
1.4051 1.3999 1.3948
1.3999 1.3948
SOO
500 900
900 1.4200
1.4200 1.4143 1.4088
1.4143 1.4088 1.4034
1.4034 1.3983 1.3932
1.3983 1.3932
510
510 918
918 1.4180
1.4180 1.4123 1.4069
1.4123 1.4069 1.4017
1.4017 1.3966 1.3917
1.3966 1.3917
520
520 936
936 1.4159
1.4159 1.4104 1.4051
1.4104 1.4051 1.3999
1.3999 1.3949 1.3901
1.3949 1.3901
530
530 954
954 1.4084 1.4032
1.4084 1.4032 1.3981
1.3981 1.3932 1.3885
1.3932 1.3885
540
540 972 1.4013 1.3963
1.4013 1.3963 1.3868
1.3915 1.3868
1.3915
550
550 990 1.3945 1.3897 1.3852
1.3897 1.3852
560
560 1008
1008 1.3880 1.3835
1.3880 1.3835
570 1026
1026 1.3818
83
83

TABLE 2.4
TABLE 2.4 - EOSBASED
EOS-BASED Tc/Tb
Tc/Tb RATIO
RATIO FOR
FOR THE
THE PR
PR EOS.
EOS.

PENG/ROBINSCN E)UNPIC
Pm/RoBmIsa OF STATE
roUATICN OF STATE

BJi1ing Point
Boiling Point Volme (Mol
~101ar Volurr
Molar (Mol iit/Spe cific Gravity)
W:rl.ght/Specific Gravity)
(K)
(K) (R)
(R) 190
190 195
195 200
200 210
210 220
220 230
230
410
410 738
738 1.3991
1.3991
420
420 756
756 1.3983
1.3983 1.3928
1.3928
430
430 774
774 1.3973
1.3973 1.3920
1.3920 1.3868
1.3868
440
440 792
792 1.3962
1.3962 1.3910
1.3910 1.3859
1.3859 1.3762
1.3762
450
450 810
810 1.3951
1.3951 1.3899
1.3899 1.3850
1.3850 1.3754
1.3754 1.3664
1.3664
460
460 828
828 1.3939
1.3939 1.3888
1.3888 1.3839
1.3839 1.3745
1.3745 1.3657
1.3657
470
470 846
846 1.3926
1.3926 1.3876
1.3876 1.3828
1.3828 1.3736
1.3736 1.3648
1.3648 1.3566
1.3566
480
480 864
864 1.3912
1.3912 1.3864
1.3864 1.3816
1.3816 1.3725
1.3725 1.3640
1.3640 1.3558
1.3558
490
490 882
882 1.3898
1.3898 1.3850
1.3850 1.3004
1.3804 1.3715
1.3715 1.3630
1.3630 1.3550
1.3550
500
500 900
900 1.3884
1.3884 1.3837
1.3837 1.3791
1.3791 1.3703
1.3703 1.3620
1.3620 1.3542
1.3542
510
510 918
918 1.3869
1.3869 1.3823
1.3823 1.3778
1.3778 1.3692
1.3692 1.3610
1.3610 1.3533
1.3533
520
520 936
936 1.3854
1.3854 1.3008
1.3808 1.3764
1.3764 1.3600
1.3680 1.3599
1.3599 1.3523
1.3523
530
530 954
954 1.3839
1.3839 1.3794
1.3794 1.3750
1.3750 1.3667
1.3667 1.3588
1.3588 1.3513
1.3513
540
540 972
972 1.3823
1.3823 1.3779
1.3779 1.3736
1.3736 1.3654
1.3654 1.3577
1.3577 1.3503
1.3503
550
550 990
990 1.3807
1.3807 1.3764
1.3764 1.3722
1.3722 1.3641
1.3641 1.3565
1.3565 1.3492
1.3492
560
560 1008
1008 1.3791
1.3791 1.3749
1.3749 1.3707
1.3707 1.3628
1.3628 1.3553
1.3553 1.3481
1.3481
570
570 1026
1026 1.3775
1.3775 1.3733
1.3733 1.3692
1.3692 1.3614
1.3614 1.3540
1.3540 1.3470
1.3470
580
580 1044
1044 1.3759
1.3759 1.3718
1.3718 1.3678
1.3678 1.3601
1.3601 1.3528
1.3528 1.3459
1.3459
590
590 1062
1062 1.3702 1.3663
1.3663 1.3587 1.3515
1.3515 1.3447
1.3447
600 1080 1.3648
1.3648 1.3573
1.3573 1.3503 1.3435
1.3435
610 1098 1.3559 1.3490 1.3424
1.3424
620
620 1116 1.3546 1.3477 1.3412
1.3412
630
630 1134 1.3464 1.3400
640 1152 1.3451 1.3388
650
650 1170 1.3376
1.3376
660
660 1188 1.3364
1.3364
84

TABLE 2.4 - EOS-BASED TTc/Tb


- /T RATIO FOR THE PR EOS.
cb

EUlTICN OF STATE
PENG/ROBINSON EOUATICN
PENG/ROBINSCN STAIE

EDiting
Boiling point
Point Volume (~lo1
Molar Voluire (Mol ight/Specific Gravity)
Wllght/Specific

(K) (R) 240


240 250 260 270 280
280 290

480 864 1.3481


1.3481
490 882
882 1.3474 1.3402
500
500 900 1.3467 1.3396
510 918 1.3459 1.3389 1.3322
520 936 1.3451
1.3451 1.3381 1.3315 1.3252
530 954 1.3442 1.3374 1.3309
1.3309 1.3246
1.3246 1.3187
540
S40 972 1.3432 1.3365 1.3301 1.3240 1.3181 1.3125
550 990 1.3423 1.3357 1.3294
1.3294 1.3234 1.3176 1.3120
560 1008 1.3413 1.3348
1.3348 1.3286
1.3286 1.3226
1.3226 1.3169
1.3169 1.3115
570 1026 1.3403 1.3339 1.3278 1.3219 1.3163 1.3109
580 1044 1.3393 1.3330 1.3269 1.3211 1.3156 1.3103
590 1062 1.3382
1.3382 1.3320 1.3261 1.3204 1.3149 1.3096
600 1080 1.3371 1.3310 1.3252 1.3195 1.3142 1.3090
610 1098
1098 1.3361 1.3300
13300 1.3243 1.3187 1.3134 1.3083
620
620 1116
1116 1.3350 1.3290 1.3233
1.3233 1.3179 1.3126
1.3126 1.3076
1.3076
630
630 1134
1134 1.3339
1.3339 1.3280 1.3224
1.3224 1.3170
1.3170 1.3118
1.3118 1.3069
640 1152
1152 1.3328
1.3328 1.3270 1.3214
1.3214 1.3161 1.3110 1.3061
650 1170
1170 1.3316 1.3259 1.3205 1.3153 1.3102
1.3102 1.3054
1.3054
660 1188
1188 1.3305 1.3249 1.3195 1.3144 1.3094
1.3094 1.3046
1.3046
670 1206
1206 1.3294
1.3294 1.3239 1.3186 1.3135 1.3086 1.3039
680 1224
1224 1.3283 1.3228
1.3228 1.3176 1.3126 1.3077 1.3031
690 1242
1242 1.3218 1.3166 1.3117 1.3069 1.3023
700 1260
1260 1.3208 1.3157 1.3108 1.3061 1.3015
710 1278
1278 1.3147 1.3099 1.3052 1.3008
720 1296 1.3090 1.3044
1.3044 1.3000
730 1314 1.3081 1.3035 1.2992
740 1332 1.3027 1.2984
1.2984
750 1350 1.3019 1.2976
760 1368 1.2968
1.2968
770 1386 1.2961
1.2961
85
85

TABLE 2.4
TABLE 2.4 - EOS-BASED
- EOS-BASED Tc/Tb
Tc/Tb RATIO
RATIO FOR
FOR THE
THE PR
PR EOS.
EOS.

PENG/ROBINSCN EUATIST
PEThG/R0BINS0N OF STAIE
mUATICN OF STATE

Point
Ik>iling Point
BDiling Molar Volurre
Molar (Mol
Vo1une (Mol ~ght/specific Gravity)
i4it/Specific Gravity)

(K)
(K) (R)
(R) 300
300 310
310 320
320 340
340 360
360 380
300
550
550 990
990 1.3067
1.3067
560
560 1008
1008 1.3062
1.3062
570
570 1026
1026 1.3057 1.3007
1.3057 1.3007
580
580 1044
1044 1.3052 1.3002
1.3052 1.3002 1.2955
1.2955
590
590 1062
1062 1.3046 1.2997
1.3046 1.2997 1.2950
1.2950
600
600 1000
1080 1.3040 1.2992 1.2946
1.3040 1.2992 1.2946 1.2858
1.2858
610
610 1098
1098 1.3034 1.2987
1.3034 1.2987 1.2941
1.2941 1.2854
1.2854
620
620 1116
1116 1.3028 1.2981
1.3028 1.2981 1.2936
1.2936 1.2850
1.2850
630
630 1134
1134 1.3021 1.2975
1.3021 1.2975 1.2930
1.2930 1.2846
1.2846 1.2767
1.2767
640
640 1152
1152 1.3014 1.2969 1.2925
1.3014 1.2969 1.2925 1.2841
1.2841 1.2763
1.2763
650
650 1170
1170 1.3007 1.2962
1.3007 1.2962 1.2919
1.2919 1.2837
1.2837 1.2759
1.2759 1.2687
1.2687
660
660 1188
1188 1.3000 1.2956
1.3000 1.2956 1.2913 1.2832
1.2913 1.2832 1.2756
1.2756 1.2684
1.2684
670
670 1206
1206 1.2993 1.2950
1.2993 1.2950 1.2907 1.2827
1.2907 1.2827 1.2752
1.2752 1.2681
1.2681
600
680 1224
1224 1.2986 1.2943
1.2986 1.2943 1.2901
1.2901 1.2822
1.2822 1.2747
1.2747 1.2677
1.2677
690
690 1242
1242 1.2979 1.2936
1.2979 1.2936 1.2895
1.2895 1.2817
1.2817 1.2743
1.2743 1.2674
1.2674
700
700 1260
1260 1.2972 1.2930
1.2972 1.2930 1.2889
1.2889 1.2811
1.2811 1.2739
1.2739 1.2670
1.2670
710
710 1278
1278 11.2964
.2964 11.2923 .2883 11.2006
.2923 11.2883 .2806 11.2734
.2734 1.2666
1.2666
720 1296
1296 1.2957 1.2916 1.2876
1.2957 1.2001
1.2876 1.2801 1.2730
1.2730 1.2663
1.2663
730 1314 1.2950 1.2909 1.2870 1.2795 1.2725 1.2659
1.2659
740
740 1332
1332 1.2942 1.2902
1.2902 1.2863
1.2863 1.2790
1.2790 1.2720
1.2720 1.2655
1.2655
750 1350
1350 1.2935 1.2895 1.2857
1.2857 1.2784
1.2784 1.2715 1.2651
760 1368 1.2928
1.2928 1.2889 1.2851 1.2778 1.2710 1.2646
770 1386 1.2921 1.2882 1.2844 1.2773 1.2706 1.2642
780 1404 1.2913
1.2913 1.2875 1.2838 1.2767 1.2701 1.2638
790 1422 1.2906 1.2868 1.2832 1.2762 1.2696
1.2696 1.2634
000
800 1440 1.2861
1 .2861 1.2825
1 .2825 1.2756
1 .2756 1.2691
1 .2691 1 .2630
1.2630
810 1458 1.2819 1.2751 1.2686 1.2625
820 1476 1.2813 1.2745 1.2681 1.2621
830 1494 1.2740 1.2677 1.2617
840 1512 1.2734 1.2672 1.2613
850 1530 1.2729 1.2667 1.2609
860 1548 1.2662 1.2605
870 1566 1.2658
1.2658 1.2600
880 1584 1.2653 1.2596
890 1602
1602 1.2592
900 1620
1620 1.2588
1.2588
910 1638
1638 1.2584
1.2584
920 1656
1656 1.2581
1.2581
86
86

TABLE 2.4
TABLE 2.4 - EOSBASED
EOS-BASED TTc/Tb RATIO FOR
/T RATIO
cb
FOR THE
THE PR
PR EOS.
EOS.
PENG/ROBI
PENG/ROBINSCN EDUATICN OF
NSaST EtThTIC OF ST
STATE

B:>i1ing Point
i1ing Point t.lJo1ar Vohare
Molar Volume (Mol
(Mol W:rl.ght/Specific Gravity)
ight/Specific Gravity)
(K)
(K) (R)
(R) 400
400 420
420 440
440 460
460 48)
480 500
500

670
670 1206
1206 1.2614
1.2614
600
680 1224
1224 1.2611
1.2611
690
690 1242
1242 1.2608
1.2608 1.2546
1.2546
700
700 1260
1260 1.2605
1.2605 1.2544
1.2544
710
710 1278
1278 1.2602
1.2602 1.2542 1.2484
1.2542 1.2484
720
720 1296
1296 1.2599
1.2599 1.2483
1.2539 1.2483
1.2539
730
730 1314
1314 1.2596
1.2596 1.2537 1.2481
1.2537 1.2481 1.2427
1.2427
740
740 1332
1332 1.2593
1.2593 1.2534 1.2478
1.2534 1.2478 1.2425
1.2425
750
750 1350
1350 1.2589
1.2589 1.2531 1.2476
1.2531 1.2476 1.2424
1.2424
760
760 1368
1368 1.2586
1.2586 1.2529 1.2474
1.2529 1.2474 1.2422
1.2422 1.2372
1.2372
770
770 1386
1386 1.2582
1.2582 1.2526 1.2472
1.2526 1.2472 1.2420
1.2420 1.2371
1.2371
700
780 1404
1404 1.2579
1.2579 1.2523 1,2469
1.2523 1.2469 1.2418
1.2418 1.2370
1.2370 1.2323
1.2323
790
790 1422
1422 1.2575
1.2575 1.2520 1.2467 1.2416
1.2520 1.2467 1.2416 1.2368
1.2368 1.2322
1.2322
000
800 1440
1440 1.2572
1.2572 1.2517 1.2464
1.2517 1.2464 1.2414
1.2414 1.2367
1.2367 1.2321
1.2321
810 1458
1458 1.2568
1.2568 1.2462 1.2412
1.2513 1.2462
1.2513 1.2412 1.2365
1.2365 1.2320
1.2320
820 1476
1476 1.2564
1.2564 1.2510 1.2459
1.'2459 1.2410
1.2410 1.2363
1.2363 1.2318
1.2318
830 1494 1.2561 1.2507 1.2456 1.2408
1.2408 1.2361 1.2317
1.2317
840 1512
1512 1.2557
1.2557 1.2504
1.2504 1.2454
1.2454 1.2406 1.2360
1.2360 1.2316
1.2316
850 1530
1530 1.2553 1.2501 1.2451 1.2403
1.2403 1.2358
1.2358 1.2314
860 1548 1.2550
1 .2550 1.2498
1 .2498 1.2448
1 .2448 1.2401
1 .2401 1 .2356
1.2356 1.2313
870 1566 1.2546 1.2495 1.2446 1.2399 1.2354 1.2312
880 1584 1.2543 1.2492 1.2443 1.2397 1.2352 1.2310
890 1602 1.2539 1.2489 1.2440 1.2395 1.2351 1.2309
900 1620 1.2536 1.2486 1.2438 1.2392 1.2349 1.2307
910 1638 1.2532 1.2483 1.2435 1.2390 1.2347 1.2306
920 1656 1.2529 1.248)
1.2480 1.2433 1.2388 1.2345 1.2304
930 1674 1.2525 1.2477 1.2430
1.2430 1.2386 1.2343 1.2303
940 1692
1692 1.2522 1.2474 1.2428
1.2428 1.2384
1.2384 1.2342 1.2301
950 1710
1710 1.2519 1.2471 1.2425 1.2382 1.2340 1.2300
960
960 1728 1.2468
1.2468 1.2423 1.2379 1.2338
1.2338 1.2298
1.2298
970
970 1746
1746 1.2465
1.2465 1.2420
1.2420 1.2377
1.2377 1.2336
1.2336 1.2297
1.2297
900
980 1764
1764 1.2463
1.2463 1.2418
1.2418 1.2375
1.2375 1.2335
1.2335 1.2296
1.2296
990
990 1782
1782 1.2416
1.2416 1.2374
1.2374 1.2333
1.2333 1.2294
1.2294
1000
1000 1800
1800 1.2414
1.2414 1.2372
1.2372 1.2332
1.2332 1.2293
1.2293
1010
1010 1818
1818 1.2411 1.2370
1.2411 1.2370 1.2330
1.2330 1.2292
1.2292
1020
1020 1836
1836 1.2368
1.2368 1.2328
1.2328 1.2291
1.2291
1030
1030 1854
1854 1.2366
1.2366 1.2327
1.2327 1.2289
1.2289
1040
1040 1872
1872 1.2365
1.2365 1.2326
1.2326 1.2288
1.2288
87
87

TABLE 2.5
TABLE 2.5 - EQS-BASED
EOS-BASED CRITICAL
CRITICAL PRESSURE
PRESSURE (MPa)
(MPa) FOR
FOR THE
THE SRK
SRK EQS.
EOS.

aI/Kw)NG uric
SOAVE/REDLICli/KK>NG
sovE/PEDLI OF STA
EOUATICN OF STATE

&Jiling Point
Boiling Point Molar Volurr
Molar Vo1une (Mol
(Mol Wright/specific Gravity)
ight/Specific Gravity)

(K)
(K) (R)
(R) 100
100 105
105 110
110 115
115 120
120 125
125

270
270 486
486 4.1446
4.1446
280
280 504
504 4.2020 3.9741
4.2020 3.9741
290
290 522
522 4.2657 4.0333
4.2657 4.0333 3.8239
3.8239
300
300 540
540 4.0973
4.3341 4.0973
4.3341 3.6905
3.8838 3.6905
3.8838 3.5147
3.5147
310
310 558
558 4.4060 4.1648
4.4060 4.1648 3.9474 3.7505
3.9474 3.7505 3.5713
3.5713 3.4077
3.4077
320
320 576
576 4.4806 4.2351
4.4806 4.2351 4.0137 3.8132
4.0137 3.8132 3.6308
3.6308 3.4642
3.4642
330
330 594
594 4.3074
4.5572 4.3074
4.5572 4.0822 3.8781
4.0822 3.8781 3.6925
3.6925 3.5229
3.5229
340
340 612
612 4.6352 4.3813
4.6352 4.3813 4.1522 3.9447
4.1522 3.9447 3.7558
3.7558 3.5833
3.5833
350
350 630
630 4.7144 4.4563
4.7144 4.4563 4.2235 4.0125
4.2235 4.0125 3.8205
3.8205 3.6450
3.6450
360
360 648
648 4.7945 4.5323
4.7945 4.5323 4.2958 4.0814
4.2958 4.0814 3.8862
3.8862 3.7078
3.7078
370
370 666
666 4.8753 4.6090
4.8753 4.6090 4.3688 4.1509
4.3688 4.1509 3.9526
3.9526 3.7714
3.7714
380
380 684
684 4.9566 4.6863
4.9566 4.6863 4.4423 4.2211
4.4423 4.2211 4.0197
4.0197 3.8356
3.8356
390
390 702
702 4.7639
4.7639 4.5163 4.2918
4.5163 4.2918 4.0873
4.0873 3.9003
3.9003
400 720
720 4.5906 4.3627
4.5906 4.3627 4.1552
4.1552 3.9654
3.9654
410
410 738
738 4.4340
4.6651 4.4340 4.2234
4.2234 4.0308
4.0308
420
420 756 4.5054
4.5054 4.2918
4.2918 4.0965
4.0965
430
430 774
774 4.3604
4.3604 4.1623
4.1623
440 792
792 4.2282
4.2282

SOAVE/REDLICli/KIDNG mtJATICN OF STME


SOAVE/1EDLI(1/KW)NG EX)UATICt STATE

&Jiling
Boiling Point Molar Volume
Voliir (Mol
(Md c Gravity)
Wright/specific
eight/Specifi

(K) (R) 130


130 135 140 145
145 150 155
320 576 3.3115
330 594 3.3674 3.2244
340 612 3.4251 3.2795 3.1452 3.0209
350 630 3.4841 3.3361 3.1994 3.0729 2.9556
360 648 3.5442 3.3937 3.2547 3.1261 3.0067 2.8956
370 666 3.6051 3.4521 3.3109 3.1801 3.0587 2.9458
380 684 3.6667 3.5113 3.3677 3.2348 3.1115 2.9967
390 702 3.7288 3.5709 3.4251 3.2901 3.1648 3.0481
400 720 3.7913 3.6310 3.4829 3.3458 3.2185 3.1000
410 738 3.8541 3.6914 3.5411 3.4019 3.2726 3.1523
3.1523
420 756 3.9171 3.7520 3.5995 3.4582 3.3270 3.2049
3.2049
430 774 3.9804 3.8129 3.6581 3.5148 3.3816 3.2577
440
440 792 4.0437
4.0437 3.8739
3.8739 3.7169
3.7169 3.5715 3.4364
3.4364 3.3107
3.3107
450
450 810
810 4.1072 3.9350
3.9350 3.7758 3.6283 3.4914
3.4914 3.3638
3.3638
460
460 828
828 3.9961 3.8348
3.8348 3.6853
3.6853 3.5464
3.5464 3.4170
3.4170
470
470 846
846 3.8938
3.8938 3.7423
3.7423 3.6015
3.6015 3.4703
3.4703
480
480 864
864 3.9529
3.9529 3.7993
3.7993 3.6566
3.6566 3.5237
3.5237
490
490 882
882 3.8564
3.8564 3.7118
3.7118 3.5771
3.5771
500
500 900
900 3.7670
3.7670 3.6305
3.6305
510
510 918
918 3.6840
3.6840
88
88

TABLE 2.5
TABLE 2.5 EOS-BASED CRITICAL
- EOS-BASED CRITICAL PRESSURE
PRESSURE (MPa)
(MPa) FOR
FOR THE
THE SRK
SRK EOS.
EOS.

ECUATICN OF
SOAVE/REDLICH/KtoONG EUzTIaT
SQAVE/PEDLICH/KWJNG OF STATE
STATE

EDi1ing Point
Boiling Point Molar Vo1un
Molar (Mol
Volurre (Mol Wright/specific Gravity)
ight/Specific Gravity)
(K)
(K) (R)
(R) 160
160 165
165 170
170 175
175 180
180 185
185

370
370 666
666 2.8404
2.8404 2.7420
2.7420
300
380 684
684 2.8896
2.8896 2.7895
2.7895 2.6957
2.6957
390
390 702
702 2.9393
2.9393 2.8375
2.8375 2.7422
2.7422 2.6527
2.6527
400
400 720
720 2.9895
2.9895 2.8861
2.8861 2.7893
2.7893 2.6983
2.6983 2.6128
2.6128 2.5323
2.5323
410
410 738
738 3.0400
3.0400 2.9350
2.9350 2.8367
2.8367 2.7443
2.7443 2.6575
2.6575 2.5756
2.5756
420
420 756
756 3.0909
3.0909 2.9843
2.9843 2.8844
2.8844 2.7906
2.7906 2.7024
2.7024 2.6193
2.6193
430
430 774
774 3.1420
3.1420 3.0338
3.0338 2.9324
2.9324 2.8372
2.8372 2.7476
2.7476 2.6632
2.6632
440
440 792
792 3.1933
3.1933 3.0835 2.9005
2.9805 2.8839 2.7930 2.7074
450
450 810
810 3.2447
3.2447 3.1333
3.1333 3.0289
3.0289 2.9308
2.9308 2.8386 2.7517
2.7517
460
460 828
828 3.2962
3.2962 3.1832
3.1832 3.0773
3.0773 2.9779 2.8843
2.8843 2.7961
2.7961
470
470 846 3.3479 3.2333
3.2333 3.1259
3.1259 3.0250
3.0250 2.9301
2.9301 2.8407
400
480 864 3.3996
3.3996 3.2834
3.2834 3.1745
3.1745 3.0722
3.0722 2.9760
2.9760 2.8853
2.8853
490 882 3.4513 3.3336 3.2232 3.1195 3.0220 2.9300
sao
500 900 3.5031 3.3838 3.2719 3.1669 3.0600
3.0680 2.9748
510
510 918 3.5549 3.4340 3.3207 3.2142 3.1140 3.0196
520 936 3.6067
3 .6067 33.4843
.4843 3.3695 3.2616 3.1601 3.0644
530 954 3.5345
3.5345 3.4183
3.4183 3.3090
3.3090 3.2062
3.2062 3.1092
3.1092
540 972 3.4671 3.3564 3".2523
3.2523 3.1541
550 990 3.4038 3.2984 3.1989
560 1008 3.3445 3.2438
570 1026 3.2887
89
89

TABLE 2.5
TABLE 2.5 - EOS-BASED
EOS-BASED CRITICAL
CRITICAL PRESSURE
PRESSURE (MPa)
(MPa) FOR
FOR THE
THE SRK
SRK EOS.
EOS.

SOAVE/PEDLICH/KW)NG mUATICN OF
SOAVE/REDLICll/KIDNG EUATICtST OF SPATE
STATE

Ebiling Point
BDiling Point Molar Vo1un
Molar Vo1ure (Mol
(Mol it/Specific
\'eight/specific Gravity)
Gravity)

(K)
(K) (R)
CR) 190
190 195
195 200
200 210
2~0 220
220 230
230

410
410 738
738 2.4984
2.4984
420
420 756
756 2.5409
2.5409 2.4668
2.4668
430
430 774
774 2.5836
2.5836 2.5083
2.5083 2.4371
2.4371
440
440 792
792 2.6265
2.6265 2.5501
2.5501 2.4778
2.4778 2.3441
2.3441
450
450 810
810 2.6696
2.6696 2.5921
2.5921 2.5186
2.5186 2.3830
2.3830 2.2605
2.2605
460
460 828
828 2.7129
2.7129 2.6342
2.6342 2.5597
2.5597 2.4220
2.4220 2.2976
2.2976
470
470 846
846 2.7562
2.7562 2.6764
2.6764 2.6008
2.6008 2.4611
2.4611 2.3349
2.3349 2.2204
2.2204
480
480 864
864 2.7997
2.7997 2.7187
2.7187 2.6420
2.6420 2.5003
2.5003 2.3723 2.2561
490 882
882 2.8432
2.8432 2.7611
2.7611 2.6833
2.6833 2.5396
2.5396 2.4098
2.4098 2.2920
2.2920
500
500 900
900 2.8867
2.8867 2.8035
2.8035 2.7247
2.7247 2.5790
2.5790 2.4474
2.4474 2.3278
2.3278
510
510 918
918 2.9304
2.9304 2.8460 2.7661 2.6184
2.6184 2.4850 2.3638
2.3638
520
520 936
936 2.9740
2.9740 2.8885 2.8076 2.6579 2.5226 2.3998
2.3998
530
530 954 3.0177
3.0177 2.9311 2.8491 2.6974 2.5603 2.4358
540 972 3.0613
3.0613 2.9736 2.8905 2.7369 2.5900
2.5980 2.4719
550
550 990 3.1050 3.0162 2.9321 2.7764 2.6357 2.5000
2.5080
560 1008
1008 3.1487 3.0588 2.9736 2.8160 2.6735 2.5441
570 1026
1026 3.1924
3.1924 3.1013 3.0151 2.8555 2.7112 2.5802
2.5002
580 1044 3.2361 3.1439 3.0566 2.8951 2.7490 2.6163
590 1062 3.1865 3.0981 2.9346 2.7867 2.6524
600 1080 3.1396 2.9741 2.8245 2.6885
610 1098 3.0137 2.8622 2.7246
620 1116 3.0532 2.9000 2.7607
630 1134
1134 2.9377 2.7968
640 1152 2.9754 2.8329
650 1170 2.8690
660 1188 2.9050
90
90

TABLE 2.5
TABLE 2.5 - E0S-BASED
- EOS-BASED CRITICAL
CRITICAL PRESSURE
PRESSURE (MPa)
(MPa) FOR
FOR THE
THE SRK
SRK EQS.
EOS.

SQVE/PEDLIQ/KW)NG EOUATICN OF
SOAVE/REDLICli/KIDNG FXUATI0N OF STATE
grATE

lbiling Point
Boiling Point Molar Volurre (Mol
Molar Vo1ui (Mol Wright/specific Gravity)
it/Specific Gravity)

(K)
(K) (R)
(R) 240
240 250
250 260
260 270
270 280
280 290
290

480
480 864
864 2.1502
2.1502
490
490 882
882 2.1845
2.1845 2.0862
2.0862
500
500 900
900 2.2189
2.2189 2.1192
2.1192
510
510 918
918 2.2533
2.2533 2.1522
2.1522 2.0593
2.0593
520
520 936
936 2.2878
2.2878 2.1853
2.1853 2.0911
2.0911 2.0043
2.0043
530
530 954
954 2.3223
2.3223 2.2184
2.2184 2.1229
2.1229 2.0350
2.0350 1.9536
1.9536
540
540 972
972 2.3568
2.3568 2.2515
2.2515 2.1548
2.1548 2.0656
2.0656 1.9832
1.9832 1.9068
1.9068
550 990
990 2.3914
2.3914 2.2847
2.2847 2.1867 2.0963 2.0128 1.9353
1.9353
560
560 1008
1008 2.4260 2.3179 2.2186
2.2186 2.1270 2.0424
2.0424 1.9639
1.9639
570
570 1026
1026 2.4606
2.4606 2.3511
2.3511 2.2505
2.2505 2.1577 2.0720 1.9924
1.9924
580
580 1044
1044 2.4952 2.3843
2.3843 2.2824
2.2824 2.1885
2.1885 2.1016 2.0210
590
590 1062
1062 2.5298 2.4175 2.3144
2.3144 2.2192
2.2192 2.1313
2.1313 2.0497
2.0497
600 1000
1080 2.5644
2.5644 2.4508 2.3463 2.2500 2.1609 2.0783
610 1098 2.5990 2.4840 2.3782 2.2007
2.2807 2.1906 2.1069
620 1116
1116 2.6336 2.5172 2.4102 2.3115 2.2202 2.1355
630 1134 2.6682 2.5504 2.4421 2.3423 2.2499 2.1642
640 1152
1152 2.7028
2.7028 2.5836 2.4741 2.3730 2.2795 2.1928
650 1170 2.7374 2.6168 2.5060 2.4038 2.3092 2.2214
660 1188 2.7720 2.6501 2.5379 2.4345 2.3388 2.2501
670 1206 2.8066 2.6832 2.5699 2.4653 2.3685 2.2787
680 1224 2.8411 2.7164 2.6018 2.4960 2.3981 2.3073
690 1242 2.7496 2.6337 2.5267 2.4278 2.3359
700 1260 2.7828 2.6656 2.5575 2.4574 2.3645
710 1278 2.6975 2.5882 2.4870 2.3931
720 1296 2.6189 2.5166 2.4217
730 1314 2.6496 2.5462 2.4503
740 1332 2.5758 2.4789
750 1350 2.6054 2.5075
760 1368 2.5361
770 1386 2.5646
91
91

TABLE 2.5
TABLE 2.5 - EOS-BASED
- EOS-BASED CRITICAL
CRITICAL PRESSURE
PRESSURE (MPa)
(MPa) FOR
FOR THE
THE SRK
SRK EOS.
EOS.
SOVE/REDL
SOAVE/REDLIaI/KIDNG EDUATICN OF
Ic/Kw)NG EQUATION OF STATE
STATE

EDi1ing Point
Boiling Point Molar Volun
Molar Vo1urre (Mol
(Mol \'eight/Specific Gravity)
ight/Specific Gravity)
(K)
(K) (R)
(R) 300
300 310
310 320
320 340
340 360
360 380
380

550
550 990
990 1.8633
1.8633
560
560 1008
1008 1.8909
1.8909
570
570 1026
1026 1.9185
1.9185 1.8496
1.8496
500
580 1044
1044 1.9461
1.9461 1.8763 1.8111
1.8763 1.8111
590
590 1062
1062 1.9738
1.9738 1.8371
1.9031 1.8371
1.9031
600
600 1000
1080 2.0015
2.0015 1.9299 1.8630
1.9299 1.8630 1.7416
1.7416
610
610 1098
1098 2.0291
2.0291 1.9566 1.8889
1.9566 1.8889 1.7660
1.7660
620
620 1116
1116 2.0568
2.0568 1.9834 1.9148
1.9834 1.7904
1.9148 1.7904
630
630 1134
1134 2.0845
2.0845 2.0102 1.9408
2.0102 1.9408 1.8148
1.8148 1.7035
1.7035
640
640 1152
1152 2.1122
2.1122 2.0370 1.9667
2.0370 1.9667 1.8392
1.8392 1.7265
1.7265
650
650 1170
1170 2.1398
2.1398 2.0637 1.9926
2.0637 1.9926 1.8636
1.8636 1.7496
1.7496 1.6481
1.6481
660
660 1188
1188 2.1675
2.1675 2.0905 2.0186
2.0905 2.0186 1.8880
1.8880 1.7726
1.7726 1.6699
1.6699
670
670 1206
1206 2.1952
2.1952 2.1173 2.0445
2.1173 2.0445 1.9124
1.9124 1.7956
1.7956 1.6917
1.6917
680
680 1224
1224 2.2228
2.2228 2.1441 2.0704
2.1441 2.0704 1.9368
1.9368 1.8187
1.8187 1.7136
1.7136
690 1242
1242 2.2505
2.2505 2.0964 1.9612
2.1708 2.0964 1.8417
1.8417 1.7354
1.7354
700
700 1260
1260 2.2782
2.2782 2.1976 2.1223
2.1976 2.1223 1.9856
1.9856 1.8647
1.8647 1.7572
1.7572
710 1278
1278 2.3058 2.2244 2.1482 2.0100 1.8878
1.8878 1.7790
1.7790
720 1296
1296 2.3335
2.3335 2.1741 2.0344
2.2511 2.1741 1.9108
1.9108 1.8008
1.8008
730
730 1314 2.3611 2.2001 2.0588
2.2779 2.2001 1.9338
1.9338 1.8226
1.8226
740 1332 2.3887 2.3046 2.2260 2.0831 1.9569 1.8444
750 1350 2.4163 2.3313 2.2519 2.1075 1.9799
1.9799 1.8662
1.8662
760 1368 2.4440 2.3581 2.2778 2.1319 2.0029 1.8880
770 1386 2.4716 2.3848 2.3036 2.1563 2.0259 1.9098
780 1404 2.4992 2.4115 2.3295 2.1806 2.0489 1.9316
1.9316
790 1422 2.5268 2.4382 2.3554 2.2050 2.0719 1.9534
1.9534
800 1440 2.4649 2.3813 2.2293 2.0949 1.9752
1.9752
810 1458
1458 2.4072 2.2537 2.1179 1.9970
1.9970
820 1476
1476 2.4330 2.2780 2.1409 2.0188
830 1494
1494 2.3024 2.1639 2.0405
840
840 1512
1512 2.3267
2.3267 2.1869
2.1869 2.0623
850
850 1530
1530 2.3510
2.3510 2.2098 2.0841
2.0841
860 1548
1548 2.2328
2.2328 2.1058
2.1058
870
870 1566
1566 2.2558
2.2558 2.1276
2.1276
880
880 1584
1584 2.2788 2.1494
890
890 1602
1602 2.1711
2.1711
900
900 1620
1620 2.1929
910
910 1638
1638 2.2146
2.2146
920
920 1656
1656 2.2364
2.2364
92
92

TABLE 2.5
TABLE 2.5 - EOS-BASED CRITICAL
- EQS-BASED CRITICAL PRESSURE
PRESSURE (MPa)
(MPa) FOR
FOR THE
THE SRK
SRK EQS.
EOS.

SOAVE/REDLICll/KIDNG EUATIT
SOE/REDLIaI/KW)NG OF STATE
EOUATICN OF STATE

a:>iling Point
Boiling Point Molar VolunE
Molar ValUlte (Mol
(Mol Wllght/specific Gravity)
ight/Specific Gravity)

(K)
(K) (R)
(R) 400
400 420
420 440
440 460
460 480
480 500
500

670
670 1206
1206 1.5987
1.5987
680
680 1224
1224 1.6195
1.6195
690
690 1242
1242 1.6402
1.6402 1.5544
1.5544
700
700 1260
1260 1.6609
1.6609 1.5742
1.5742
710
710 1278
1278 1.6816
1.6816 1.5939
1.5939 1.5145
1.5145
720
720 1296
1296 1.7023
1.7023 1.6136
1.6136 1.5333
1.5333
730
730 1314
1314 1.7230
1.7230 1.6333
1.6333 1.5522 1.4783
1.5522 1.4783
740
740 1332
1332 1.7437
1.7437 1.6531
1.6531 1.5710 1.4963
1.5710
750
750 1350
1350 1.7645
1.7645 1.6728
1.6728 1.5898 1.5143
1.5898 1.5143
760
760 1368
1368 1.7852
1.7852 1.6925
1.6925 1.6086 1.5323
1.6086 1.5323 1.4627
1.4627
770
770 1386
1386 1.8059
1.8059 1.7122
1.7122 1.6274 1.5503
1.6274 1.5503 1.4799
1.4799
780
780 1404
1404 1.8266 1.7319
1.7319 1.6462 1.5683
1.6462 1.4971 1.4319
1.4319
790 1422
1422 1.8473 1.7516 1.6650 1.5863 1.5143 1.4484
000
800 1440
1440 1.8680 1.7713
1.7713 1.6838 1.6042 1.5316
1.5316 1.4649
1.4649
810 1458 1.8886 1.7910 1.7026 1.6222 1.5488
1.5488 1.4815
820 1476 1.9093
1 .9093 1.8107
1 .8107 1.7214
1 .7214 1.6402 1.5660
1 .5660 1.4980
830
830 1494
1494 1.9300 1.8304 1.7402
1.7402 1.6582
1.6582 1.5832
1.5832 1.5145
1.5145
840 1512 1.9507 1.8501 1.7590 1.6761 1.6005
1.6005 1.5311
850 1530 1.9714 1.8698 1.7778 1.6941 1.6177 1.5476
860 1548 1.9920 1.8895 1.7966 1.7121 1.6349 1.5641
870 1566 2.0127 1.9092 1.8154 1.7300 1.6521 1.5806
880 1584 2.0334 1.9288 1.8341 1.7480 1.6693 1.5971
890 1602 2.0540 1.9485 1.8529 1.7660 1.6865 1.6136
1.6136
900 1620 2.0747 1.9682 1.8717 1.7839 1.7037 1.6301
910 1638 2.0954 1.9879 1.8905 1.8019 1.7209 1.6467
920 1656 2.1160 2.0075 1.9092 1.8198 1.7381 1.6632
930 1674 2.1367 2.0272 1.9280 1.8378 1.7553 1.6797
940 1692 2.1573 2.0469 1.9468 1.8557 1.7725 1.6962
950 1710 2.1780 2.0665 1.9655 1.8737 1.7897 1.7127
960 1728 2.0862 1.9843 1.8916 1.8069 1.7292
970 1746 2.1058 2.0031 1.9095 1.8241 1.7457
980 1764 2.1255 2.0218 1.9275
1.9275 1.8413 1.7622
990 1782 2.0406 1.9454 1.8585 1.7787
1000 1800 2.0593 1.9634
1.9634 1.8756 1.7952
1010 1818
1818 2.0781 1.9813
1.9813 1.8928
1.8928 1.8117
1020
1020 1836 1.9992
1.9992 1.9100 1.8282
1030 1854
1854 2.0172 1.9272 1.8446
1.8446
1040
1040 1872
1872 2.0351 1.9444 1.8611
93
93

TABLE 2.6
TABLE 2.6 - EQS-BASED
- EOS-BASED TTc/Tb RATIO FOR
/T RATIO
cb
FOR THE
THE SRK
SRK EQS.
EOS.

SOAVE/REDLIQi/KONG EOUATICN OF
SOA.VE/REDLICli/KIDNG E2UTIC OF STA
STATE

B:>iling Point
Boiling Point Molar Vo1un
Molar Vo1une (Mol
(Mol W:dght/specific Gravity)
it/Specific

(K)
(K) (R)
(R) 100
100 105
105 110
110 115
115 120
120 125
125

270
270 486
486 1.6049
1.6049
280
280 504
504 1.6033
1.6033 1.5876
1.5876
290
290 522
522 1.6014
1.6014 1.5860
1.5860 1.5715
1.5715
300
300 540
540 1.5992
1.5992 1.5841
1.5841 1.5699
1.5699 1.5565
1.5565 1.5439
1.5439
310
310 558
558 1.5967
1.5967 1.5819
1.5819 1.5680
1.5680 1.5549
1.5549 1.5425
1.5425 1.5308
1.5308
320
320 576
576 1.5940
1.5940 1.5795
1.5795 1.5659
1.5659 1.5530
1.5530 1.5409
1.5409 1.5294
1.5294
330
330 594
594 1.5910
1.5910 1.5769
1.5769 1.5635
1.5635 1.5509
1.5509 1.5390
1.5390 1.5277
1.5277
340
340 612
612 1.5878
1.5878 1.5740
1.5740 1.5610
1.5610 1.5486
1.5486 1.5370
1.5370 1.5259
1.5259
350
350 630
630 1.5844
1.5844 1.5709
1.5709 1.5582
1.5582 1.5461
1.5461 1.5347
1.5347 1.5238
1.5238
360
360 648
648 1.5809
1.5809 1.5677
1.5677 1.5552
1.5552 1.5434
1.5434 1.5323
1.5323 1.5216
1.5216
370
370 666 1.5772
1.5772 1.5643
1.5643 1.5521
1.5521 1.5406
1.5406 1.5296
1.5296 1.5192
300
380 684
684 1.5733
1.5733 1.5607
1.5607 1.5489 1.5376 1.5269
1.5269 1.5167
1.5167
390
390 702 1.5571 1.5455
1.5455 1.5345
1.5345 1.5240
1.5240 1.5140
400
400 720
720 1.5420 1.5312 1.5210
1.5210 1.5112
410 738
738 1.5384
1.5384 1.5279 1.5179
1.5179 1.5083
1.5083
420 756 1.5245
1.5245 1.5147
1.5147 1.5054
1.5054
430
430 774
774 1.5114
1.5114 1.5023
1.5023
440
440 792
792 1.4992
sotvE/rIIai/KwJNG mUATICN OF STA
SOA.VE/REDLICli/KKNG WJPIT STATE

!biting
Boiling Point Vo1une (Mol
Molar Vo1tir ict/Specific
W:dght/specific Gravity)
(K) (R) 130 135 140
140 145 150 155
320 576 1.5184
1.5184
330 594 1.5170 1.5067
340 612 1.5153 1.5053 1.4957 1.4866
350
350 630 1.5135 1.5037 1.4943 1.4853 1.4767
360 648 1.5115 1.5019 1.4926 1.4838
1.4838 1.4754 1.4673
370 666 1.5093 1.4999 1.4908 1.4822 1.4739 1.4659
300
380 684 1.5070 1.4977 1.4889 1.4004-
1.4804 1.4723 1.4645
390 702 1.5045 1.4955 1.4868 1.4785 1.4705 1.4628
400 720 1.5019 1.4931 1.4846 1.4764 1.4686 1.4611
410 738 1.4992
1 .4992 1.4905
1 .4905 1.4822
1 .4822 1.4742
1 .4742 1.4666
1 .4666 1.4592
1 .4592
420 756 1.4964 1.4879 1.4798 1.4720 1.4645 1.4572
430 774 1.4936 1.4852 1.4773 1.4696 1.4622 1.4552
440 792 1.4906 1.4825 1.4747 1.4671 1.4599 1.4530
450 810 1.4876 1.4796 1.4720 1.4646 1.4576 1.4508
460 828 1.4768 1.4693 1.4621 1.4551 1.4485
470 846 1.4665 1.4594 1.4526 1.4461
480
400 864 1.4637 1.4568 1.4501 1.4437
490 882 1.4541 1.4475 1.4413
500 900 1.4449 1.4388
510 918 1.4363

j
94

TABLE 2.6 - EOS-BASED Tc/Tb


- T /T RATIO FOR THE SRK EOS.
cb

S0VE/PEDLIGI/KW)NG EUATIC1
SOAVE/REDLICli/KK>NG EOUATICN OF STATE

Boiling Point
Ibiling Molar Volume
Volurre (Mol ight/Specific Gravity)
Wright/Specific

(K) (R) 160 165 170 175 180 185

370 666 1.4583 1.4509


380 684 1.4570 1.4497 1.4428
390 702 1.4555 1.4484 1.4416 1.4350
400 720 1.4539 1.4469 1.4402 1.4337 1.4275 1.4214
410 738 1.4521 1.4453 1.4387 1.4324 1.4262 1.4203
420 756 1.4503 1.4436 1.4371 1.4309 1.4249 1.4190
430 774 1.4483 1.4418 1.4354 1.4293 1.4234 1.4177
440 792 1.4463
1 .4463 1.4399
1 .4399 1.4336
1 .4336 1.4276
1 .4276 1.4218
1 .4218 1.4162
1 .4162
450 810 1.4442 1.4379 1.4318 1.4259 1.4202 1.4147
460 828 1.4420 1.4358 1.4298 1.4241 1.4185 1.4130
470 846 1.4398
1 .4398 1.4337
1 .4337 1.4278
1 .4278 1.4222
1 .4222 1.4167 1.4113
1 .4113
480 864 1.4375 1.4315 1.4258 1.4202 1.4148 1.4096
490 882 1.4352 1.4293 1.4237 1.4182 1.4129 1.4078
500 900 1.4328 1.4271 1.4215 1.4162 1.4110 1.4059
510 918 1.4304 1.4248 1.4193 1.4141 1.4090 1.4040
520 936 1.4280 1.4225 1.4171 1.4120 1.4069 1.4021
530 954 1.4201 1.4149 1.4098 1.4049 1.4001
540 972 1.4126 1.4077 1.4028 1.3981
550 990 1.4055 1.4007 1.3961
560 1008 1.3986 1.3941
570 1026 1.3920
95
95

TABLE 2.6
TABLE 2.6 - EOS-BASED
- EOS-BASED TTc/Tb RATIO FOR
/T RATIO
cb
FOR THE
THE SRK
SRK EOS.
EOS.

mUATICN OF
SOAVE/REDLICli/KIDNG E)2U1TIC
SOAVE/PEDLIQ/KONG OF STATE
STATE

lbiling Point
Boiling Point Volume (Mol
Molar Volune
Molar (Mal 1ight/Specifi c Gravity)
\feight/specific Gravity)

(K)
(K) (R)
(R) 190
190 195
195 200
200 210
210 220
220 230
230
410
410 738
738 1.4145
1.4145
420
420 756
756 1.4134 1.4079
1.4134 1.4079
430
430 774
774 1.4121 1.4067
1.4121 1.4067 1.4015
1.4015
440
440 792
792 1.4108 1.4055
1.4108 1.4055 1.4004
1.4004 1.3906
1.3906
450
450 810
810 1.4093 1.4041 1.3991
1.4093 1.4041 1.3991 1.3895
1.3895 1.3803
1.3003
460
460 828
828 1.4078 1.4027
1.4078 1.4027 1.3977
1.3977 1.3883
1.3883 1.3793
1.3793
470
470 846
846 1.4062 1.4012
1.4062 1.4012 1.3963
1.3963 1.3870 1.3782 1.3699
1.3870 1.3782 1.3699
400
480 864
864 1.4045 1.3996
1.4045 1.3996 1.3948
1.3948 1.3857 1.3770 1.3688
1.3857 1.3770 1.3688
490
490 882
882 1.4028 1.3980
1.4028 1.3900 1.3933
1.3933 1.3843 1.3758 1.3677
1.3843 1.3758 1.3677
500
500 900
900 1.4010 1.3963
1.4010 1.3963 1.3917
1.3917 1.3828 1.3745 1.3665
1.3828 1.3745 1.3665
510
510 918
918 1.3992 1.3945
1.3992 1.3945 1.3900
1.3900 1.3813 1.3731 1.3653
1.3813 1.3731 1.3653
520
520 936
936 1.3974 1.3928
1.3974 1.3928 1.3883
1.3883 1.3798 1.3717 1.3640
1.3798 1.3717 1.3640
530
530 954
954 1.3955 1.3910
1.3955 1.3910 1.3866
1.3866 1.3782 1.3703 1.3627
1.3782 1.3703 1.3627
S40
540 972
972 1.3936 1.3891
1.3936 1.3891 1.3848
1.3848 1.3766 1.3688 1.3613
1.3766 1.3688 1.3613
550
550 990
990 1.3916 1.3873
1.3916 1.3873 1.3831 1.3672 1.3599
1.3749 1.3672
1.3831 1.3749 1.3599
560
560 1008
1008 1.3897 1.3854
1.3897 1.3854 1.3813
1.3813 1.3733 1.3657 1.3585
1.3733 1.3657 1.3585
570
570 1026
1026 1.3877 1.3835
1.3877 1.3835 1.3794
1.3794 1.3716 1.3641 1.3571
1.3716 1.3641 1.3571
580
580 1044
1044 1.3857
1.3857 1.3816
1.3816 1.3776 1.3556
1.3699 1.3625 1.3556
1.3776 1.3699
590
590 1062
1062 1.3797 1.3757
1.3757 1.3681
1.3681 1.3609
1.3609 1.3541
600 1000
1080 1.3739 1.3664 1.3593 1.3526
1.3664 1.3593 1.3526
610 1098 1.3510
1.3577 1.3510
1.3647 1.3577
620 1116
1116 1.3629 1.3560
1.3560 1.3495
630 1134
1134 1.3544 1.3480
1.3544 1.3400
640
640 1152
1152 1.3464
1.3528 1.3464
650 1170 1.3448
660 1188 1.3433
96
96

TABLE 2.6
TABLE 2.6 - EOS-BASED
- EOS-BASED TTc/Tb
cb RATIO FOR THE SRK EOS.
/T RATIO FOR THE SRK EOS.

mUATIOO OF
SOAVE/REDLICli/KltONG EX)UATICtST
SOAVE/EDLICH/KDNG OF STATE
STATE

EDiting Point
Soiling Point Molar VolunE
Molar (Mol
Vo1une (Mol waight/specific Gravity)
Vight/Specific Gravity)
(K)
(K) (R)
(R) 240
240 250
250 260
260 270
270 280
280 290
290

480
400 864 1.3610
1.3610
490
490 882
882 1.3600
1.3600 1.3527
1.3527
500
500 900 1.3590
1.3590 1.3518
1.3518
510
510 918
918 1.3579
1.3579 1.3508
1.3508 1.3440
1.3440
520
520 936
936 1.3567
1.3567 1.3497
1.3497 1.3431
1.3431 1.3367
1.3367
530
530 954 1.3555
1.3555 1.3486
1.3486 1.3421
1.3421 1.3358
1.3358 1.3298
1.3298
540
540 972 1.3542
1.3542 1.3475
1.3475 1.3410
1.3410 1.3349
1.3349 1.3289 1.3232
1.3232
550
550 990
990 1.3530
1.3530 1.3463 1.3400
1.3400 1.3339
1.3339 1.3280
1.3280 1.3224
1.3224
560
560 1008
1008 1.3516
1.3516 1.3451
1.3451 1.3388
1.3388 1.3328
1.3328 1.3271
1.3271 1.3216
1.3216
570
570 1026
1026 1.3503
1.3503 1.3439
1.3439 1.3377
1.3377 1.3318
1.3318 1.3261
1.3261 1.3207
580
580 1044 1.3489
1.3489 1.3426 1.3365 1.3307 1.3251 1.3198
590
590 1062 1.3475 1.3413 1.3353
1.3353 1.3296 1.3241
1.3241 1.3188
1.3188
600 1080 1.3461 1.3400 1.3341 1.3284
1.3284 1.3230 1.3178
610 1098 1.3447 1.3386 1.3328
1.3328 1.3273 1.3219 1.3168
620 1116 1.3433 1.3373 1.3316 1.3261 1.3208 1.3158
1.3158
630 1134
1134 1.3418 1.3359 1.3303 1.3249 1.3197 1.3147
640 1152 1.3403 1.3346
1.3346 1.3290 1.3237 1.3186 1.3136
1.3136
650 1170
1170 1.3389
1.3389 1.3332
1.3332 1.3277
1.3277 1.3225
1.3225 1.3174
1.3174 1.3126
1.3126
660 1188 1.3374 1.3318 1.3264
1.3264 1.3212 1.3163
1.3163 1.3115
1.3115
670 1206 1.3359 1.3304 1.3251 1.3200 1.3151 1.3104
680 1224 1.3345 1.3290 1.3238 1.3187 1.3139 1.3092
690 1242 1.3276 1.3224 1.3175 1.3127 1.3081
700 1260 1.3262 1.3211 1.3162 1.3115 1.3070
710 1278
1278 1.3198 1.3150 1.3103 1.3059
720 1296 1.3137 1.3091 1.3047
730 1314 1.3125 1.3079 1.3036
740 1332 1.3067 1.3024
750 1350 1.3055 1.3013
760 1368 1.3002
770 1386 1.2990
97
97

TABLE 2.6
TABLE 2.6 - EOS-BASED
- EOS-BASED Tc/Tb
Tc/Tb RATIO
RATIO FOR
FOR THE
THE SRK
SRK EQS.
EOS.

SOAVE/REDLICli/KIDNG EUATIC
SOVE/REDLIGI/KW)NG OF STME
mUAT!CN OF STATE

]biling Point
Boiling Point Molar Volurre
Molar (Mol
Vo1une (Mol weight/Specific Gravity)
ict/Specific Gravity)
(K)
(K) (R)
(R) 300
300 310
310 320
320 340
340 360
360 380
380

550
550 990
990 1.3170
1.3170
560
560 1008
1008 1.3163
1.3163
570
570 1026
1026 1.3154
1.3154 1.3104
1.3104
580
580 1044
1044 1.3146
1.3146 1.3096
1.3096 1.3048
1.3048
590
590 1062
1062 1.3137
1.3137 1.3088
1.3088 1.3041
1.3041
600
600 1080
1080 1.3128
1.3128 1.3000
1.3080 1.3033
1.3033 1.2945
1.2945
610 1098
1098 1.3119
1.3119 1.3071
1.3071 1.3025
1.3025 1.2938
1.2938
620
620 1116
1116 1.3109
1.3109 1.3062
1.3062 1.3017 1.2930
1.2930
630 1134
1134 1.3099
1.3099 1.3053
1.3053 1.3008
1.3008 1.2923 1.2843
1.2843
640
640 1152
1152 1.3089
1.3089 1.3043
1.3043 1.2999
1.2999 1.2915
1.2915 1.2837
650 1170
1170 1.3079 1.3034 1.2990
1.2990 1.2908 1.2830 1.2757
1.2757
660 1188
1188 1.3069 1.3024
1.3024 1.2981 1.2900 1.2823 1.2751
670
670 1206
1206 1.3058
1.3058 1.3014
1.3014 1.2972
1.2972 1.2891 1.2816 1.2745
1.2745
680
680 1224
1224 1.3048
1.3040 1.3004
1.3004 1.2963 1.2883
1.2883 1.2008
1.2808 1.2738
1.2738
690
690 1242
1242 1.3037 1.2994
1.2994 1.2953 1.2874 1.2801
1.2874 1.2801 1.2731
1.2731
700 1260 1.3026
1.3026 1.2984
1.2984 1.2943 1.2866
1.2866 1.2793
1.2793 1.2725
710 1278
1278 1.3015
1.3015 1.2974
1.2974 1.2934
1.2934 1.2857
1.2857 1.2785
1.2785 1.2718
1.2718
720
720 1296 1.3005
1.3005 1.2964
1.2964 1.2924 1.2848 1.2777
1.2848 1.2711
730 1314
1314 1.2994
1.2994 1.2953 1.2914 1.2840 1.2769
1.2840 1.2703
740 1332 1.2983
1.2983 1.2943 1.2904 1.2831 1.2761 1.2696
750 1350
1350 1.2972 1.2933 1.2894
1.2894 1.2822 1.2753 1.2689
760 1368
1368 1.2961
1.2961 1.2922 1.2884 1.2813 1.2745 1.2681
770 1386 1.2950 1.2912 1.2875 1.2804 1.2737 1.2674
700
780 1404 1.2940 1.2901 1.2865 1.2795 1.2729 1.2666
790 1422 1.2929 1.2891 1.2855 1.2785 1.2720 1.2659
000
800 1440 1.2881
1 .2881 11.2845
.2845 1.2776
1 .2776 1.2712 1.2651
1 .2651
810 1458 1.2835 1.2767 1.2704 1.2643
820 1476 1.2825 1.2758 1.2695 112636
..2636
830 1494 1.2749 1.2687 1.2628
840 1512 1.2740 1.2679 1.2620
850 1530 1.2731 1.2670 1.2613
860 1548 1.2662 1.2605
870 1566 1.2654 1.2597
880 1584 1.2646 1.2590
890 1602 1.2582
900 1620 1.2575
910 1638 1.2567
920 1656 1.2560
98
98

TABLE 2.6
TABLE 2.6 - EOS-BASED
EOS-BASED Tc/Tb
Tc/Tb RATIO
RATIO FOR
FOR THE
THE SRK
SRK EOS,
EOS.

S0AVE/RED
SOAVE/REDLICH/KW>NG mUATICN OF
LIQi/KWG EUZ.TIaI OF STATE
STATE

EDiling Point
Boiling Point Molar Volun
Molar (Mol
Volume (Mol \\eight/specific Gravity)
Vit/Specific Gravity)

(K)
(it) (R)
(R) 400
400 420
420 440
440 460
460 480
480 500
500

670
670 1206
1206 1.2677
1.2677
680
680 1224
1224 1.2672
1.2672
690
690 1242
1242 1.2604
1.2666 1.2604
1.2666
700
700 1260
1260 1.2660 1.2599
1.2660 1.2599
710
710 1278
1278 1.2654 1.2593
1.2654 1.2593 1.2536
1.2536
720
720 1296
1296 1.2647 1.2587
1.2647 1.2587 1.2531
1.2531
730
730 1314
1314 1.2641 1.2582
1.2641 1.2582 1.2526
1.2526 1.2472
1.2472
740
740 1332
1332 1.2634 1.2576
1.2634 1.2576 1.2520
1.2520 1.2467
1.2467
750
750 1350
1350 1.2628 1.2570
1.2628 1.2570 1.2515
1.2515 1.2463
1.2463
760
760 1368
1368 1.2621 1.2564
1.2621 1.2564 1.2510
1.2510 1.2458 1.2408
1.2458 1.2408
770
770 1386
1386 1.2558
1.2614 1.2558
1.2614 1.2504
1.2504 1.2453 1.2404
1.2453 1.2404
780
780 1404
1404 .2607 11.2551
11.2607 .2551 11.2498
.2498 .2399
1.2448 11.2399
1.2448 .2353
11.2353
790
790 1422
1422 1.2600 1.2545
1.2600 1.2545 1.2493
1.2493 1.2443 1.2395
1.2443 1.2395 1.2349
1.2349
000
800 1440
1440 1.2593 1.2539
1.2593 1.2539 1.2487
1.2487 1.2437 1.2390
1.2437 1.2390 1.2345
1.2345
810
810 1458
1458 1.2586 1.2532
1.2586 1.2532 1.2481
1.2481 1.2432 1.2385
1.2432 1.2385 1.2340
1.2340
820
820 1476
1476 1.2579 1.2526
1.2526 1.2475
1.2475 1.2427 1.2380
1.2427 1.2380 1.2336
1.2336
830
830 1494
1494 1.2572 1.2520
1.2572 1.2520 1.2469
1.2469 1.2421 1.2375
1.2421 1.2375 1.2331
1.2331
840 1512
1512 1.2565
1.2565 1.2513
1.2513 1.2463 1.2416 1.2370
1.2416 1.2370 1.2327
1.2327
850 1530
1530 1.2558 1.2506
1.2558 1.2506 1.2457 1.2410 1.2365 1.2322
1.2322
860 1548
1548 1.2551 1.2500 1.2451 1.2405 1.2360
1.2360 1.2318
1.2318
870 1566 1.2544 1.2493 1.2445 1.2399 1.2355 1.2313
880 1584 1.2537 1.2487 1.2439 1.2394 1.2350 1.2308
1.2308
890 1602 1.2530 1.2480 1.2433 1.2388 1.2345 1.2303
900 1620
1620 1.2523 1.2474
1.2474 1.2427 1.2382 1.2340
1.2340 1.2299
1.2299
910 1638 1.2516 1.2467 1.2421 1.2377 1.2334
1.2334 1.2294
1.2294
920 1656 1.2509 1.2461 1.2415 1.2371 1.2329 1.2289
930 1674 1.2502 1.2454 1.2409
1,2409 1.2365 1.2324 1.2284
940 1692 1.2495 1.2448 1.2403 1.2360 1.2319 1.2279
950 1710 1.2488 1.2441 1.2397 1.2354 1.2314 1.2274
960 1728 1.2435 1.2391 1.2349 1.2308 1.2270
970 1746 1.2429 1.2385 1.2343 1.2303
1.2303 1.2265
980 1764 1.2422
1.2422 1.2379 1.2338 1.2298
1.2298 1.2260
990 1782
1782 1.2373 1.2332 1.2293
1.2293 1.2255
1.2255
1000 1800 1.2367
1.2367 1.2327
1.2327 1.2288 1.2250
1010
1010 1818 1.2361
1.2361 1.2321
1.2321 1.2283
1.2283 1.2246
1.2246
1020
1020 1836
1836 1.2316 1.2277
1.2316 1.2277 1.2241
1.2241
1030
1030 1854
1854 1.2310 1.2272
1.2310 1.2272 1.2236
1.2236
1040
1040 1872
1872 1.2305
1.2305 1.2267
1.2267 1.2231
1.2231
99
99

2.6
2.6 EOS Predictions
EQS Predictions using
using EQSBased
EOS-Based Critical
Critical Properties
Properties
This section
This section gives results of
gives results of application
application of
of the
the method
method
just described
just described for
for estimating
estimating critical
critical properties
properties andand
acentric factor
acentric factor of
of petroleum
petroleum fractions.
fractions. Reservoir fluids
Reservoir fluids
reported in
reported in the
the literature
literature have
have been
been chosen
chosen Detailed
Detailed
discussion and
discussion and tabulation
tabulation of of data
data can
can bebe found
found inin
Appendix B.
Appendix B.
Hoffman, Crump,
Hoffman, Crump, and
and Hocott
Hocott present
present compositiona
compositionall andand PVT
PVT
data for
data for aa reservoir
reservoir oil
oil and
and its
its gas
gas cap
cap fluid. Extended
Extended
analysis of
analysis of the
the heptanesplus
heptanes-plus mixture
mixture toto CC35
3 is given
5 is given for
for
the oil. Mole
the oil. Mole fractions, molecular
molecular weights,
weights, andand specific
speci fic
gravities correspond
gravities correspond toto fractions with
with boiling
boiling points
points of
of
normal paraffins.
normal paraffins. Methane content
Methane content is is 5252 mol%
mol-% and
and
heptanes-plus consists
heptanesplus consists ofof 36.84
36.84 mol%
mol-% with
with anan average
average
molecular weight of
molecular of 198.7
198.7 and
and specific
specific gravity of of 0.8409.
0.8409.
Reported bubble
Reported bubble point
point pressure
pressure is
is 3840
3840 psia
psia (26.47
(26.47 MPa)
MPa) at
at
201 0
201 of (93.89
F (93.89 C).
OC).
Katz and Firoozabadi
Katz Firoozabadi report that aa match of the measured
bubble point
bubble point can be achieved using the PR EQS EOS with
increasing interaction
increasing interaction coefficients between methane and all
C7+
+ groups, with a value of 0.17 for the heaviest fraction,
7
C
C35.
35 They do not give the critical properties and acentric
C
.
factor used, although it is assumed one of the empirical
correlations is used (probably Cavett and Edmister). Using
critical properties based on the PR EOS
EQS (see Appendix B), an
estimated bubble point is predicted as 3829 psia, or 0.3%
low. Interaction coefficients are not used. The predicted
saturated oil density is 0.6867 glcc,
g/cc, compared with the
experimental value of 0.6672, or 2.9% high; estimated
density is not reported by Katz and Firoozabadi.
The gas-cap
gascap fluid reported by Hoffman, et ale al. is analyzed in
SCN fractions up to C22 22
C (see Appendix B); properties are
close, but not exactly the same as for the equilibrium
reservoir oil. Methane content is 91.35 mol-% mol% and
heptanes-plus
heptanesplus consists of 1.54
1.54 mol-%
mol% with average molecular
weight of 141.25 and specific gravity of 0.7867. Predicted
composition
composition from the bubble point VLE calculation calculation above
above
resulted
resulted in in methane
methane content
content of 91.70 mol-%,
mol%, heptanes-plus
heptanesplus
consisting
consisting of of 1.318
1.318 mol-%
mol% with
with average molecular weight
weight of
128.00
128.00 and
and specific
specific gravity
gravity of of 0.7854;
0.7854; note
note the specific
specific
gravity
gravity isis in
in good agreement
agreement withwith the experimental
experimental value,
but
but molecular
molecular weight
weight is
is less
less accurate,
accurate, possibly
possibly suggesting
suggesting
that
that the
the use
use of
of paraffin molecular
molecular weights
weights by
by Hoffman,
Hoffman, etet ale
al.
is
is not
not satisfactory.
satisfactory.

If
If the
the resulting
resulting composition
composition from
from the
the bubble
bubble point
point flash
flash is
is
used,
used, retaining
retaining only
only components
components up
up to
to C22,
22 the
C
, the point
point at
at
100
100

which Hoffman,
which Hoffman, etet al.
ale end
end their
their analysis
analysis and and the
the point
point at
at
which predicted
which predicted composition
composition (from
(from the the bubble
bubble point
point
calculation) equals
calculation) equals 0.001
0.001 mol%,
mol-%, aa dew
dew point
point is is predicted
predicted at
at
3706 psia.
3706 psia. If the exact
If the exact composition
composition to to C3C35
5 is used,
is used, the
the
dew point
dew point will
will be
be exactly
exactly equal
equal to
to the
the bubble
bubble point
point (3865
(3865
psia). This
psia). This shows
shows the
the sensitivity
sensitivity in dew point
in dew point prediction
prediction
due to
due to aa roundoff
round-off error
error in
in composition
composition of of less
less than
than 0.001
0.001
mol-%!
mol-%!

Using the
Using the gas
gas compositions reported
reported byby Hoffman,
Hoffman, etet al.
ale the
the
PR EOS
PR EOS predicts
predicts aa dew
dew point
point at 201 of of 4044 psia, some
201 F
0 of 4044 psia, some
5.3% high. This
5.3% This is
is worse
worse than
than the prediction
prediction given
given byby Katz
and Firoozabadi
and Firoozabadi (+0.8%). Unfortunately
Unfortunately they
they do not report
report
critical properties of
the critical of petroleum
petroleum fractions (or the
used). Also, Katz
correlation used). and Firoozabadi
Firoozabadi use an empiri-
empiri
cal relation to
cal to calculate methane interaction
interaction coefficients
coefficients
petroleum fractions as
for petroleum as aa function ofof specific gravity.
Table 2.72.7 illustrates howhow different critical properties
properties
affect predicted dew point pressures.
pressures. Apparently Katz and
Firoozabadi use the Cavett and Edmister correlations. It is
obv ious that the dew point prediction is dependent
obvious dendent on the
properties used to describe the petroleum fractions.

TABLE 2.7 - EFFECT OF CRITICAL PROPERTIES USED WITH THE


PENG/ROBINSON EOS TO PREDICT THE HOFFMAN ET AL.


RESERVOIR GAS DEW POINT PRESSURE.

Dew Point Pressure (psia)


Predicted With Katz/
without Firoozabadi
Methane Methane
Correlation Binaries Binaries
Experimental : 3841
1. PR-Based
PRBased ...... :: 4044 (+5.3)
PR-Based1 ::
2. PR-Based 3706 (-3.5)
3. Katz/Firoozabadi results
(same as 51)
5?) : 3870 (+0.8)
4. Riazi/Daubert + + Edmister: 3322(-13.5)
3322(l3.5) 3632 (-5.4)
(5.4)
5. Cavett ++ Edmister : 3668 (-4.5) 3866 (+0.7)
6. Lee/Kesler : 3523 (-8.3) 4049 (+5.4)
1 PR-2
PR2 represents the prediction using gas composition up
to C22
22 resulting from the PR EOS prediction of bubble
C
point pressure for the reservoir oil (using PR-based
PRbased
properties)
properties).
101
101

Calculated liquid densities and yields are compared with


experimental values in Table 2.8. The various PR
predictions correspond to the six listed in Table 2.7, where
PR-3,
PR3, PR-4,
PR4, PR-5,
PR5, and PR-6
PR6 use methane binaries suggested by
Katz and Firoozabadi.

Table 2.8 - COMPARISON


RISON OF MEASURED
1
COMPP
MEPSURED AND
ND EXPERIMENTAL
1
P EXPERIMENTPL LIQUID
DENSITIES FOR THE HOFFMAN,
N, ET AL.
1
HOFFMP IL. RESERVOIR GAS
S
1
GP

Liquid Density, g/cc


(Liquid Yield, bbl/MMscf)
Press. ______________________________________________________________ __
Press.
(psia) Exp. PR-1
PRi PR-2
PR2 PR-3
PR3 PR-4
PR4 PR-5
PR5 PR-6
PR6

2915 0.6565 0.6637 0.6749 0.5921 0.6364 0.6300


(9.07) (9.31) (4.53) (9.69) (8.37) (9.75) (10.21)
2515 0.6536 0.6709 0.6798 0.6020 0.6475 0.6392
-

(12.44) (11.97) (6.61) (12.49) (12.01) (12.61) (12.93)


2015 0.6538 0.6822 0.6885 0.6159 0.6619 0.6520

(15.56) (14.53) (8.75) (15.02) (15.33) (15.23) (15.48)


1515 0.6753 0.6967 0.7003 0.6315 0.6779 0.6665
-

(16.98) (16.09) (10.2) (16.51) (17.30) (16.74) (17.00)

1015 0.7160 0.7148 0.7172 0.6486 0.6957 0.6834


(16.94) (16.45) (10.68) (16.80) (17.79) (17.01) (17.30)


515 0.7209 0.7390 0.7420 0.6675 0.7164 0.7029

(15.08) (14.97) (9.56) (15.29) (16.17) (15.45) (15.73)

Absolute
Pbsolute 2.32 3.07 2.80 1.50
1.50 2.48
Average
P
v
1erage 42. 36 )
(3.65) ((42.36) (4.46) (2.54)
(2.54) (3.93)
Error (%)

Cavett/Edmister (PR5)
Results indicate that the Cavett/Edmister (PR-5) combination
combination
best, though the proposed
performs best, proposed EOSbased
EOS-based properties
properties give
give
Interestingly, liquid yields for
excellent results as well. Interestingly,
predictions based
predictions based on
on calculated
calculated gas
gas composition (from
(from the
bubble point prediction) are very poor, despite
bubble despite the good
liquid densities.
predictions of liquid indicates that
This indicates
measured compositions are reliable and that determination of
composition from the bubble point calculation can lead to
VLE predictions
erroneous VLE predictions in
in the twophase
two-phase region.
102
102

Next we
Next we consider
consider thethe data
data presented
presented by
by Olds,
Olds, Sage,
Sage, and
and Lacey
Lacey
in 1945.
in 1945. Extensive
Extensive experimental
experimental results
results are
are given
given for
for six
six
recombined systems,
recombined systems, each
each measured
measured atat three
three temperatures
temperatures
( 100, 190,
(100, 190, and
and 250
250 F).
OF) The hexanesplus
The hexanes-plus fraction was was
into seven
fractionated into seven cuts
cuts with
with approximately
approximately equal
equal weight
weight
fractions (-40%).
fractions (-10%). Properties
Properties ofof the
the separator
separator gas
gas and
and liquid
liquid
are given
are given in
in the
the original
original work,
work, however
however recombined
recombined reservoir
reservoir
mixtures are
mixtures are given
given in
in Appendix
Appendix BB including
including aa split
split of
of the
the
hexanesplus fraction for each
hexanes-plus fraction each reservoir mixture.
mixture.
Critical properties
Critical properties ofof the
the petroleum
petroleum fractions are are
calculated using
calculated using the
the EOSbased
EOS-based method
method and
and the
the PR
PR EQS.
EOS.
Comparisons are
Comparisons are presented
presented in
in Table
Table 2.9
2.9 for saturation
saturation
pressures, and saturated
pressures, saturated vapor
vapor and
and liquid
liquid densities. Binary
Binary
interaction coefficients are
interaction are set equal
equal to zero
zero in all cases.
Absolute average deviation for saturation pressure
Absolute pressure is
is 4.57%
4.57%
not including the leanest mixture
not mixture (G0R=14440
(GOR=14440 scf/stb),
scf/stb), and
5.45% for all mixtures.
5.45% Dew points for very lean lean
measure experimentally, and
condensates are difficult to measure
therefore it should be reasonable to question measurements
of the 14440-GOR
14440GOR mixture. Maximum error is less than 10% 10%
otherwise. Considering the range of temperatures and
otherwise.
compositions and lack of any adjustment or use of binary
interaction coefficients, the predictions are very good.
Also, the transition from bubble-
bubble to dew-point
dewpoint is correctly
predicted.

Saturated liquid and vapor densities are all overpredicted.


Absolute average deviation is 5.14% with maxilllJm
maximum error of
8.1%. Saturated liquid densities are predicted more
accurately than vapor densities. The general trend for
overprediction is opposite that which is usually observed
with the PR EOS,
EDS, using empirical property correlations.

Predictions of the Olds/Sage/Lacey data presented in 1949


are reviewed in Table 2.10. Once again the PR EOS
EQS is used
and properties are calculated using the procedure given in
the previous section. No binary interaction coefficients
are used.
Absolute average deviation for saturation pressures (all are
bubble points) is 5.61%, with a maximum error of 13.7%. The
errors are random in nature which is somewhat unexpected,
al though bubble points at 100
although 0 F were always worse than at
100F
higher temperatures. Excluding the 100 OF F data gives an
0
absolute average deviation in bubble point pressur of 3.0%
wi th a maximum error of 4.0%.
with Descrepencies at lower
temperatures are difficult to explain experimentally.
Saturated
Saturated liquid densities are
are predicted with an absolute
average deviation of 3.30%
3.30% with a maximum error of 6.3%.
6.3%.
103
103

Interestingly,, the
Interestingly the best
best predictions
predictions occured
occured at
at the
the lowest
lowest
temperature of
temperature of 100
100 0of;
F predictions of
; predictions of density
density were
were made
made at
at
the experimental
the experimental bubble
bubble point
point pressure
pressure and
and not
not at
at the
the
predicted value.
predicted value.
From results
From results presented
presented in
in this
this section
section itit can
can be
be concluded
concluded
that the
that the present
present method
method ofof defining
defining critical
critical properties
properties
based on
based on an
an EQS
EOS isis reasonably
reasonably accurate for providing
providing
predictions ofof saturation
saturation pressures and
and mixture densities.
densities.
It also appears
It appears that VLE predictions areare good.
good. The method
is certainly not inferior to empirical correlations
correlations and has
the advantage of of being consistent
consistent with the E0S EOS used,
easy reproduction
allowing for easy reproduction of
of results.
results. ForFor accurate
predictions it is absolutely necessary to have accurate
chemical analysis of the reservoir mixture, preferably preferably
including distillation data with measurements of specific
molecular weight
gravity and molecular weight for each fraction.
104
104
TABLE 2.9
TPBLE 2.9 - COMPPRISON
COMPARISON OF
OF SPJURP
SATURATED
T
1 PROPERTIES FOR
ED PROPERTIES FOR OLDS_SPGE_LI:\CEY
OLDS-SAGE-LACEY
RESERVOIR MIXTURES (1945).
RESERVOIR

Temp-
Temp Saturation Pressure
Saturation Pressure (psia)
(psia) Saturated Density
Saturated (lb/ft 3)
Density (lb/ft
)
3
erature
erature
(F)
(F) Meas.
Meas. Calc.
Caic. ll(%)
A(%) EXp.
Exp. Calc. 3
Calc.
3 (%)
ll(%)

552 (0.0571)2
(scf/bbl) : 552
Ratio (scf/bbl)
Gas/Oil Ratio (0.0571)2
100
100 1112
1112 1065
1065 -4.2
4.2 42.55
42.55 43.34
43.34 +1.8
(1072)1
(1072) (43.36)
(43.36)
190
190 1410
1410 1383
1383 -1.9
1.9 39.68 40.52
40.52 +2.1
( 1389)
(1389) (40.53)
(40.53)
250
250 1675
1675 1549
1549 -7.5
7.5 37.52
37.52 38.50
38.50 +2.6
+2.6
(1552)
(1552) (38.50)
(38.50)

Gas/Oil Ratio (scf/bbl) 940 (0.1213)2


(scf/bbl) :: 940 (0.1213)2
100
100 1870
1870 1723
1723 -7.9
7.9 39.65
39.65 40.88
40.88 +3.1
(1748)
(1748) (40.91)
(40.91)
190
190 2210
2210 2174 -1.6
1.6 36.13 37.78
37.78 +4.6
(2196) (37.79)
250 2380 2375 -0.2
0.2 33.66 35.44
35.44 +5.3
+53
(2394) (35.52)
(0.2867)2
Gas/Oil Ratio (scf/bbl) : 2205 (0.2867)2
100
100 3430
3430 3102
3102 -9.6
9.6 34.13
34.13 35.44 +3.8
(3136) (35.47)
190
190 3542 3691 +4.2 29.61 31.52 +6.5
(3715) (31.54)
250 3595 3880 +7.9 27.07 28.75 +6.2
(3896) (28.75)
(28.75]

Gas/Oil Ratio (scf/bbl) : 5361 (0.5335)2


(0.5335)2

100 4490 4348 -3.2


3.2 27.01 28.54 +5.7
(4408)
(1i408) (28.56)
190 4590 4836 +5.4 22.90 24.40 +6.6
(4878) (24.41)
250 4630 4869 +5.2 20.37 21.85 +7.3
(2901
(2901)) (21.86)
(0.6292)2
(sct/bbl) : 7393 (0.6292)2
Gas/Oil Ratio (scf/bbl)
100 4560 4615 +1.2 24.05 25.99 +8.1
(4579) (26.01)
190 4730 4981 +5.3 20.46 22.02 +7.6
(5027) (22.03)
250 4780 4933 +3.2 18.35 19.65 +7.1
(4969
(4969)) (19.65)
(0.8111)2
Gas/Oil Ratio (scf/bbl) : 14440 (0.8111)2
100 3835 4556 +18.8 19.08 20.05 +5.1
(4614) (20.06)
(20.06]
190 4305 4709 +9.4 16.24 16.96 +4.4
(4754) (16.97)
250 4440 4504 +1.4 14.49 15.15 +4.6
(4540) (15.16)
105
105

TABLE 2.10
TABLE 2.10 - COMPARISON
COMPARISON OF
OF SATURATED
SATURATED PROPERTIES
PROPERTIES FOR
FOR OLDSSAGELACEY
OLDS-SAGE-LACEY
MIXTURES (1945).
RESERVOIR MIXTURES

Temp-
Temp Bubble-Point Pressure
BubblePoint Pressure (psia)
(psia) Bubble-Point Density
BubblePoint (lb/ft 3)
Density 3
(lb/ft
)
erature
erature
(F)
(F) Meas.
Meas. Calc.
Caic. (%)
t.(%) Exp.
Exp. Calc. 3
Calc.
3 (%)
t.(%)

(scf/bbl) : 274 (0.02066)2


Ratio (scf/bbl)
Gas/Oil Ratio (0.02066)2
100
100 817 796
796 -3.8
-3.8 49.12 49.87 +1.5
+1.5
(779 )1
(779)1
(49.81)
190
190 1020
1020 1067
1067 +4.6
+4.6 46.36
46.36 47.96
47.96 +3.5
+3.5
( 1056)
(1056) (47.89 )
(47.89)
250 1170
1170 1236
1236 +5.6 44.66
44.66 46.54
46.54 +4.2
+4.2
(1223)
(1223) (46.46)
(scf/bbl)
Gas/Oil Ratio (sc/bbl) 460 (0.05082)2
460 (0.05082)2
100
100 1540
1540 1361 -11.6
11.6 47.96 48.34 +0.8
((1346)
1346) (48.28)
190 1830
1830 1805
1805 -1.4
1.4 44.92 46.29 +3.0
(1785) (46.22)
250 2020
2020 2051 +1.5 43.08 44.78 +3.9
+39
(2027) (44.68)

(scf/bbl)
Gas/Oil Ratio (scf/bbl) 620 (0.07539)2
620 (0.07539)2
100
100 2085 1799 -13.7
13.7 46.62 47.19 +1.2
(1778) (47.13)
190 2439 2360 -3.2
3.2 43.55 . 45.04 +3.4
+34
(2329) (44.98)
250 2670 2656 -0.5
0.5 41.53 43.50 +4.7
(2620) (43.42)
(0.10311)2
(scf/bbl) : 811 (0.10311)2
Gas/Oil Ratio (scf/bbl)
100 2656 2273 -14.4
14.4 44.68 45.96 +2.9
(2242) (45.90)
190 3067 2944 -9.0
9.0 41.98 43.73 +4.2
(2901) (43.67
(43.67))
250 3384 3284 -3.0
3.0 39.70 42.21 +6.3
6.3
(3235) (42.14)

1
1 Values in parentheses are predictions using EOS-based
EOSbased critical
properties but assuming the paraffin relation for acentric
factor (Eq. 2.10).
2
2 Values in parentheses are weight fraction of
of the separator gas used
to make the mixture.
3 Saturated densities are calculated at the experimental saturation
pressure assuming the mixture is a single phase.
106

NOMENCLATURE
NOMENCLPJURE

Kw
Kw =
= Watson (Universal Oil Products) characterization
factor
Mi == molecular weight of i
Mn+ == average molecular weight of aa mixture of
of petroleum
fractions with a lowest carbon number n, e.g., C C7+
+
7

Pc
Pc =
= critical pressure, absolute units

Qi =
= cumulative normalized molecular weight
variable of i
S == sum used to calculate K
Kw which results in the
measured Cn+ specific gravity
C

Tb = boiling point, absolute units


Tc = critical temperature, absolute units
=

xi == mole fraction of i
Xi == cumulative normalized mole fraction of i
xn+ = mole fraction
= of a mixture of petroleum fractions
with aa lowest carbon number
nuirber n, e.g., C
C7+
+
7

a == parameter in the molar distribution model defining


the form of
of the distribution

Yi =
= specific gravity of i

Yn+ = average specific gravity of a mixture of petroleum


fractions with a lowest carbon number n, e.g., 7C7+
C
+

A == deviation, %
%
= lOOx(calculated-measured)/measured
= lOOx(calculatedmeasured)/measured

nn =
= parameter in the molar distribution model
representing the approximate minimum molecular
weight of compounds found in aa mixture

w
w =
= acentric factor,
= -log(Pv/Pc)-l.O
= log(p/p)l.O at T/Tc=O.7
T/Tc0.7
107
107

Chapter 33
Chapter
FLOW IN
FLOW IN POROUS
POROUS MEDIA
MEDIA

dont get
"don't get no
no respect"
respect said
said Morris
Morris the
the cat
cat

3.1 Introduction
3.1 Introduction to
to Fluid
Fluid Flow
Flow in
in Porous
Porous Media
Media
Darcys law
Darcy's law first
first appeared
appeared in
in 1856.
1856. ItIt states
states thJt
thit an
an
incompressible fluid
incompressible fluid ofof constant
constant viscosity,
viscosity, p, flowing aa
ll, flowing
given distance
given distance inin aa porous
porous media
media ofof uniform
uniform quality
quality has
has aa
velocity, v,
velocity, v, directly
directly proportional
proportional to the pressure drop,
to the pressure drop, ~. Ap.
written in
Written in equation
equation form,
form,

vv == C-6p
CAp ............................. (3.1)
(3.1)

where it
where it is
is assumed
assumed that the direction
direction of flow
flow is
is from
from high
high
to low pressure;
to low pressure; both v v and 6p
Ap are considered
considered positive
positive byby
definintion. The
definintion. The constant
constant CC is inversely
inversely proportional
proportional to to
viscosity and
viscosity and dependent
dependent on the flow geometry
geometry and
and porous
porous
materi al.
material. For linear flow along a distance
For L, Darcy
distance L, Darcy slaw
s law
can be
can written
be written

vv == k(Ap/L ) (3.2)
k(Ap/)JL) (3.2)

where
where kk is is aa consta
constant defined by
nt defined by Darcy
Darcy asas permea
permeability.
bility.
Perme ability
Permeability is is aa proper
property
ty ofof thethe porous
porous media
media depend
dependent
ent onon
pore
pore size
size distrib
distribution
ution and and tortuos
tortuosity (relative
ity (relativ path of
e path of
fluid
fluid flow).
flow). The origina
The original units used
l units used by by Darcy
Darcy were
were
v(centi meter/ second
v (centimeter/second)),, Ap(atm
6p(atmosphere),
osphere), ll(centipoise),
p(centi poise), and
and
L(cent imeter), resulti
L(centimeter), resulting
ng in in thethe unit
unit for
for permea
permeability
bility (in(in
abbrev iated notatio
abbreviated notation)
n) asas 2(cm
(c
/ 2
s)(cp/s)(cp)/atm,
)/atm
m, since since defined
defined asas aa
darcy.
darcy.
For
For most
most reservo
reservoir engineering
ir engine applications
ering applica tions the the unit
unit
millida rcy onet
millidarcy - one-thousandth
housandth of of aa darcy
darcy - is
is used.
used. This This
results
results becaus
because permeabilities
e permea usually encoun
bilities usually encountered range
tered range
from
from 11 to
to 100
100 md.md. Low
'Low-permeability' reservoirs
permeability reservo lie below
irs lie below
the value of
the value of 1 md,1 md, and and 'high-permeability'
highpermeability resevoirs
resevo irs gogo
beyond
beyond 100
100 mdmd upup toto tens
tens of
of darcies
darcies. . High permea
High permeabili ties
bilities
are
are not
not always
always aa blessin
blessing due toto mecha
g due mechanical instability
nical instabi lity ofof
the rock/p ore
the rock/pore system.
system . Low-permeability
Low reservoirs
permeability reservo irs areare
108
108

becom
becoming imporrtant
more impo
ing more rce since
as aa resource
tant as sent
they represent
since they
the reserv
the reser ves which were
es which behind
left behi
were left oil and gas were
when oil
nd when and gas were
iful..
plenttiful
plen

Darcy
Darc ys's law proba
law has prob bly been
ably writte
been writt in hund
enn in eds, if
hundrreds, not
if not
with different
all with nome
rent nom nclature! These
encla ture! These
thousa
thou sand formss - all
of form
ndss of

includ
inclu alizat
generraliz
dee gene ions
ation to radial/cyl
s to ndric
l/cyliindrical and spher
al and sphe ical
rical
etriess,, vecto
geometrie r,
r, finite
finit -diffe
ed ifferrence
ence ,, and al
differential
formss.. It does
form doesn nt beforree one forge
long befo
take long
't take ts the
the most
most
imporrtant
impo aspec
tant aspe t
ct of
of Darcy
Darc 's
ys law that of
- that
licity..
of simplicity

Muskat give numer


givess num ouss inva
erou uable
invalluab examp
le exam ples of the appl
les of catio
appliicati on n
of Darcy
Darc 's law, rang
ys rangin ingg from simp simpllee to to di fficu
diffi cult lt
catio
appliicati
appl ns.
ons. i recal l
l from one of my lectures at Stanf Stanfordord
wheree Dr. Ramey said that if
U. wher if you think you you disco ver
ver a new
new
proble m, it is best to first
firs t check
chec k
solut ion to a fluid flow prob
solution lem,
y
Muska
Mus bookss and pape
t 's book
kats paperrss to make sure it hasn'
hasn tt alread
alrea dy
d. Two excel
solveed.
been solv lent examp
excellent appear
les appe
examples ar in the sectio
secti onsns
of this chapt
chap er
ter on multip
mult hase
ipha se flow and effects of partially
penet rating
penetratin wells.. Somet
g wells Sometim es it seems that the craze over
imes
ricall simul n is aa result of those
ation
simulatio those who don'tdont have the
numeerica
num 's
patien
patience ce to read MusMuska t, but would rathe
kat, r redisc
redis overr Darcy
cove Darcys
law in finite -diffe
finited iffer ence form;
rence excep
form; exce tions
ption s are well taken .

ing sectio
section reviewss multip
n review multipha hase se flow in porou porouss
The follow
following
to each
which relies on extension
media,, which
media of Darcy
Darc 's
ys law
phase.. Simil
phase Similarar to equil
equilibri cons ants
um const
ibrium tants and phase
phas e behav
beha ior
vior
calcu lation
lations, s, descr on of multi
iption
descripti multipha phasese flow relie s on the
defin ition of relati relative permeabil ities.
ve perm ities. Analo Pnalogougouss to the
ibing two-p
two hase
phase equil
equilibriibriaa,,
equat ion of state for descr
equation describin g
on
modelss exist for estim ating relati
model relative ve perm eabili
eabil ties
ities based
base d
the chara
charactercteriz on of the porou
ation
izati porouss media
med ia . Unfor
Unfo tunate
rtuna ly
tely the
chara cter of reser voir rocks
character rocks,, with which we are conce concerne rned,
d,
varies consi derab
considera ly from point
bly poin t to point
poin t.. Also,
Also , the model
mod s
els
for descr
describinibingg relati ve perme
relative permeabilabilit y
ity are more primi
prim tive
itive than
those for
those tor descr ibing
describin phase equil
g phase equilibriibriaa,, and they are limite limited d
in their abili ty to predi predict ct the effec ts of press ure,
raturere,, and comp ositio
composi n.
tion. This resul ts in in, the very
tempe
temperatu
ge' relati
relativeve
diffi cult engin ing task
eering
engineer of defin ing 'avera
ave rage
perm eabilities.
permeabil ities.
109
109

Where Darcy's
Where Darcys lawlaw has
has been
been shown
shown to to bebe applicable
applicable to to
multip hase flow, it
multiphase flow, it is
is deficient
deficient inin describing
describing thethe relation
relation
between velocity
between velocity andand pressure
pressure drop
drop when
when flow
flow is
is not
not laminar.
laminar.
High velocit
High velocityy flow
flow requires
requires another
another model,
model, the
the most
most accepted
accepted
being Forscheimer's
being Forscheimers equation,
equation,

vv ++ Bv
2
By2 = Cip
= C-6p ................. (3.3)
(3.3)

where B
where B is
is proportional
proportional toto density,
density, asas well
well asas having
having the
the
same relatio n to
same relation to viscosity
viscos ity and
and geometry
geometry as as constant
constant C.
C.
Section 3.4
Section 3.4 considers
considers application
application ofof the
the Forsheimer
Forsheimer equation
equation
to multirate
to multirate testing
testing of
of oil
oil and
and gas
gas wells.
wells.
Another application
Another application of of Darcy's
Darcys law
law is
is toto help
help solve
solve the
the
diffusi vity equatio
diffusi vit y equation relating pressure,
n relatin g pressu re, position,
position, and
and time
time
to rate.
to rate. The The simplest
simplest solution
solution to this problem
problem results
results byby
assuming incompressible
assuming incompressible flow,
flow, thereby eliminating
eliminating the
the time
time
variable.
variable. Muskat uses this assumption
Muskat assumption to develop
develop many
many
useful engineering
useful engineering solutions
solutions to difficult
difficult problems.
problems. Amoung
Amoung
these are
these are multiphase
multiphase flow and partial penetration
penetration effects,
effects,
two subjects
two subjects consider
consider in this chapter.
chapter.
Compressible flow,
Compressible flow, on the other hand, must consider consider
transie
transientnt (timedependent)
(time-dependent) effects..
effects Solution
Solution of
of
compr essible flow
compressible flow proble
problems an import
ms has been an important tool to the
ant tool to the
study
study of of oil
oil and gas gas well perform
performance.
ance. The simple
The simplest
st
solutio
solutionn assum
assumes,es, amoung
amoun g other condit
other condi tions
ions,, a
a fully
fully
penetra ting well
penetrating well in in anan infinite
infinite system
system (no(no bound
boundaries)
aries)
produc ing at
producing at aa consta
constant rate. After
nt rate. After some
some time,
time, the
the pressu
pressure
re
drop
drop at at the
the weilbo
wellborere isis closely
closely approx
approximated
imated by by aa
logarit hmic functio
logarithmic function n of
of time,
time,

p(r,t )
6p(rw,t) = Dlog(t
Dlog(t)
) ++ EE (3.4)
(3.4)

Constants DDand
Constants and EE are
are depend
dependent on rate
ent on rate (assum
(assumed constant),
ed consta nt),
permea bility, well
permeability, well geome
geometry (e.g, wellbo
try (e.g, wellbore radius and
re radius and total
total
thickne ss), compr
thickness), essibility of
compressibility of the
the format
formation and fluid,
ion and fluid,
viscosi ty,
viscosity, and
and porosit
porosity.
y.
110

Consi
Consid ering the press
dering pressuure radiu s in the system,
re drop at any radius
tten
rewriitten
Eq. 3.4 can be rewr in a
a more gener
generaall form as,

~p(r, t)
Ap(r,t) =
= -OEi
Dt)
/
2 (-r 2 /t)r
Ei( + F (3.5)
+ F

where Ei is the expon


expone ntial integral, which for large times
ential
or small radii simpl i fies to the logar
simplifies hmicc appro
ithmi
logarit approx ximat ion
imatio n
gi ven by Eq. 3.4. Is
given As time proce
procee ds, the press
eds, pressuure
re drop at
the no-flo
nofloww bound ary will begin to effec t the press
pressuure
re drop
wellbore.
at the weilbo re. That is, Eqs. 3.4 and 3.5 assume an
ption which
infinite reservoir with no boundaries, an assum
longerr valid when ~p
is no longe Ap at re reach ess some value
reache
(say 11 psi).
When boundary effects become promi promin ent, a more rigoro
nent, rigorouuss
sivityy equat
equatio n must be
ion used. The
solut ion to the diffusivit
solution
re in a
exact solut ion
solution for press
pressuure
re drop at the well bore
weilbo
n of
ion time plus an
circular bounded system is a linear funct functio
functi on
infinite series of expon expone ential
ntial Bessel
and Bessel functio n
expresssion
expre s,
sions,

p(r,,t)
~p(rw t) =
= Gt
Gt +
+ H ,re/rw)) (3.6)
SUM(tt,re/rw
H ++ SUM(

where const
consta nts G
ants C and H H also are depen depend ent on rate,
dent
perm
permeaeabili ty, well geometry (part icula
bility, rly the ratio , re/rw ),
re/rw),
total comp
compressressib y, viscosity, and poros
ility,
ibilit poro ity.
sity. It can be
shown that after only a very short short time the sum of
expon
expone Bessell funct
ntial and Besse
ential functio ns becomes negl
ions ble and that
negliible
re drop is a linear funct
pressure
pressu ion
functio n of time. In fact, the
re drop
ure in an infin ite system
transition from when the press pressu
t that
changeess to press
chang pressu re drop in a bound
ure ed sytem is so short
shor
log relati on and the linea r relati
relat ons
ions (Gt+H
(Ct+H ) are
semilog
the semi- relation
sufficient for most pract ical appli
practical appl catio
icati ns.
ons. This is not the
case for other reservoir geom geome etries
tries which may have long
perio ds.
trans ition period s.

fy discu
simpliify
To simpl discuss ion of press
ssion op solut
redrrop
pressuure-d ions to
solutions
transient flow problems, the commo n pract
prac ice
tice is to use
dimenssionle
dimen ss quan tities
ionless dimen
dimens
sionle ss
ionless pressure, PO,
PD
dimenssionle
dimen ss time, to,
ionless tD, and dimen
dimens sionle ss
ionless radiu s, rO,
rj,
define
definedd below assum ng consi
assumiing stentt units,
consisten


__

111

PO
PD = (qiB
= (q~/k/kh)p
h)6p (3.7a)
(3.7a )

tD = 2
(k/4
) .tpcr (3.7b)
(3.7b)

ro
rD = r/r
= r/rw (3.7c
(3.7c))

rOe
rDe = re/rw
= ..... ..... ..... ..... ..... ..... ..... (3.7d)
(3.7d )

where qq =
= rate (velo city
(veloci ty times area) , p)J == viscos
area), visco sity,
ity,
BB == forma
formattion
hh == thickn
thick ness,
volumee factor, kk = permea
ion volum =
perm eabili ty,
bility,
ess, ~t == porosi
poros ity,
ty, Ct == total
ct total compr
comp ressib ility
essibil ity
(rock plus fluid), rw == weilbo
radiu s.
boundary radius.
wellbore radiu s, and
re radius, and r
ree = =
exter nal
externa l

Using Eqs. 3.7,


3.7, earlier
er relat
relatiions
ons for pressu
pressure
re drop can be
writte n exactly
written exact ly,,

po(ro
(
p
=
0
) 1,=l,tO
r t) = 0.5ln
= 0.5ln(t
)
0 (tO) ++ 0.404535 (3.4)

po(ro ,tD)
pD(rD ,to) =2
=-0.5 Ei(-r
0.
/
)
0 5Ei(
t 0 2r
/tO) (3.5)

po(ro
(
p
=
0
) 1,=l,tO
r t) =2
2to/r Oe
2t/ 2 In(rO )) -3/4
re ++ ln(rDe
=
e _3/4
~ 2 exp(-a
ex
t
( an
D n 2t).
p( rD 2(anrO
O)J1J1e)
an e)
+2 z
+ 2 1: (3.6)
(3.6)
..

an2(J
n=l (
a
(
(
2 ana 12(an
J
re)
n rOe)-
n J12(a
))i Jin))

where an are the roots of Ji(anre


Jl(anrOe)Y l(an)-
)Yi(an Jl(an)n)Yi(a
)Ji(a Yl(anrOe)
nre)
0.0.
equal to 0.0.
112
112

topic
IA topic which recei
which receiv veses almoalmos stt no attention
no atten tion in in the the
traditiona
tradi petrol
tionall petro eum-e
leum en ngine ering curri
gineering curricula cula is is
const
cons ressu
ant-ppress
tant re
ure produ
prod ction,
uctio n, and
and the
the resulting
resul ting rate rate
decline.
decli ne. This indicates,
This indic perha
ates, perh ps, the
aps, the lacklack of of understanding
unde rstan ding
aboutt what
abou what thethe petro eum engi
petrolleum engin eer is
neer is supp suppo se to
ose to do do -

determ
deter ine the
mine rates of
the rates gas, and
oil, gas,
of oil, and watewaterr as as aa function of
func tion of
tions.
condiition s. It is
It is alsoalso due to the
due to the fact
time and
time produ
and prod cing
ucin g cond
that for many
that many years
year s oil
oil and
and gas
gas produ
prod ction
uctio n werewere regu ated,,
regullated
ei therr by
eithe econom
by econ omic ic or ical forces.
poli tical
or polit s. Translated into
Tran slate d into
simpllee term
simp the well
termss,, the could
wellss coul d prod produ uce more than they
ce more than they were
were
allowed
allow ed to produ
to prod uce.ce. Those
Those days
days are
are over
over now, at
now, least for
at least for
is thatthat most most wellswell s produ
prod cing
ucin g
the most
the part, and
most part, and aa resultt is aa
today
toda produ
are prod
y are ced to
uced poten
their pote
to their tial (or are regul
ntial (or are regu ated
lated by
by
minimuum
minim surface
m surfa ce pressure). ure). In practtical
In prac ical termsterm s this
this means
means
many
that many
that wells
well s produ
prod ce
uce at
at a
a const
cons ant
tant bottom
botto mhoholele pressure, ure,
naturral
with aa natu
with declin
al decli nee inin rate. The The flow flow equations
equa tions dicta ting
ting
ressu
ant-ppress
consttant
cons re prod
ure produ ction
uctio n is unknown to
is unkno wn to most
most petrol
petro eum
leum
sion in in tradi tiona
tiona ll unive
univ rsity
ersit y
engin
engi eers,
neer s, andand its inclusion
es is emm
studiies
stud emmin inenent.
t. The topic is
The topic covered
is cove red in Sectio
Sect ion n 3.5
3.5 of
of
this
this chapt
chap er.
ter.

Anoth
Pnot herer very useful dime dimen sionle
nsio nless ss quanquanttity ity is is the skin skin
factor sugg sted by Hurs
suggeested Hurstt and van Everd Ever ingen
ding en. . Actua
Ictua lly
lly
same concconce eptpt when discu ssing
ssing the effec tt
Muskat sugg sts the
suggeests the same r
nss on on well prod produ ctivit y
uctiv ity (he calle dd the facto
of perforatioration
C, and subse quent
subseque ntly ly discussed its its equiequiv alenc
valen with aa redu
cee with reducceded
wellb
weil ore radius, rw=
bore we-C).
rw'=rrwe_ C). Skin,Skin , as it
it will be
be referr
refer ed
red
fter,, offerss a .con
hereaafter
to here -conv enien
veni entt way to desc descrribe ibe the
ase in pressure drop at the wellb
weil ore
bore due to
increase or decr decreease
nonid
noni eal effects. The most
deal commo n skin is due to damage
tion during drilli
n during drill ng;
ing; perme
perm abilit
eabil ityy in the
from mud filtrafiltratio
press ure
nearwellbor
near-w region
eilboree regio n is redureducced,ed, causin
caus ingg an extra
drop. In this study
drop. study we consi consider der the skin due to partial
tion, resul ting in nonra nonradial stream
dial stream
ration
penettratio
pene n of a forma formation ,
lines near the well. well. It is shown that the original Muskat
solut ion is equiv
solution equivalen alentt to the Brons Brons and Martin Marting g solut ion,
solution,
expr ssed
expre in analy tical form.
form .
but can be essed
113
113

3.2 Corey/Burdine
3.2 Corey/Burdine Relative
Relative Permeability
Permeability Model
Model
The flow
The flow of
of more
more than
than one
one fluid
fluid phase
phase in
in porous
porous media
media
can be classified into
can be classified into several
several groups:
groups:

immiscible without
immiscible without mass
mass transfer
transfer between
between phases
phases
immiscible with
immiscible with mass
mass transfer
transfer between
between phases
phases
miscible
miscible
partially miscible
partially miscible

amoung several
amoung several otherother categories
categories including
including non-Newtonian
nonNewtonian
flow. Pn example of
flow. An example of immiscible
immiscible flow
flow without
without mass
mass transfer
transfer
is oil
is oil displacement
displacement by by water,
water, assuming
assuming the
the two
two do
do not
not create
create
an emulsion.
an emulsion. An
In example
example of of immiscible
immiscible flowflow wi th mass
with mass
transfer is
transfer is flow
flow of of saturated
saturated oil
oil and
and its
its solution
solution gas.
gas. An
In
example of
example of miscible
miscible flow flow is
is carbon-dioxide
carbondioxide injection
injection in in an
an
oil reservoir
oil reservoir where where first-contact
firstcontact miscibility
miscibility is is achieved.
achieved.
In this
In this case
case there
there areare three
three phases:
phases: the
the untouched
untouched oil,
oil, the
the
injecte d ,
2
C0
injected C02, and and thethe resulting
resulting mixture.
mixture. An
In example
example ofof
partially miscible
partially miscible flow flow isis injection
injection of dry dry gas
gas into
into an
an oil
oil
reservoir, in
reservoir, in which the injected injected gas, after numerous numerous
contac ts with
contacts with the the reservoir
reservoir oil, becomes
becomes progressively
progressively
richer until
richer until it it isis almost (i.e., partially)
partially) miscible
miscible with
with
the origina l reservo
the original reservoir ir oil.
The present
The present discussion
discussion will only cover immiscible immiscible fluid
fluid
flow, and it
flow, and it will will concentrate
concentrate on definition
definition of relative
of relativ e
permea bilities. Most
permeabilities. Most of this section repeats or or extend
extendss the
the
exellen
exellentt notes
notes on on relativ
relative permeability
e permea relations
bility relatio written by
ns written by
Standi ng at NTH in
Standing at NTH in 1975. Plthou
1975. Although
gh no no new
'new' results
results or or
develo pments are
developments are given
given (for
(for which
which i am am respon
responsible),
sible), itsits
inclusi on is justifie
inclusion is justified when we
d when we consid
consider the import
er the importance
ance ofof
relativ
relativee permea bility to
permeability to multip
mUltiphase flow in
hase flow in porous
porous media.
media.
The
The work
work by
by Svein
Svein Havig
Havig (one
(one of
of my
my studen
studentsts atat NTH)
NTH) should
should
be consid ered as
be considered as a serious contrib
a serious contribution
ution to to the
the applica
application
tion
and
and charac terization of
characterization of relativ
relative permeability
e permea theory to
bility theory to
North
North Sea
Sea chalk
chalk reservo
reservoirs.
irs.
114
114

The follow
The following itions
ing definition shoulldd he
s shou helpfful
be help to the
ul to follow
the follo ing
wing
ssion::
discussion
discu

ive Permeabil
Relattive
Rela ty:
eabiliity:
krw
krw = kw/k
= kw/k
kro
kro =k
= ko/k
/
0 k

krg
krg = kg/k
kg/k
krx
krx = ko/ k = kgx/
kox/k kgx/k
= k

kk = abso
= ute perm
absollute abilit
permeeabil ity nonreeacti
y to nonr liquid
ve liquid
active

kw = effective perm
kw abilit
permeeabil y to wate
ity phasee
waterr phas

ko = effective
= eabiliity
permeabil phasee
ty to oil phas
kg = effective permeabil
= eabiliity phasee
ty to gas phas

gx = effective perm abilit


permeeabil y to oil or gas
ox = kkgx
kkox = = ity
system where
e system
in a two phase
phas waterr,, the
where wate
secon phase,, is at its irredu
d phase
second cible
irreducib le
satur ation, Siw
Sj

ve perme abilit
permeabil y of a given
ity phase
given phase
Somewhat logic ally, relati relative
phase
phas e..
strong funct
is a strong functionion of of the satur ation of that
Satur ation
Saturatio merely the volum
n is merely volumee of a givengive n phase
phas e divide
divid d
ed by
total
the tota l pore volum
volu me e conta
cont ined by fluid . Althou
ained lthough gh relati
relative ve
perme abilit
permeabil ityy has also been shown to vary with surfa ce
tensio
tension n betwe
betweenen phasess
phase and rock/w
rock ater
/wat er affin ity
(wett abilit
(wettabil y),
ity), the stron gest facto rs affecting relati relative ve
perme
permeabil ty are satur ation, satur ation
abiliity histo ry, and pore
size distr butio
distri ibuti on.n.
The Corey
Corey/Bu/Burd model is perha
ine model
rdine perhapsps the most widely known and
most widely
commonly used relati on in the petrol
relation petro eum
leum indus try.
industry. It
tant facto rs mentio
men ned
tione d above
abov e,,
accou nts for the three impor
accounts important facto
of
and it has been modif ied to accou
modified accountnt for trapp ing effec ts
phase.. No accou
a third phase accountnt is made for for eithe surface tensio
either surfa tension n
or wetta
wettabili ty..
bility In gener
general,al, satur ation histo ry -
re
draina ge versus imbib
drainage itionn is only
imbibitio only consi deredd for the
considere
phase..
etting phase
nonwetting
The model relie
The model relies s on estimates of
on estim pore size distri
of pore butio
distributi n, A,
on,
which
which can
can be
be determ
determineinedd from capil
capil lary press ure
measu remen
measurem ts, and
ents, irreducibl
and irred ucib e
le wettin
wett g-pha
ing se
phas e satur
satur ation
115
115

(assumed to
(assumed to be
be water
water in
in the
the present
present discussion),
discussion), Siw.
. The
1
Sj The
first
first step step is is toto calculate
calculate effective
effective saturations.
saturations.
Considering three-phase
Considering threephase drainage
drainage relative
relative permeability,
permeability,
the following
the following definitions
definitions can
can be
be used:
used:

Effective Saturations:
Effective Saturations:

Swe
we
5 = (Sw-Siw)/(l-Siw)
= (Sw_Siw)/(l_SiwJ ....................... (3.8a)
(3.8a)

Soe
oe
5 = So/(l-Siw)
So/(l.-S) (3.8b)
(3.8b)
Sge = Sg/(lSiw) .............................. (3.8c)
(3.8c)

where
where is
Siw is the
the irreducible water
water (wetting-phase)
(wettingphase)
saturation, 0
S is
saturation, So is the the oil
oil saturation, Sg
g is the
5 the gas
gas
and Sw
saturation, and
saturation, S is is the total water saturation (mobile
(mobile
plus irreducible).
plus irreducible).

The drainage
The drainage relative permeability relations for three
three phase
phase
flow (which simpli
flow (which fies to two phase flow when
simplifies when the
the third
third
phase, gas
phase, gas or oil, is
or oil, is not present) are:

ThreePhase
Three-Phase Drainage
Drainage Relative Permeabilities:

(2+3X)/x
(2+3),)/),
krw
krw =5

Swe
w e ......................... 3.9a
(3.9a)

kro 2 (2+x)/x (2A)/x


= krxSoe {(Soe_Swe) Swe } .. (3.9b)

krg = }
4
krxsge2{1_(soe_Swe)(2+ (3.9c)
(3.9c)

where krx is
where krx is defined
defined above
above asas the
the relative
relative permeability
permeability ofof
oil
oil or
or gas
gas in
in aa twophase
two-phase system
system where
where water,
water, the
the second
second
phase,
phase, isis at
at its
its irreducible
irreducible saturation.
saturation. These
These relations
relations
should
should be
be applicable
applicable to to the
the following
following processes:
processes:
solution
solution gas
gas drive
drive
gas
gas displacing
displacing or
or replacing
replacing oil
oil during
during
gas
gas injection
injection or
or gravity
gravity drainage
drainage
gas
gas displacing
displacing water
water during
during storage
storage
116
116

It has
It been found
has been using
that usin
found that g the traditiona
the tradi of
ition of
tionall definition
gas satur
tive gas
effective ation
ation is
is not
not usual
usua ly
lly suffi cient
cient due
due to
to
tion effec ts.
ification
and stratifica
ation and ts. AA
critical gas saturation
al gas
modif
mod ified gas saturation
tive gas
ied effective ly prefe rred,
usuallly
is usua
ation is rred,

Sge
Sge = (Sg+S
= (Sg+ ro-l)/(
Sm1 Sm-Si
)/(Sm Siw) (3.10))
w) (3.10

where Sm will be
Sm will calledd the
be calle Corey saturation
the Corey ation variable. ble. ItsIts
where SgcSgc is the trappe
is the trapp edd gas
gas
value
valu is not equa
e is equall to to
g
5 c, where
l-Sgc
ation
saturation .
. Such
Such an
an inter preta tion
tion m1ght be
might be assumed based based
on the math
on matic
matheemat chara
al char
ical acter of 5
cter of Sm - i.e., when
m i.e., when Sg=l-S m,
zero as doesdoes gas gas relativeive perm eabili
eabil ty.
ity. If
If Sm
m
5
5 e becomes zero
SQe
g interp retati
preta on
tion might
might be
be
g less than unity then such
is such an inter
d.
argueed.
argu In fact, Corey shows
In shows from interp
inter retati
preta on
tion of
of
hase gas/oil relat
two-pphase
two relatiiveve perm ability data
permeeabil ity data that Sm>l
m>
5
1
resul ts
ts due to strat ifica tion
tion paral
para lel
llel to flow,
flow while
, whil e 1Sm<l
m
5 <
i ficati on perpe
perp ndicu
endi lar
cular to flow.
flow .
resul ts due
due to
to strat
strat ifica tion
of
ts will obvi obvio usly influe nce
ousl y influ ence the value
valu e
gas effects
cal gas
Critical
Sm as well.
well . My exper
expe ience
rienc e based
based interp
on inter retati
preta on of
tion
m
5 on resul ts
carbo
carb nate
onat e relat ve permeabilities (relyi ng
relatiive (rely ing mainly
than
given by Havig) sugge
Havig) sugg sts that
ests t~at 5 Sm
m is alway
always s great
grea er
ter
unity whenwhen both AA and Sm m are used to fit experiment
5
experimental al
ro data.
krglkro
krg/k

Concerning the estimate of A, it can be theo etica


theorretic lly
ally
using capillary press ure data. From a plot of
determ
deter mine d using
ined
capillary pressure versus effec tive water
wate r satur ation ,
, Swe,
w
5 e
on log-lo
loglog valuee of A
paperr,, the valu
g pape A is found from the negat ive
negative
e.. If capil
slope lary press ure data are not
rocall of the slop
reciproca
ty
available from the same core on which relat relatiive eabiliity
ve permeabil
value
e of A
A can be determ
deter ined
mine d
data are measured, the valu ve
relatiive
simul taneo
simultane usly
ousl y with the valuvaluee of Sm m by fitting relat
5
abilit
permeeabil
perm ityy data.
A minim
A izatio
minimiza tion routinee must be used to determ
n routin determineine the
bestfit
best- fit of A m The simpl
A and Sm.
5 simplestest appro ach,, used in my own
approach
ine the possipossible rangee of A
ble rang A and Smm
5
appli catio
applicati ns, is to determ
ons, determine
(e.g., A=0.5
X=0.5,3. 0 and Sm=0
,3.0 m
5
0
1
, .9,1.3
9
3= ), calcu late the absol
abso ute
lute
avera
averagege devia betweeen
tion betwe
deviation n In(X
ln(Xex expp)) and In(Xc al c ) where XX is
ln(Xcalc)
either a relatirelativeve perme
permeabilabilit y or relati
ity relativeve permeabil ty
eabiliity
histo ram of the avera
aver ge
age devia
devi tion
ation to
ratio, and plot a histog gram
allow easy determ
determinainatio n of A
tion A and Sm m by eye. The graph
5 grap ical
hical
metho
method helps determ
d also helps deter ine
mine the sensi
sens tivity
itivit y of the match to
A and Sm.
A m
5
Havig,, has fit gas/o il relative perme
Havig abilit
permeabil y data from over
ity
fi fty carbo
fifty natee sampl
carbonat es, taken from five North Sea
samples,
117
117

reser voirs in the Ekofi sk area.


Ekofisk He uses an advan ced
advanced
nume
numerica
ricall routin
routine
e for determ ing the A
determing A and Sm Sm which
minim
minimize
izess the sum of squar es of the logari
squares thm to gas/o il
logarithm
relati
relative
ve perme
permeabil
abilit
ityy ratio s. Part of his resul ts are
prese
presented
nted in Table
Table 3.1. Note that all best-
bestfits
fits have Sm
great
greater
er than unity. i have check m
5
ed this tenden
checked cy
tendency on other
other
samplles
samp es from the North
North Sea.

Havig
Havig analyzes the data using
using trend analy sis and proposed
proposed
the follow
following
ing gener alized
generaliz ed corre lation
lation,,

A
A = 1.995
1.99533 - 4.065
9Siw
4.O659Sj w (3.11)
Sm = 1.044
= 1.0444
4 + O.051
0.0516A
6A (3.12))

Comp
Com arison
paris on with exper iment
experime al data using
ntal 3.11 and 3.12
using Eqs. 3.11
gives excelllent
gives exce lent results consi derin
consideri ngg the rang
rangee of data and
gener
general
al diffic
difficulty
ulty in correlatin
lating param
g the para eters
mete rs AA and Sm.
Sm.
118
118

able 3.1
able SAMPL
3.1 - SAMP

MATCH
OF MATC
LEE OF ING THE
HING COREY
THE COREY MODE L TO
MOOEL MEASU
TO MEAS RED
URED
RELAT
RELA PERME
IVE PERM
TIVE ABILIT
EABIL ITYY DATA
DATA USING
USING PARAM
PARA ETERS
METE RS
and 5
XA and m g)
(Haviig)
Sm (Hav
kai
kai)
e
Sample
l
A Sm Siw (md
(md Errorr2
2
Erro
m
5

A/X-l1 1.569
1.569 1.206
1.20 6 0.108
0.10 8 0.399
0.39 9 7.5
7.5 0.369
0.36 9
A/x
A/X-22
A/X 2.240
2.24 0 1.150
1.150 0.123
0.12 3 0.395
0.39 5 6.2
6.2 0.819
0.81 9
1.145
1.145 0.126
0.12 6 0.258
0.25 8 0.34 0.207
0.20 7
A/X-33
A/X 0.969
0.96 9
A/X-44
A/X 0.671
0.67 1 1.286
1.286 0.360
0.36 0 2.0
2.0 0.026
0.02 6

B/X-l1
B/X 1.224
1.224 1.144
1.144 0.145
0.14 5 0.402
0.40 2 2.6
2.6 0.207
0.20 7
0.993
0.99 3 1.093
1.093 0.148
0.14 8 0.383
0.38 3 2.5
2.5 0.073
0.07 3
B/X-22
B/X
0.101
0. 101
B/X-33
B/X 1.467
1.46 7 1.108
1.108 0.178
0.17 8 0.400
0.40 0 2.1
2.1
1.100
1.100 0.171
0.171 0.401
0.40 1 2.0
2.0 0.537
0.53 7
B/X-44
B/X 1.223
1.22 3
4
B/X-55
B/X 1.025
1.02 5 1.115
1.115 0.137
0.137 0.387
0.38 7 1.9
1.9 0.134
0.13
B/X-6
B/X6 1.056
1.056 1.093
1.093 0.170
0.170 0.392
0.39 2 1.8
1.8 0.100
0.10 0
B/X-7
B/X7 1.174
1.174 1.093
1.093 0.139
0.139 0.377
0.37 7 1.7
1.7 0.282
0.28 2
1.103
1.103 0.220
0.22 0 0.329
0.32 9 1.7 0.158
0.15 8
B/X-88
B/X 0.997
0.997
3
B/X-9
B/X9 0.961
0.96 1 1.121
1.121 0.165
0.16 5 0.367
0.36 7 1.6 0.293
0.29
1.082
1.082 0.158
0.15 8 0.356
0.35 6 1.2
1.2 0.172
0.17 2
B/X-I1D0
B/X 1.096
1.096
9
B/x11l
8/X-l 1.004
1.004 1.098
1.098 0.176
0.176 0.350
0.35 0 1.0
1.0 0.119
0.11
B/X-12 1.058
1.058 1.059
1.059 0.192
0.192 0.324
0.32 4 0.62 0.341
0.34 1

C/Y-l
C/Y1 2.496
2.49 6 1.149
1.149 0.130
0.13 0 0.383
0.383 7.4 0.567
0.567
1.1888 0.113
0.113 0.336
0.336 3.8
3.8 0.440
0.44 0
C/Y-22
C/Y 2.072
2.07 2 1.18
C/Y-3 1.715
1.715 1.089
1.089 0.124
0.12 4 0.333
0.333 3.2 0.766
0.766
C/Y-4
c/Y4 2.326
2.32 6 1.252
1.252 0.123
0.12 3 0.313
0.313 2.8 0.567
0. 567
C/Y-5 3.369
3.369 1.204
1.204 0.184
0.184 0.314
0.31 4 2.3 0.630
0.630
1.120
1.120 0.154
0.154 0.305
0.30 5 1.9 0.375
0.375
C/Y-66
C/Y 1.884
1.884
1.100
1.100 0.141
0.141 0.288
0.28 8 1.7 0.781
0.781
C/Y-7
c/Y- 7 1.594
1.594
C/Y-88
C/Y 1.068
1.068 1.227
1.227 0.133
0.133 0.270
0.270 1.3 0.709
0.709
1.116
1.116 1.155
1.155 0.130
0.13 0 0.228
0.228 0.85 0.136
0.136
C/Y-99
C/Y

1.533
1.533 1.124
1.124 0.043
0.043 0.309
0.309 2.8 0.064
0.064
D/Y-11
D/Y
0.493
D/Y-2
D/Y2 4.779
4.779 1.246
1.246 0.091
0.091 0.327
0.32 7 2.4 0.493
1.096
1.096 1.144
1.144 0.076
0.076 0.288
0.288 1.7 0.059
0.059
D/Y-3
D/Y3
0.334
0.334
D/Y-4
D/Y4 3.778
3.778 1.416
1.416 0.061
0.061 0.271
0.271 1.4
D/y-5
D/Y5 1.743
1.743 1.203
1.203 0.117
0.117 0.231
0.231 1.4 0.181
0. 181
D/Y-6
D,A6 1.449
1.449 1.085
1.085 0.035
0.035 0.264
0.264 1.14 0.423
0.423
2.503
2.503 1.101
1.101 0.110
0.110 0.247
0.247 0.83 0.377
0.377
D/Y-7
D/Y7

E/Z-l
E/Z1 1.103
1.103 1.062
1.062 0.362
0.362 1.6 0.531
0. 531
0.859
0.859 1.009
1.009 0.302
0.302 0.9 0.263
0.263
E/Z-2
E/Z-2

1.095
1.095 1.072
1.072 0.372
0.372 1.93 0.082
0.082
F/Z-l
F/i-I
0.071
0.071
F/Z-2
F /z 2 1.441 1.294
L294 0.374
0.374 1.14
F/Z-3
F/Z3 1.459
1.459 1.180
1.180 0.373
0.373 1.69 0.072
0.072
F/Z-4
F/Z4 1.921 1.107
1.107 0.084
0.084 0.358
0.358 5.9 0.653
0.653
1.889 1.125
1.125 0.075
0.075 0.322
0.322 4.2 0.685
0.685
F/Z-5
F/Z5

1 Field/ matition-S
Forma
Field/For onSamample
ple
2
2 squares
Sum of squar es of ln(krg/kro )exp-
-ln(kr ln(kr
)exp_lfl( g/kro
krg/k ro.)c aic..
)calc
The match of data is usual
usua ly
lly excel
exce lent
llent when this value
value
is less than 1.0.1.0.
119
119

The relation for kkrx


rx given by Havig is,
is,

kkrx
rx = 1.0
= 1.0 - 4.538Siw
5385 +

4
jy + 3.876Siw
2
3.876Sj
2
(3.13)

which gives values considerably lower than calculated using


the relation suggested by Standing (developed at Chevron
Research Laboratory),

kkrx
rx = 1.08
= - 1.11Siw

Q73.5.2
l.llS - 0.73Siw
2
(3.14)

Havig also compares pore size distribution factors


calculated by matching krg/k ro data (Table 3.1) with A
krg/kro A
calculated from capillary pressure data. Table 3.2 3.2 shows
his results. It appears that the values fit by matching
gas/oil relative permeabilities are lower than those found
from capillary pressure data. If capillary pressure data
were available for the same samples analyzed for gas/oil
relative permeabilities then the match could have been been
performed holding AA constant (equal to the capillary
pressure determined value) and varying only Em.
Sm.
Unfortunately it is seldom the case that both both capillary
capillary
pressure and gas/oil relative
relati ve permeability
permeability data areare
available from the same sample.

Table 3.2
Table 3.2 - COMARlSON OF PORE
- C0MRIS0N PORE SIZE
SIZE DISTRIBUTION
DISTRIBUTION FPCTORS
FACTORS
CALCULATED BY
CPLCULPJED BY FITTING
FITTING G1\S/OIL
GAS/OIL RELPTIVE
RELATIVE
PERMEABILITY DIT
PERMEABILITY DATA NDAND BY
BY ANPLYZING
ANALYZING CPPILLRY
CAPILLARY
PRESSURE DATI\.
PRESSURE DATA.

Formation
Formation Fit 1
Fit
1 No.
No. Pc Data
Pc Datal No.
No.

xX 1.14
1.14 17
17 2.24
2.24 18
18
YY 2.17
2.17 17
17 2.61
2.61 99
ZZ 1.33
1.33 88 2.12
2.12 11

1 Represent arithmetic
Represent arithmetic averages
averages for
for the
the samples
samples
listed in
listed in Table
Table 3.1.
3.1.
120
120

The imbibi
The imbibition relation
tion relatio for the
n for the nonwetting phase in
nonwetting phase in aa
two-phase system
twophase (e.g., gaswater)
system (e.g., gas-water) is given by
is given by

krg =SgeF2
SgeF 2 '{l-(l-S (2+A)/A
)/}} (3.15)
krg = geF)
{1(lSgeF)( (3.15)

where 5
where SgeF
g is the
eF is the effecti
effective free gas
ve free gas saturat
saturation, given by
ion, given by

SgeF = 0.5{(Sge_Sger)+/(SgeSger)4(Sge_Sger)/C}

(3.16)
(3.16)

and CC is the trappin


and trapping constant.
g consta nt. It is
It is determined
determined
experimentally
experimentally by
by measuring
measuring the
the trapped
trapped gas
gas resulti ng from
resulting from
water flooding
water flooding a a core,
core, starting
startin g at
at different
differe nt initial
initial gas
gas
saturations.
saturations. i have tabulated
tabulat ed C
C for several
severa l data
data sets
sets
reported
reporte in the
d in the literatu
literature:
re:

TABLE
ThOLE 3.3
3,3 - TRAPPING
PPING CONSTANTS
1
TRP -CONSThNTS FOR SEVERAL ROCK TYPES

Formation/Type
Formation/Type Siw
Sj A C
C

Chalk
Chalk 0.152 0.464 0.350 1.98
Abo
bo
1
P 0.200 0.769 0.130 0.597
Lansing K.C.
Lansing 0.121
0.121 0.644 0.251 0.387
Smackover (TX)
Smackover(T X) 0.045
0.045 0.458
0.458 0.311
0.311 1.603
1.603
Smackover(MS)
Smackover(MS) 0.210 0.632
0.632 0.137
0.137 0.739
0.739
Alendum
PJendum 0.020
0.020 10. O( aD)
1O.O() 0.450
0.450 4.6171
4.617
Berea
Berea 0.190
0.190 1O.0(
iO.O(cx)
aD) 0.230
0.230 1.2731
1.273
Torpedeo
Torpedeo 0.230
0.230 1.273
1.273

1Values
Values determined
determined by
by fitting
fitting relative
relative permeability
permeability
data were
data were 1.8
1.8 and
and 0.8,
0.8, respectively,
respectively, for
for the
the Alendum
Alendum
and
and Berea
Berea samples.
samples.

Imbibition water relative


Imbibition water relative permeability
permeability can
can be calculated
be calculated
using
using the
the drainage
drainage relation
relation (Eq.
(Eq. 3.9a)
3.9a) without error.
without great error.
great
Three-phase
Threephase imbibition
imbibition relative
relative permeability ns based
permeability relations based
relatio
on
on the
the Burdine/Corey
Burdine/Corey model
model have
have not in
not appeared in the
appeared the
literature.
literature
121
121

Ppplication of
Application of imbibi
imbibition
tion relati vee permeabili
relativ ties has
permeabilities has
direct application
direct application to
to the
the following
following reservoir
reservoir processes:
processes:

water
water displacing
displacing oil
oil or
or gas
gas during
during water
water
injection or
injection or water
water influx
influx
oil
oil condensation
condensation during
during depletion
depletion of
of
gasconden sate reservoirs
gas-condensate reservoirs

3.3 Constant-Rate
3.3 ConstantRate Testing
Testing of
of Solution-Gas
SolutionGas Drive
Drive Reservoirs
Reservoirs
The analysis
The analysis of of well
well test
test data
data obtained
obtained from
from wells
wells
produc ing from saturated
producing from saturated oil
oil reservoirs
reservoirs involves
involves accounting
accounting
for two-phase
for twophase gas/oil
gas/oil effects.
effects. Several
Several non ideal
nonide al conditions
conditions
violati ng
violating the
the liquid-like
liquidlike assumptions
assumptions implicit
implicit in
in
traditional solutions
traditional solutions ofof the diffusivity
diffusivity equation
equation are:

two
two phases
phases flow,
flow, instead
instead of one

the
the second
second phase,
phase, gas, and in some cases the saturated
saturated
oil are not slightly compressible
oil are not slightly compressible but show relatively
relatively
large volumetric
large volumetric changes due to pressure
pressure variation
variation
saturation
saturation becomes
becomes an additio
additional variable
nal variabl e in the
diffusi vity
diffusivity equatio
equation
n which can not, aa priori, be
be
related
related to
to pressu
pressure, position,
re, positio n, or time

the
the phase
phase behavi or re
behavior re gas/oil
gas/oil exchange
exchange between
between phases
phases
is not well defined
is not well defined but
but must
must be
be approximated
approximated using
using
solutio
solutionn gas/oil
gas/oil ratios
ratios arci
arcj ormati
formation volume factors
on volume factors

These
These problems
problems are are serious
serious obstac
obstacles
les toto the
the analyti
analytical
cal
solutio n of the consta
solution of the constant rate two-phase problem.
nt rate twophase problem. The The best
best
that
that can
can be be hoped
hoped for
for is
is anan approx
approximate solution,
imate solutio and one
n, and one
which
which must
must be be varifie
vari fied
d byby numer
numerical calculations
ical calcula tions andand field
field
data.
data. Papers
Papers 1.7 A. 7 and
and I.8
A. 8 consid
consider some of
er some of the
the problems
problems
associa ted with
associated with arrivin
arrivingg at at approximate
approximate solutio
solutions.
ns. The
The
first
first of of these
these deals
deals mainly
mainly withwith well
well testing
testing during
during
transie nt flow
transient flow (before
(before boundary
boundary effects
effects become
become import
important).
ant).
The
The second
second deals
deals more
more with
with pseudo
pseudosteady state flow
steady state flow which
which isis
mainly
mainly dominated
dominated by by depleti
depletion effects resultin
on effects resulting from
g from
boundary
boundary conditi ons. This
conditions. This section
section review
reviews paper P.7
s paper A.7 and
and
poses
poses practic
practical al questio
questionsns to to the
the potenti
potential application
al applica tion of of
methods
methods proposed
proposed in in that
that work.
work.
122
122

Raghavan
Ragha gives resul
van gives results
ts of of numer ical simula
numerical tions for
simulations for aa well
well
producing
produc ing atat consta
constant
nt oiloil rate from an initially saturat
rate from an initia lly ed
saturated
reservoir.
reser voir. His purpos
His purpose e is investigate the use of aa
is toto investi gate the use of
pseudopressure
pseudo function,
pressure functio m(p), toto linea
n, m(p), rize - at
linearize at least

least
approximately
approx imately - thethe diffu
diffusivity equation. As first defined
sivity equatio n. Ps first defined
by Evinge
by Evinger and Muska
r and Muskat for steady
t for steady state and later
flow, and
state flow, later
suggested
sugges ted byby Fetkov
Fetkovich
ich for analysis of transient flow, the
for analys is of trans ient flow, the
pseudopressure
pseudo function
pressure functio has the
n has the form,
form,

m(p)
m(p) =.fkro/p
Jkro/~080 dp
oBo dp ... (3.17)
(3.17)

where integra
where integration proceeds
tion procee from aa referen
ds from ce pressu
reference re, Pref
pressure, Pref,
to the wellbore pressure,
to the weilbore pressure, Pw Pw. 80th
Both visco sity,
viscosity, ~o, and oil
and oil
formation volume factor
formation volume factor (FVF
(FVF)),
, 8
,
0
B , are
are for
for all
all prac tical
practical
0 mal
purposes
purpos )nl Y functio
es only functions
ns of of pressu
pressurere (assum ing isother
(assuming isothermal
conditions
conditions).
Oil relat
relative permeability,
ive permea kro , is
bility, kro, is essen tially aa functio
essentially functionn of
of
Oil
saturation, saturation history,
histo ry, and pore
pore size
size distr ibution.
distribution.
saturation, saturation
Neglecting
ting the latte
latter two effec
r two effects, kro can be
ts, kro be consid ered
considered
Neglec
only a function of saturation.
only a function of satur ation . This simpli fies
simplifies the
the analys is
analysis
considerably, and is assumed
assum ed by all those who have
have attemp ted
attempted
considerably,
to
to derive
derive an approx
approximate
imate solution
solution to the two-phase gas/oil
twophase gas/oil
problem. however, thatthat these two
these two
problem. It should be remembered,
remembered, however,
assumptions are clearly violated
violated in
in practical
practical
assumptions
situations -i.e.,
situations i.e., (1) saturation
saturat ion changes
change s during
drawdown/buildup in the same
the same
drawdown/buildup and multirate
multirate tests are not in
direction,
direction, and (2) (2) rock properties homog
properties are never homogeneous eneous
throughout
throughout the reservoir.
reser voir.

Starting
Starting based
based on on the
the assumption
assumption that that kkro is aa sole function
sole function
ro is in
of
of saturation,
saturation, the the problem
problem with with solving
solving the integral in
the integral
Eq. pressu
to pressure. re. Ragha van
Eq. 3.17
3.17 involves
involves relating
relating saturation
saturation to Raghavan
rationalizes
rationaliz es two
two empirical
empiri cal saturation/pressure
saturat ion/pre ssure relat ions -
relations

one buildup - basedbased on his resul


on his results ts
one for
for drawdown
drawdown and and one
one for
for buildup

and
and interpretation
interpretation of of numer
numer ical
ical simulations. IUthou
simulations. Al though gh
empirical,
empiri cal, he
he shows
shows that
that the
the m(p)
m(p) solution
solutio can be
n can applied
be applied
sucessfully
sucessfully to to drawdown
drawdown and buildup test
and buildup inter preta
test interpretation. tion.
Results
Results are are better
better for for drawdown analys
drawdown analysis is during
during the the
infinite-acting
infiniteacting period,period, and and his interpreta
his interpretation tion method
method forfor
buildup
buildup is is only
only considered
considered for for aa wellwell producing under
producing under
depletion
depletion (pseudosteady
(pseudosteady state) state) prior
prior to shutin. Despit
to shutin. Despite the e the
limitations
limitations and and approximate
approximate nature nature of of his resul ts, Ragha
his results, Raghavan van
shows
shows the
the applicability
applicability of of thethe pseudopressure approach to
pseudopressure approach to
oil
oil well
well testing
testing in in saturated reservoirs
saturated reservoirs. .

Paper
Paper A. 7 proposes
A.7 proposes aa semi-analytical
semianalytical relation between
relation between
saturation
saturation and
and pressure.
pressure. develo ped from
ItIt isis developed from the the
123
123

diffusivity equations
diffusivity equations for for oil
oil and
and gas
gas phases
phases separately.
separately.
The main assum
The main assumptionption isis that
that saturation
saturation is is only
only aa function
function ofof
pressure and
pressure and not
not time
time oror position.
position. The The saturation-pressure
saturationpressure
relation reduces
relation reduces to to Martin's
Martins relation
relation at at early
early times
times when
when
pressu re gradien
pressure gradients ts are
are small.
small. At Pt long
long times
times itit reduces
reduces to to aa
relation equivalent
relation equivalent to to assuming
assuming constant
constant gas/oil
gas/oil ratio,
ratio, R,
R,
which is equiva
which is equivalent lent toto the
the original
original Evinger/Muskat
Evinger/Muskat proposal.
proposal.
This is
This is interesting
interesting when when we we consider
consider thatthat the
the relation
relation
develo ped
developed in in paper
paper A.a l.8 should
should onlyonly apply
apply during
during the the
infiniteacting period
infinite-acting period while
while thethe Evinger/Muskat
Evinger/Muskat relation
relation is is
developed for
developed for application
application during
during steady
steady or or pseudosteady
pseuciosteady
state conditions.
state conditions. The
The transition
transition fromfrom the
the Martin
Martin relation
relation
to the Evinge r/Musk
to the Evinger/Muskat at relation
relation is is usually
usually very
very short,
short, and
and
the merit
the merit of
of the
the general
general relation
relation is is therefore
therefore minor.
minor.
What is
What is of
of value
value in in paper
paper A.7,
1.7, and
and interestingly
interestingly isis not
not
mentio ned by Ragha van,
mentioned by Raghavan, is that producing
is producing gas/oil
gas/oil ratio is is
essentially constant
essentially constant during
during the entire infinite-acting
infiniteacting
period. The
period. The practical
practical significance
significance is that the original
original
Evinge r/Musk at approa
Evinger/Muskat approach - an engineering
ch engineering approach
approach which can
can
be solved
be solved by by aa simple
simple graphical
graphical procedure
procedure - applies to
to
constant rate
constant rate transient
transient drawdown analysis.
analysis. Interestingly,
Interestingly,
the buildup procedure
the buildup procedure suggested
suggested by Raghavan is also also
equiva lent to the
equivalent to the Evinger/Muskat
Evinge r/Musk at procedure.
procedure. This isis not
not
discus sed by
discussed by either
either Raghavan or Boe, et al., probab probably
ly
becaus
becausee the Evinger/Muskat method already existed and would
the Evinger/Muskat would
lessen
lessen the
the appare
apparent nt signifi
significance
cance ofof their work.
work.
Paper
Paper Ik.7
A.7 sugges
suggests ts an
an alterna
alternative method for
tive method for calcula
calculating the
ting the
buildu
buildupp m(p)
m(p) functio
function n i.e. , applyi
i.e., applyingng the Martin
the Martin
saturat ionpressure relatio
saturation-pressure relation during buildu
n during buildup. p. This is
This is
suppor ted theoret
supported theoretically
ically by by arguin
arguing that pressu
g that pressure gradient
re gradient at at
the
the wellbo
wellborere isis zero
zero during
during shutin.
shutin. The The differe
difference between
nce betwee n
Ragha vans buildu
Raghavan's buildup p proced
procedure (equivalent
ure (equiv alent toto the
the consta
constant GOR
nt GOR
Evinge r/Muskat assump
Evinger/Muskat assumption) and the
tion) and the one
one based
based on on Martin
Martin's
s
saturat ion relatio
saturation relation is not
n is not discus
discussed.
sed. It It was
was found
found inin extra
extra
simula tions during
simulations during our our work
work onon paper
paper /.7
A.7 that
that the
the buildu
buildupp
proced ure is
procedure is not
not exact,
exact, asas might
might be be inferre
inferred from results
d from results wewe
presen
present.t. This
This is is despite
despite the the correct
correct calcula
calculation
tion of of
saturat ion at
saturation at all
all points
points inin thethe reservo
reservoir during buildu
ir during buildupp
using
using the the Martin
Martin relatio
relation.
n. Apparently
Pppare ntly the the theory
theory of of
superp osition
superposition has
has its its limitat
limitations
ions when using
when using the the
pseudo pressure functio
pseudopressure function, which itself
n, which itself isis only
only an an approx
approximate
imate
lineari zation of
linearization of the
the diffusi
diffusivity equation.
vity equatio n.
Pn
An interes ting feature
interesting feature ofof the
the Evinge
Evinger/Muskat constant
r/Muskat consta GOR
nt GOR
method
method is
is that
that saturat
saturation
ion is is not
not directl
directly involved
y involv ed inin the
the
calcula tions.
calculations. The
The relativ
relative permeability
e permea relation
bility relatio which isis
n which
import ant is
important is oil
oil relativ
relative permeability
e permea bility asas aa functio
function
n ofof
gas/oil
gas/oil relativ e permea
relative permeability ratio. The
bility ratio. The form
form of
of this
this
functio n, examp
function, les of
examples of which
which can
can bebe found
found inin the
the origina
originall

124

Evinger/Mu
Evinge skat
r/Musk at work and paper A.8, does not vary
consi
considderab ly for various rock types.
erably types . ivably the
Conceivably
on could be determined
relatiion
relat from produ
produc ction
tion data, and
perhapss with less accur
perhap accuraacy,
cy, from well test data. Equations
Equati ons
given in the previous sectio sectionn (drain
(draina age
ge funct
functio ions)
ns) can be
krg/k ro
te a seriess of krg/kro
generaate
used to gener versu
versus s k
kro
ro curve
curvess for
ndentt of how the relat
Independen
values of AA and Sm. Indepe
various values
on
relatiion
d be the same relati
relat on
ion which is used
is obtained, it shoul should
mater ial
for materi balance
al balanc e calcula tionss for the entiree reservoir.
calcu lation
It is unlik
unlike ly that indiv
ely idual
individ curvess for speci
ual curve specifi c wells can
fic
be determined, and moreover the tI pseud
pseudo opres
pressu sure
re approaach
appro ch
dered
ered an exact solut
solutioion,
n, but merely aa
shoul
should d not be consi
consid
answerr
obtainn a betterr answe
means to obtai than if press
pressu ure
re alone had
been used.

What can be concluded from this discu sion,, as is state


discusssion stated d in
paper A.8, is that the origi origina nal l Eving
Evinge er/Mu skat
r/Musk at metho d of
ng satur
relatiing
relat ion to press
ation
saturat pressu ure
re is reliab
relia le
ble for evalu
evalua ating
ting
pseudopres
the pseudo sure
pressu function
re functio n used for interpretation of test
data from drawdown and buildup in wells produc ing from
producing
ed reservoirs
satur ated
saturat . Resul
Result ts
s shoul
should d be as accur
accura ate
te as
calcu
calcula ted using metho
lated ds propo
propos sed
ed by Ragha van and Boe,
Boe,
infin ite-ac
ale during infinite
et al.
at ting
actin g and deple
depletition.
on. Once more,
s that had Muskats
appearrs
it appea contr ibutio
t' s contrib utionsns been consi
consid dered
ered
more serio usly,
serious ly, that consi
consid derab
erable le time and effor t (and
ical simul
numerical
many numer simula ation s) had been saved.
tions) saved.
125
125

3.4 Deliverability Performance Using Multirate Testing


As mentioned in the introduction, Darcy's
Darcys law is not
applicable when fluids flow at very high velocities.
Recalling the expression for velocity (Eq. 3.2) but written
in terms of radial/cylindrical geometry, we have

= (k/~)dp/dr
vv = = (k/~r)6P/ln(re/rw)
(k/p)dp/dr = (k/pr)p/ln(re/rw) (3.18)

where 6p
p represents the pressure drop between external
radius, rre,
e , and the radius to the wellbore,
weilbore, rw.
r. Two
observations can be made: first, high velocities result for
low viscosities, and second, high velocities occur at small
radii. On the average, gas viscosities are two orders of
magnitude less than oil viscosities (e. g., D.
(e.g., Dl vs 11 cp).
0.01
We should therefore expect high velocity flow and subsequent
breakdown of Darcy's
Darcys law for gases flowing near the
wellbore.
weilbore. This is, in fact, what has been observed in
experimental studies and field production testing.
Recently, Fetkovich has shown that high velocity flow (HVF)
also occurs in oil wells producing at high rates.

Traditional well testing has several purposes, including the


determination of deliverability. That is, given an
allowable pressure drop in the reservoir - dictated by

well bore and surface transportation -


factors between the welibore

what rate will result. Darcy's law is applicable, then


If Darcys
surface rate, q, equals velocity multiplied by area
perpendicular to flow, A=2irrh,
A=2nrh, divided by a conversion
factor, B, relating volume at reservoir conditions to volume
at surface conditions,

qq = vA/B
= 2nkh6P/~Bln(re/rw)
vA/B == 21rkhp/iiBln(re/rw) (3.19)
(3.19)

Depending on whether steady state or pseudosteady state


conditions are considered,
conditions considered, Ap
6p represents pressure drop
between the external reservoir pressure, Pe
between Pe' or
or average
reservoir pressure,
reservoir pressure, PR
PR, and wellbore flowing pressure,
pressure, Pwf
Pwf,
respecti vely; for aa given test,
respectively; test, however,
however, this
this distinction
distinction
is not
is not really important.
important.
The first observation to
The to make about Eq.
Eq. 3.19
3.19 is
is that aa plot
plot
of rate, q,
of q, versus
versus pressure
pressure drop, Ap,
6p, should
should result
result in aa
126
126

straight line
straight line with
with slope
slope proportional
proportional toto the
the permeability
permeability
thickness product,
thickness product, kh.
kh. This
This suggests
suggests that
that aa single
single rate
rate
test, producing
test, producing long
long enough
enough toto reach
reach steady
steady oror pseudosteady
pseudosteady
state conditions,
state conditions, will
will provide
provide the
the information
information necessary
necessary to
to
predict rate
predict rate at
at other
other pressure
pressure drops.
drops. This
This concept
concept isis used
used
extensively by
extensively by Muskat
Muskat and
and other
other early
early reservoir
reservoir engineers,
engineers,
and it
and it has
has been
been termed
termed productivity
productivity index,
index, 3=q/Lp.
J=q/6p.
It was
It was soon
soon realized
realized that
that the
the effect
effect ofof high
high velocity
velocity flow
near the
near the wellbore
wellbore causes
causes problems
problems in in applying
applying productivity
productivity
index to
index to gas
gas wells. In In practical
practical terms,
terms, the
the rate predicted
predicted
by the
by the relation
relation q=JAp
q=J6p where
where 3J isis determined
determined at
at rate, qql,
,
1
and pressure
and pressure drop, Ap 6p 1, is
,
1 is too large
large ifif the new pressure
pressure
drop, Ap
,
26P2, is
is larger
larger than
than Pl6Pb and too too small ifif the new
new
pressure drop is smaller
pressure smaller than Pi 6P1. By applying the
Forscheimer equation
Forscheimer equation (Eq.
(Eq. 3.3),
3.3), aa new relation can can be
be
surface flow rate,
written for surface

qq =
= 2nkh6p/~B{ln(re/rw)+Oq}
2irkhp/jiB{ln(r/r)+Dq} (3.20)

where 0D is a constant dependent on rock and fluid


properties. Unfortunately, Eq. 3.20 is nonlinear in rate.
Practical experience shows that a good approximation is,

qq ~ J'(6p)n
J(ApY (3.21)

where exponent nn represents the correction for Oq.


Dq. If 0
D is
large then n approaches
n 0.5, and for small 0, n
D, n approaches
1.0 and Darcy's
Darcys law is valid.

The essential difference between the relation q=J6p


q=Jp and Eq.
3.21 is the first has only one unknown, J,
3, whereas the
second
second has two unknowns, J'
3 and n. The logical result is
that at least two rates are needed for wells experiencing
HVF. Usually the reservoir engineer requests more than two
rates during a production test to bo ensure accurate
determination of the two constants.
The most common multirate tests are true isochronal,
flow-after-flow
flowafter--flow (FAF),
F),
1
(FP and modified isochronal. An
isochronal test, as suggested
suggested by the name, produces a well
for
for aa specified
specified period, 6t,
t, followed
followed by an
an extended
extended shut in
shutin
until
until pressure
pressure builds
builds up
up to
to its
its original
original value,
value, repeats
repeats
127
127

production at at aa different
different rate
rate for
for the
the same
same length
length ofof time,
time,
t, repeats
6t, repeats another
another extended
extended buildup,
buildup, and
and so
so on.
on. Four
Four rates
rates
and three
and three buildups
buildups are
are common,
common, the
the last
last rate
rate usually
usually being
being
produced long
produced long enough
enough to reach pseudosteady
pseudosteady state
state flow.
flow. It
It
can be shown
can shown forfor a true
true isochronal testtest that
that production
periods dodo not
not need to to be the same length,
length, only
only that the
pressures chosen for for analysis occur at the same time after after
start
start of the flow period. Since
Since transients from from previous
flows and buildups should,
flows should, theoretically, disappear before
the next flow starts, it does not matter if the rates are
increasing or decreasing (time for transients to die out is
not dependent on the rate, only the length of the flow
period).
period)
flowafterflow test should only be run if,
The flow-after-flow if, during each
flow period, pseudosteady state is reached. The analysis is
not dependent on the length of each test or if rates
increase or decrease. This type of testing is seldom
applicable unless the reservoir formation has high
permeability and/or limited drainage area and surrounding
producers.
The modified isochronal test was suggested to eliminate the
long buildup periods often required by true isochronal
tests. The length of buildup is aa strong function of
permeability
permeability,, and therefore many tight gas reservoirs
requires excessive shut in periods (equivalent with lost
shutin
production
production revenue) to obtain
obtain deliverability performance.
The
The modified test is based on an approximation of the
superposition principle. suggests
Work i have completed suggests
that the approximate
that approximate nature of the modified
modified isochronal
isochronal test
test
has
has validity
validity if
if flow is
is radial
radial (i.e.,
(i.e., Eq.
Eq. 3.4
3.4 applies)
applies) but
but
that
that problems
problems arise
arise when
when flow is
is linear
linear or
or in
in transition
transition
between
between linear and
and radial
radial flow.
Modified
Modified isochronal
isochronal testing
testing is
is identical
identical to
to true
true isochronal
isochronal
testing
testing with
with the
the exception
exception that
that buildup
buildup periods
periods are
are of
of the
the
same
same duration
duration as
as drawdowns,
drawdowns, and
and that
that average
average pressure
pressure used
used
to
to analyzes
analyzes each
each rate
rate is
is the
the pressure
pressure atat the
the end
end of
of the
the
buildup just
buildup just prior to
prior to start
start ofof production
production for
for the
the given
given
rate.
rate.
Paper A.a proposes
Paper P.8 proposes aa loglog
log-log type
type curve
curve and
and generalized
generalized
procedure
procedure for analyzing multirate test
for analyzing multirate test data.
data. It is
It is
applicable
applicable toto oil
oil and
and gas
gas wells
wells and
and has
has the
the advantage
advantage of
of
yielding
yielding the
the value
value ofof D0 directly,
directly, without
without making
making the
the
assumption
assumption inherent
inherent in in the
the traditional
traditional analysis
analysis that
that log(q)
log(q)
vs
vs log(Ap)
log(6p) isis linear
linear for
for all
all drawdowns
drawdowns (Eq.
(Eq. 3.21).
3.21). TheThe
method
method also
also is
is superior
superior toto the
the alternative
alternative (mathematica
(mathematically
lly
equivalent) method
equivalent) method of of plotting
plotting p/q
6p/q versus
versus qq onon linear
linear
paper,
paper, the
the problem
problem with
with which
which isis the
the difficulty
difficulty in in
128
128

conceptualizing
conceptualiz the quantity
ing the quantity Ap/q6p/q and
and shifting the resulting
shifting the resulting
curve due
curve due to
to transient
transient effects.
effects. The
The proposed
proposed method
method plots qq
plots
versus
versus Ap6p on
on log-log
loglog paper,
paper, and
and the
the best-fit
bestfit match
match is
is easily
easily
shi fted
shifted to
to account
account for
for transient
transient changes.
changes. It
It also
also allows
allows
direct
direct graphical
graphical determination
determinatio n of
of absolute
absolute open
open flow
flow
potential,
potential, both
both for
for the
the transient
transient condition
condition and
and stabilized
stabilized
flow.
flow.

3.6 ConstantP
3.6 Constant-Pressure Rate Solution
ressure Rate During Depletion
Solution During Depletion
Traditionally,, solution
Traditionally solution ofof the diffusivity equation
the diffusivity equation
using the
using the constantpr
constant-pressure inner boundary
essure inner condition has
boundary condition has
been equated
been equated with
with Hurst
Hurst and
and van
van Everdingens application to
Everdingen's application to
water influx.
water influx. Interestingly
Interestingly,, their
their historical paper on
historical paper on the
the
subject does
subject does notnot tabulate
tabulate oror present graphically the
present graphically the
dimensionlesss rate
dimensionles rate solution.
solution. This
This isis despite
despite the fact that
the fact that
roots of
roots of the
the Bessel
Bessel function
function which must be
which must solved to
be solved to
determine constantpr
determine constant-pressure rate) are
(cumulative rate)
essure flux (cumulative are the
the
same needed
same needed to to calculate
calculate dimensionles rate. The
dimensionlesss rate. The logical
logical
reasoning for
reasoning for their omission
omission is that the the application of
application of
constant-pressure
constantpr analysis was
essure rate analysis obvious when
was not obvious when the
the
solution
solution was producing wells at that time
was found. Most producing time were
were
regulated, which
regulated, which meant
meant they used only part of the reservoir
energy (pressure drop) available and had no problem with
energy (pressure with
maintaining
maintaining the allowable rates. Also, the energy crisis
lso, crisis
had not occured and only the best reservoirs were produced,
had not
meaning
meaning those with high permeabilities.
permeabilities. Stimulation had not
had not
become
become popular or necessary, and the concept of a well with
well with
an effective dimensionless rDe=re/rw of 10,
dimensionless radius, rDe=re/rw' or
50, or
10, 50,
even
even 100
100 was unheard of. For these reasons it
it was not
not
obvious
obvious that the constant-pressure
constantpressure rate solution had had aa
function.
function.

Today
Today it
it might be guessed that over over half the producing
the wells producing
oil
oil and gas are are produced at a constant bottomhole flowing
constant bottomhole flowing
pressure.
pressure. In
In fact,
fact, anyany well
well requiring stimulation will,
stimulation will,
sooner
sooner or
or later,
later, produce
produce at and
at constant pressure - and probably
constant pressure probably
sooner!
sooner! The
The first
first tabulations of dimensionless rate
of dimensionless
solutions for bounded
solutions for bounded reservoirs
reservoirs appeared
appeared in
in the Russian
the Russian
literature in
literature in the the mid-1950's
mid1950s by
by Tsarevich
Tsarevich and
and Kuranov.
kuranov. They
They
reorganize the
reorganize the original
original analytical
analytical solution
solution of
of Hurst
Hurst and
and van
van
Everdingen, resolve
Everdingen, resolve (and
(and present)
present) the
the first
first five
five roots
roots of
of
the Bessel function
the Bessel function expression,
expression, and
and tabulate/plot
tabulate/plot the
the
results.
results. Since
Since values
values of of the
the roots
roots areare not found in
not found the
in the
Western literature,
Western literature, they
they have
have been
been recalculated
recalculated for
for a
a large
large
number
number of
of dimensionless
dimensionless radii radii andand are
are presented
presented in Table
in Table
3.4.
3.4.
129

The exact solution for dimensionless rate is an infinite


sum of exponential terms,

qo
q == Lz cnexp{-(bn/rOe)2tO},
t0} (3.22)
2
cnexp{(bfl/rDe)
n=1
n =1

and cumulative influx, QO,, which


0
Q is merely fqO(tO)dto
.1q(t)dt
evaluated from 0 to to,
t, given by,

QO =
= (ro e-1)/2 -
(rDel)/2 Lz cn(rOe/bn)exp{-bn/r Oe) 2t O}
cn(rDe/bfl)exp{bn/rDe)
t
2 0}
n =1
n=1
(3.23)
where qO
q is dimensionless rate, q
1( t JllB/kh
q(t)pB/kh(p (Pi -Pwf ) , to
pf), 0 is
t
dimensionless time, kt/~llctrw2,
, and rOe
2
kt/4ctr rDe is dimensionless
external radius, re/rw. Constant b1 1 is the first and
b
smallest root of the equation

Y1(bn)Jo(bn/IDe) J1(bn)Yo(bn/rDe) = 0 .... (3.24)

which results from the exact solution to the


constant-pressure
constantpressure problem originally solved by Hurst.
Constant cn is given by

(bn)
2
2Y1
= (3.25)
1 (b/rjj)
Y

.-
(b
)
1

JO, Jj,
where 0
J
, J1' 0
VO, and Yj,
Y
, V1, are regular Bessel
Bessel functions of
one.
order zero and one.

Not until the late


Not late 1970's
1970 s and early 1980's western
1980 s did the Western
li terature begin
literature begin taking
taking notice of the applications
applications offered
offered
by the constantpressure
by constant-pressure solution. Fetkovich shows that
Fetkovich
constant-pressure production
rate decline resulting from constantpressure production is
is
exponential, an observation made in in the work
work by
by Tsarevich
and Kuranov (and reported by ArpsArp's the same year, based on
field data). Fetkovich also suggests
suggests that the analytical
constant-pressure solution
constantpressure solution be combined with the empirical
Arp's decline equations
Arps equations to form aa powerful
powerful diagnostic tool
tool
relating production and
relating and time - the relation most
most critical
critical to
to
engineering and
engineering and economic
economic considerations.
considerations.
130
130

TABLE 3.4
TABLE 3.4 - FIRST
FIRST FIVE
FIVE ROOTS
ROOTS OF
OF THE
THE BESSEL
BESSEL FUNCTION
FUNCTION EXPRESSIO
EXPRESSIONN
(EQ. 3.24)
(EQ. 3.24) AND
AND THE
THE DIMENSION
DIMENSIONLESS TIME tD*
LESS TIME tD* AT
AT WHICH
WHICH
THE EXPONENT
THE EXPONENTIAL EXPRESSION
IAL EXPRESSIO IS WITHIN
N IS WITHIN 1%1% ACCURACY
ACCURACY..
D:imensionless
DinEnsionles s
Radius
Radius tD* nn bn
bn cn
c::n

1.5
1.5 55.706E-02
.706E02 11 4.334821*00
4.33482E+00 4.41653E+00
4.416531*00
22 1.40172E+01
1.40172E+O 1 4.04006E+O
4.040061*000
33 2.34902E+01
2.34902E+01 4.01428E+00
4.014281*00
44 3.29355E+01
3.29355E+01 4.00721E+0O
4.00721E+OO
55 4.23717E+01
4.23717E+01 4.00416E+0O
4.00416E+OO

2.0
2.0 2.243E-01
2.243E01 11 2.72155E+OO
2.72155E+00 .41705E+00
22.41705E+OO
22 9.29180E+OO
9.29180E+00 .03945E+00
22.03945E+OO
33 1.56283E+01
1.56283E+01 .01407E+00
22.01407E+OO
44 2.19343E+01
2.19343E+O 1 .00724E+O0
22.00724EH-OO
55 2.82301E+01
2.82301E+O 1 .00436E+O0
22.00436E+OO

3.0
3.0 8.729Fr01
8.729E01 11 1.87679El+OO
1.87679E+00 .40979E+00
11.40979E+OO
22 6.91216E+OO
6.91216E+0O .04157E+O0
11.04157E+OO
33 1.16863E+01
1.16863E+01 .01567E+00
11.01567E+OO
44 1.64255E+01
1.64255E+01 .00809E+O0
11.00809E+OO
55 2.11529E+01
2.11529E+O 1 .00370E+O0
11.00370E+OO

4.0
4.0 1.925E+OO
1.925E+00 11 1.57382E+OO
1.57382E+00 .06666E+00
11.06666E+OO
22 6.10644El+OO
6. 10644E-t-00 .10766E01
77.10766Fr01
33 1.03633E+01
1.03633E+O 1 .84021E01
66.84021Fr01
4 1.45823E+O1
1.45823E+01 6 .75872E01
6.75872E-01
55 1.87882E+01 .72357E01
66.72357Fr01

5.0 3.371E+OO
3.371E-t-00 1 11.41180E+00
.41180E+OO 8.90488EO1
8.90488Fr01
2 5.696081*00
5.69608E+00 5 .46042E01
5.46042Fr01
3 9.69592E-1-O0
9.69592E+OO 5 .18995E01
5.18995Fr01
4 1.36560E+01
1.36560E+O1 5 .10351E01
5.10351Fr01
5 1.76020E+01
1.76020E+01 5 .06480E01
5.06480Fr01

6.0 5.201E+OO
5.201E+00 11 1.30843E+OO
1..30843E+0O 7 .81811EO1
7.81811E-01
2 5.44496E+OO
5.44496E+00 4 .46993E01
4.46993E-01
33 9.29138El+OO
9.29138E+00 4.20395Fr011
4.20395E0
44 1.30968E+01
1.30968E+01 4 .11379E01
4.11379Fr01
55 1.68874E+01
1.68874E-1- O1 4 .07239E01
4.07239Fr01

7.0
7.0 7.416E+OO
7.416E-4-00 11 1.23557E+OO
1.23557E+00 7 .07293E01
7.07293Fr01
22 5.27416E+OO
5.27416E+00 3 .81835E01
3.81835Fr01
33 9.01868E+OO
9.01868E+00 3 .54910E01
3.54910Fr01
44 1.27214E+01
1.27214E+01 3 .45626E01
3.45626Fr01
55 1.64087E+01
1 .64087E+O1 3 .41263E01
3.41263Fr01

8.0
8.0 1.001E+01
1.OO1E+O1 11 1.18079E+O0
1.18079E+OO 6 .52581EO1
6.52581Fr01
22 5.14964E+OO
5.14964E+0O .35051EO1
33 .35051E-01
33 8.821411*00
8.82141E+0O 3 .09227E01
3.09227E-01
44 1.24512E+01
1.24512E+01 2 .98809E01
2.98809Fr01
55 1.60650E+01
1.60650E+01 2 .94271E01
2.94271E-01
131

TABLE 3.4 continued

Dimensionless
Diirnsiori1ess
Radius tn* n bn cn
en

10.0 1.631E+01
1 .631E+01 1 1.10269E+OO
1 .10269E+0O 5.76811EH>1
5 .76811E01
2 4.97885E+OO 2.72455EH>1
2.72455E01
3 8.55430E+OO
8.55430E+0O 2.48732E-01
2.48732E01
4 1.20868EH-01
1.20868E+O1 2.36630EH>1
2.36630E01
5 1.56029EH-01
1 .56029E+01 2.31845EH>1
2.31845E01

12.0 2.410EH-01
2.410E+O1 1 1.04869EH-OO
1.04869E+00 5.26121E-01
5.26121EO1
2 4.86589E+OO
4.86589E+O0 2.32426EH>1
2.32426E01
33 8.37994E+OO
8.37994E+O0 2.06639EH>1
2.06639E01
4 1.18509EH-01
1.18509E+01 1.97230EH>1
1.97230E01
55 1.53052EH-Ol
1.53052E+01 1.92306EH>1
1.92306E01

14.0 3.335EH-01
3.335E+O1 1 1.00849E+OO
1.00849E+O0 4.89355EH>1
4.89355E01
22 4.78479E+OO 2.04509EH>1
2.04509E01
33 8.25629E+OO
8.25629E+00 1.79797EH>1
1.79797E01
4 1.16847EH-Ol
1 .16847E+01 1.7002SE-01
1 .70025E01
5 1.50963EH-01
1.50963E+01 1.65046EH>1
1.65046E01

16.0 4.407EH-01
4.407E+01 1 9.77006E-ol
9.77006E01 4.61214EH>1
4.61214E01
22 4.72322E+OO
4.72322E+O0 1.83868EH>1
1.83868E01
3 8.16353E+OO
8.16353E+O0 1.59684EH>1
1.59684E01
4 1.15607EH-01
1.15607E+01 1.SOlllEH>1
1.50111E01
5 1.49411EH-01
1.49411E+01 1.45062EH>1
1.45062EO1

18.0 5.623EH-01
5.623E+01 1 9.51463E-Ol
9.51463E01 4.38822E-ol
4.38822E01
22 4.67459E+OO
4.67459E+O0 1.67935EH>1
1.67935E01
33 8.09076E+OO 1.44369EH>1
1.44369E01
4 1.14642EH-01
1 .14642E+O1 1.34899EH>1
1 .34899E-01
5 1 .4820BEH-01
.48208E+O1 1.29863EH>1
1 .29863E01

20.0 6.982EH-01
6 .982E+O1 1 9.30177EH>1
9 .30177E01 4.20469EH>1
4 .20469E01
2 4.63500E+OO
4.63500E+00 1.S5234EH>1
1.55234EO1
3 8.03207E+OO
8.03207E+O0 1.32157EH>1
1.32157E01
4 1.13867EH-Ol
1.13867E+01 1.22888EH>1
1.22888E01
5 1.47244EH-01.
1.47244E+O1. 1.17876EH>1
1.17876E01

25.0 1.101EH-02
1.1O1E+02 1 8.89299EH>1
8.89299E01 3.86060EH>1
3.86060E01
22 4.56145E+OO 1.32353EH>1
1.32353E01
3 7.92432EH-OO
7.92432E+O0 1.10579EH>1
1.10579EO1
4 1.12455EH-01
1.12455E+O1 1.01S70EH>1
1.01570EO1
5 1.45500EH-Ol
1 .45500E+O1 9.66404EH>2
9 .66404E02

30.0 1.592E+02 1 8.59514EH>1


8.59514E01 3.6171SEH>1
3.61715E01
2 4.51000E+OO 1.16972EH>1
1.16972E01
33 7.85018E+OO
7.85018E+00 9.6193SEH>2
9.61935E02
4 1.11493EH-Ol
1.11493E+01 8.75311EH>2
8.75311E02
5 1.44318EH-01
1.44318E+O1 8.27094EH>2
8.27094E02
132
132

TABLE 3.4
TABLE 3.4 continued
continued

Di.trensionless
Dinnsi on1ess
Radius
Radius tn* nn hi
bn cn
en

40.0
40.0 2.837E+02
2.837E+02 11 8.17934Fr01
8.17934E0 1 3.28786E0 1
3.28786Fr01
22 4.44127E+OO
4.44127E+00 9.73492E0
9.73492Fr022
33 7.75275E+OO
7.75275E+00 7.81798E--0
7.81798Fr022
44 1.10243E+01
1.10243E+01 7.00636E0 2
7.00636El-02
55 11.42797e+01
.42797E+01 .54739E02
66.54739El-02

50.0
50.0 44.429E+02
.429E+02 11 77.89445Fr01
.89445E01 .06991E01
33.06991Fr01
22 4.39638E+OO
4.39638E+00 8.51618E0 2
8.51618El-02
33 7.69032E+OO
7.69032E+00 6.72065E0 2
6.72065El-02
44 1.09451E+01
1.09451E+01 5.95321E0
5.95321E-022
55 11.41842E+01
.41842E+01 .51553E02
55.51553Fr02

100.0
100.0 1.749e+03
1.749E+03 11 7.16692E-01
7.16692E0 1 2.54234E0 1
2.54234El-01
22 4.28994E+OO
4.28994E+00 5.86124E0
5.86124Fr022
33 7.54643E+OO
7.54643E+00 4.40421E0
4.40421Fr022
44 1.07663E+01
1.07663E+01 3.77283E0
3.77283Fr022
55 1.39720E+01
1.39720E+01 3.40733E0
3.40733Fr022

200.0
200.0 6.844E+03
6.844E+03 11 1
6.60753El-01
6.60753E0 2.16711E0
2.16711Fr011
22 4.21634E+OO
4.21634E+00 4.25008E0
4.25008Fr022
33 7.45082E+OO
7.45082E+00 3.06613E02
3.06613Fr02
4 1.06510E+01
1.06510E+01 2,55277E0
2.55277Fr022
55 1.38382EH-01
1.38382E+01 2.25461E0
2.25461Fr022

500.0 4.130EH-04
4.130E-f04 1 6.03471E01
6.03471E-01 1.81181E01
1.81181Fr01
2 4.14842E+OO
4.14842E+0O 2.95441E02
2.95441Fr02
3 7.36585E+OO
7.36585E+00 2.04155E02
2.04155Fr02
4 1.05512E+01 1.64977E02
1.64977El-02
5 1.37249E-f-01
1.37249E+01 1.42285E02
1.42285El-02
1000.0
1000.0 1.605E+05
1 .605E+05 11 5.68803El-01
5 .68803E01 1 .61125E01
1.61125Fr01
22 4.11089E+OO
4.11089E+00 2.32612E02
2.32612El-02
33 7.32030E+OO
7.32030E+00 1.56657E02
1.56657El-02
44 1.04989E+01
1.04989E+01 1.24338E02
1.24338El-02
55 1.36667EH-01
1.36667E+01 1.05721E02
1.05721El-02
2000.0
2000.0 6.238EH-05
6.238E+05 11 5.39461E01
5.39461E-01 1.45044E01
1.45044El-01
22 4.08123E+OO
4 .08123E+00 1 .87680E02
1.87680El-02
33 7.28503E+OO
7.28503E+00 1.23717E02
1.23717El-02
44 1.04591E+01
1.04591E+01 9.67663E03
9.67663El-03
55 1.36228E+01
1.36228E+01 8.13277E03
8.13277El-03
4000.0
4000.0 2.424E+06
2..424E+06 11 5.14223E01
5.14223Fr01 1.31865E01
1.31865El-01
22 4.05722E+OO
4.05722E+00 1.54506E02
1.54506Fr02
33 7.25699E+OO
7.25699E+00 1.00054E02
1.0oo54Fr02
44 1.04278E+01
1.04278E+01 7.73025E03
7.73025Fr03
55 1.35887E+01
1.35887E+01 6..43498E03
6.43498Fr03
133
133

TABLE
TABLE 3.4
3.4 continued
continued

Diirnsion1ess
Dimensionless
Radius
Radius tn nn tn
bn en
cn

10000.0
10000.0 1.458E+07
1.458E+07 11 4.85704E-01
4.85704E01 1.17711E-01
1 .17711E01
22 4.03172E+OO
4.03172E+00 1.22540E-02
1 .22540E02
33 7.22776E+OO
7.22776E+0O 7.78092E-03
7 .78092E03
4 1.03954E+01
1.03954E+01 5.93389E-03
5 .93389E03
55 1.35538E+01
1.35538E+O1 4.88921E-03
4 .88921E03

25000.0 8.780E+07
8.780E+07 11 4.61458E-01
4.61458E01 1.06288E-01
1 .06288E01
2 4.01137E+OO
4.01137E+00 9.95097E-03
9 .95097E-03
3 7.20473E+OO
7 .20473E+00 6.21915E-03
6 .21915E03
4 1.03703E+01
1.03703E+O1 4.69244E-03
4 .69244E03
5 1.35269E+01 3.83470E-03
3 .83470E03

100000.0 1.330E+09 1 4.30803E-01


4. 30803E01 9.26732E-02
9 .26732E02
2 3.98738E+OO
3.98738E+00 7.52598E-03
7 .52598E03
3 7.17803E+OO
7.17803E+00 4.61482E-03
4 .61482E03
4 1.03415E+01 3.43797E-03
3 .43797E03
5 1.34963E+01 2.78251E-03
2 .78251E03

250000.0 8 .024E+09
8.024EHl9 1 4.13591E-01
4.13591E01 8.54380E-02
8 .54380E02
22 3.97474E+OO
3.97474E+00 6.37797E-03
6 .37797E03
33 7.16415E+OO
7.16415E+00 3.87056E-03
3 .87056E03
4 1.03267E+01 22.86469E-03
.86469E03
55 1.34807E+01
1.34807E+01 2.30682E-03
2 .30682E03

1000000.0
1000000.0 11..219E+11
219E+ll 11 3.91084&-01
3.91084E01 77.64036E-02
.64036E02
22 3.95909E+OO
3.95909E+00 55.08188E-03
.08188E03
33 7.14712E+OO
7.14712E+00 33.04481E-03
.04481E03
4 1.03086E+Ol.
1.03086E+0] 22.23491E-03
.23491E03
55 1.34617E+01
1.34617E+01 11.78848E-03
.78848E-03
134
134

Unfortunately
Unfortunatel y the new
the new interes
interest t in constantpr
in essure
constant-pressure
solutions
solutio ns is
is still
still in
in aa stage
stage of
of infancy,
infancy, being
being mainly
mainly used
used
by
by theoreticians
theoret icians as
as aa new
new field
field wi thin
within which
which to
to publish
publish..
The most
The most obvious
obvious applica
applications
tions of of constantpr essure and
constant-pressure and
decline
decline curve
curve analysis
analys is reported
reporte d in
in the
the recent
recent literatu re
literature
have been
have been attacked
attacked with with threedimen
three-dimensional sional simula
simulators, not
tors, not
even first
even first having
having plotted
plotted ratetime
rate-time data data on on loglog paper to
log-log paper to
satisfy
satisfy their
their preconceived
preconceived opinions
opinions that
that decline
decline curve
curve
analysis
analys is, as
is is, as stated
stated by by Nind,
Nind, merely convenience, aa
II merely aa convenience,

method that
method that is is amenable
amenable to to mathematica
mathematical l or or graphical
graphical
treatment,
treatm ent, andand has
has nono basis
basis in in physical
physical laws governing the
laws governing the
flow of
flow of oil
oil andand gas
gas through
through the the formation.
formation."

3.6 Partial Penetr


3.6 Partial Penetration Effects on
ation Effects on Fluid
Fluid Flow
Flow
One of
One of the
the most
most common
common reducti ons in
reductions in produc tivity is
productivity is
due to
due to partial
partial penetra
penetration, which results
tion, which when the producing
results when the producing
intervall of
interva of aa well
well constit
constitutes only aa fractio
utes only fraction the total
of the
n of total
contributing
contrib uting (pay) thickn
(pay) thickness.
ess. Reasons for partial
Reasons for partial
penetration
penetra include:
tion includ e:

avoiding and gas


avoiding water and gas coning
coning
avoiding intervals
avoiding interva with weak
ls with weak mechanical rock proper
mechanical rock ties
properties
lost hole due to mechanical problems
lost
selective testing during explor
selective production testing ation
exploration
poor
poor log
log interpretation
interpretation by the service company
company
inability liquids
inability of air rigs to drill while producing liquids
malfunction of the perforating
perforating gun

The partialpenetration problem is one which has


The partial-penetration been
has been
studied
studied and solved for many years. Muskat presented one of
one of
the
the first
first solutions
solutions in 1927 for the analogous problem of
problem of an an
electrode
electrode partially
partially penetrating
penetra ting a large cylindrical
a large cylind rical
conducting
conducting disk; Kozeny gave the problem problem aa slightlyslightly
different
different treatment in 1933, resulting in a simple and
in 1933, resultin g in a simple and
useful
useful expression
expression for for partial penetration skin (or its
partial penetra tion skin (or its
equivalent,
equivalent, which didn't
didnt have
have a
a name
name then).
then). These
These earlies
earliest t
solutions
solutions assume
assume steady
steady state
state flow, and only later - first
flow, and only later first
with
with numerical
numerical solutions
solutions and and later analytically - did
later analytically did the
the
transient problem receive
transient problem receive attention.
attentio n. For
For practical
practic al purposes
purposes
it
it is
is the
the steady
steady state
state solution
solution whichwhich is important since
is important the
since the
transient effects
transient effects die
die out
out extremely
extremely early,
early, with
with the
the possib
possiblele
exceptions of low-permeability
exceptions of lowpermea bility reservoirs
reservo irs or
or infinte simal
infintesimal
penetration.
penetration.
135
135

Probably because
Probably because the problem
problem isis so obvious
obvious and
and has
has such
such
profound
profound practical implications
implications - so
so much
so that
that even
even
theoreticians see
see them
them - itit has received
received more attention
attention than
it really merits. Consider, for example,
Consider, example, what
what is
is most
cOlmlonly
commonly referred to in
in the
the petroleum
petroleum 11 terature
literature as the
as
first solution for partial penetration skin: Brons and
Marting's results based an
Martings on aa numerical
numerical solution
solution of Nisle
Nisle'ss
analytical solution.
approximate analytical purpose was to
Their purpose
propose aa simple
propose simple relation for skin,
skin, expressed as

s = (l/bl){ln(h/r)C(b)}
= (l/b-l){ln(h/rw)-G(b)} (3.26)
(3.26)

where G(b) is a function of b


"where b (the fraction of the total
formation, h, penetrated by the well). Since this function
cannot be expressed analytically, it has been calculated
numerically for a range of bb values.
... values.II

If we now move back to Muskat's


lf Muskats solution some 30 years
earlier, we can rearrange (Eq. 66 in Physical Principles
of Oil Production) and derive the analytical expression
for G(b),
0(b),

G(b)
0(b) = M/2(1-b)
= M/2(lb) - In(4)
ln(4) (3.27)

where
M = exp{r{0.875b)r{0.125b)/r{
M = 1-0.875b)r{ 1-0.125b)}
exp{IO.875b)rO.l25b)/fll-O.875b)fllO.125b)}

(3.28)
...

and r{x)
flx) is the gamma function of x. Table 3.2
compares numerical values of G(b)
0(b) with analytical values.
136
136

TABLE 3.2
TABLE 3.2 - COMPARIS
COMPARISON
ON OFOF ANALYTIC
ANALYTICAL AND
AL AND
NUMERICAL
NUfrERICA VALUES OF
L VALUES OF THE
THE PARTIAL
PARTIAL
PENETRATION
PENETRAT FACTOR G(b).
ION FACTOR G(b).
G(b)
G(b)

Brons/
Brons/ Muskat
Muskat MM
bb Marting
Marting (3.27)
(3.27) (3.28)
(3.28)

0.1
0.1 2.337
2.337 2.337
2.337 6.7022
6.7022
0.2
0.2 1.862
1.862 1.862
1.862 5.1966
5.1966
0.4
0.4 1.569
1.569 1.569
1.569 3.5470
3.5470
0.6
0.6 1.621
1.621 1.620
1.620 2.4051
2.4051
0.8
0.8 1.995
1.995 1.992
1.992 1.3507
1.3507

Brons and
Brons and Marting
Marting state
state that the
the Muskat
Muskat solution
solution (and
(and their
their
form using
form using G(b))
G(b)) is
is only
only valid ifif the ratio h/rw
h/rw is not
is not too
too
small; the
small; the quantity
quantity should actually
actually be Ikh/kv h/r w,, and
be /kh/kvTh/rw and aa
minimum value
minimum value of
of 50 marks the point when Eq. 3.27 3.27 can be be
used. Considering
used. Considering the extreme case when Ikh/ky=1 (usually
/kh/kv=1 (usually aa
realistic value
realistic value is about 3) 3),, rw=O.S very large
rw=O. 5 feet l(aa very large
wellbore)
welibore) suggests
suggests that the total thickness of the reservoir
reservoir
can not
can be less than 25 feet. The limitation is obviously
not be
of
of little
little importance since reservoirs with thicknesses less less
than
than 25 feet probably never have partial penetration
penetration
problems!
problems!

Eqs. 3.27 and 3.28 provide the analytical solution to


Eqs. 3.27 to
partial
partial penetration skin as formulated by Brons and Marting.
Marting.
The
The form
form is general and easy to solve, solve, requiring onlyonly
four values
four values of the gamma function. And most of all, the
solution
solution came from Muskat some
some fifty years ago, desguised
in
in aa form so close to the present-day
presentday skin factor that it it
boggles
boggles the mind.
mind.
137
137

NOMENCLATURE
NOMENCLPJURE

an
a = root
root
= of
of the
the Bessel
Bessel function
function expression
expression
resulting
resulting from
from solution
solution of
of the diffusivity
the diffusivity
equation
equation assuming
assuming constant
constant rate
rate production
production

A=
= area
area perpendicular
perpendicular to
to flow
flow

bbnn == root
root of
of the
the Bessel
Bessel function
function expression
expression
resulting from solution
solution of
of the diffusivity
diffusivity
equation
equation assuming
assuming constant wellbore
flowing
flowing pressure
pressure

b = fraction
= of the formation penetrated and
open to flow
B =
B = constant in the Forcheimer equation;

=
= formation volume factor, res/std volume

Bo
0
B = oil formation volume factor, res/std volume
=

cn = constant in the dimensionless


= dimensionless rate solution

C
C =
= constant defining Darcy's
Darcys law;
=
= constant defined by Muskat, equivalent to
skin factor;
=
= trapping constant in Corey/Burdi
Corey/Burdine
ne
relative permeability relations

Ct
ct = initial
= total rock
initial or
or
compressibility
plus fluid compressibil
average reservoir
average
at
ity at
reservoir pressure
pressure
D,E,F,G,H
D,E,F,G,H =expressions
=arbitrary constants
arbitrary constants in
in the
the general
general
expressions for pressure drop
for pressure drop
exp(x)
exp(x) eX
= ex
Ei(x)
-Ei(-x) =exponential
=exponential integral of
integral of xx
G(b)
G(b) =analytical
=analytical expression suggested
expression suggested by
by Brons
Brons
and Marting
and Marting for
for relating
relating partial
partial penetration
penetration
ratio, b,
ratio, b, to
to skin
skin effect
effect
hh =total
=total reservoir
reservoir thickness
thickness
3J = productivity
= productivity index,
index, =q/tp
=q/6p
J'
3 =constant
=constant in
in the
the approximate
approximate rate
rate equation
equation
for wells
for wells experiencing
experiencing high
high velocity
velocity flow,
flow,
approaching 3J as
approaching as nn approaches
approaches 11
138
138

JO,Jl,YO,Yl =regular
= regular Bessel functions of
Bessel functions of order and 11
order 00 and
kk = =absolute
absolute permeability
permeability
kair
kair =permeability
=permeability to
to air
air
kh/kv
kh/kv =ratio
=ratio of
of horizontal
horizontal to
to vertical permeability
vertical permeability
kox,kgx =effective
=effective permeability
permeability to nonwetting phase
to nonwetting phase
(oil or
(oil or gas)
gas) in
in aa twophase, oil/water or
two-phase, oil/water or
gas/water system
gas/water system atat irreducible
irreducible water
water
saturation
saturation

krw,kro,krg
krw,kro,krg =relativ
=relative permeabilities
e permeabilitie to water,
s to water, oil,
oil,
and gas
and gas phases,
phases, respectively
respectively
krx
krx =relativ
=relative permeabiliaty at
e permeabiliaty at kkox (or
0 (or kgx)
kgx )
kw,ko,kg
kw,ko,kg =effective
=effective permeabilitie
permeabilities
s to water, oil,
to water, oil,
and gas
and gas phases,
phases, respectively
respectively

LL = length
length traversed during
= during flow
m(p) = oil
oil pseudopressu
= pseudopressure
re function

MM = factor relating G(b) to its analytical


=
expression given by Muskat
nn = exponent in the approximate rate equation
=
for wells experiencing high velocity flow,
= 0.5 for turbulence-dominated
= turbulencedominated flow
= 1.0 for laminar, Darcy flow
=

PO
PD = dimensionless
= dimensionless pressure

6p = pressure drop causing flow


= flow

PR
PR = average
average
= reservoir pressure
pressure

Pwf
Pwf = wellbore
wellbore flowing
= flowing pressure
pressure

qO = dimensionless
dimensionless rate
= rate

QO = dimensionless
dimensionless cumulative
= cumulative rate
rate or flux
or flux

qq = volumetric
volumetric flow
= flow rate
rate

rr = radius
radius from
= from well
well centerline
centerline

re
re = external
external radius
= radius defining
defining no- boundary
flow boundary
noflow
139
139

rO
rD == dimensionless
dimensionless radius,
radius, =r/rw
=r/rw

rOe
rDe =
= dimensionless
dimensionless external
external radius,
radius, =re/rw
=re/rw

rw
r =
= wellbore
welibore radius
radius

rw' == apparent
apparent wellbore
wellbore radius,
radius, different
different from
from
the
the true
true value
value to
to skin
skin effects
effects

ss == skin
skin factor,
factor, equivalent
equivalent to aa dimensionless
dimensionless
pressure drop
pressure

geF =
SgeF
5 = effective
effective free
free gas
gas (nonwetting-phase)
(nonwettingphase)
saturation

Siw
Sj == irreducible water (wetting-phase)
(wettingphase)
saturation

Sm
S == Corey
Corey saturation variable

SUM =
= expression for a sum of Bessel functions

Sw,So,Sg = saturations of water, oil, and gas phases,


=
respectively
Swe,Soe,Sge =
= effective saturations of water, oil, and
gas phases, respectively

Swi == initial
initial water
water (wettingph
(wetting-phase) saturation
ase) saturation

tt = time
= time
to
tD = dimensionles
= dimensionlesss time
time
vv = velocity
= velocity
r(x)
rtx) = gamma function
= gamma function of
of xx
, == porosity,
porosity, fraction
fraction of
of bulk
bulk volume
volume
~ = dynamic
= dynamic viscosity
viscosity
AA== pore
pore size
size distribution
distribution factor
factor
140
140

REFERENCES:
REFERENC Chapters 11 and
ES: Chapters and 22

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GPA
Tulsa, Oklahoma
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142
142

Schmidt, C.
Schmidt, G. and
and Wenzel,
Wenzel, H.:
H.: A
"A Modified
Modified van
van der
der Waals
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ci. (1980)35,150 31512.

Smith, R.L.
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1408-1414.
14081414.

Soave, C.:
Soave, G.: Equilibrium
"Equilibrium Constants from aa Modified
Constants from Modified
Redlich-Kwong
RedlichKw ong Equation
Equation of
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State, Chem.Eng.Science
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cience (1972)27,
1197-1203.
1197-1203.

Spencer, C.F.
Spencer, C.F. and
and Daubert,
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T.E.: A
"A Critical
Critical Evaluation
Evaluation of
of
Methods
Methods for the
the Prediction
Prediction of
of Critical
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of
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(May 1973)19,3,48
1973)19,3,482-486.
2486.

Standing, M.B. and


Standing, M.B. and Katz,
Katz, D.L.:
D.L.: Density
"Density of
of Natural
Natural Gases,
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Trans. AIME
Trans. AlME (1942)146,14
(1942)146,140-149.
0149.

Standing, M.B.
Standing, M.B. and
and Katz,
Katz, D.L.:
D.L.: Density
"Density of
of Crude
Crude Oils
Oils
Saturated with
with Natural Gas,
Gas," Trans.
Trans. AIME
AlME (1942)146,15
(1942)146,159-165.
9-165.

Standing, M.B.
Standing, M.B. and
and Katz,
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uid Equilibria of
Natura! GasCrude
Natural Gas-Crude Oil Systems,
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Usdin, E. and McAuliffe,


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143
143

REFERENCES:
REFERENCES: Chapter
Chapter 33

rps, J.
Arps, J.: ..1nalysis
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144
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171176. ---
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A.1-1
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The Accuracy of PVT Parameters Calculated


From Computer Flash Separation at Pressures
Less Than 1,000 psia
0.S. Glasb,, SINTEF/U
.S. Glas0 SINTEFI U.. of Trondheim
of Trondheim
CC.H. Whitson, Rogaland
.H . Whitson. Rogaland District
District C
C..
..

Introduction
StandingI derived a set of equations that fit the
Standing pressure. Psp
P sp is measured in psia. psia, and F is a
equilibrium constant data of Katz and Hachmuth 22 at
Hachmuth characterization factor. Equations for constants a and c
pressures less than 1.000 1,000 psia (6.895 MPa) and appear in Ref. I.
1.
temperatures below 250F (121 (121C). devia
dc). A standard devia- factor. F, as defined by Hoffman
The characterization factor,
tion (SO)
(SD) of3.5%
of 3.5% between calculated and chart K values etal.,4
er al. is
,

is reported by Standing.
Standing.
Not reported.
reported, however,
however. is the accuracy of of the Katz and F=b(lITb -lITsp )' ..... ... .............. .. (2)
F=b(1ITb1IT
)
5
Hachmuth K values applied to reservoir fluids of various
paraffinicities and containing significant amounts of temperature. Tsp.
where separator temperature, OR. Tb is the
Ti,,, is in R,
nonhydrocarbons.
nonhydrocarbons. Because the data of Katz and and average
average boiling-point
boiling-point temperature
temperature in R,
OR. and
and coefficient
Hachmuth were for an Oklahoma City crude oil oil contain
contain- bb is
is defined for the
the pure
pure components
components C C 3, IC
,
3 iC 4. nC
,
4 iC s
nC 4 , IC
.
4 ,
5
ing
ing no nonhydrocarbons,
nonhydrocarbons. it was necessary to investigate
investigate ,
5nC s , and
nC and C
6
C 6 as
as
their
their general
general applicability.
10g(~)
A separator
separator flash
tlash program
program waswas developed
developed that
that incor
incor- // Pc
porates
porates the
the Standing
Standing K-value
K-value equations.
equations. The
The program
program logt
\ 14.7
14.7
was
was used toto analyze
analyze 15 15 crude
crude oils
oils from various
various regions
regions of
of b=--=-~
b= . . . . . . ... . . . .. . .. . .. . ... (3)
(3)
the
the world,
world. some containing
containing substantial
substantial amounts
amounts of of (lITb -liTe)
(I/Tb l/T)
nonhydrocarbons.
nonhydrocarbons . Flash
Flash parameters
parameters were
were calculated
calculated and
and
compared
compared withwith experimental
experimental values
values obtained
obtained from
from aa All
All other
other fractions
fractions except
except C _
7
C 7 + (i.e..
(i.e . C
C IC
,
1 C 2. CO
,
2 CO 2 , N
.
7 N 2,
,
2
PVT
PVT analysis of the
analysis of the fluid
tluid samples.
samples. GOR,
GOR. average
average gasgas and H 2 S) have
and H-,S) have modified
modified values
values ofof bband Tb , and
and Tb, and these
these
gravity,
gravity. stock-tank
stock-tank oiloil gravity, and bubble-point
gravity. and bubble-point forma
forma- values
values cancan be
be determined
determined by by the
the procedure
procedure outlined
outlined inin
tion
tion volume factor were
volume factor were used
used in
in the
the comparisons.
comparisons. Ref.
Ref. 1.I.
The
The K K value
value for
for the
the C 77++ fraction
fraction waswas determined
determined by by
Flash
Flash Program
Program Description
Description the
the equation
2
equation 2
Our
Our vapor
vapor and
and liquid
liquid equilibrium
eqUilibrium calculations
calculations involved
involved
use
use of
of the
the Katz
Katz and
and Hachmuth
Hachmuth K K values
values fitted
fitted by
by Stand
Stand- Kc,+ =0.15XK
KC O.I5XKcc , . .. . . .. . ... . . . . ..... . . .. (4)
(4)
ing.
ing. The
The algorithm
algorithm used
used for
for calculations
calculations isis described
described by
by
Standing. 3 The
3
Standing. The basic e~uation for
basic equation for fitting
fitting K-value
K-value data
data where
where K Kc, waswas calculated
calculated as as aa pure
pure component.
component. Ref. Ref. 1I
given
given by Hoffman er
by Hoffman et al.
4
al. was
was used in this
used in this study:
study: provides
provides an an alternative
alternative method
method to to determine
determine KC K c . ThisThis
.

method
method was was not
not available
available to to the
the authors
authors atat the ti~e this
the time this
I study
study was was conducted.
conducted. We We recommend
recommend that that the
the procedure
procedure
K=
_
0 _1O(a+ci
K=_lO(a+cF), . . .. . . .. . . . . . .. . . . . . .. ... .(I)
(I) given
given inin Ref.
Ref. I1bebe used
used toto determine
determine KC 7K c . AA check
. check was
was
Psp
Psp made
made to to see
see what,
what, ifif any,
any, error
error resulted
resulted'rrom using Eq.
Eq.
from using
4.4. ItIt was
was found
found that
that there
there isis no
no significant
significant loss
loss of
of ac
ac-
where
where coefficients
coefficients aa and
and cc are
are functions
functions of
of separator
separator curacy
curacy inin calculated
calculated flash
flash parameters
parameters unless
unless the
the oil
oil con
con-
0149-213618210008-8033$0c325
0149-21311182J1W!!L803.25
tains
tains aa large
large C7C7+ fraction
mclion (greater
(greater than
than 0.70).
0.70).
Copyright
Copyright 1982
1982Society
Societyof01 Petroleum
Petroleum Engineers
Engineersof01AIME
AIME The
The flash
flash program
program assumes
assumes thatthat I1 mol
mol ofof reservoir
reservoir
AUGUST
AUGUST 1982
1982 1811
1811
jiiP

A.1-2
TABLE
TABLE 1-SURFACE
1SURFACE PROPERTIES
PROPERTIES AND EXPERIMENTALLY DETERMINED OIL
OIL FORMATION
FORMATION
FACTOR AT SATURATION PRESSURE
VOLUME FACTOR
Nonhydrocarbon
Nonhydrocarbon Content
in Total Surface Gas
Gas
R (mol%)
R ~g
Yg TT Bob
Sample
Sample (scfISTB)
(scf/STB) (air= 1)
(air= ~API ~
F (F)
(oF) (RB/STB) 2
N 2
CO S
2
H
Middle East
Middle East no
770 0.729
0.729 44.8 12.40 210 1.450
North Sea
North Sea 786
786 0.755
0.755 36.7 11.90
11.90 196
196 1.435
1.435
California
California 104
104 0.881
0.881 27.0 11.42
11.42 102
102 1.061
1.061
Michigan
Michigan 230
230 0.935
0.935 26.0 11 .82
11.82 83 1.109
1.109
California
California 788
788 0.850
0.850 33.7 11.66
11 .66 242 1.498
1498
California 710
710 35.1 11 .66
11.66 242 1.433
Mississippi 326 0.864 37.2 11 .74
11.74 253 1.313
1.313 9 7 5
FA-1
FA-1 840 1.248
1.248 27.9 11.38
11.38 240 1.593 6 57
GL-1
GL-1 1,344
1,344 0.985 48.1 12.00 248 1.850 24 4

GL-2
GL-2 1,452
1,452 1.034
1.034 47.7 12.00 249 1.901 21 4 2
North Sea
North 497
497 0.936
0.936 36.9 11.80 150 1.253
North Sea
North 497
497 0.936
0.936 36.9 11 .80
11.80 280 1.363
North Sea
North 1,052
1,052 0.746
0.746 33.8 11.75 215 1.512

fluid is flashed at first-stage separator pressure and correlation. The second method of determining Bob
B uses
temperature. Liquid from each subsequent stage of a North Sea correlation by Gl~.
66 This correlation was
Glas.
separation is flashed until the final liquid feed is flashed developed for North Sea crude oils but has been proved
at stock-tank (nth-stage) conditions, p,
5
p s/ and T
5s1
T
. ,' At each paraffinici~. A
equally applicable to oils of varying paraffinicity.
stage, the composition and moles of liquid and vapor are 7 for
Standing
comparable correlation was developed by Standing
calculated and converted to a basis of II STB (0.2 stock- mixtures of California oils and gases. The paraffinicity
tank m)
3
m 3 ) oil. From these data, total GOR, average gas
of the samples used was calculated from a method
gravity, stock-tank oil gravity, and bubble-point forma- 88 Some of these examples are
developed by Whitson.
Whitson.
tion volume factor are calculated. compared in Tables 11 and 2. Four of the 15 samples con-
Two methods are used to calculate bubble-point for- tamed relatively large amounts of nonhydrocarbons
tained
mation volume factor. The first combines gas and stock- .
2
CO
CO ,
2
N
2, N 2 , and H
22 S, as shown in Table 1.
H
tank oil weights with bubble-point oil density as follows.
Results and Discussion
I
/I
Experimental and calculated values of total GOR,
~ Wgj+Ws/o
Wgj+Wsto forma
average gas gravity, stock-tank oil gravity, and forma-
Bob
b=
0
B = ;=1 . . .. . ................ (5) 15 samples were compared in
tion volume factor for the 15
5.6146pob
Pob
56146 Califomia were analyzed
this study. Samples marked "California"

at several separator conditions. Separator pressure and


The bubble-point oil density either is reported from PVT temperature were varied for separator designs from one
analysis or is calculated from the Alani and Kennedy
5
Kennedys to three stages.

2COMPARISON OF EXPERIMENTAL AND


TABLE 2-COMPARISON AND CALCULATED
CALCULATED FLUID PROPERTIES
Bubble-Point Formation
Com~uter
Computer Flash
Flash Data
Data Volume Factor,
Volume Factor. RB/STB
RBlSTB
GOR
GOR From Bubble-Point
From Bubble-Point
ri evi-
Devi- From Correlation
From CorrelationS
6 DensityS
5
Density
~API
YAPI
A
R ation
atlon ~g Deviation
DevT:tion Deviation
Deviation Bob
ob
8 Deviation
Deviation Bob
BOb Deviation
Deviation
Sample (scfISTB)
(scflSTB) ~(%) (air =
(air 1)
= 1) (%)
(%) ~API (%)
(D,i) (RB/STB) (%)
(%) (RB/STB)
(RB/STB) (%)
(%)
Middle East
Middle East 740
740 390 0702
3.90 0.702 3.70
3.70 45.8
45.8 -2.23
2.23 1.400
1,400 3.45
3.45 1.412
1.412 2.62
2.62
North
North Sea 758 3.55
3.55 0.758
0.758 0.40
-0.40 36.5
36.5 0.54
0.54 1.407
1.407 1.95
1.95 1.408
1.408 1.88
1.88
California
California 107
107 2.88 0.914
-2.88 0.914 3.75
-3.75 27.3
27.3 -1.11
1.11 1.048
1.048 11.23
23 1.058
1.058 0.28
0.28
Michigan
Michigan 219
219 4.78 0.886
478 0.886 5.24
5.24 264
26.4 -1.54
1.54 1.085
1085 2.16
2.16 1.094
1.094 1.35
1.35
California 820
820 -3.90
3.90 0.894
0.894 5.18
-5.18 34.5
34.5 2.37
-2.37 1.507
1.507 -0.60
0.60 1.494
1 494 0.27
0.27
California
California 6n
677 4.65
4.65 0.711
0.711 37.0
37.0 5.41
- 5.41 1.380
1.380 3.70
3.70 1.395
1.395 2.65
2.65
Mississippi 296 9.20 0.969
0.969 1215
-12.15 377
37.7 -1 .34
1.34 1.219
1.219 7.16
7.16 11.243
243 5.33
533
FA-1 860 2.38
-2.38 1.221
1.221 2.16
2.16 27.2 2.51
2.51 1.609
1.609 -1.00
-, 1.00 11.574
574 11.19
19
GL-1
GL-1 1,301
1,301 3.20 0.916
0.916 7.01
7.01 50.3
50.3 -4.57
4.57 1.844
1.844 0.32
0.32 11.765
765 4.59
459
GL-2
GL-2 1,359
1,359 6.40
6.40 0.945
0.945 8.61
8.61 49.9
49.9 -4.61
4.61 1.912
1.912 - 0.58
0.58 11.851
851 2.63
2.63
North Sea
North Sea 495
495 0.40 0.971
0.40 0.971 3,74
-3.74 37 0
37.0 -0.27
0.27 1.279
1.279 - 2.08
2.08 1.279
1 279 - 2.08
2.08
North
North Sea
Sea 495
495 0.40
0.40 0.971
0.971 3 74
-3.74 37.0
37.0 0.27
-0.27
1.349
1.349 11.03
03 1.386
1 386 - 11.69
69
North Sea
North Sea 1,057
1,057 0 48
-0.48 00.758
758 1.61
-1.61 36.0
36.0 -6.51
6.51 1.580
1.580 - 4.50
- 450 11.549
549 - 2.45
2 45
Summary for
for All Samples
Samples
Number of
Number samples compared*
of samples compared" 18
18 15
15 18
18 20
20 20
20
deviation, %
Average deviation,
Average D,i) 2.18
2.18 -0.35
0.35 - 2.49
2.49 0.99
0.99 0.96
0.96
SD,
SD,%% 4.16
4.16 5.37
5.37 3.50
3.50 22.75
75 22.39
39

Some comparisons
'Some cornpansons involve he same
involve lhe same sample
sample.

1812
1812 JOURNAL OF
JOURNAL PETROLEUM TECHNOLOGY
OF PETROLEUM TECHNOLOGY
A.1-3
A.1-3

Statistical analysis
Statistical analysis of of the
the data gave average
data gave average deviation,
deviation. RR == total
total producing
producing GOR
GOR from
from flash
flash separation,
separation.
SD, and
SD, and number
number of comparisons for
of comparisons each parameter.
for each parameter. scf/STB (std
scf/STB (std m 3
m 3 Istock-tank m
/stock-tank )
3
m 3)
Results are
Results found in
are found Table 2.
in Table 2. Although
Although 15 15 samples
samples do do TT == reservoir
reservoir temperature,
temperature. OF F (OC)
(C)
not constitute
not constitute an
an exhaustive
exhaustive analysis,
analysis, applicability
applicability of the
of the Tb
Tb = average boiling-point
average boiling-point temperature
temperature,, OR R (K)
(K)
correlations isis supponed
correlations supported by by the wide range
the wide range of
of oil
oil types
types
studied. Tc
T = critical temperature,
critical temperature, OR R (K)
(K)
studied.
Comparison of 5 ==
T
Tsp separator temperature,
separator temperature, OR R (K)
(K)
Comparison of the
the calculated
calculated andand experimental
experimental datadata
for these samples
for these samples did
did not
not deviate
deviate substantially
substantially from pure
from pure
Wg =
Wg = weight of
weight of gas
gas [basis:
[basis: I1 STB
STB (0.2
(0.2 stock-tank
stock-tank
m)
3
m 3 ) oill,
oil], Ibm
Ibm (kg)
(kg)
hydrocarbon samples,
hydrocarbon samples, suggesting
suggesting that
that the
the modified
modified
0
W weight of of 11 STB 3 ) oil,
parameters for
parameters for nonhydrocarbon
nonhydrocarbon KK valuesvalues are
are sufficiently
sufficiently W sto =
= weight STB (0.2(0.2 stock-tank
stock-tank m )
3
m oil,
accurate for
accurate estimating their
for estimating their phase
phase behavior.
behavior. Ibm
Ibm (kg)
(kg)
"( API
YAPI == (141 0
(l41.51"(o)-131.5=stock-tank

1
.5
) y 131 .5=stock-tank oil oil gravity
gravity
Conclusions
Conclusions from flash
from flash separation
separation
The Katz
I.I. The and Hachmuth
Katz and 22 K-value
Hachmuth K-value data
data seem
seem to be
to be "( g == average specific
average specific gravity
gravity ofof total
total surface
surface
Yg
applicable to
applicable to most
most black
black oils, independent of
oils, independent paraffinici
of paraffinici- gases from
from flash
flash separation
separation (air=
(air= I)
ty and large
ty and large content
content of
of nonhydrocarbons
nonhydrocarbons in the surface
the surface 3)
Pob
h
0
P == bubble-point oil oil density, Ibm/cu ft (kg/m )
3
(kg/rn
gases, at
gases, pressures below
at pressures below 1,000
1,000 psia (6.895 MPa)
psia (6.895 and
MPa) and
temperatures below
temperatures below 250F (121C).
250F (121 0c).
2. The
2. The usefulness
usefulness of
of Katz
Katz and Hachmuths work is ex-
and Hachmuth's ex Subscripts
tended by equations
equations developed by Standing
Standing1 that fit the i = components (e.g . C
(e.g., ,
1
C \0 C
,
2
C 2 , etc.)
etc.)
tended
K-value data of Katz and
K-value and Hachmuth. Modified = = I, 2, ... n
jj = stage number, where jj=l, . . .

parameters are
parameters are presented
presented toto generate K values for the
light components
components (C 1i , C ,
2
C .
7
CO ,
2
N and HH,2 S), with a References
light , 2, CO 2, N 2, and
special correlation given for the C7+
special 7 fraction.
C Standing. M.B.
I. Standing, MB.:: "A Set of Equations for Computing Equilibrium
A Set
Ratios of a Crude Oil/Natural Gas System System at Pressures Below
3. Results from a computer flash separator program 1.000 psia,"
1,000 psia. J. Pet.
Per. Tech. (Sept. 1979) 1193-1195.
11931195.
that used Standing's
that Standings equations for calculating K values
2. Katz. D.L. and Hachmuth. D.H. D.H.:: "Vaporization
Vaporization Equilibrium
yielded average deviations of 2.
yielded 2.18, 0.35, and
18, -0.35, Oil-Natural Gas System."
Constants in a Crude Oil-NaJural System, md. Ind. and Eng.
Eng.
2.49% and SD's
-2.49% SDs of 4.16,5.37,
4.16, 5.37, and 3.50% for GOR, Chem. (Sept. 1937) 29, 1072-\077.
Chem. 10721077.
average gas gravity, and stock-tank oil gravity, respec
average respec- 3. Standing. M.B.:
3. MB.: Volumetric Phase Behaviour of Oil Field
tively. Bubble-point formation volume factor, calculated Hydrocarbon Systems,
Systems. Chevron Oil Field Research Researeh Co Co.... La
tively. (Sept. 1970),43-56.
Habra, CA (Sept. 1970), 4356.
with bubble-point
with bubble-point oil density and a correlationcorrelation by 44.. Hoffman.
Hoffman. A.EA.E.. Cnimp. J.S
.. Crump, J.S.,. and Hocott.
Hocoti. C.R.:
CR.: " Equilibrium
6 yielded average deviations of 00.96
Glas.
Glas0,6 .96 and 0.99% Constants for a GasCondensate System." Trans
Gas-Condensate System. . . AIME (1953)
Trans.,
and SD's
and SDs of 2.39 and 2.75%
2.75%.. 198, 1-10.
198, 1-10.
5. Alani.
5. Alani . G.H.
G.H. and Kennedy. T,H.: T.H.: "Volumes Liquid Hydrocar
Volumes of Liquid Hydmcar-
bons
bons at
at High
High Temperatures Pressures. Trails
Temperatures and Pressures. .. AIME
Trans., AIME (1960)
(19601
Nomenclature
Nomenclature 219.
219. 288292.
288-292.
6 . Glas,
6. Glas16, @. : Generalized
. "Generalized Pressure-Volume-Temperature
Pressure-Volume-Temperature Correla Currela-
a =
a = variable in K-value equation iions.
tions." J. Pet.
Pet. Tech.
Tech . (May
(May 1980)
1980) 784-795.
784-795 .
= variable in characterization factor equation
bb = equation 7.
7. Standing.
Standing. M.B..
M.B.: A " A Pressure-Volume.Temperature
Pressure-Volume-TemperalUre Correlation
Correlation
(or
for Mixtures of Califomia
Milttures of California Oils
Oils and
and Gases. Drill. and
Gases. " Drill. alld Prod.
Prod.
B(,h
Bob == oil formation
formation volume
volume factor at
at bubble-point
bubble-point Prai.,
Prac. . API
API (1947)
(1947) 275.
275 .
(saturation) pressure.
pressure, RB/STB
RB/STB S8. Whitson.
Whitson. C H. Characterizing
C.H.: "Chamcterizmg Hydrocarbon Plu~ Fraciions.
Hydrocarbon Plus Fmctiun~."
(res
(res m
/mstock-tank
3 3/stock-tank m)
3
m J) paper
paper EIJR
EUR 183183 presented
presented atat the
the European
European Offshore
Offshore Petroleum
Petmleum
Conference
Conference andand Exhibition,
Exhibition. London,
London. Oct. 21-24. 1980.
Oct. 21-24, 1980.
= variable
cC = variable inin K-value
K-value equation
equation
IVi == volume
volume fraction
fraction of
of component
component ii SI
SI Metric
Metric Conversion
Conversion Factors
Factors
F
F == characterization
characterization factor bbl x 1.589
bbl 1.589873
873 E-OI
E0l = 3
m

(
OF
F (OF-32)/1.8
(F32)/l.8 =

Fp = ( 6
=
J.X
i )x(l/,)=para
Ii xThl
1=1
v,)
T
ffinicitv
x(II,,(,,)=paraffinicity scf xx 2.86364
scf 2.86364 E-02
E02 = std m
characterization
characterization factor
factor Conversion factor
Conversion ractor isis enact
exact JYf
JPT
Pc = critical pressure,
=critical pressure, psia
psia (MPa)
(MPa) Original
OnglnaJ manuscript
manuscript received
received inin Society
Society of
of Petroleum
Petroleum Engineers
Engineers office
oHice May11.
May 11 . 1979.
1979.
= separator
Psp = separator pressure.
pressure, psia
psia (MPa)
(MPa) Revised
RevIsed manuscript
manuscript received
received Feb
Feb 23.
23. 1982
t 982.

AUGUST
AUGUST 1982
1982 1813
1813
A.2-1
A. 2 1

Characterizing
Characterizing Hydrocarbon Plus Fractions
Curtis Whitson.**
Curtis H. Whitson, SPE. U.
SPE. U. of Trondheim
of Trondheim

Abstract
Methods are developed for characterizing the molar than six. Molecular weight and specific gravity (or den- den
distribution (mole fraction/molecular weight relation) sity) of the C 77 ++ fraction may be the only measured data
C
and physical properties of petroleum fmctions
fractions such as available.
7 +-).
(C
heptanes-plus (C7 ). These methods should enhance
Preferably. a complete true-boiling-point (TBP)
expenmental
equation-of-state (EOS) predictions when experimental analysis should be performed on tluids fluids to be matched by
data are lacking. an EOS. Distillation experiments yield boiling points.
The three-parameter gamma probability function is gravities, and molecular weights. from which
specific gravities.
distribution, as well as to
used to characterize the molar distribution. molar distribution is found directly. Special analyses of
fit experimental weight and molar distributions and to TBP data can also provide estimates of the
generate synthetic distributions of heptanes-plus paraffin/napthene/aromatic (PNA) content of of SCNSCN
fractions. groups. which are useful useful in some property correlations.
correlations. 5
2
physical prop
Equations are provided for calculating physical prop- Unfortunately,
Unfortunately. such high-quality data are seldom
erties such as critical pressure and temperature of single- available for tluids fluids being matched or predicted by an
carbon-number (SCN) groups. A A simple three-parameter EOS. If
EOS. If data
data otherother than lumped C C 7 + properties are
7
equation is also presented for calculating the Watson available, they
available. they might include aa partial partial component
component
characterization factor from molecular weight and and analysis (weight distribution) from chromatographic
specific gravity. measurements. In this case, case. only
only weight
weight fractions of of
Finally, a regrouping scheme is developed to
Finally. to reduce SCN ~roups are reported:
SCN. groups reported: normal
normal boiling
boiling points,
points. specific
specitic
extended analyes
analyses to only a few multiple-carbon-number
multiple-carbon-number gravities,
gravities. and molecular weights
and molecular weights (needed
(needed to to convert
convert to a
(MCN) groups. Two sets of of mixing rules are considered.
considered. molar basis)
basis) simply
simply are are not
not available.
available.
giving
giving essentially the same results when
essentially the used with
when used with the
the Compositional
Compositional simulationsimulation basedbased on on anan bUS
EOS involves
involves
proposed regrouping procedure.
procedure. two
two major
major problems: (1) how to
(I) how to split
"split" aa C C 7 + fraction

7
into
into SCNSCN groups groups with with mole fractions,
fractions. molecular
molecular
Introduction weights. and and specific
specitic gravities that match match measured
measured
During the development of the
During the application
application of of EOSs
EOS's toto 7
CC 7 + properties,
properties. and and (2)
(2) if
if aa partial
partial extended
extended analysis
analysis
naturally
naturally occurring hydrocarbon mixtures.
occurring hydrocarbon mixtures. itit has
has become
become (e.g..
(e.g .. CC IIi + )) isis available,
- available. howhow to to extend
extend itit to
to higher
higher carcar-
clear that insufficient description
clear description of heavier hydrocar
of heavier hydrocar- bon
bon numbers.
numbers.
bons (e.g .. heptanes
bons (e.g.. heptanes and
and heavier) reduces the
heavier) reduces the accuracy
accuracy The first
The first step
step in in addressing
addressing these
these problems
problems isis to tind aa
to find
of PVT
of PVT predictions. Volatile oil
predictions. Volatile and gas-condensate
oil and gas-condensate versatile,
versatile. easy-to-use
easy-to-use probability
probability function
function for for describing
describing
volumetric phase behavior
volumetric phase particularly sensitive
behavior isis particularly sensitive toto molar
molar distribution.
distribution. The The distribution function should should
composition
composition andand properties
properties ofof the heaviest components.
the heaviest comPonents. allow
allow consistent
consistent matching
matching and and reasonable
reasonable extension
extension of of
Until recently there
Until recently there has not been
has not been published
published in in technical
technical partial
partial analyses.
analyses. Also, Also. itit should
should not not contain
contain too too many
manv
journals
journals aa comprehensive
comprehensive methodmethod for for characterizing
characterizing unknown
unknown or or difficult-to-determine
difficult-to-determine parameters.
parameters. This Thi's
compositional paper presents
paper presents such such aa probabilistic
probabilistic model
model and and describes
describes
compositional variation,
variation. which
which wewe call molar distribu
call "molar distribu-
its
its application
application to to several
several reservoir
reservoir fluids
tluids under
under "Molar
Molar
tion.
tion. Several authors L3
Several authors have given
15 have given lucid
lucid descriptions
descriptions
of Distribution .. ,
Distribution.
of petroleum
petroleum fraction
fraction characterization, though they
characterization. though they deal
deal
mainly with physical The
The second
second step step inin characterizing
characterizing plus plus fractions
fractions in. in-
mai.nly with physical property
property estimation.
estimation. Usually,
Usually. only
only
aa single volves
volves estimating
estimating SCN SCN group
group specific
specific gravities,
gravities. which.
which.
smgle heptanes-plus
heptanes-plus (C 7
(C 7 T ) fraction
fraction )umps
lumps together
together
thousands together
together with with estimated
estimated molecular
molecular weights
weilZhts (from
(from the the
thousands of of compounds
compounds with with aa carbon
carbon number
number higher
higher
probabilistic model). could
probabilistic model). could be be used
used toto estimate
e,!;timate critical
critical
Now
Now at RogaJand Dint
at flogaland Dist C.
C. properties
properties required
required by by EUSs.
EOSs . WeWe address
address this this problem
problem
0197-7250182/0081 -2233S00 25
01977250/83/0081.2233S00 25
~nd suggest
and suggest aa simple
simple methodmethod for specitic gravity
for specific gravity estima
estima-
Copyright
Copynght 1983
1983 Society
SocIety of
01 Petroleum
Petroleum Engineers 01 A/ME
Engtneers 0? AI ME tion
tion under .Physical Properties
under "Physical Properties Estimation.
Estimation." The The
AUGUST 1983
AUGUST 1983 6K3
A.2-2
A.2-2

(b) ProbabilisticModel
Probabilistic Model
The three-parame
The three-parameter gamma function
ter gamma (Type 33 of
function (Type of the
the
Pearson )
8
system 8 was chosen for
Pearson system ) was chosen for describing molar describing molar
z
theproba
ofthe
" 12
0 distribution. Fig.
distribution. showsthree
Fig. lalashows examplesof
threeexamples proba-
C)
ClD .101
Eachcurve
model. Each
bility model.
bility curvehas thesame
hasthe expectedvalue
sameexpected valueofof
U. (forour
xx (for purposes this
ourpurposes corresponds toto measured
this corresponds measured C 7+
UiUI
weight). For
molecular weight).
molecular For aa= = I,I. the distribution isis ex
the distribution ex-
~
-J

accelerated ex
0
0.01 ponential. Values less
ponential. Values less thanthan one give accelerated
one give ex-
ponential distributions
ponential distributions. , while greater than
values greater
while values than one
one
left-skewed distributions. Note that as aa ap
yield left-skewed
yield distributions . Note that as ap-
proaches infinity. the
proaches infinity, becomes normal,
distribution becomes
the distribution normal.
0.001 though folded
though the minimum
"folded" atat i,.,.,. the molecular weight
minimum molecular weight
100 200 300 400 500
included inin the
included C 7 + fraction.
the C
+
7 fraction.
The probability density
The probability p(x). isis given
function. p(x).
density function, given byby
(a)
~
'CL (x_.,.,)a-t exp[(xi)/f
(X_)a exp[(x-.,.,)/131
]
3
Z 0.008 Mel 200 p(x) =
p(x) . .. .... ........ (1)
(1)
z
0
0
8
0
~ . .2
/3aF(a)
l3 a r(a)
z~ 0.006
D
U.
ap 101 where
where a, a, /3,
13, and are parameters
and .,., are defining the
parameters defining the distribu
distribu-
I
tion. can be
tion . i.,., can accurately since
estimated accurately
be estimated represents the
since itit represents the
U,
z minimum molecular
minimum weight to
molecular weight to be included in
be included in the
the C,,
C n ++
directly from a, and
Ui
a fraction. If
fraction. given. (313 isis found
If aa isis given, found directly from .,." a,
,
and
~ the measured C,,
the measured molecular weight.
en + molecular M n + . aa can
weight, M,, .
can bebe fit
fit
aj 0.002
measured molar- molar- andand weight-distri bution data, data. or
-J

< to measured
to weight-distribution or
aCD ZI . 7
Z AREA
estimated using
estimated using an empirical relation.
an empirical relation.
~
0
0.

The cumulative probability


The probability function. P(Xsx), is
function. P(Xx). is the
the
200
200 300
300 400
400 500
500
100
MOLECULAR
integral of
integral P(x) from .,., to
of P(x) to x, x.
MOLECULA R WEIGHT
WEIGHT

Fig. 1-lIIustration
Fig. 1Illustration of the probabilistic
probabilistic model several
model for several
values
values of parameter
parameter a. P(Xx)=p(x)
P(Xsx) = (2a)
dx . .. .. . .... . .. ... . ... ... (2a)
rp(X) tU,

" occurrence (normalized


(normalized
and represents the frequency of occurrence
method
method is is based on the Watson characterization 66
factor,
characterization factor. to x.r.. The
mole fraction) in the interval .,., to ex
analytical ex-
The analytical
. which is shown
which is shown to relate specific
specific gravity.
gravity, molecular pression for the cumulative probability function
probability function is 8
is8
weight.
weight, andand boiling
boiling point by a simple three-parameter
simple three-parameter CD

equation.
equation. A A second
second alternative
alternative is general
is based on the general- P(Xs.x)=e- Y ' 2: lv~.,.j/r(a+j+I)J,
[y/r(a+jl)1 (2b)
.. .. .. (2b)
ized
ized propenies
properties proposed
proposed by Katz Katz and Firoozabadi.7
Firoozabadi, j=o
j=O
somewhat
somewhat modified
modified to to make
make their use use more
more consistent.
consistent.
and with v=(xi)/(3.
with y=(x-T/)/I3.
The last section. "Regrouping
The last section, Regrouping (PseudoiZalion)
(Pseudoizatio n) and problem itit is
distribution problem
molar distribution is
Eq. 22 to
apply Eq.
To apply
To the molar
to the
Mixing
Mixing Rules."
Rules, deals
deals with
with the
the problem
problem of
of reducing
reducing the
the terms and to
to define variables in practical
necessary to define variables in practical terms and to
necessary
complexity of
complexity of fully
fully extended
extended characterizations
characterizations to only aa
to only frac
mole frac-
calculate mole
how the
show how
show relation can
the relation used to
be used
can be to calculate
few
few MCN
MCN groups.
groups. Several
Several mixing
mixing rules
rules are
are proposed
proposed for for frac
weight frac-
them weight
molecular weights.
tions, molecular
tions. and from
weights, and from them
the pseudoization (regrouping)
the pseudoization (regrouping) process.
process. Also.
Also. simple
simple
Fig. I).
(see Fig.
tions (see
tions I).
relations
relations are
are given
given to to estimate
estimate how many MCN
how many groups
MCN groups SCN-group
the SCN-group
variable x.r in
The variable
The merely the
Eq. 22 isis merely
in Eq.
are
are required
required and
and how
how thethe regrouping
regrouping can can bebe performed
performed
weight. or
molecular weight.
molecular or
consistently
consistently..
Several
Several examples
examples are are given
given to to illustrate
illustrate some
some of the
of the xM. .......... .. ...... . . .. . . ......... . (3a)
x=M
capabilities
capabilities and
and limitations
limitations of
of the
the proposed
proposed methods.
methods.
They
They also
also indicate
indicate the sensitivity of
the sensitivity of EOS
EQS predictions
predictions to to defined as
parameter isis defined
The parameter.,.,
The as the minimum molecular
the minimum molecular
CC
7 7 + characterization
characterization.. weight expected to
weight expected the CC,,
occur inin the
to occur n + fraction. That
+ fraction That is,
is.
ze,ro probability
there isis ze.ro
there fp(x)=O)
probability [P(x) =0) for occurrence of
for occurrence com
ofcom-
Molar
Molar Distribution
Distribution pounds with
pounds weight less
molecular weight
with molecular . the CC
than .,., . IfIf the
less than 77+
The
The problem
problemof ofestimating
estimating reservoir-fluid
reservoir-fluidmolar distribu
molardistribu- considered, then
fraction isis considered.
fraction =92 (the
then .,.,=92 molecular weight
(the molecular weight
tions
tions was
was encountered
encountered when when aa commercial
commercial EOS EQS PVT PVT toluene) would
of toluene)
of would be be aa good for q.. Experience
estimate for.,.,
good estimate Experience
package
package was used. ItIt became
was used. became evident
evident that proper
that proper shown that
has shown
has that aa good approximation of
good approximation of .,.,r isis given by
given by

characterization of
characterization of heavier
heavier components
components was important
was imponant
for
forobtaining
obtainingaareasonable
reasonablematch matchof ofexperimental
experimentaldata.data. ItIt i3bi
= 14n .. . ........ .. ......... . . . ..... . (3b)
.,.,=14n-6
was
was decided
decided toto examine
examine existing molar-distribution
existing molar-distnbution
(mole
(mole fraction/molecular
fraction/molecular weight)weight) datadata for
for similarities
similarities foraaCC,,
for traction.. Eq.
n " fraction 3h isisaauseful
Eq. 3b relation
empincal relation
useful empirical
and characteristics
and characteristic s that
that could
could bebe used
used to
tO describe
describe but should not be considered a restraint
but should not be considered a restraint on the model . on the model
hydrocarbon
hydrocarbonsystems.
systems. An An imponant
important requirement
requirementfor the
forthe Consideringthe
ConSidering the remaming
remainingtwo Eq. 1.2.aa
parameters inin Eq
twoparameters
distribution
distribution model
model waswas itsitsability
ability toto match
match weight frac
weight frac - property ofofthe
useful property
and13./3. aa useful
and the three-parameter gamma
three-parametergamma
tions
tionsreponed
reported from
fromchromatographic
chromatographicstudies. studies. function isis that
function that the product a/3
the product a/3 equals
equals the anthmetic
the arithmetic
684 OFPETROLEUM
SOCIETlOF
SOCIETY JOURNAL
ENGINEERSJOURNAL
PETROLEUMENGINEERS
t,84
A.2-3
A.2-3

average molecular weight.


average molecular M" + minus
weight. M,, .". or
minus TI, or

Application of
Application the Molar
of the Molar
M" + -.,,=a{3
Distribution Model
Distribution Model
TI= ... .. .. .. . .. . . . . .... . . . . . .. (3c)
(3c)
Direct Estimate
Direct of aa
Estimate of
M" + isis measured
where M,,
where measured directly.
directly. An of a can
estimator of
An estimator can be calculated using
be calculated the following
using the following
There are
There are several
several empirical
empirical correlations available for
correlations available for proposed empirical relation.
proposed empirical relation. II
estimating
estimating a from randomly
randomly sampled
sampled data
data such
such as aa fully
as fully
extended calculated from
extended molar distribution. {3 isis easily calculated (0.5000876+0. 1648852 Y0.0544174
a=y-I (0.5000876+0.1648852
a=Y Y-0.0544174 2
Y
) ,
y1).
other variables.
the other variables.
. ........ .. ......... . .. (10)
(10)
(3=(M" + TI)/a
/3=(M,, -.,,)/a . . . . . ....... ... . . ...... ... (3d)
(3d) where
where
Y= ln[(M ++ TI)
Y=ln[(M" I I)
G)l . . .. .... .... .. . ..... ((II)
-l1)/rnG)j
The cumulative of occurrence.
cumulative frequency of Ij. for com
occurrence. f. com-
pounds M j _ 1 and
boundaries M_
pounds having molecular weight boundaries and and
and
M j is merely
M,

Ii = Jr p(.r)
Ij =
Mj
1
M
dx=
p(:c) Lt
rnG=
=

[IT'=11
N

I =
(M, -l1):'] IJ:
(M j TI)] 12)
11:,,+ . . . . . . . . . . . .. . ((12)

,w
Mj_1 Eq. 10
Eq. 10 isis valid for 0<
0< Y<0.5772 (i.e.. a~ 1.0).
(i.e .. a 1.0) . G
IIlG
merely geometric average molecular-weight
merely represents a geometric molecular-weight
P(r)(M~Mj)-P(r)(M~Mj_I)) '
1
P(r)(MM,)P(r)(MM,_ . . ..... . .. (4) variable. For Eq. 10 distribu
10 to be useful for the molar distribu-
problem. it is necessary to have measured SCN
tion problem, SCN mole
The frequency.
frequency, I;. is directly proportional toto mole
J, fractions and They should
accurately. They
and molecular weights accurately. should
fraction ::j.,. constitute a full compositional analysis. preferably
also constitute
having a diminishing or neglible quantity of the last frac
of the frac-
::j=l; '::" ++ . . ... . .. ..
-=
-I_il
.-

.,
. . . . . .. . . . . . . . . . . ... . (5)
. . .
. tion. nonexistent, a set
Lion, N. Since such analyses are nearly nonexistent.
tables' has been developed when only par-
of correction tables
The average molecular weight in the same interval is tial analyses are available (the limitation of aa ~ 1.0 I .0 men-
given by tioned previously is also lifted in the present use of Eq.
M;= 10).
10).
ii=
P(M~M,
a+l).a+ I)-P(M~M ; _I .a+
,a+1)P(MM
P(MM
,
1 ,_I) Determining a by Minimization
.,,+a{3
TIad . . .. (6)
. . .
function, E(a).
The error function. defined
E(a. used to optimize aa is detined
P(M~M;.a)-P(M~M
P(MM,,a)P(MM,_
1 ; _I.a)
a) as the sum of the squares of differences in measured and
calculated compositions and is given by
where all PCX ~x) functions.
P(Xx) functions, independent of the a used
.v,v
.e.. aa or a+
(i(i.e., I). use J3(3 as detined
a+l). defined in Eq Eq.. 3d
[(3=(M,, TI)/al.
[3=(M '" -.,,)/al E(a) = L: (::;
( -:)~ ... ... .... ...... .......
l3a)
(13a)
i=II
Fig. la shows how Eqs. 2 through 6 were used to con-
Ia shows con
functions in Fig.
vert the probability density functions Ia to molar
Fig. la fit.. and
if a molar distribution is to be tit
distributions
distributions..
_Given
Given SCN
SCN mole fractions (::;)(:, ( and molecular weights
and molecular .vV
fraction.. I".
(M,), weight fraction
(M;). f,; . is
is given
given by
by E(a) = L: (j'".;
(f -i,,;)~) ..... . .... . .... . .. . (( l3b)
13h(
;="
I = II

I,, common
f,;=::;M;lC::" M,, J.
=z,M,/(c,, + M,,'" ) (7)
. ....... . ......... . . . (7) distribution isis to be tit
if aa weight distribution (the more common
fit ((he
(e.g..
case) Calculated values are marked with a tilde (e.g
case).. Calculated ..
The per)
P(rj function.
function, given
given by Eq. 2. can be simplitied
by Eq. to
simplified (0 :;) .
facilitate
facilitate its
its calculation
calculation on
on aa computer
computer byby avoiding
avoiding inclu- minimization of
The minimization of E may proceed by aa simple
may proceed secant
simple secant
sion of
sion of the
the gamma
gamma function
function inside
inside the
the summation. Using
summation. Using or half-interval method
or method.. Two procedures for performing
Two procedures pertbrming
the
the recurrence
recurrence property
property of
of the
the gamma function. F. yields
gamma function. r. minimization have proved
the minimization Reasonable limits
useful. Reasonable
proved useful. limits
w are 00.5
for aa are
for .5 (0 3.0.
to 3.0.
e-
e \' v'~ IX> \.j
P(r)(X~x)=---
P(r) (Xx)=
rCa)
F(a)
L:
c
j =O
-' - .. ....... ..(8)
(a+j)!
(aj)
(8)
The method, called the "constant
first method.
The first
interval (CMWI)
weight interval" (CMW[).. is the simpler. In this
is the
molecular
constant molecular
case, a
this case.
value of
value chosen (e
of 11TI isis chosen (e.g..
.g .. from Eq. 3b).
from Eq. 3b). and length
the length
and the
where
where the
the summation
summation can
can be
be ceased
ceased when
when between molecular weight boundaries
between molecular weight boundaries is set (0 a con- is set to a con
such as
stant, such
stant. 14, the
as 14. the molecular weiht of
molecular weight of aa CH group:
CH2 group:
Ej+I-Ej<lO-b
E < 10

. .. . ............ . ...... .. . (9)
(9) this technique is
this technique is called CMWI- I.. An
called CMWI-I alternative isis to
An alternative to
define the
define molecular weight
the molecular weiht of of the tirst component. C".
first component. C,.
The
The proposed
proposed probabilistic
probabilistic model
model isis not physical
twe physical
not aa true and the
and the molecular
molecular weight (e.g..
interval (e.g
weight interval and then
14). and
.. IH. then
model.
model. OneOne assumption
assumption isis the
the continuous relation be-
continuous relation be- find the
tind value of."
the value of TI that satisfies this
that satisties (trial-and
condition ((nal-and-
this condition
tween molecular
tween weight and
molecular weight and mole fraction. This
mole fraction. assump-
This assump- procedure):: th
error procedure)
error this technique
is techn ique isis called CMWI-2.. In
called CMWI-2 In
tion.
tion, however.
however, along along with
with others implicit in
others implicit its
in its both cases
both molecular weight
cases molecular boundaries are
weieht boundaries separated by
are separated by
mathematical
mathematical form. form, seems
seems asas reasonable
reasonable as. as. for exam-
for exam- constant, except
aa constant. except forfor the
the last
last fraction. which has
fraction, which infinity
has intinity
ple.
ple. the assumption in
the assumption in distillation
distillation (TBP) analysis that
(TBP) analysis that as its
as boundary .
upper boundary
its upper
cumulative
cumulative volumevolume and
and bOIling
boiling point
point have continuous
have aa continuous ' These
These lables can be
tables can be oblalned he aUlhol'
from Ihe
orreotly Irom
obtainea dtreclly author NTH setroeum Depi
ITH Pelroleum Dent
relation.
relation. 'l . W

O34 Trondhelm.
7034 Norway
Trondhe,m Norway

AUGUST
AUGUST 1983
983 6KS
A.2-4
A.2-4

1CONSTANTS a,
TABLE 1-CONSTANTS
TABLE a, b, AND cc USED
b, AND IN THE
USED IN THE GENERALIZED
GENERALIZED
PHYSICAL PROPERTIES
PHYSICAL PROPERTIES CORRELATION (Eq. 14)
CORRELATION (Eq. 14)

Average
Average
Absolute
Absolute Maximum
Maximum
Constants Used
Constants Eq. 14
in Eq.
Used in 14 Data
Data Deviation
Deviation Deviation
Deviation
bb cC Points Range (%)
(%) (%)
M
Property
(mass/mole) 4.56730 x 10
4.56730x 10 - s
aa
2.1962
2.1962 -1 .0164
1.0164
--
186
186
ange
general
general' 2.6
2.6
(0/a)

11.8
11.8
(mass/mole) 1.66070
1.66070xx 10
i0 _4 (51)t
(Sl)t
Tc
T (OR)
(R) 2.42787 x 10
2.42787x 10 ' 0.58848
0.58848 0.3596
0.3596 126
126 general
general' 1.3
1.3 10.6
10.6
(K)
(K) 1.90623 10t (SI)
1.90623xx 10' (51)
Pc
P (psia)
(psia) x i09
3.12281xl0
3.12281 -2.3125
2.3125 2.3201
2.3201 103
103 general'
general 3.1
3.1 9.3
9.3
(kPa)
(kPa) 5.53028 i09 (SI)
5.53028xx 10 (51)
Pc (psia)
P 2.41490 x 10'4
2.41490x 10 -3.86618
3.86618 4.2448
4.2448 48
48 >
5
T >850 o R"
Tb850R 0.11
0.11 13.2
13.2
(kPa) 1.71589
4 x 10'4 (51)
1.71589x10 (SI)
Vcm (cu ftllbm-mole)
Vcm (Cu tt/lbm.mole) 7.04340x i07
7.04340 x 10- 2.3829
2.3829 -1 .683
1.683 102
102 general'
general 2.9
2.9 11.2
11.2
(m 3/kg'
3
(rn 1kg mole) 1.78420
1.78420xx 10
i0- - 7 (51)
(SI)
Vc
V (cu ftllb)
(Cu ft/lb) 7.52140 i0-3
7.52140 x 10- 0.2896
0.2896 -0.7666
0.7666 103
103 general
general' 2.3
2.3 9.1
9.1
(m
/
3
(m 3/kg)
kg) 5.56680
5.56680xx 10
i0 - 4 (51)
(SI)
Vim (cm
V,,,, (cm
f
3 3/g-mole)
g-mole) 7.62110xl0-s
7.62110x 10 2.1262
2.1262 -1.8688
1.8688 128
128 general'
general 2.8
2.8 9.5
(mkg
/
3
(m 3/kg 'mole)
mole) 2.65940 x 10 -,(SI)
2.65940x (51)
pp (g/cm 3 )
)
2
(g/crn 9.82554 x 10
9.82554x 10 -' 0.002016
0.002016 1.0055
1.0055 128
128 general'
general 0.028
0.028 0.91
0.91
(kglm3)
)
3
(kg/rn 9.83719 1022 (SI)
9.83719 xx 10 (51)

Cons,.n'5
Constants a. O. and cC are lhose
I . b. those originally
originally rlljlOnad
reported by Aiazl and
by Riazi and Oauben.
Daubert. " who
who claim
claim the
lhe correlations
correlallons are
are reliable or boiling
reliable for points up
boiling po,nls up to
10 850F
850"F e Except
xcept in
In
Ihe
the case of criliCai pressure. lhe
critical pressure. correlallons appear 10
the correlations to be acceplable
acceptable atal higher
higher boiling po,nIS: br
boiling points for example.
example. the original constants
Ihe original conSlanlS yielded an absolute
yielded an absolule
deVIation of only'
average deviation 52/o In
Only t 52% in the 850
850 10to ,200
200F a F range
range
.. Consl anls a.
Constants b. and c were delermlned
a, O. determined from muillple
multiple regressIon
regression analYSIS on data
analysis on dala rlljlOned
reported In Ael t8
in Ret ,8
fUse
tUse ofof Sl
SI unns
units Imphes
implies thai
that boiling
boiling po,nl
point IS
is given
gwen In
in degrees
degrees KelVin. WIth the
Kelvin. with Ihe calculaled propeny haVIng
calculated property having Ihe appropriate Sl
the appropriate St units
unils given ri Col.
given in Cot. 1,

The second method, called "variable variable molecular of an SCN


SCN group. then Tb is the normal boiling point of
interval (VMWI). allows the interval between
weight interval" that group. If 9 is a property of
of an MCN group. then T" ,
1
T
boundaries to vary between two limits. 14i 10
limits, such as 14;-10 is an average boiling point,
point. the type being dependent on
+ 2. The first lower boundary is set by ." (Eq. 3b
14i+2.
and 14; which propeny
property is estimated [see Regrouping (Pseudoiza-
(Pseudoiza
or by detining
defining molecular weight of the first component).
component). tion) and Mixing Rulesi.
Rules).
The upper boundary is then varied until either the Constants a, b,
b. and c are presented
presented in Table 1I for
measured SCN mole or weight fraction is matched or the several properties relevant to EOS calculations.
upper or lower boundary is exceeded. The resulting up up- Concerning the original constants developed for Eq. 14.
per boundary is then used as the lower boundary for the Ref. 17 states that "prediction
prediction accuracy is reasonable
next SCN. If VMWI is usedused,. the minimization of EE must over the boiling point range 100
overthe 100-- S50
850FF [310 - 730 K].
[310-730 K]."
proceed by interval halving. found, however.
It was found. however, that the accuracv
accuracy using the
original constants for critical temperature ~as good for
was go;d
Physical Properties Estimation the boiling-point range up to 925 K K (l200F).
11200F). Critical
1930s. process and chemical engineers have
Since the 1930s. pressure predictions did not.
not, however.
however, show good ac- ac
been using physical property correlations based on the curacy using the original constants for boiling points
point and .specific gravity of SCN and MCN
boiling gaint greater than 730 K (850F). It was necessary to deter
K (S50F). deter-
groups. I12.13
groupS. . 13 The chemical makeup of petroleum mix- mix mine constants for extending Eq Eq.. 14 using data from
tures was later characterized by Watson 3
Watson b . 13 using the Ref. IS.
18.
same two properties.
property correlations have been revised and
Physical propeny Watson Characterization Factor
extended several times: Ref. IS 18 presents numerous cor- cor K. is given by
The Watson characterization factor. K.
relations commonly used in industry. Tabular and
graphical forms of the correlations have slowly slowLy been KTVt/y
K=Tb Ihl,,( . . . . . .... .. ... . . .. . .. . . . . . . (IS)
(15)
replaced by multiconstant equations used for program- program
ming.. Generally these equations are complex best-tit
ming best-fit where T"Tb is normal or cubic-average boiling point in
polynomials. 14 l4l6
16 degrees Rankine and "(y is specific gravity at 290 K K
A recent physical prornyproperty correlation was proposed (60F). If SI units are used (i.e .. T"
(i.e.. T,, is given in degrees
by Riazi and Daubert. II I It was chosen tor for this study Kelvin).. the right side of Eq
Kelvin) 15 should be multipl
Eq.. IS multiplied
ied by
simple to use.
because itit is simple use, having only three constants
constants.. 1.216 (= I.S
1.21644 1.8 Ih)) . (Appendix A presents a discussion of
and is
and is claimed
claimed to be he based onon EOS principles. Also. Also, it another characterization factor and compares it with the
found that it led
was tound led to simple
simple relations for
for estimating Watson factor.) K defines relative paraftinicityparaffinicity of a
Watson characterization
the Watson characterization factor
factor.. hydrocarbon fraction
fraction.. with a typical range from 10.0 (0.0
The equation
The equation formform of all correlations
of all correlations is
is the same. (highly aromatic) to 13 (3.0
.0 (highly paraffinic
pamffinic ).
useful relation between K. molecular weight.
A useful weights and
9=a
9=a T,f-'/'
17 ...... .. . . .. . . ... . .. .... . . :.
T = (14)
1(4) .
specific gravity can cart be developed by using th~ Riazi
the Riazi-
Daubert relation for molecular weight.
where 99 is a physic~1
physical property : critical pressure or
temperature. molecular weight. etc. If 99 is the property
etc. If M=4 .5673 x 10 - 5 Ti
M=4.5673 262
T I %2 'Y
. -I.l}(().l
. ...

. . . ... . . . .
(16)
686
686 SOCIETY OF PETROLEU~
SOCIETY OF PETROLELM ENGI
ENGIEERS JOL RNAL
NEERS JOURNAL
A.2-S
A.2-5

which, when
when combined
combined with
with the detinition of
the definition K. yields
of K, yields TABLE 2COMPARISON
TABLE 2-COMPARISON OF TRUE (Eq.
OF TRUE 15) AND
(Eq. 15) AND ESTIMATED
ESTIMATED
17) WATSON
(Eq. 17)
(Eq. CHARACTERIZATION FACTORS
WATSON CHARACTERIZATION FACTORS
K4.5579 MO.15178 y"y o
K=4.5579 5178
M 84573 .
-o.~m . .. ... . ....... (17)
(17) Watson
Watson
Molecular
Molecular Specific
Specific Characterization Factor
Characterization Factor"
To test the validity
To validity of
of Eq. 17. 17. data from 12 12 systems
systems Sample
Sample Weight
Weight Gravity
Gravity Measured
Measured Calculated
Calculated
given
given inin Ref. 19.
19,99 from Ref.
Ref. 12. and 4 pure
12. and pure compounds
compounds 1 to A
A 110
A A 44 243
243 0.888
0.888 11.6
11.6 11.60
11.60
compared. K factors calculated from experimental
were compared. experimental A 5 to A 10
A5toAi0 191
191 0.828
0.828 11.9
11.9 1186
11 .86
data and the definition of K (Eq. 15).
data 15). using
using cubic
cubic A 11
A 11 187
187 0.837
0.837 11.7
11.7 11 .72
11.72
A 13
A 13 205
205 0.867
0.867 11 .6
11.6 11.54
11 .54
average boiling
average boiling point and specific gravity,
and specific are compared
gravity. are compared
81t083
B 1 to B 3 106
106 0 .733
0.733 12.0
12.0 12.03
12.03
with values estimated by by Eq.
Eq. 17 17 (see
(see Table
Table 2).
2) .
84
B4 114
114 0.739
0.739 12.0
12.0 12.08
12.08
characterization fac
A procedure based on the Watson characterization fac- 88t089
B8toB9 167
167 0.813
0.813 11.8
11 .8 11.81
11 .81
tor is proposed for estimating SCN boiling boiling points
points and 810
B to B8 12
10 to 12 158
158 0.800
0.800 11 .9
11.9 11.87
11 .87
specific gravities. It It is assumed that SCN SCN molecular
molecular 813
B13 114
114 0.765
0.765 11.7
11 .7 11.73
11 .73
available. for example from the molar
weights are available, molar 814
B 14 171
171 0.802
0.802 12.0
12.0 11.99
11.99
815
B 15 207
207 0.827
0.827 12.0
12.0 12.02
12.02
distribution model, and C C,,II ++ specific gravity is is deter
deter- 0.812 11.8 11.82
11.82
816
B16 167
167 0.812 11.8
mined experimentally. First. First. K is assumed constant for
assumed constant 11.87
Cl1
C 116
116 0.757
0.757 11.88
11 .88 11.87
all SCN fractions. SCN SCN specific gravities are are calculated
calculated C2
C 2 205
205 0.936
0.936 10.70
10.70 10.81
10.81
from Eq. 17 and molecular weights. weights. A A trial-and-error
trial-and-error C3
C3 245
245 0.848
0.848 11.92
11 .92 12.07
12.07
procedure is performed until a value of K gives SCN C4
C4 132
132 0.800
0.800 11.54
11 .54 11.55
11 .55
C5
C5 152
152 0.850
0.850 11.23
11 .23 11.21
11 .21
specific gravities with an average that matches m;tches the the
176
176 0.894
0.894 10.95
10.95 10.98
10.98
measured value. (Haaland 10 recently modified this pro
value . (Haaland

2 pro- C6
C 6
0.804
0.804 11.9
11 .9 11.84
11 .84
C7
C7 160
160
variation in K for
cedure by generalizing the variation tor SCN
SCN groups C8 195
195 0.826
0.826 11.91
11 .91 11.93
11 .93
up to C 4400
C
.) .) SCN boil ing points are calculated from K
boiling C9 107
107 0.771
0.n1 11.55
11 .55 11.54
11 .54
and SCN specific gravities (Eq. (Eq. 15). n-C s
5
n-C 72.1
72.1 0.636
0.636 12.94 12.80
12.80
As an alternative to this procedure. a set of general ized
generalized C
H
6
CeHe 78.05
78.05 0.882
0.882 9.75
9.75 9.82
9.82
properties is presented. They are modified from data data 6
n-C
nC s 11413
11413 0.707
0.707 12.65
12.65 12.54
12.54
C 7 He
8
H
7
C 92.06
92.06 0.870
0.870 10.16
10.16 10.19
10.19
Firoozabadi. 7 Unfortunately,
presented by Katz and Firoozabadi.
7 Unfortunately. it
may be difficult to match measured C/I C,, + specific gravity Samples labeled
Samples A and
labeled A and 8B are
are CC 7.
7 * Iracllons. whereas
Iractions, whereas samples labeled
labeled C are Slock
Care stock-
if generalized SCN values are used. used. lank samples The
001 samples
lank oil our samples
last lour
The lasl are pare
samples are pure componenlS
componenls

Generalized Physical Properties


It was found that tabulated molecular weights (Table I1 of
Ref. 7) were inconsistent with plotted data (Fig
Ref. (Fig.. 2 of
_
c
5
=
1

4
0
.
0 y, =0.14
668
OCI_C; .i c "Y; -0.0668 . . . . .... .. . .. . . . . (18)
Ref. 7). Molecular weights tor for SCN groups 22 through
45 are clearly inconsistent. An analysis and comparison
18 and binary interaction coefficients presented in
Eq. 18
of both sets of data with sources from which they were
graphically presented Table 33 should be used only with the Peng-Robinson
developed indicated that the graphicully EOS.:!1 -
22
EOS.
molecular weights were more correct (the tabulated ex
tabulated ex-
trapolation for C 22
C 11 through C 45
C 45 results merely from ad- ad Regrouping (Pseudoization) and
dition of 14 to the previous molecular weight). Mixing Rules
Instead of reading numerical values from Fig. II of
Ref. 7. the extrapolation was performed using the Riazi- Riazi The cost and resources required for simulating phase and
Daubert correlation form (Eq. 16) based on generalized volumetric behavior increases considerably with the
gravities.. Since tabulated and number of components used to describe the fluid fluid..
boiling points and specific gravities
graphical values of molecular weight in the region C 6II
C Some authors have suggested that us as few as 2 or as
through C 22
C consistent, these values were tit
11 were consistent. fit by many as 50 components may be required to predict
regression, yielding modified constants:
nonlinear regression. constants: behavior. In general. it might be reasoned
reservoir-fluid behavior.
=2.4820 x 10-
aa=2.4820x 10. 7 b=2.9223
b2.9223.. and C=2A750.
C=2.4750, Molec-
Molec that the accuracy of EOS p"redictions increases with the
predictions inc-reases
ular weights in Table 3 tor for C
2
C 11 through C 45
C 45 were calcu-
calcu number of components used to describe the reservoir
lated using these constants in Eq. 14 instead of those in fluid.. Based on experience. two observations can be
fluid
Eq. 16. Other molecular weights (C 66 through C11)
(C C22 are made: (I)
made: (1) it is not merely the number of fractions used.
the same as as originally presented in Ref.Ref. 77.. SCN normal but what spectra of components they represent that af- af
boiling points and specific gravities (converted from fects the accuracy of predictions. and (2) with proper
originally reported.
densities) are also the same as Originally grouping. the increase in accuracy resulting from more
Critical properties of SCN
Critical SCN groups 6 through 45 were rapidly..
fractions diminishes rapidly
calculated using Eq Eq.. 14 appropriate constants in
14 and appropriate following.
Questions arising in this regard include the tollowing:.
Table I.1. [Modified constants
constants with boiling points greater I1.. How many pseudocomponents are required? -
730 K (850F)
(850F) were used for criticalcritical pressure 2. How should they be he chosen from a partial or com-com
than 730
estimation.jJ Acentric factors were calculated using the
estimation. plete C 77 + analysis?
C
Edmister equation. 11 - 3. What mixing rulesrales should be used for calculating
Binary interaction
interaction coefficients between methane and pseudocomponents?
properties of the pseudocomponents"? -
SCN groups are are also
also presented in Table 3. Thev They were Based on preliminary results of EOS predictions tor for
estimated from the graphical correlation propo~ed proposed by fluids, several guidelines are proposed for the
reservoir fluids.
and Firoozabadi. 7 represented by
Katz and pseudoization process.

AUGUST
AUGUST 1983
1983 687
687
A.2-6
A.26

TABLE 3GENERALIZED
TABLE SINGLECARSONNUMBER PHYSICAL
3-GENERALIZED SINGLE-CARBON-NUMBER PHYSICAL PROPERTIES
PROPERTIES

Watson
Watson PR
PR EQS
EOS
Normal
Normal Specific
Specific Character-
Character Critical
Critical Critical
Critical Methane
Methane
Boiling Point
Boiling Point Gravity
Gravity ization
ization Molecular
Molecular Temperature
Temperature Pressure
Pressure Acentric
Acentric Interaction
Interaction
SCN
SCN ~~
(K) (R) (60/60)
(60/60) Faclor
Factor Weight
Weight (K)
~ ....L!!!..
(CR) (kPa)
(kPa) (psia)
(psia) Factor
Factor Coefficient
Coefficient
66 337
337 607
607 0.690
0.690 12.27
12.27 84
84 512
512 923
923 3340
3340 483
483 0.250
0.250 0.0298
0.0298
77 366
366 658
658 0.727
0.727 11 .96
11.96 96
96 548
548 985
985 3110
3110 453
453 0.280
0.280 0.0350
0.0350
88 390
390 702
702 0.749
0.749 11 .87
11.87 107
107 575
575 1036
1036 2880
2880 419
419 0.312
0.312 0.0381
0.0381
99 416
416 748
748 0.768
0.768 11 .82
1182 121
121 603
603 1085
1085 2630
2630 383
383 0.348
0.348 0.0407
0.0407
10
10 439
439 791
791 0.782
0.782 11 .83
11.83 134
134 626
626 1128
1128 2420
2420 351
351 0.385
0.385 0.0427
0.0427
11
11 461
461 829
829 0.793
0.793 11.85
11.85 147
147 648
648 1166
1166 2230
2230 325
325 0.419
0.419 0.0442
0.0442
12
12 482
482 867
867 0.804
0.804 11.86
11.86 161
161 668
668 1203
1203 2080
2080 302
302 0.454
0.454 0.0458
0.0458
13
13 501
501 901
901 0.815
0.815 11 .85
11.85 175
175 687
687 1236
1236 1960
1960 286
286 0.484
0.484 00473
0.0473
14
14 520
520 936
936 0.826
0.826 11.84
11.84 190
190 706
706 1270
1270 1860
1860 270
270 0.516
0 .516 00488
0.0488
15
15 539
539 971
971 0.836
0836 11 .84
11.84 206
206 724
724 1304
1304 1760
1760 255
255 0.550
0.550 0.0502
0.0502
16
16 557
557 1002
1002 0.843
0.843 11.87
11.87 222
222 740
740 1332
1332 1660
1660 241
241 0.582
0.582 0.0512
0.0512
17
17 573
573 1032
1032 0.851
0.851 11 .87
11.87 237
237 755
755 1360
1360 1590
1590 230
230 0.613
0.613 0.0523
0.0523
18
18 586
586 1055
1055 0.856
0.856 11 .89
11.89 251
251 767
767 1380
1380 1530
1530 222
222 0.638
0.638 00530
0.0530
19
19 598
598 1077
1077 0.861
0.861 11.91
11.91 263
263 778
778 1400
1400 1480
1480 214
214 0.662
0.662 0.0537
0.0537
20
20 612
612 1101
1101 0.866
0.866 11 .92
11.92 275
275 790
790 1421
1421 1420
1420 207
207 0.690
0.690 0.0544
0.0544
21
21 624
624 1124
1124 0.871
0.871 11.94
11.94 291
291 801
801 1442
1442 1380
1380 200
200 0.717
0.717 0.0551
0.0551
22
22 637
637 1146
1146 0.876
0.876 11 .95
11.95 300
300 812
812 1461
1461 1330
1330 193
193 0.743
0.743 0.0558
0.0558
23
23 648
648 1167
1167 0.881
0.881 11.95
11.95 312
312 822
822 1480
1480 1300
1300 188
188 0.768
0.768 0.0565
0.0565
24
24 659
659 1187
1187 0.885
0.885 11 .96
11.96 324
324 832
832 1497
1497 1260
1260 182
182 0.793
0.793 0.0571
0.0571
25
25 671
671 1207
1207 0.888
0.888 11 .99
11.99 337
337 842
842 1515
1515 1220
1220 177
177 0.819
0.819 0.0575
0.0575
26
26 681
681 1226
1226 0.892
0.892 12.00
12.00 349
349 850
850 1531
1531 1190
1190 173
173 0.844
0.844 0.0581
0.0581
27
27 691
691 1244
1244 0.896
0.896 12.00
12.00 360
360 859
859 1547
1547 1160
1160 169
169 0868
0.868 0.0586
0.0586
28
28 701
701 1262
1262 0.899
0.899 12.02
12.02 372
372 867
867 1562
1562 1130
1130 165
165 0894
0.894 0.0591
0.0591
29 709 1277
1277 0.902 12.03
12.03 382
382 874
874 1574
1574 1110
1110 161
161 0.915
0.915 0.0595
0.0595
30
30 7i9
719 1294
1294 0.905 12.04
12.04 394
394 882
882 1589
1589 1090
1090 158
158 0.941
0.941 0.0599
0.0599
31
31 728
728 1310
1310 0.909 12.04
12.04 404
404 890
890 1603
1603 984
984 143
143 0.897
0.897 0.0605
0.0605
32
32 737
737 1326
1326 0.912
0.912 12.05
12.05 415
415 898
898 1616
1616 952
952 138
138 0.909
0.909 0.0609
0.0609
33 745
745 1341
1341 0.915
0.915 12.05
12.05 426
426 905
905 1629
1629 926
926 134
134 0.921
0.921 0.0613
0.0613
34
34 753
753 1355
1355 0.917
0.917 12.07
12.07 437
437 911
911 1640
1640 896
896 130
130 0.932
0.932 00.0616
.0616
35
35 760
760 1368
1368 0.920
0920 12.07
12.07 445 917 1651
1651 877
877 127
127 0.942
0.942 0.0620
0.0620
36 768 1382 0.922
0922 12.08
12.08 456
456 924
924 1662 850 124
124 0954
0.954 0.0623
37 774 1394
1394 0.925 12.08
12.08 464
464 929
929 1673
1673 836 121
121 0.964
0.964 0.0627
0.0627
38 782 1407 0.927 1209
1209 475
475 935 1683
1683 811
811 118 0975
0.975 0.0630
0.0630
39 788 1419
1419 0.929 12.10
12.10 484 940 1693
1693 795
795 115
115 0.985 0.0633
0.0633
40 796 1432 0.931 12.11
12.11 495 947 1703
1703 771
771 112 0.997 0.0635
0.0635
41 801 1442 0.933 12.11
12.11 502 951
951 1712
1712 760
760 110
110 11.006
006 0.0638
0.0638
42 807 1453 0.934 12.13
12.13 512 955 1720
1720 741 108
108 1 016
1.016 00640
0.0640
43 813 1464 0.936 12.13
1213 521 960 1729
1729 727 105 1 026
1.026 00642
44 821 1477 0.938 12.14
1214 531 967 1739 706 103 1 038
1038 000645
.0645
45 826 1487 0.940 12.14 539 97i
971 1747
1747 696 101
101 1 048
1.048 00.0648
,0648

Regrouping Scheme M is the molecular weight of the last SCN group


where M.v
Consider EOS EQS predictions
predictions using two groupings of C 77 .,.
C fraction.. and 1=
(which may actually be a plus fraction) 1 1.I. 1
2
SCN fractions: (I) (1) C
.
7
C 7. CC.II. C ~. C
C.. 110.
C
. 0 C 1II
C
. 1 and C 1
C
. 112- ... NN,.
- ~. Molecular weights of SCN groups falling
and (2) C 1II.I~'
C
7.1(}. C
C7.m. is.. C 1~-15.
1-14 C 15.18. 9-25 and C .
5
C2 will
It will
1ti-'5 ' It within the boundaries of these values are included in the
be shown that the latter choice yields considerably considerably better MCN group. I.
results than the tonner.former, with aa complete SCN SCN description
of
of the
the C 77 + fraction
C
fraction used
used asas the base of comparison.
base of comparison. (See Mixing Rules
:vIixing
Figs. 2a and lb.)
2a and 2b Two sets of mixing rules for calculating .:ritical proper
critical proper-
AA method
method is proposed tor for estimating the number of of ties (including acentric factor and
(including acentric and specitic gravit) of
specific gravity) of
MCN
MCN groups needed needed torfor adequate plus-fraction
plus-fraction descrip-
descrip discussed The pseudoization process
MCN groups are discussed.
tion.
tion, as as well as as which
which SCNSCN groups belong
belong to the MCN does not appear. from preliminary calculations.
from preliminary in
calculations, to in-
group. It
group. It is
is based
based onon Sturge's rule and
Sturges rule and the
the observation
ohseration fluence EOS
tluence completeness.
greatly. For completeness.
EQS predictions greatly.
that the
the proposed
proposed distribution
distribution model
model isis similar
similar to aa tolded
folded however, both
however. compared
both methods of pseudoization are compared.
log-nonnal
lognormal distribution.
distribution. TheThe number of of MCN groups.
MCN groups. Method II employs simple molar weighting . 13 Method 2
N g is
N:,. is given by by relies onon various average boiling points to calculatecalculate
MCN properties.
V~ =
N Int(lI +
=IntI 3.3 'Iog
+3.3 log w(N
- V
01 II
-II). .. . .......... (19)
(19) volumetric propertie~
and volumetric
Molar and of MCN
properties of \4C groups
groups are
are
always calculated
always calculated using the mIxing
using the mixing rules
rule
For
For black-oil
black-oil systems. this number
systems. this probably can
number probably can be
he ,
reduced
reduced by
The
by one
one .
The molecular
molecular weIghts
weights separating
separating each
each MCN
MCN group
croup
M,= L: (:.;1:.,)
) M(
(2, i1, (21)
................. . ... (2 1)
are
are taken
taken as
as and
and

M, =M"
M, exp( I/N~)
=M !exp!1 lI:V) 'IntM M,, )I '.
1mM vIIW,,)1I
(20) . . .. . .... . (22))
. (22

688
h88 SOCIETN OF
SOCIETY OF PETROLEUM E\Gl.EERSJO1
PETR)LEL\l E'IGI~EERS R\L
JOURNAL
A.2-7
A.2-7

and Ref. 12 suggests


Ref. 12 suggests that
that pseudocriticai
pseudocritical volume
volume should
should 0.7
and
(b)
be calculated
be calculated using
using weight
weight fractions
fractions 0.8
LIOUID
u
C,
~
C,

1 E
a. 0.5
L: (f/f,,,)
(/. .;lIIV/) V,:i
0,

Vpd=
V
,
0= V d . . . . . . . . . . . . . . . . . . (23)
(23) >=
>-

~
U)
zz
0.4
UI
~ 0.3
where z,
where and i ...1 are the
z/ and the sums of Zi and
of , I ...i found inin
and f,., o
w
Lii
MCN group
MCN group I. I
!C 0.2

~
MCN acentric
MCN acentric factors
factors are
are usually
usually calculated
calculated using
using D
I
Kay's mixing
Kays mixing rule,
rule. though
though Robinson
Robinson and Peng 5 suggest
and Peng
3 suggest en
U) 0.1
aa considerably
considerably more
more complicated
complicated expression.
expression.
w/=
WI -log 10
= logo 300 400 500 800 700 800

1
[[ L: (z/c,)p
(z;!Z/)'Pd .1O-II+
10 Wi l]/Pd) 1.0.
1w]/p,}
-1.0 .... (24)
(24) .

2500
(a)

of PNA groups with


with aa .. 2
for averaging the acentric factor of
given SCN. No comparison document the ad
comparison is given to document ad-
...
Q.

'c
vantage of using Eq. 24. Ii 1500 C,4
~~~I.Ml
"""
___ .D.u~!!I!!lOJ-.. ___ '-lI:j_
'c
.!~.!l_

iiJen
....'... .,...,..
SCN 'IICH 1111 l1U
So -"CN ''!is '1Il
Method 1: Pseudocritical Mixing Rules. On the
1: Pseudocritical the basis
basis ~ 1000 ,. SCN 6ll!.
Q. a - ll'SiCNI

..
24. one can use pseudocnticai
of results given in Ref. 24, pseudocritical a ' I I I ' $CNI l SI'

Kays mixing
pressure and temperature calculated using Kay's 500 , l CiII(&SU'fO,lIorllllllU
'ST I~.':"I 0' aClf Io1'1!

rule in the Peng-Robinson EOS22 22 with reasonable


E0S
processes. No indication
matching success of thermal processes. o
200 300 400 500
500 600
600 700
700 800
BOO
was given.
given, however.
however, whether the same was true for more
TEMPERATURE. K
TEMPERATURE. K
complicated systems such as miscible gas injection.
However.
However, since the mixing rules are simple and easy to 2Effect 01
Fig. 2-EHect .
7
C
of several C Peng
7 + characterizations on Peng-
apply. they are presented as Method I1 in this paper. Robinson EOS for the HoHman
EQS predictions lor Hoffman et a/.
al.
1 reservoir oil.
P pel =
=L: (z,I:/) P"I'
(/c!) p (23)
. . . . . . . . . . . . . . ..... . (25)
,
= L: (z;!z,)T.-;
TfI("=
1
T,. (z,/z,)T,., . ........... .. .. .... (26)
True critical temperature of MCN groups is calculated
and
, using weight-average boiling point.

w,= L: (z;!z,)w; . (27) Tel


Ti., =a T b y . . . .. . .. .... . .. . .. ... .. .. (30a)
bw' -y".
T,,,.,
Method 2: A vel"..ge Boiling Points. This method is
Average molal
Pseudocritical temperatures are calculated using molal-
based on relations developed between molal-. weight-.
average boiling points.
and mean-average boiling points.
points, and pseudocritical
pseudocntical and
critical properties. 122 h , -y... . . ... . ... . ..... . ....... . (30b)
Molal-average boiling point for for MCN groups is
T,,,., =a T
1
Tb,,,,,,,
hlll

,
calculated using Kay's
Kays mixing rule. Pseudoreduced
Pseudo temperature. used for calculating
reduced critical to!mperature.
defined by
pseudocritical pressure. isis then detined
TT,,,,=
hlll ,= L: (z/z,)T/J;
)T .
(c,/c
,
1 (28a)
. . . .. .. .. . . . . . . .. (28a)
TC,/T[N.,
Tprc.i TcflTflcf.
Tflrcl=a (30c)
. . ... . . . . .. . . . . . .. . ... . .. (30c)
Weight-average
Weight-average boiling
boiling point
point for
for MCN
MCN groups
groups is
is
calculated
calculated using
using weight
weight fractions
fractions as
as the mixing using mean-
are calculated using
pressures are
Pseudocritical pressures
Pseudocritical
,
parameter and
and isis given
given by
by average boiling
average point.
boiling point.
1=
Thll"
T,,,, = L: CI,,;li,,,)
f],., /f.,) T!Ji
T,, . . . . . . . . .... . . . (28b)
(28b)
PfleI=aTh,b
P,wi =0 Tb,
b (3 Ia)
-y' . . . . .. .. . . ....... ... ... .. (3Ia) . .

Cubic-average
,
Cubic-average boiling
boiling point
point isis given
given by
by
pseudoreduced
graphical relation between pseudo
The graphical cntical
reduced critical
=[ L: (fl/li,.,)T,,;,
Thd=[
1
T,,,. j . .. .. . .. ... ... (28c)
(f,,if.,) T,,, j3 (28c) temperature
to give
curve-fit to
curve-tit give
pseudoreduced
and pseudo
temperature and cnticai pressure
reduced critical was
pressure 12 was
where
where volume
volume fractions
, /, are
fractions], are merely given by
merely given by

rcf = 1+8.467' 29 56T, (31b)


f,;=/".;/-y;./,., = L: III
Pfl
P/,r(I +8.467Tt 2
i.654T
T+ 1.654 T1 +2956, T3. . . (31 b)
i, f,,.' ... . . . . .. .... ... (29)
.

(29)
Mean-averuge
Mean-average boiling point. T",.
boiling point. T,,,, isis detined as the
defined as arith
the arith- where T=
where T"rcl-1.1. Combining
TTpr,.i Eqs. 31a
Combining Eqs. 31a and Sib
and 31 yields
b yields
metic
metic avenlge
average of
of true
true molal-
molal- and
and cubic-average boiling
cubic-average boiling the relation
the relation for calculating critical
for calculating of MCN
pressure of
critical pressure \ICN
points.
points. groups.
groups.
AUGUST
LtJGUST 1983
983 689
689
A.2-8
A.2-8
0.04 rL..,.,-....-..-,.----,......-';........-.----,..-.--.....,
0.04
PcI=PprclPpcl' . . . . . . . . . . . . . . .. . .. . . .. . . . . (32)
(32)
-: c/ =PprdPpc!
~ exPfRIMEHTAL
EXPERIMENTAL
...\ ....
~ - - ESTIMATED a- 1.61
ESTIMATED - 1.8 I
Critical
Critical volumes
volumes can be estimated
can be using mean-average
estimated using mean-average
Z 0.03
0.03 USING
USING C7.Ce,Cg.C,a. boiling point.
boiling point.
t;:.... ~\. .

Q
O I ESTIMATED
ESTIMATeD -a- 1.86
1.se

~
.... USING
USING 8
,
7
C Ce, -.C20.
C7,C 20
C
.

:...
C.)
Vja T,fj ................. .. .. ... .. . (33)
(33)
LI.. 0.02l
0.02 / \ ..
w
LU
.....
-J
o
O
::i
t
L ! ..
Constants
ing
a. b,
Constants a,
on which
ing on
b. and
which property
are those
and cc are those found
found in Table 1,I. depend
in Table
being estimated.
is being
property is estimated.
depend-

0.01
0.01 l
Results and Discussion
Results and Discussion
I-
Molar Distribution
Molar Example: Reservoir
Distribution Example: Reservoir Oil Oil
0.0
0.0 ~~-""""'-'--'--~l-......-~...........&..-'-'o_.......I-"':::;:::~ Experimental data
Experimental presented by
data presented by Hoffman
Hoffman er II. 15 ft)r
et a!. for
o
0 100
100 200
200 300
300 400
400 500
500
calculating
calculating critical
critical properties
properties of reservoir black
of aa reservoir black oil oil con
con-
MOLECULAR WEIGHT
MOLECULAR WEIGHT
stitute
stitute one of the
one of most comprehensive
the most comprehensive analyses analyses available
available
Fig. 3Comparison
Fig. 3-Companson of of experimental
experimental and
and estimated
estimated molar
molar in the
itt literature: mole
the literature: fmctions, molecular weights.
mole fractions, weights.
distribution tar
distribution for the
the Hoffman et al.
Hoffman et a/. reservoir oil C
reservoir oil C7
.
7 gravities, and normal boiling
specific gravities,
specific points are
boiling points are reported
reponed
(CMWI's used).
fraction (CMWts for SCN groups 77 through
SCN groups through 35. 35.
The
The Ref. 25 25 oil was chosen
chosen to to illustrate
illusu-.ue the the versatility
versatility
proposed molar distribution model.
of the proposed exhibits a
model. ItIt exhibits
distribution. which is
bimodal molar distribution, is unusual. This This
special case
special case reveals limitations of of the proposed model.
but also shows its flexibility.
but also flexibility .
0.04
0.04.-, --...,...----T. . . . --.-,--.. . . .,.......--.,.---_- complete 35
The complete 7
C 7-through-C ~5 molar
-Cthrough-C
reduced to three partial analyses: analyses: (1) .
7
C
(I) C 7. C
analysts was
molar analysts
.
5
C
was
II. Cq.
C 9,
EXPERIMENTAL
EXPERIMENTAL -
C IS"':: and (3) C .
7
-
CIQ+;
10
C
(2) C .
7
C 7 , C, C M . .
1
C C7.
: 6.--A EXPERIMENTAL WEIGHT
0.031-
0.o3-
EXPERIMENTALWEIGHT
ERACTIONS CONVERTEO
FRACTIONS. CONVERTED -l
8
C
C 8 .. . C
. 0
C ~o + . These were first used to estimate
. c!stimate a us us-
z
z \ SING PARAFFIN
uSING ARARFIN
8 ing Eq. 10 correction tables.
10 and correction Next. the partial molar
tables. Next,
Q
0 \ '~OL=CULAR WEIGHTS
VO.ECuLAP .IEi0iTS
t-
-

. O) distributions were fit tit using the CMWI-2 method method.. Final- Final
oC0
-

B
8 \lATCHEO
MATCHED WEIGHT
WEIGhT
C
C. - .,/
Iy.
ly, the partial weight distribution C II . 11 .
. . .. C 15 -
~
.
ONS I "'.
FRACTIONS .601
= 1.501
U 0.02t-

0.02
-B
C
C EXTENOEO
EXTENDED MOLAR -
was tit fit using the variable VMWI method.
W
..... DISTRIBuTION Estimates of a calculated from Eq. 10 and correcllon correction
o:;
0
-

- 0 -
:5 tables were I. 1.61. 1,81.
61. I. 81. and 1.86
I. 86 for the three partial
0.01-
O.o1
analyses. respectively. Corresponding values of 17q were
C3S 91.6. 91 .2 and 91.1.
91.6,91.2 91. 1. Using these parameters in the pro- pro
/ \ distribu
0.0 ......_ _........._ _ _ _ _ _ _ _ _-....;;;::o=.::..O.=--_6_~ posed probabilistic model gave the two molar distribu-
ao I 86..
o 100 200 300 400 500 600 tions presented in Fig. 3 for a= I 61 and a=
a = 1.61 a 1.86
MOLECULAR
MOLECULAR WEIGHT
WEIGHT When the same three panial distributions were
partial molar distnbution~
fit using the CMWI-2 procedure (olM, (.M = = 14 and
Fig.
Fig. 4-Comparison
4Comparison of experimental
experimental and convertedl 7=
M
M7 = 100). optimal values of a= a= 1.78. 1.93 1.93.. and 1.64
matched/extended
matched/extended molar distributions for the calculated Corresponding value~
were calculated. values of 'q1 were 91 .2. 2.
Hoffman et
Hoffman et a/.
al. reservoir
reservoir oil
oil C
.
7
C 7 ' fraction
fraction (VMWl's
(VMWIs
91.0. and 91.5. Each distribution was extended to C .1 5
used
used in
in Region
Region 8).
B).
by using the same molecular weight interval. interval. Results
were nearly identical to those presented in Fig. 3. 3
Although matches of molar distribullon~ presented in
distributions presc!med
Fig. 3 are reasonable. the proposc!d proposed model did not
0.4
3.4 reproduce bimodal behavior. Another
reproduce nother approach wa~ was
c\
chosen to extend
chosen extend the C C 15
5 - panial analysis..
partial analysi~
.'. EXPERIMENTAL
EXPERIMENTAL
Fig. 44 presents
Fig. presents the matched matched and extended molar
and c!;'(tended molar
6c.
- BSTIMATE0.
ESTIMATED 1.18
",. 1.18
0.3~
Q3.\ distribution. First. First, weight fmctions fractions of SCN SCN groups 7
oil 7 _ _.- MATCHED
~ MATCHED.a. 1.10
I.I0
zz
.

fractions by using
-

00 through 10 10 were converted to mole fractions


were convened
;::

.
0C.) paraffin molecular weights. Weight
paraffin molecular fractions of
Weight fraction~ carbon
of ~arbon
number groups
groups 11 through 15
II through 15 + were thenthen titfit byh u!>ing
using
...
a:LI.. 0.2,...
0.2 number
g= 148
17= (calculated from
148 (calculated from Eq.Eq .3ht
were
3b) and V.IWI method
the VMWI
and the method .
w "
....I
00 Optimal aa was
Optimal was 1.5. although values
1.5, although values II A4 to to 1.6 ielded
I 6 yiclded
::;
0.1-
0.1- near-perfect matches..
near-perfect matches

Iolar Distribution
Molar Distribution Example: Reservoir Gas
Example: Reservoir (as
0.0 '
100
100 150
150 200
200 250
250 300
.300 350
350 a!. 15 present
er ul.
I-Iottman er
Hoffman data for
experimental data
present c!;'(penmemal or the 7-
C
the C.,
MOLECULAR
MOLECULAR WEIGHT
WEIGHT fraction of
fraction the gal>
of the gas-cap
-~ap tluid associated owv i(h
fluid Jssociatc!d ith (hc previous
the previou~
reservoir oil.
reservoir The complete
oil. The complete molar distribution was
molar distribution was reo
re
Fig.
Fig. 5-Comparison
5Comparison of of experimental
experimental andand estimated/matched
estimated/matchea
molar
molar distributions
distributions for
for the
the Hoffman et a/
Hoffman at al reservoir
reservoir gas
gas duced to
duced to the same three
the ~ame anal\ses a:-.
panial analy~es
three panial as Inin (he
the
CC,l ' fraction
fraction (CMWl's
(CMWI s used)
- useo) previous example
prevlou~ example . Estimated
Estimated value~ from Eq.
of C{a from
values of Eq. 10 it)

090 SOt ii: Fy OF


,)OCIET'r 1W PETROLEL\I 10 R\.\L
EMiI\ E[:RS JOUR:"JAL
PETROLEI.\l E:"IGI:'I.EERS


A.2-9
TABLE 4COMPARISON OF SCN CRITICAL PROPERTIES BASED ON EXPERIMENTAL AND
TABLE 4-COMPARISON
ESTIMATED BOILING POINTS AND SPECIFIC GRAVITIES

Based on KK Factors From Eqs. 18a through 18d


Boiling
Based on Experimental BOiling and Paraffin Mole Weights
Points and Specific Gravities
Normal
Critical Boiling Specific
Boiling Critical
Pressure Temperature Acentric Point Gravity Pressure Temperature Acentric
SCN (kPa) (K) Factor ~ (K) (60/60)
(60160) (kPa) (K) Factor
7 3223 559.1 0.2763 349.1 0.6981 3162 525.5 0.2679
8 2814 585.3 0.3228 379.0 0.7253 2857 559.1 0.3080
9 2603 612.8 0.3565 407.7 0.7513 2620 591.0 0.3457
10 2348 634.4 0.3981 435.2 0.7764 2430 621.5 0.3815
11 2179 656.0 0.4328 462.0 0.8008 2275 651.0 0.4155
12
12 2056 676.8 0.4632 484.4 0.8120 2105 672.8 0.4526
13
13 1957
1957 696.6 0.4912 505.7 0.8212 1956 692.8 0.4896
14
14 1908
1908 717.2 0.5 107
0.5107 526.1 0.8295 1828 711.7 0.5263
15
15 1811
1811 733.4 0.5404 546.0 0.8382 1718 730.1 0.5626
16
16 1682 745.6 0.5800 565.3 0.8462 1621 747.7 0.5989
17 1519 753.2 0.6350 583.6 0.8526 1533 764.0 0.6357
18 1465 767.2 0.6623 601.3 0.8586 1454 779.5 0.6729
19 1406 779.6 0.6926 618.8 0.8651 1385 794.9 0.7100
20 1409 796.5 0.7002 636.2 0.8723 1324 810.4 0.7468
21 1368 808.6 0.7248 652.7 0.8780 1266 824.7 0.7847
22 1328 820.0 0.7499 669.3 0.8845 1216 839.1 0.8225
23 1311 827.1 0.7625 685.1 0.8896 1168 852.5 0.8617
24 1274 836.8 0.7879 700.9 0.8955 1125 866.0 0.9008
25 1239 846.3 0.8130 716.7 0.9022 1087 879.9 0.9397
26 1204 855.2 0.8396 732.3 0.9087 961 893.4 0.9033
27 1171 863.9 0.8661 747.6 0.9150 913 906.5 0.9245
28 1142 872.4 0.8924 762.6 0.9211 870 919.4 0.9460
29 1111
1111 880.2 0.9203 m.3
777.3 0.9270 830 932.0 0.9678
30 1083 887.8 0.9479 791.9 0.9327 793 944.3 0.9900
31 972 895.1 0.9036 806.2 0.9383 759 956.3 1.0125
32 937 902.1 0.9161 820.3 0.9437 728 968.1 1.0354
33 906 908.7 0.9281 834.2 0.9490 698 979.7 1.0587
1.0587
34 874 914.7 0.9400 847.8 0.9542 671 991.1 1.0826
35 846 920.3 0.9513 958.9 0.9942 496 1081.3 1.3149

Multi-Carbon-Number properties Multi-Carbon-Number properties


using Kay's
Kays mixing rule using average boiling points
2765 596.4 0.3359 2816 599.6 0.3359
2014 689.3 0.4777
0.4m 2044 691.3 O.4m
0.4777
1669
1669 745.5 0.5875 1671 746.6 0.5875
1356
1356 807.9 0.7315 1370
1370 809.6 0.7315
1065 883.1 0.9004 1112
1112 885.2 0.9004

and correction tables were 1.18.1.18, 1.20.


1.20, and 1.21. respec
1.21, respec- posed by Haaland
20
Haaland 20 and molecular weights resulting
tively. The value of 11 was 92.6 for all three estimates from the match and extension of C ,
7
C ,
8
C
7. C ,
9
C
8, C 9, and C \0o+
cr.
of a. data presented earlier. This case might represent a
partial analyses were fit by the CMWI-2
The three panial typical situation when few experimental data are
method (aM; (jaW, =
= 14 andR 77 =
and M = 100). Optimal values of a Cr availablei.e.,. a worst-case example.
available-i.e
1. 10, 1.07.
were 1.10. 1.08, with corresponding values of
1.07, and 1.08. SCN physical properties calculated from measured
=93.0. 93.1, and 93.1
11=93.0.93.1. boiling points and specific gravities were then regrouped
Fig. 5 presents the predicted molar distributions. using the two procedures outlined previously under
There was essentially no difference between predicted Regmuping (Pseudoization) and Mixing Rules..
"Regrouping Rules.... Table
partial distributions-i.e.,
distributions for the three panial distributionsi.e.. it 4 presents these results. Little difference in MCN prop-prop
was sufficient to use only C ,
7
C 1\00+ mole (or
C
+
88 . . . C
C
7, C . . . observed, though it may be more pronounced as
erties is observed.
weight) fractions to yield an excellent match of the com-com the number of MCN groups decreases.
plete molar distribution.
EOS Application: Reservoir Oil
Physical Properties Example: Reservoir Oil The previous examples are attempts to illustrate how the
This example is divided into two parts: (1) estimation of proposed methods can be used. They have also given an
SCN physical properties and (2) pseudoization or indication of the accuracy these methods provide. Since
regrouping of SCN physical properties. the purpose of C77 + characterization is to improve EOS
C --

Two sets of SCN physical properties were estimated predictions. several examples were generated using the
using the Riazi-Daubert correlations (Eq. 14 and Table Peng-Robinson EOS. The Hoffman et at. reservoir oil
er al.
1); Table 4 gives these results. The first set was was chosen since it offered a sound basis for com- corn
calculated from measured boiling points and specific parisonie..
parison-i.e complete, ex-
EQS predictions based on complete.
. EOS cx
gravities reported by Hoffman et
er al.
at. The second set was perirnental molar distribution and properties.
perimental
calculated using the variable K-factor correlation pro-
pro.. EQS predictions were used to compare various
Three EOS
AUGUST 1983 691
A.2-10
A.2-1O

+
7
C
C 7 + characterizations: (I) (1) phase envelope estimation 3. A method is proposed for estimating specific
(bubble- and dewpoint loci). (2) critical point estimation of SCN groups. It is based on
gravities and boiling points ofSCN
and (3) equilibrium phase density estimation. Although factor, which is assumed
the Watson characterization factor.
critical point and dewpoint regions of this system were constant for all SCN groups.
conditions, the exam-
clearly outside realistic operating conditions. exam 4. As an alternative to this method.
method, a set of genemlized
generalized
ple still gives an indication of C + characterization on
77 +
C physical properties is proposed. It is based on boiling
EOS
EQS predictions. points, gravities, and molecular weights
points. specific gravities.
EQS predictions for
Figs. 2a and 2b present results of EOS originally presented by Katz and Firoozabadi. Molecular
five different C77 +
C + characterizations. Brief descriptions weights for SCN groups 22 through 45 are extrapolated
of the five follow this section. All data used by the EQSEOS in a more consistent manner. The Riazi-Daubert correla-
correla
can be found in Table 4 or can be calculated using equa-equa tions are used to calculate generalized critical properties;
cases, the measured
tions presented in the text. For all cases. acentric factors and methane binary interaction coeffi-
coeffi
bubble-point pressure [2640 kPa at 366.9 K (383 psi at cients (for the Peng-Robinson EOS) are calculated using
200.8F)] was matched using the binary interaction other correlations.
coefficient between methane and the last component (be 5. A procedure is proposed for regrouping SCN groups
it an SCN or MCN fraction). into a minimum number of pseudocomponents. It
Case 3 represents the base case. All SCN measured estimates the number of MCN groups needed and deter deter-
acen
properties were used to estimate critical properties. acen- mines which SCN groups constitute each MCN group.
tric factors, and methane binary interaction coefficients. Two sets of mixing rules are proposed for calculating
The complete C 7
C
35 7 -through-C 35 molar distribution was
-through-C MCN critical properties.
also used. 6. Examples show that the accuracy of EQS EOS predic
predic-
Case 2 represents a regrouping of the SCN properties tions is not dependent merely on the number of C 7 ++
from Case 33 using the pseudocritical Kay's Kays mixing fractions but also on which components are tound found in
23
rule.
rule. 23 As indicated in Table 4 and substantiated by EOSEQS each fraction.
calculations, the two different mixing rules did not alter
calculations.
predictions appreciably.
Case I used the first four SCN properties from Case 3. Nomenclature
but lumped all remaining groups into a C 122 + fraction. a.b.c = = constants in the generalized physical-
The C 12 12 + properties were calculated using Kay's mi~
Kays mix properties correlation
rule,
ing rule. E(a) = error function
(a)
Cases 4 and 5 should be compared with each other.other, as If == frequency of occurrence
well as with Case 33 (base case). They represent. in a
sense, the worst possible cases. That is.
sense. distribu
is, molar distribu-
f,,. =
In. = weight fraction
tions were merely assigned values of a= c= I1 and 2. Also.
Also,
= single carbon number index (=n.
i =
they were extended only to C 2
C
.
222
+ . The C
7
C specific
7 + specitic
n+ I ... N)
n+l...N)
gravity and variable K factors:!o
20 were used to estimate
factors I == multiple carbon number index (= I. 2.
specific gravities and boiling points. These cases in in- 33...Ng)
... Ng)
(1) the intluence
dicate (I) influence of molar distribution and (2) the Ja = factor, fraction
= Jacoby aromaticity factor.
accuracy one might expect from EOS EQS predictions using K = = Watson Characterization Factor.
Factor, oR';'
R
only C 77 + properties and proposed methods of
C - m GG = = geometric average molecular weight
characterization. M = = molecular weight
weigh. kg/mol
Conclusions M n ~ = = molar average molecular weight.
weight. kg/mol
M = = average molecular weight. kg/mol
An attempt has been made to develop a systematic n = = first C,, + fraction
first SCN in a C"-

characterization scheme for describing the molar molar


distribution and physical properties of hydrocarbon plus
N = = last SCN (or MCN) in a C,, C" + fraction
fractions. Its purpose is to enhance the predictive Ng = = number of MCN groups
capabilities of EQSs applied to naturally occurring
of EOS's pp = = pressure. kPa (psia)
methods, as summa-
hydrocarbon mixtures. Proposed methods. summa p(x) =
p(x) = probability density function
here, were developed with the assumption that
rized here. P(X
P(X .t) =
Sx) = cumulative probability function
minimal experimental data are available and that a cer cer- T= = temperature. ORR (K)
necessary.
tain degree of estimation and extrapolation is necessary. Trb =
Ttb = true boiling point
1. A
I. A probabilistic model based on the gamma distribu
distribu- Tbb =
T = boiling point
tion function is proposed for describing the molar f h == mean average boiling pOint point
distribution of plus fractions such as C 77 + . This model
C - V = volume. m
V 33 (cu ft)
m
can be used to estimate.
estimate, match.
match, or extend experimental x = = measured variable
molar distributions. Examples are presented to illustrate xX == all values of variable
several uses of the proposed model.
2. The Riazi-Daubert generalized physical properties
y = = normalized molecular weight variable
correlation is extended for
fbr critical
cntical pressure estimation at Y= = variable
vanable in a estimation
estimation equation
equation

boiling points higher than 730 K K (850F). correla


850F. The 'correla- :: =
= mole fraction
non is also used to develop a generalized relation be
tion be-
weighi, specific gravity.
tween molecular weight. gravity, and the Wat-
Wat Subscripts
son characterization factor. b =
= boiling point

692
b92 SOCIETY OF PETROLEU~1
PETROLEI \1 ENGINEERS JOURNAL
JOURNAL

---
A.2-11
A.21 1
0.4' , - - -......- - - , - - - - - . - - - . - - - - . . . - -_ _
1.2
--JACOBY CORRELATION EO. A-I JSCN MO~ECU~R WEIGHTS 12.5
12.5
(AROMATICITY FACTOR. Ja) EO. 17 AIIO Sl'EClFIC GRAVITIES 0:

00
1.1 2uC
Co
III
0:
o...
0.40 U

0III0 !
CC
!. g z

. 1.0
...
g O,lI
.-
i
C,

>>. c
!:> 0.9 .... .. ~c:
~
~ ~ 120
20
> ~
4(
a:(Zr t 0 . c
::
u
0 0.81- 0.7 .' .. O.lD
~
z
Q(3
U.
!!a
0 .
0.5
0
~ ;
ua
(3
0.7 0.3
III
Q.
0.2 ,,--
CL 0.1 ......
U, 025
II)
o.o....~
0.6
~ __ __ __ ___ __
~ ~ ~ ~ ~_~
i " 5

50
50 100
100 150
150 200
200 250
250 300
300 350
350 5 10
IC 15
IS 20
20 25
25 lO
30 35
35
51NGLE
SINGLE CARSON
CARBON NUMBER
NUMBER
MOLECULAR WEIGHT
MOLEClA.AR WEIGHT

Fig. A-iComparison of
Fig. A-1-Comparison of specific gravity and
specific gravity and molecular
molecular Fig.
Fig. A-2-Comparison
A-2Comparison of of the
the variation
variation in
in two
two characterization
characterization
weight relations
weight relations based
based onon two
two different
different character-
character- factors as
factors as a function
function ofof SCN
SCN forfor the
the Hoffman
Hoffman sf
et a/.
al.
ization factors.
ization factors. reservoir
reservoir oil
oil C
77 +* fraction.
C fraction.

bc =
be = cubic volume average
cubic volume boiling point
average boiling References
bi = normal boiling point of SCN ii
= nonnal

bm = = molal average
average boiling point 1. Hopke, S.W.
I. Hopke. S.W. and
and Lin.
Liii. C.J.:
C.J.: "Applications
Applications of of the BWRS Equation
to Absorber Systems."
Systems. Proc Proc.,.. 53rd
53rd GasGas Processors
Processors Assn. Conven-
Conven
bw =
bw = weight average boiling point
average tion (\974)
(1974) 63-71.
63-71.
ce =
= critical property 22.. Bergman. D. F.: "Predicting
D.F.: Predicting the the Phase Behavior of Natural Gas in
cm = = molar critical property
Pipelines."
Pipelines. PhD dissenation.
dissertation. U. of Michigan. Ann Arbor (1976). 11976).
em
3. Erbar. J.H. Prediction of Absorber Oil K-Values and En-
J.H.:: "Prediction En
G = = geometric average
thalpies."
thaipies, Research Report 13. 13. Gas Processors Assn" Assn,. Tulsa
Im = liquid molar
1m (1977).
nn == first SCN group in the C"0 ++ fraction
C 44.. Cavett. R.H RH.:
tions-Vapor-Liquid
.: "Physical
Physical Data for Distillation Calcula-
tionsVapor-Liquid Equilibrium."
Equilibrium, Proc Proc.. . 27th APt
Calcula
API Meeting.
Meeting,
N = = last SCN (or MCN) in the C C4
n + fraction San Francisco (1962).
n+ = = plus fraction beginning with SCN group
5. Robinson. D.B. and Pengo Peng, D.-Y.
D.-Y.:: "The
The Characlerization
Characterization of Ihe the
cnn Heptanes and Heavier FmclionsFractions, ... Research Report 28. 28, Gas Proc
Proc-
C essors Assn
Assn.,.. Tulsa (1978).
N+ = last MCN group in the C 1n +
C, 4- fraction 6. Watson. K.M KM.. .. Nelson. E.F.,E.F .. and Murphy.
Murphy. G.B.: "Character-
Character
ization of Petroleum Fraclions."
ization Fractions, bid, Ind. and
and EnEng. Chem. (1935)
if. Chem. (19351 27.
27,
pc =
pc = pseudocritical property
1460-64.
1460-64.
pr =
pr = pseudoreduced critical property (from 7. Katz.
7. Katz. DL.
D.L. and Firoozabadi,
Firoozabadi. A. A.: Predicting
"Predictinll PhasePhase Behavior of
ec/epc)
9,.19 Condensate/Crude-OiI Systems Using Methane
Condensate/Crude-Oil Methan"e Interaction
Inleraction Coeffi
Coefti-
pc ) cients." J.J. Pet.
Per. Tech. (Nov(Nov.. 1978)
cients. 1978) 1649-55: Trans .. AIME. 228.
1649-55; Trans., 228.
= weight
w =
w 8. Pearson,
8. Pearson. K.: K. : Contributions
"Contributions to to the
Ihe Mathematical
Mathematical TheoryTheory of
Evolution. H.
Evolution. II. Skew
Skew Variations
Variations in in Homogeneous
Homogeneous Material.
Material."
Philosophical Trans .. Royal
Philosophical Trans., Royal Society
Society of of London,
London. Series
Series AA (1895)
(1895)
Greek
Greek 186,
186. 343-414.
343-'14.
9. Edmister.
9. Edmister. W.C.:
W.C.: Improved
"Improved Integral
Integml Technique
Technique for for Petroleum
Petroleum
Ot,13, T/ = parameters in the gamma distribution
= distribution Dislillation Calculations,
Distillation
1685-90.
1685-90.
Calculations." md. Ind. and and Eng.Eng. (hem,
Chem. (1955)
(1955) 47.47.
function 10.
10. Taylor.
Taylor. DL.D.L. andand Edmister,
Edmister. W.C.:
W.C .: Solutions
"Solulions for for Distillation
Distillalion
l' ==specific gravity
gravity at 60F
60F and
and 60
60 psia
psia Processes
Processes Treating
Treating Petroleum
Petroleum Fractions,
Fractions." AIChE 4IChEJ. J. (Nov.
(Nov. 1971)
1971)
r = gamma
= gamma function 17.
17. 1324-29.
1324-29.
11. Greenwood,
11. Greenwood. iA. J .A. and
and Durand,
Durand. D D.:: "Aids
Aids forfor Fitting
Fitting the
Ihe Gamma
Gamma
5
~ = binary
= binary interaction
interaction coefficient
coefficient Distribution
Dislribution by by Maximum
Maximum Likelihood,
Likelihood." Te,hno,nerrics
Technumetrics (1960)(1960) 2,
2.
A~ = average deviation
= average =(calculated-
deviation =(calculated 35-65.
35-65.
measured)/measured
measured)/ measured 12.
12. Smith.
Smith. R.L.
R. L. and
and Watson,
Watson. KM..K. M.: Boiling
"Boiling Points
Points and
and Critical
Critical Pro
Pro
e9 = property
= property perties
29.
of Hydrocarbon
perties of
29. 1408-14.
1408-14.
Hydrocarbon Mixtures.
Mixtures." md. Ind. and
and Eng.
Eng. (hem.
Chem. (1937)
(1937)

pp = liquid
= liquid density,
density. kg/m
3
kg/m 3 (ibm/cu
(lbm/cu ft)
ft) 13. Watson,
13. Watson. KM. K.M. and and Nelson,
Nelson. E.F.:
E.F. : Improved
"Improved MethodsMethods for for Ap
Ap-
TT = variable in property correlation
= variable in property correlation proximating
proximating Critical
tions,
tions." md.
Critical and
Ind. and
and Eng.
and Thermal
Eng. Che,n.
Thermal Properties
Chem. (1933)
Properties of
(1933) 25. 25. 880-87.
of Petroleum
880-87.
Petroleum FracFmc-
ww = acentric
= acentric factor
factor 14.
14 . Kesler,
Kesler. MG..
M.G .. Lee,
Lee. 8.1.,
B.I .. and
and SandIer,
Sandler. SI.:S.I.: "A Third Parameter
A Third Parameter
for Use inin General
for Use General Thermodynamic
Thermodynamic Correlations.
Correlations." hid, Ind. and
and Eng.
Eng.
(hem.
Chem. Fund.
Fund. (1979)
(1979) 18.18. 49-54.
4954.
15.
IS. Kesler.
Kesler. MB. and Lee.
M.B. and Lee. B.l.:
B.I.: Improve
"Improve Predictions
Predictions at of Enthaips
Enthalp) ofof
Acknowledgments
Acknowledgments Fractions,
Fractions." Hydrocarbon
H.\'drocarbon Processing
Processing (March
(March 1976)1976) 153-58.
153-58.
16.
16. Hariu.
Hariu. OH.
O .H. and
and Sage.
Sage. R.C.:
R.C .: Crude
" Crude SpliiSplit Figured
Figured by by Corn
Com-
II thank
thank E,E. and T.C.
E.E. and T.C. Whitson.
Whitson. L. L. and
and B.P.
B.P. Walker.
Walker. J.J. puter.
pUler." Hydrocarbon
Hydrocarbon Processing
Processing (April
(April 1969) 143-48.
969) 143-48.
Faust 17.
17. Ri2zi.
Riazi. MR.
M.R. andand Daubert, T.E.: Simplify
Daubert. T.E.. "Simplify Property
Property Predictions.
Prediclions. "
Faust and
and the late John
the late Hassler-all independent
John Hasslerall independent oil
oil and
and Hydrocarbon
Hydrocarbon Processing
Processing (March(March 1980)
1980) 115-16
115-16.
gas
gas personsfor
persons-for continual
continual encouragement
encouragement during
during 18 . Selected
18. "Selected Values
Values of of Properties
Pmpenies of of Hydrocarbons
Hydrocarbons and and Related
Related
preparation
preparation and
and completion
completion of this work.
of this Support from
work. Support from Compounds.
Compounds. " API API Project
Projecl 44. T.:xas A&M
+4. Texas A&M UU .. College
. College Station.
Stalion.
Frying
Frying Pan
Pan Publications
Publications inc.
Inc. isis gratefully
gratefully acknowledged.
acknowledged. (1969).
(19691.

AUGUST
AUGUST 1983
1983 693
693
A.2-12
A.2-12
A~1-COEFFICIENTS
TABLEA-iCOEFF
TABLE ICIENTS USED THEYARBOROU
USEDININTHE YARBOROUGH SPECIFICGRAVITY
GH SPECIFIC GRAVITY
ION
CORRELATION
CORRELAT

Jacoby
Jacoby
Aromaticity
Aromaticity
(Fraction) 0
b b,b , 2
b
b2 3
b
b
(Fraction) 3
0.0 - 7.43855 x 100-2 - 1.72341
1.7234 x 10. 0
1x10i 1.38058 x 10 -3
1.38058x10-
3 2
3.34169x1
-3.34169 X 10- 02
0.0 7.43855x1
2 -2 2
0.1
0.1 -4.25800

4.25800xx101
10 - I 7.00017 x 10-1
-7.00017x10-1 -3.30947 10- 5
3.30947 xx10 -

8.65465xx1010-
8.65465
0.2
0,2 -4.47553 x 100- I
4.47553x1 -7.65111x10-1
7.65111x1
1 0 1.7798
4 x 10- 4
1.n9822x10 1.0774
1 x 10- 1
1.0n466x10
0.3
0.3 -4.39105 x 100- I
4.39105x1 -9.44068 x10_i
9.44068x 10- 1 4.9370
4 x 10- 4
4.937088x10 1.1926 x 10- 1
1.192677x10
0.4
0.4 -2.73719x10-
2.73719x1 01 - 1.39960 x 10.
1.39960x1 00 3.805644x10
3.8056
3 x 10 -3 5.920055x10
5.9200
2 X 10- 2
0.6 412x10 3
-7.39412x10- 3x10* 0
-1.97063x10
1.9706
0 5,8727
3 x 10- 3
5.872733x10 1.67141x1
2
-1.67141x10- 02
0.6 739
3
0.8 -3.17618x 10-
3.17618x1 0
1 -7.78432x10-1
7.78432x1 0 2.5861 x 10- 3
2.586166x10 1.0838
3 2x10
1.08382x10@--1
0.8

~ J . -cI ~'" = 0- = t\. -t ~ ::.) ~'= Ot -/ C Jet -c/~~


:c .
(11.. c h d
d /111
x
1:;: 13.5
:.:
13.5
J a (yO
6
4
8
+
=('Y- 8 .
O.8468+ l5,8/M)I(0.2 456 1.77/ill).
15.8/M)/(O.2456-1.77/M). (A-i)
(A-I)
-

YAABOAOUGH
YARBOROU CG'lAELATIGN
GH CORRELAT ION (b)
(b) a
Ii RATZ-FIRO
KATZ-FIROOZA8AGI GENERALizeD
OZABAOI OSNERALIZ DATA
ED DATA
0 HAALAND
HAALAND INORTH
CNOATH SEA)
SEAl ia 0.1
13.0
I- 13.0
Also shown
Also Fig. A-i
shown inin Fig. curves generated
several curves
are several
A-I are
- .

(J
C) HOFFMAN, ES AL. OIL generated
factor. The
ion factor,
oC
C
U
II. using Eq.
using 17 and the Watson characterizat
Eq. 17 and the Watson characterization The
zz 12.5
0
12.5 difference in
difference in correlations seems to
correlations seems only qualitative.
be only
to be qualitative.
indicates increas
0
I-
I For where the
example. where
For example, the Watson factor indicates
Watson factor increas-
~w
C
12.0
12.0 ing paraffinicity,
ing Jacoby factor indicates decreasing
the Jacoby
paraffinicity, the factor indicates decreasing
I-
(J illustrated in
This isis illustrated
aromaticity. This
aromaticity. Fig. A-2.
in Fig, which plots
A-2. which plots
~ 11.5
11.5 each characterizat
each factor vs.
ion factor
characterization SCN for
vs. SCN Hoffman et
the Hoffman
for the et
oC
C
J:
(J
reservoir oil.
al. reservoir
at. oil.
0
11.0
11.0 Yarbor
27 ough
Yarborough 27 used the the Jacoby correlation to
Jacoby correlation to generate
generate
~
0
I/) aa set of curves relating specific gravity to SCN. Unfor
specific gravity to SCN. Untor-
Cl,
behavior for
unusual behavior for low
I-
oC 10.5
10.5 tunately, the relation has an unusual
tunately, low
~ 40 attempt "toto
00 10
10 20
20 30 40 50
50
SCN groups. This may be a result result ofof his
his attempt
SINGLE
SINGLE CARBON
CARBON NUMBER for carbon
fractions
reflect the behavior of the distillation fractions for carbon
Fig.
Fig. A3-Variation
A-3Variation in
in Watson
Watson characterization
characterization factor as a numbers up to C 1133
C
, ...
function
function of
of SeN.
SCN. Yarboroughs Fig.
The proposed best fit of Yarborough's Fig. 19 is
19 is

19.
19. Simon.
Simon. R. R. and
and Yarborough.
Yarbomugh. L.: L.: "A
A Crillcal
Critical Pressure
Pressure Correlation 1
y
+
0
I b
i+
=exp b 3 ln(i)],........ (A-2)
[b i+b
for
for Gas-Solvent-Reservoir
Gas-Solvent-Reservoir Oil Systems. 1.
Oil Systems." I. Pel. Tech. (May
Pet. Tech.
1963) 556-60: Trans
1963) 556-60: . AIME.
Trans., AIME. 228.228. constants bb ,
0 , bb.,,
1
b and b 1 are given in Table
20.
20. Haaland.
Haaland, S. S..: "Characterization
Characterization of of Nonh
North SeaSea Crude
Crude Oils
Oils and
and
where constants
where o b, 2 , and b 3 are given in Table
0.6. and
and
Petroleum A-i for
A-I values of
for values =00, 0.1.
of JJa =0.0. 0.2. 0.3.
0.1. 0.2. 0.4. 0.6.
0.3. 0.4.
Fractions, MS
Petroleum Fractions." MS thesis.
thesis. Norwegian
Norwegian Inst. Inst. of of
specific
of specific
Technology. 0.8. Linear interpolation
0.8, Linear between values
interpolation between values of
Technology, U. U of of Trondheim.
Trondheim, Norway.
Norway. June
June 1981.
1981.
21.
21 Edmister.
Edmister, W.C.W.C.:: Pet. Refiner (1958)
Per. Refiner (1958) 37.
37. 173.
173. recommendedi.e., if
gravity isis recommended-i.e.,
gravity if JJ,a =0.5.
=0.5. use coeffi
use coeffi-
22.
22. Peng.D.-Y
Peng. D.-Y and and Robinson.
Robinson. D.B.:
D.B.. "A A New
New Two-Constant
Two-Constant Equa- Equa for 0
J =0.4 and 0.6 to calculate
cients for J a =0.4 and 0.6 to calculate two specific
cients two specific
tion of
tion of Slate."
State, Ind. and EnR.
md. and Chem. Fund.
Eng. Chem. Fund. (1976)
(1976) 15.
15. 59-64.
59-64 gravity for
specific gravity
which specific
from which for JJ =0.5 isis
23. gravities, from
gravities. a =0.5
23. Kay.
Kay, W W B.B.:: "Density
Density of of Hydrocarbon
Flydrucarbon Gases
Gases and
and Vapors
Vapors atat High
High
Temperature
Temperature and and Pressure."
Pressure, Ind.md. and
and Eng. Chern. (1936)
Eng. Chem. (1936) 28.28. found,
found.
1014-19.
101419. Yarboroughs curves
Yarborough's curves for foria=O and 0.6
0.3. and
J a =0.1.1, 0.3. were
0.6 were
24. Lee.
24. Lee. S.T
ST.,. etet af.:
al.: "Experimencal
Expenmerital and and Theoretical
Theoretical Studies
Studies onon the
the to Watson characterizat ion factors
converted to Watson characterization tactors using Eq.
converted using Eq.
Auid
Fluid Propenies
Properties Required
Required for forSimulation
Simulation of ofThermal
Thermal Processes."
Processes, Results are
weights. Results
molecular weights. are plotted in
plotted in
17 and
17 paraffin molecular
and paraffin
Soc.
Soc. Pel. Eng, J.J. (Ocl.
Per. Eng. (Oct. 1981)
1981) 535-50.
535-50.
variation inin KKisis dissimilar
the variation
that the for
dissimilar for
25. Fig. A-3.
Fig. showing that
A-3. showing
25. Hoffman.
Hoffman, A.E A.E.,. Crump.
Crump. J.S .. and
iS.. and Hoeon.
Hocott. C.R.:
C R.. "EqUilibrium
Equilibrium
1 has has aa
Constants
Constants forforaa Gas-Condensate
Gas-Condensate System."
System. Trans .. AIME
Truns.. AIME (1953)
(1953) each value of
each value of JJ
,
0 though the
a' though curve for
the curve for J=0.3
1
Ja =0.3
198.
198, 1-10.
1-10. similar to the one proposed
variation similar to the one proposed by Haaland.
variation by Haaland.
26. Jacoby, R.R.:
26. Jacoby. : "NGPA
NGPA Phase Phase Equilibrium
Equilibrium Project."
Project, Proc .. API
Proc.. API does not
There does
There appear toto be
not appear be any advantage toto the
real advantage
any real the
(1964)
(1964) 288.
288. Jacoby aromaticity
Jacoby factoror
aromaticity factor orYarborough's modification.
Yarboroughs modification.
27 . Yarborough.
27. Yarbomugh, L.: L.: ..Application
Application of ofaaGeneralized
Generalized Equation
Equationof ofScate
State
,0
toPetroleum
Petroleum Reservoir
ReservoirFluids . Equation
Fluids. Equationof ofSlate
StareininEngineering
Enqineeriny Although the
Although the Watson was used
factor was
Watson KK factor study,
this study.
used inin this
con
and Research,K.C.
andResearch. K.C.Chao
Chaoand andR.L.
R L. Robinson
Robtnsonir.Jr. (eds.).
(eds.,,Advances
Advances this should not alter the general conclusions
this should not alter the general conclusions made con- made
ininChemistry
ChemistrySeries.Series, Amer.
Amer. Chem.
Chem Soc.Soc (1978)
(1978) 182.
182. 386-439.
386-439 cerning CC
cerning 7 characterization and
7 ++ characterization and its effect on
its effect EOS
on EOS
APPENDIX predictions.
predictions.
APPENDIX
An
An Alternative
Alternative Characterization
Characterization SI Factors
Conversion Factors
Metric Conversion
SI Metric
Parameter:
Parameter: TheJacoby
The Jacoby Aromaticity
Aromaticity Factor
Factor R
OR (R/l.8)
(OR/I.8) ==
KK
Although
Althoughthe theWatson
Watsoncharacterization
characterizationfactor
factorwaswaschosen
chosen 6.894 757
psi xx 6.894757
psi E+00
E+OO = kPa
= kPa
totocorrelate
correlatemolecular
molecularweight.
weight.specific
specificgravity.
gravity,and
andboil-
boil.
ing
ing point.
point, anan alternative
aromaticity
alternative would
would have
have been
been the
the Jacoby
Jacoby Conversoon
Conversionfacto< I. enact
actorsexact SPEJ
SPEJ
aromaticityfactor,
factor,J a' 2626Fig.
Fig.A-I
A-ishows
showsthe thevariation
variationinin
specific
specificgravity
gravitywithwithmolecular
molecularweight
weightforforseveral
severalvalues
values Onglnal
Originalmanuscript receivedIninSoclely
rttanuscriptreceIVed hnglneersollice
PetroleumEngineers
Society0'atPetrOleum Aug 3.
olfice 980
Aug 3. 1980
acceoted'01tarpublicallon Nov20. 981 ReVised
201981 received Dec 28
manuscriptreceIVed
Revisedmanuscnpi
Plll81
Paceraccep.ed tiublicationNov Oec. 28.
ofofJ ia
a' The
Theoriginal
originalcurves
curvespresented
presentedbybyJacoby
Jar obywere
werefitfit 982 SPE 2233) hot presented at the 1d80 European
1982 PIII81 (SPE 12233) firs. pI_lea a.lne 1980 EUIOll8an Ollsha,e Petrotetlm
Pper Ottsrrare Petroleum
bybythetheequation
equation Confelence
Conterencoand held,n inLonoon.
Exflioitronheld
aridExnlbilion LondonOCt Ocr2121-24
- 24

694 OFPETROLEUM
SOCIETYOF
SOCIETY JOURNAL
EG1NEERSJOURNAL
PETROLEUMENGINEERS
694
A.3-1
A.3-1

Evaluating Constant
Evaluating Constant-Vol
-Volume
ume Depletion
Depletion Data
Curtis H.
Curtis H. Whitson,
Whitson, Rogaland
Rogaland District
Districi C.
C.
Stein B.
Stein Torp,*
B. Torp, * Norwegian
Norwegian Ins\. o Technology
Inst. of Technology

Abstract
Abstract
This paper presents methods for evaluating constant- tion, however, is somewhat difficult to follow and not
volume depletion (CVD) data obtained from experimen-
volume experimen extensively known or used by petroleum engineers. The
analyses of gas condensates and volatile oils.
tal analyses material-balance
material-balance relations are presented here in equation
Theoretical and practical developments
Theoretical developments are supported by fonn
form using current SPE nomenclature.
nomenclature.
experimental data from a North Sea gas-condensate
experimental gas-condensate Based on material-balance-derived
material-balance-derived properties, a
fluid..
fluid method is proposed for calculating black-oil PVT prop prop-
three major contributions of the work are: (1)
The three (I) erties - i.e., FVF's
FVFs and solution GORs GOR's used in two-
presentation of material-balance
presentation material-balance equation~
equations to calculate
calculate phase flow equations and reservoir material balances. balances.
fluid properties
fluid properties from measured CVD data, (2) a simple method was first suggested by
The method by Dodson et al. 22 in
method for calculating black-oil fonnation
method formation volume facfac- 1953 solution-gas/crude-oil
1953 for solution-gas/ crude-oil systems. Their method, method,
and solution GOR's
tors and GORs using material-bala nce results
material-balance however, requires expensive and time-consum time-consuming ing liquid
and separator flash program, and (3) investigation
and aa separator investigation of sample removals
sample removals and and experimental
experimental flash separations.
separations.
the Peng-Robins
the Peng-Robinson on (PR) equation of state
state (EOS)
(EOS) as aa The proposed
The proposed method
method follows the the Dodson
Dodson et et a!.
af. pro
pro-
tool
tool for
for matching measured PVT PVT data andand studying
studying cedure but
cedure but uses experimental
experimentally detennined vapor
ly determined vapor comcom-
vapor/liquid
vapor/liquid phase
phase behavior during
during CVD.
CVD. positions and
positions and material-bala
material-balance-derived liquid composi
nce-derived liquid composi-
tions together
tions together with
with aa multistage
multistage separator
separator flash
flash program.
program.
Introduction
Introduction PVT properties
PVT properties calculated
calculated using
using this
this method
method are are com
com-
CVD
CVD experiments
experiments areare performed
perfonned on gas condensates
on gas condensates and and pared with
pared with those
those predicted
predicted by by the
the PRPR EOS.
EOS.
volatile
volatile oils to simulate
oils to simulate reservoir
reservoir depletion
depletion performance
perfonnance Though more
Though more complicated,
complicated, empirical
empirical equations
equations of of
and
and compositiona
compositionall variation.
variation. Measured
Measured datadata can be used
can be used state are
state are also
also used
used to to evaluate
evaluate CVDCVD data.
data. Several
Several in in-
in aa variety
in of reservoir
variety of reservoir engineering
engineering calculations,
calculations, among
among 4

3
vestigators have used
vestigators 3,4 have used the
the PRPR EOS
EOS to to simulate
simulate PVTPVT
the
the mostmost useful
useful being
being material-bala
material-balancence calculations,
calculations, studies of
studies of light
light gas
gas condensates
condensates and and crude
crude oils.
oils. Unfor
Unfor-
generating
generating black-oil
black-oil PVT
PVT properties
properties and,
and, more
more recently,
recently, tunately most
tunately most studies
studies have
have emphasized
emphasized K-value
K-value predic
predic-
the
the tuning
tuning ofof empirical
empirical EOS.
EOS. All
All these
these applications
applications are
are tions instead
tions instead ofof volumetric
volumetric predictions,
predictions, and and most
most have
have
addressed
addressed in in this
this paper.
paper. avoided systems
avoided systems operating
operating near
near the
the critical
critical point.
point. Results
Results
Few
Few engineers
engineers areare aware of useful
aware of useful fluid
fluid properties
properties that
that have varied
have varied considerably
considerably,, depending
dependin} on on which
which properties
properties
can
can be be derived
derived from
from CVD
CVD datae.g.,
data-e.g., /iquid
liquid composition
composition are compared.
are compared. Conrad
Conrad and and Gravier
4Gravier propose
propose aa method
method to to
(and therefrom
(and therefrom K-values),
K-values), density, and molecular
density, and molecular mass
mass improve liquid-densit
improve liquid-density estimations by
y estimations by adjusting
adjusting proper
proper-
of
of thethe CC 7 - fraction,
7 fraction, vapor
vapor density,
density, andand total
total system
system ties of
ties of the
the heaviest-plus
heaviest-plus fraction
fraction (boiling
(boiling point
point andand
molecular
molecular mass.mass. Only
Only experimental
experimental CVDCVD datadata and
and sim
sim- methane interaction
methane interaction coefficient). Firoozabadi etet al
coefficient). Firoozabadi al. 3
ple material-bala nce
ple material-balance equations
equations are
are used
used toto calculate
calculate these
these studied another
studied another lean
lean gas
gas condensate
condensate and and found
found that
that byby
data.
data. AA procedure
procedure outlining
outlining these
these calculations
calculations waswas first
first adjusting only
adjusting only the
the methane-hea
methane-heavy fraction interaction
vy fraction interaction
presented
presented by by Reudelhuber
Reudelhuber andand Hinds.
Hinds. I Their
Their descrip
descrip- coefficient, the
coefficient, the PRPR EQSEOS highly
highly overestimate
overestimated liquid
d liquid
volumes.
volumes.
Nowwith
Now Esso E&P
WIth Esso E&P Norway
NorwayInc
Inc About 30
About 30 CVD
CVD studies
studies performed
perfonned by by commercial
commercial and and
01.19.21 3618310031-0067$C0 25
private laboratories
private laboratories werewere analyzed
analyzed using
using the
the material-
material-
0149-21J6/831003t.()(l67S00 25
Cooyright
Copyright 1983
t983Society
SocIetyofofPetroleum
PetroleumEngineers
Engin"r.ofofAIME
AIME balance approach.
balance approach. AA NorthNorth Sea
Sea rich
rich gas
gas condensate
condensate was was
blO
610 JOURNALOF
JOURNAL OFPETROLEU
PETROLEUM TECHNOLOGY
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A.3-2

chosen toto hebe analyzed


chosen analyzed using
using the
the PR
PR EOS.
EOS. This
This choice
choice =n
II ,"=
L
1 kU +11.h
+11 .." . . . .. . . . . .. . .. . . . . . . . . .. .... .(1)
(I)
wasbased
was basedon consistencyofofmeasured
onconsistency measuredCVD CVDdatadataasasin
in-
dicated
dicated by
by material-balance
material-bala nce calculations
calculations and
and availability
availability and
and
of extended
of extended compositiona
compositional data for
l data for the
the heptanes-plu
heptanes-plus s
fraction .
fraction. II,~jk
(4 ':'j~ =IIU 'Xj"+,.j
Lk Xjk
11 +II,'k 'Yj~ . . .... . . . . . .. .. . 2)
(2)

where
where tt moles of
II L isis moles ofliquid compositionx.
with composition
liquid with xj . n is
",. is
Description of
Description of CVD
CVD Process
Process L
moles of
moles of vapor
vapor with composition Yj. and
with composition and n,n, isis total
total
AACVDCVDexperiment
experiment isisconducted
conducted atat reservoir
reservoirtemperature
temperature molesininthe
moles thesystem withcomposition
system with composition:j. eachassociated
Zj. each associated
and begins at saturation pressure . Cell
Cell volume.
volume, 1 ' or
Vccll or
and begins at saturation pressure. 1
V
. with pressure stage
with pressure stagek.k. Subscriptj designatescomponents
Subscriptj designates components
the volume
the volume contained
contained by by the
the saturated
saturated fluid, used asas aa
fluid. isis used ethane. etc.
methane. ethane.
methane. etc. Eq. states that
Eq. 1 I states moles of
total moles
that total ofthe
the
reference volume.
reference volume . two-phase system
two-phase system equals the sum
equals the sum of and vapor
liquid and
of liquid vapor
Mercury
Mercury isis withdrawn
withdrawn from from the the bottom
botlom of of thethe cell.
cell. while Eq.
moles. while
moles, Eq. 22 states molesof
total moles
that total
states that ofcomponent]
componentj
thereby lowering
thereby lowering the the pressure
pressure as as fluid
fluid expands.
expands . DuringDuring two-phase system equals moles of j inin the
the two-phase
inin the system equals moles of] the liquid
liquid
this process,
this process, aa second
second phase
phase evolves
evolves - either
either retrograde
retrogmde plus moles of] in the vapor. The
plus moles of j in the vapor. The only data measuredonly data measured
liquid (for
liquid (for gas
gas condensates)
condensates) or or solution
solution gas (for volatile
gas (for volatile directly and
directly and appearing eitherof
appearing inin either ofthe equations isis vapor
the equations vapor
oils).
oils). composition. The
composition. remaining unknowns can
The remaining unknowns can bebe deter
deter-
Mercury withdrawal
Mercury withdrawal isis ceased
ceased when when aa predetermine
predetermined d mined from
mined reported CVD
from reported CVD data and modified
data and forms of
modified forms of
pressure isis reached.
pressure reached. SomeSome laboratories measure liquid
laboratories measure liquid the material-bala
the material-balance nce relations.
relations.
volumes at
volumes at several
several pressures
pressures before
before any vapor has
any vapor has been
been Then we
Then we note that total
note that moles at
total moles equals initial
stage kk equals
at stage initial
removed ; these
removed: these volumes,
volumes. reportedreported relative
relative to to , 1
VVccll
1'
moles minus
moles cumulative moles of vapor
minus cumulative moles of vapor produced. produced.
represent constant-com
represent constant-composition depletion. They
position depletion. They closely
closely We assume aa basis
We assume basis ofofone initialfluid.
mole initial
one mole fluid. n,
1n'l = 1,
I.
approximate volumes
approximate volumes thatthat would
would have have been measured ifif
been measured yielding
yielding
the
the process
process had
had been
been CVD.
CVD. (This
(This was
was checked
checked using the
using the
k
PR EOS
PR EOS simulator
simulator for lean lean and
and rich condensates: see
rich condensates: see also
also
Ref. 5.)
Ref. 5.) n,k = 1- ~ ,
1
n 7
&lpi ' .... ... .. .. .. .. .. .... .. (3)
(3)
Mercury isis reinjected
reinjected into
into the
the cell at constant pressure
at constant pressure i=2
while simultaneously
while simultaneous ly withdrawing an equivalent volume
of vapor. When initial cell volume
of vapor. reached. mercury
volume is reached, mercury The same material balance
The same can be
balance can on aa compo
applied on
be applied compo-
nent basis.
nent in
basis, resulting in
injection is ceased. Withdrawn vapor is analyzed using
injection
gas
gas chromatography
chromatography to determine composition. composition . YJ v,.' k
Moles of vapor produced. nn,,,
Moles p. are calculated using the n,k 'Z)k =Z)I
na =cj - ~ &lp; Yji
(4)
. ..... .. . . . . ... (4)
real gas law and are reported as a cumulative percent of
real gas of
; =2
initial moles
moles.. Compressibility
Compressibility factor. factor, Z. also is
calculated
calculated by noting produced vapor surface volume and where &linpj is the
pi is moles ~f
incremental moles
the incremen~al of va~r produced
vapor p~uc~d
equivalent cell cell volume (at pressure and temperature) .
(at pressure during stage Iz.. and
from the cell during and Zj l IS fluid
initial flUid
the Inttlal
is the
From measured
measured vapor gravity gravity and and composition. composition at
composition conditions)..
at Stage I1 (saturated conditions)
heptanes-plus
heptanes-plus molecular back-calculated. Liquid
molecular mass isis back-calculated. Liquid vapor remaining in
Moles of vapor
Moles the cell
in the can be
cell can calculated
be calculated
volume isis measured
volume measured visually
visually and and reported
reported as percent of
as aa percent ot using aa volumetric balance and and the gas law
real gas
the real (pV =
law (pV =

cell
cell volume.
volume, which which isis actually
actually aa type
type of of hydrocarbon
hydrocarbon liq- liq nZRn.
nZRT).
uid
uid saturation.
saturation. SSL. L. basis of
the basis
Recalling the
Recalling initial fluid.
mol initial
of 1I mol volume
cell volume
fluid, cell
The
The experimental procedure
experimental procedure isis repeated
repeated several times
several times can be
can calculated from initial fluid properties.
be calculated from initial fluid properties. which for which for
until
until aa low pressure isis reached.
low pressure reached. The The remaining
remaining liquid liquid isis condensates is
gas condensates
gas is
removed
removed,. distilled
distilled,. andand analyzed
analyzed using using gas chromatog
gas chromatog- Z, -RT
with Zr R'T
raphy.
raphy. Measured
Measured liquid liquid composition
composition should check with
should check VVce
cell -=
(5a)
.. . . . . .. . .. . .. . . . . . . .... (5a)
material-balance-derived
material-bala nce-derived composition
composition. . (Some
(Some major
major Pa
Pd
laboratories
laboratories smooth
smooth and and adjust
adjust measured
measured vapor vapor composi-
composi as aa liquid
(existing as bubble-point
at bubble-point
liquid at
for volatile
and,, for
and oils (existing
volatile oils
tions
tions until
until the
the material
material balance
balance checks.
checks. This procedure isis
This procedure
pressure).
pressure).
discouraged. ItIt isis good
discouraged. good practice
practice to to ask laboratory
ask ifif aa laboratory
reports
reports measured
measured or or smoothed
smoothed data data,. and
and to to what extent
what extent 1 =Mb1pb (5b)
VV
1cell bPb . .. . .. .. . . ...... . . .. . . .. .. . . (5b)
1
.

material-balance-derived
material-balance-derived data data are used inin final
are used final CVDCVD
reports.)
reports.)
where RR =
where 8 3143 J/mol-K
= 8.3143 preferred SI
for preferred
J!rnol-K for and RR
units.. and
SI units
== 10.732
10.732 psia-cu ftimol-R
psia-cu ft/mol -oR for units. Mb
field units.
for field Mb andarid Pb
p,
Material-Balance
Material-Balance Equations
Equations molecularmass
bubble-point molecular
are bubble-point
are massandand density respective
density.. respective-
Liquid
Liquid Composition
Composition and
and K-Value
K-Value Calculations
Calculations lyly. Zd andPPd
Zd and d are dewpotnt flUId
are dewpoint factor
compressibility factor
fluid compressibility
Perhaps
Perhaps the
the most
most useful
useful application
application of constant-volume
ofconstant-volume and respectively.
pressure. respectively
and pressure.
depletion data is
depletion data is for
forcalculating
calculating liquid
liquidcompositions
compositions that.
that. At eachdepletion
Ateach liquid volume
pressure liquid
depletion pressure. measured
volume isismeasured
together
together with
with measured
measured vapor
vaporcompositions.
compositions. yield high-
yield high- visually ,
11
fractionS of cell
. volume.
reported asas aa fraction . S u . of cell volume
and reported
visually and
pressure
pressure K-values
K-values having
having several
several important reservoir-
important reservoir- Liquid volume. then can he calculated
Liquid volume . V Lk . then can be calculated from
,
from

and
and process-engineering
process-engineering applications.
applications. To To arrive the
arrie atat the
final
final expression
expression for
for liquid
liquid composition
composition in
in terms
terms of
ot , ' V,
VL, =S
Vu=Su1 11
V, ell ' ...... . . . . . . . . . . . . . . . . . . (6)
measured
measuredCVD CVDdata.data, we
we tirst
firststate
statemole
moleand
andcomponent
component
material and. balance. vapor
volutnebalance.
fromaavolume volume. V,.,
. V"" . isis
materialbalances.
balances, respectively.
respectively,asas and , from vaporvolume

MARCH
MARCH1983
1983 611
A.3-3
A.3-3
I F F
gi g2 g3 where M
where "; isisthe
M,. the vapor
vaporphase
phase molecular
molecularmass stage i.i.
massatatstage
BothM,.
Both M andandM M ,. can
canbe
becalculated
calculatedusing
usingKay'
Kayss mixing
mixing
rule
rule and
and appropriate
appropriate component
component molecular
molecular masses.
masses.
STO
1 2
S T0 Vapor
Vapor mass
mass cancan be be calculated
calculated by
by noting
noting that
that mass
mass
"510 equals molecular
equals molecular mass mass times moles, or
times moles. or
V
VgV
R 39 .-.l R 30 . - mm,.kk= n ,,*vk M ,'1.:.
Mv& 13 )
. . . . . . ( (13)
A9 STO
2
VSTO 40 V510
VSTQ

p Z.T Liquid mass


Liquid mass then
then isis calculated
calculated as
as the
the difference
difference be-
be
91 92 3 * SW
8
9 T.p 0 V tween total
tween total mass
mass and
and vapor
vapor mass.
mass.
SW L
5

mLk=mll.:-m" k ' .... .. ........ . ......... . (14)


(14)
LIQUIO
l
Having calculated
Having calculated masses
masses and
and volumes
volumes of of equilibrium
equilibrium
PVT CELL
CELL
PVT liquid and
liquid vapor, respective
and vapor. respective densities
densities can
can be
be calculated
calculated
Fig. 1Schematic 01of the procedure lor directly: pp = mlV
directly: in/V (where
(where volumes
volumes comecome from
from Eqs.
Eqs. 66
Flg.1-Schemalic the procedure for calculating
calculating black-oil
black-oil
properties.
PVT properties. and 7).
and 7).
PVT
An independent check
An independent check ofof vapor
vapor density
density can
can bebe used
used to
to
check the
check consistency of
the consistency of measured
measured ZZ factors.
factors. The
The rela-
rela
tion isis derived
tion derived directly
directly from
from the
the real
real gas
gas law
law and
and can
can be
be
stated as
stated as
V,.
V,'k = 1 S,)V
, =(i-SLk>Vccll'
1 (7)
. . .. . ... .. .... .. . . . . ... (7) M,.,, 'Pk
M,'k P1.
P,'k = Zk' ' ..... .... ..... ...... . ... .. (15)
(15)
Using the
Using the real
real gas
gas law.
law, the
the corresponding
corresponding moles
moles of
of vapor
vapor Zk R
RTT
nt1 are calculated
I'k are
vk calculated from
from We also
We also can
can calculate
calculate molecular
molecular massmass of
of the
the
V,. equilibrium liquid.
equilibrium liquid, and
and specifically
specifically its
its heptanes-plus
heptanes-plus
Pk,V,'k
n"k=
= (8)
... ... ...... ... . . . . . . ... .. (8) fraction. Rewriting the mass
mass balance asas
Zk' RT
Zf, R 'T
where vapor
where vapor compressibility
compressibility factor.
factor. Zk.
Zk, which is rn, =Mu
mlk 1 'nu
M n +M,'k tt . . . . . . . . .. . . . .... (16)
+Mk n,./.:

vk (16)
measured at each stage k.
measured at each stage corresponds to pressure Pk'
k. corresponds p.
All unknowns in
All unknowns in Eq. now have
Eq. II now have been defined in terms we can solve for liquid molecular mass. M
M,Lk.
of measured
of measured CVD
CVD data except liquid
data except liquid composition.
composition, which M,. 'nvk
m,/ -M,'k
mlk vk
when written in
when written in terms
terms of
of the other variables becomes Mu
1
M . . .... . ........ .. ... . (17)
(17)
nu
fl Lk
rk jk
tt ,k Yjk
= nlk ' Zjk -n,'k ' Yjk . . .. .......... .. ..... (9)

Xjk
-jk
Using Kays
Kay's mixing rule, the heptanes-plu
heptanes-plus
s molecular
nlk -n"k

mass can be back-calcula


back-calculated
ted to yield
Equilibrium constants
Equilibrium constants or
or K-values
K-values are defined as the
detined as N-I
ratio of equilibrium vapor
ratio of equilibrium vapor to liquid
to liquid composition. or

M
MLk - 2:
;=1
M;Xki
1
K
Kjk =.v/k /x ' . . . .. .. .. .. . . . .... . ... .. .. .. (10)
=Yjklxjk (10) M
+
7 + = ---"--''----- , .. .. ........ (18)
M Lk7= (18)
Xk7 +
An effective
An effective means
means ofof correlating
correlating and
and checking
checking the
the
consistency where
where MM; are
1 are molecular
molecular masses
masses of
of pure
pure components.
components.
consistency of of calculated
calculated K-values (i.e . liquid
K-values (i.e.. liquid composi
composi-
tions) The
The average
average C
+
7 molecular mass
C 7 + molecular mass ofof the
the two-phase
two-phase
tions) isis to
to plot
plot log
log Kp
Kp vs.
vs. the
the component
component characteriza
characteriza-
system
system should
should be
be calculated
calculated using
using the
the relation
relation
tion
tion factor,
factor. F,F. as
as suggested
suggested byby Hoffman
Hoffman et al. 66
et al.
nLk x k7 M
fl(Xk7 7
+M U7 ++ +fl
+n kYk7 +M vk7 ++
vkYk7 Mk7
Physical M
+
7 = - - - - - - - - - . . . . . . . (19) (9)
Physical Property
Property Calculations
Calculations nux k7 + +fl
+n vkYk7
vkYk7 +
CVD data also can be
CVD data also can be usedused to
to calculate
calculate physical
physical proper
proper-
ties of
ties of equilibrium
equilibrium vapor
vapor and
and liquid. A mass
liquid. A mass balance
balance isis
employed
employed to to carry
carry out
out the
the necessary
necessary calculations:
calculations: Black-Oil
Black-Oil PVT
PVT Properties
Properties
Dodson
Dodson er al. 22 suggested
et al. suggested an an experimental
experimental procedure
procedure for
for
mIl.: =mu +mvk .. . ... . ... . . . ......... .. . (11)
(II) determining
determining so-called
so-called black-oil
black-oil PVT
PVT properties
properties used
used inin
two-phase
two-phase flow flow equations
equations and and solution-gas
solution-gas drive
drive
where
where rnm I isis total
total mass
mass of of the
the system,
system. mL m L isis liquid
liquid mass
mass material-bala nce relations.
material-balance relations. Current
Current laboratory
laboratory propro-
and
and rn.
m ,. isis vapor
vapor mass
mass atat stage
stage k.k. Another
Another wayway of ofstating
stating cedures
cedures for
for estimating
estimating oil oil formation
formation volume
volume factor,
factor, B
,
0Bo
the
the mass
mass balance
balance isis that
that total
total mass
mass atat stage
stagekkequals
equals initial
initial and
and solution
solution GOR. Rso ' only
GOR, R.(,. only approximate
approximate the Dodson etet
the Dodson
mass
mass minus
minus cumulative
cumulative vaporvapor massmass produced
produced from from the
the al.
al. method
method without
without flashing
flashing the the liquid
liquid phase
phase atat each
each
cell.
cell. Recalling
Recalling the the basis
basis of of 1 I mol
mol initial
initial fluid,
fluid. and
and stage
stage of of the
the differential
differential vaporization
vaporization process.
process. ForFor
thereby
thereby equating
equating initial
initial mass
mass with
with initial
initial (saturation)
(saturation) medium
medium toto lowlow volatile
volatile crudes,
crudes. this
this procedure
procedure appears
appears
molecular
molecular mass, mass. M,M,.. gives
gives valid
valid fhr
for most
most engineering
engineering calculations.
calculations. Also,
Also, vapor
vapor
k solution
solution GOR.
GOR. R, .
5Rsg. isis assumed
assumed toto equal
equal infinity
infinity - i.e.,
i.e .

mIl.: =Ms - 2:
;=2
tlnp; M,.; .. - . .. .. . . . . - . .(12)
(12) liquid
liquid condensation
Highly
condensation isis neglected.
Highly volatile
volatile oils
oils and
neglected.
and gasgas condensates
condensates usually
usually can-
can-
612
612 JOURNALOF
JOLRNAL OFPETROLEU
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2.0
2.0
0.030
0.030
u NS-l
NS1 PENSROBINSON RESULTS
-o-PENG-ROBINSON
0 RESULTS NS1
NS - l
'" 280 F
280F
0
___ MATER IAL BALANCE
-r1ATERIAL BALANCE RESULTS
RESULTS 280F
280F

- 0.025
0.025
-<>- PENSROBINSON
0 PENG- ROBI NSON 1FACTORS
l-FAC TORS
S

;,
csMATERIAL
USING PR
USING
BALANCE RESULTS
-O-MATERIAL BALANCE
P-R LiQUID
RESULTS
LIQUID VOLUMES (SL)
VOLUMES 15
L /

/
!II 11.8
!II'" -<>- MEASURES
MEASURED 1FACTORS
l -FACTORS
",'
.8

0'":: 0
:: SEPARATOR
SEPARATOR CONDIT1ONS
CONDIT IONS'
u u PRESSURE
PRESSURE TEMPERATLRE
TEMPERATURE
c c
0 . 020
3.020 ~ (e
(psia)
S1a ) ( o F)
(F)

r~ E
S
... 11..6b 1014 . 7
1014.7 155
155
::> ::>
0 2b4.7
264.7 80
80
-' -' 14.7
14.7 60
bO
0
0 0
:> :>
z
z 0. 015
0.015 z
~
...c~
0
~
C 1.4
1.4
/
E
S E
S

'"~
0
0 . 0 10
0.010
'"
~
0

'"c -'

'" 0
1.2
1.2
STANDING LOW
STAND1NG LOW PRESSURE,
PRESSURE ,
0.005
0.005 BLACK OIL" KVALUE
" BLACK OiL K-VALUE
CORRELATION USES
CORRELAT ION USED

000 0L-~-1""00:-;'0~-2--o':-00;-'--'--73o""0~0"""'-4
o . 000 3000 ~0'::00~-'--75:!:00::0:----~b7:o~0-::-0~-!;;!lODO
4000 5000 6000 7000 1. 0 0~~~1
1.01 0"'00~"""2:-:oo~0""""~3~00-:-:0:-'-""""'4oo:':-'-0~~5"'0':-oo:-O-""""6000~"""'~7~000
1000 2000 3000 6000 5000 6000 7000
1000 2000
PRE SSURE, ps,.
PRESSURE, PRESSURE, ps IA
PRESSURE, s ia

Fig. 2Gas
2-Gas FVF vs. 280F
VS . pressure for NS-1 at 280F. FVF vs.
4-0il FVF
Fig. 4Oil
Fig. at 280F.
pressure for NS-1 at
vs. pressure 280F.

~2000~~~~~~~~~~~~~~~~~~~~
200C
50000 PENGROBDNSON RESULTS
RESULTS NST
NS -l
....'" - 0 - PENG-ROBINSON
0
F
-0-
-0
a--
-
PENG-ROBINSON
PENGROBiNSON RESULTS
MATERiAL BALANCE RESULTS
- MATERIAL ...
~ -a- MATERIAL
-<>-
~
MATERIAL BALANCE RESULTS
BAlANCE RESULTS
MATERIAL BALANCE
0 MATERIAL BALANCE RESULTS
280 "F
280
USING DATA
USiNG MEASURED DATA
NS1
NS -l
'", USING PR LIQUID VOLUMES (SL>
USING P-R LT
1
, 28o'
280 F F 5l0
~ 40000
40000 '"0' 1500
1500
'" 0 C0NDITiONS
SEPARATOR CONDITIONS'
SEPARATOR
.;
0 ~

~
c PRESSURE
PRESSURE TEMPERATURE
c '" (psu)
(psla) (1 Fl
'"-' 30000
30000 o
0
-'
1016.7
1014.7 155
155
I
o
~ 1000
I 264.7 80
'"
C 1000 14.7
14.7 60
60
'"
Z
0 zS
o
0
oS
0 ~
~ 20000
20000 ::>
0
::>
0
-' o-'
0 SlU10 111(. lOio Pili H:."
"''',ul
o0 <II 11l.'1 OIL "

.'"
o0
0-
SEPARATOR
SEPARATOR CO!lDITIONS
CONDITIONS
TEMPERATURE
Q
:;0
~
500
500
COlllf LAl l OIiI uu o

c 1000cr- PRESSURE
10000 PRESSURE TEMPERATURE
r -

-
(psla)
(Dsa)
1014.7
10)..7
(
155
155
F)
F) ~

-t. ' ..
264 .7
26..? 80
SO "'1~ '~,' I
14.7
16.7 60
60 , ... ,.
\ ol,,);..c.
1
u.
~,
"
, ',I
.l

00 1000 2000
2000 3000
3000 4000
4000 5000
5000 6000
6000 7000
lO00 00 1000
1000 2000
2000 3000
3000 4000
4000 5000
5000 6000
6000 7000
7000
PRESSURE,. ps,a
PRESSURE AS 3
PRESS,.RE,
PRESSURE, OS
DS 'aa

Fig. 3-Vapor
Fig. 3Vapor solution
solution GOA pressure for NS-1
GOR vs. pressure NS-1 at 280F
at 280F 5Liquid solution GOA
Fig. S-Liquid pressure for NS-1
vs. pressure
GOR vs. at 280F.
NS-1 at 280F.

not be
not he described by the
described by the same
same differential process The
differential process. The determined from
tions determined from CVDCVD analysis (measured or
analysis (measured or
basic
basic problem
problem posed
posed by by these
these more volatile fluids
more volatile is that
fluids is that calculated) are
calculated) are flashed through aa multistage
flashed through separator
multistage separator
during
dunng two-phase
two-phase tlow
flow there
there ex ist both
exist both twoiwo phases
phases andand representing field
simulator representing
simulator conditions. Fig.
tield conditions. deserihes
F1g I1 describes
two
two components.
components. That That isis.. flowing
flowing oil oil contaInS solution
contains solution the process
the diagrammatically.
process diagrammatically.
gas
gas that.
that. when
when undergoing
undereoing pressure
pressure reduction. evolves
reduction, evolves beginning our
Before beginning
Before discussion of
our discussion of the proposed
the proposed
and
and mixes
mixes with
with the
the existing vapor phase.
existing vapor Likesvise.
phase LikeWise. method,
method, let let us define the
us define four basic
the four propernes used
PVT properties
basic PVT used
tlowing
flowing gasgas contains
contains retrograde
retrograde liquid
liquid that evolves
also evolves
that also two-phase flow
in two-phase
in and reservoir
flow and material-balance equa-
reservoir material-balance equa
and
and mixes
mixes with
with the
the existing
existing liquid
liquid whenwhen pre~sure
pressure tions: Bo
tions B,, isis liquid volume of
liquid volume 1 at
x
of Xl at reservoir conditions
reservoir conditions
declines.
declines. This
This complex
complex thermodynamic phenomenon i~.
thermodynamic phenomenon is. divided by
divided stock-tank oil
by stock-tank oil volume from flash
resulting from
volume resulting of
flash of
for
for all practical purpose~
all practical purposes.. imposl>ible
impossible to simulate in
to simulate in the
the x ;; R
xl R w,, isis surface
surface gas gas volume
volume resulting the flash
from the
resulting from of
flash of
labomtory
laboratory.. divided by
Xl divided stock-tank oil
by stock-tank oil volume from tlash
resulting from
volume resulting flash
An
An alternative
alternative method
method isis suggested
suggested that.that. by making
by making of xl : Bg is vapor volume of .v, at reservoir conditions
of 1
.t B. is
, vapor volume of v at reservoir conditions
certain
certain simplifying
simplifying assumptions
assumptions,. approximates
approximates the true
the true divided by
divided surface gas
b surface volume resulting
gas volume the flash
from the
resulting from flash of
of
model
model described previous( Individual
described previoul>ly. lndi idual phase coinposi-
phase composl and Rs
.\', : and R~ isis surface
surface gas volume resulting
gas volume front the
resulting from the

MARCH
St \R(H 1l/!!3
O-)5 613
613
A.3-5
A. 3-5
TABLEl-MEASURED
TABLE 1MEASUREDCONSTANT-VOLUME
CONSTANT-VOLUME DEPLETION
DEPLETION DATA
DATA
FOR THE
FOR THE NS-l
NS-1 FLUID
FLUID AT
AT 280F
280F (psi a)
(psia)

Compositions
Compositions

Equilibrium
Equilibrium
EquilibriumVapor
Equilibrium Vapor Liquid
Liquid
Experi
Experi- Calcu-
Calcu
mental
mental lated
lated
Component
Component 6764.7 5514.7
6764.7 5514.7 4314.7
4314.7 3114.7
3114.7 2114.7
2114.7 1214.7
1214.7 714.7
714.7 714.7 714.7
714.7
Carbondioxide
Carbon dioxide -----
2.37
2.37
-----
2.40
2.40
-----
2.45
2.45
-----
2.50
2.50
-----
2.53
2.53
----- -----
2.57
2.57 2.60 00.59
.59
714.7
0.535
2.60 0.535
Nitrogen
Nitrogen 0.31
0.31 0.32
0.32 0.33
0.33 0.34
0.34 0.34
0.34 0.34 0.33 0.02 0.Q17
0.34 0.33 0.02 0.017
Methane
Methane 73.19
73.19 75.56
75 .56 77.89 79.33
77.89 79.33 79.62
79.62 78.90
78.90 77.80 12.42 10.704
77.80 12.42 10.704
Ethane
Ethane 7.80
7.80 7.83
7.83 7.87
7.87 7.92
7.92 8.04
8.04 8.40
8.40 8.70 3.36 3.220
8.70 3.36 3.220
Propane
Propane 3.55
3.55 3.47
3.47 3.40
3.40 3.41
3.41 3.53
3.53 3.74
3.74 3.91 2.92 2.896
3.91 2.92 2.896
isobutane
isobutane 0.71
0.71 0.67
0.67 0.65
0.65 0.64
0.64 0.66
0.66 0.72
0.72 0.78 0.91 0.916
0.78 0.91 0.916
n-butane
n-butane 1.45
1.45 1.37
1.37 1 31
1.31 1.30
1.30 1.33
1.33 1.44
1.44 1.56 2.09 2.103
1.56 2.09 2.103
isopentane
isopentane 0.64
0.64 0.59
0.59 0.55
0.55 0.53
0.53 0.54
0.54 0.59
0.59 0.64 1.40 1.417
0.64 1.40 1.417
n-pentane
n-pentane 0.68
0.68 0.62
0.62 0.58
0.58 0.56
0.56 0.57
0.57 0.61
0.61 0.66 1.60 1.624
0.66 1.60 1.624
Hexanes
Hexanes 1.09
1.09 0.97
0.97 0.88
0.88 0.83
0.83 0.82
0.82 0.85
0.85 0.90 3.68 3.755
0.90 3.68 3.755
Heptanes-plus
Heptanesplus 8.21
8.21 6.20
6.20 409
4.09 2.64
2.64 2.02
2.02 1.84
1.84 2.12 71 .01 72.815
2.12 71.01 72.815
Totals
Totals 100.000 100.000
100.000 100.000 100.000
100.000 100.000
100.000 100.000
100.000 100.000
100.000 100.000 100.000 100.000
100.000 100.000 100.000
Mc
Me7
184.0
184.0 160.0
160.0 142.0
142.0 127.0
127.0 119.0
119.0 115.0
115.0 114.0
114.0 213.0
213.0 207.8
207.8
ic.. 0.816
0.816 0.799
0.799 0.783
0.783 0.770
0.770 0.762
0.762 0.758
0.758 0.757
0.757 0.833 0.843
/'c 7 0.833 0.843
ZZ 1.238
1.238 1.089
1.089 0.972
0.972 0.913
0.913 0.914
0.914 0.937
0.937 0.960
0.960
fl O/
np. % 0.000
0.000 9.024
9.024 21 744 38.674
21.744 38.674 55.686 72.146 81
55.686 72.146 .301
81.301
SL, % 0.0 14.1 19.7
SL' % 0.0 14.1 19.7 21 .6
21.6 21.3
21.3 20.2
20.2 19.3
19.3

flash of of Y,v divided


divided by stock-tank oil volume resulting
by stock-tank where IIn., , is moles of stock-tank oil resulting from
tlash ,SIO
1 from the
the
from flash
from flash of.\',
1 ' where
ofv where X.rj are
are liquid
liquid compositions
compositions deter-
deter of n reed
flash of" moles of reservoir vapor.
teed
mined from
mined from material-balance
material-balance equations
equations and Yj are vapor The major assumption implicit in the proposed method method
compositions measured
compositions measured experimentally
experimentally.. is that liquid and vapor compositions are solely solely depen-
depen
First, liquid
First, liquid composition
composition Xxj is flashed using a set of dent on pressure.
pressure. That is, the composition/pressure
composition/pressure relarela-
appropnate K-values
appropriate K-values and and basic vapor/liquid equilibria
basic vaporlliquid tion is unique and not altered by by physical flow.
equations. [Glaso
equations. [Glas0 and Whitson
and Whitson 7 have documented
documented that Examples of PVT properties for a rich gas
Examples gas condensate
condensate
Standings
Standing' s8 low-pressure K-value equations
low-pressure K-value equations are quite ac- ac (NS-I) are presented in Figs. 22 through 5.
(NS-l) Here wewe have
have
5. Here
curate
curate for for flash
flash calculations
calculations of black oils.
of black oils. WeWe have
have since
since compared
compared properties
properties calculated
calculated using
using material-bala
material-balance
nce
found
found thatthat they
they areare also
also accurate
accurate for flash calculations of of results with
results with those
those calculated
calculated using
using PR
PR EOS
EOS simulated
simulated
many gas condensates
many gas condensates - e.g..
e.g., systems
systems with
with GORs
GOR's less less data.
data. Identical
Identical low-pressure
low-pressure K-values
K-values were
were used
used for
for both
both
than
than about
about 50,000
50,000 scf/STB
scf/STB (9000
(9000 stdstd m 3 /stock-tank
/mstock-tank
3 sets
sets of
of data.
data. Vapor
Vapor solution
solution GORs
GOR's areare nearly
nearly the
the same
same
)
3
m .J
J The sum of surface
m ) . ] The sum of surface gas gas volumes
volumes divided
divided byby stock-
stock- for both
for both methods
methods of of calculation.
calculation. Liquid
Liquid solution
solution GORs
GOR ' s
tank oil volume
tank oil volume isis defined
defined asas the
the liquid
liquid GOR.
GOR, ,. R.,,,.
1
R 1 and oil
and oil FVFs
FVF's are are both
both low
low for
for material-bala
material-balance-derived
nce-derived
Oil
Oi I FVF.
FVF. B ,
1
B. is calculated from the
II ' is calculated from the relation
relation properties.
properties. The The difference
difference isis aa result
result ofof thethe
stages underestimat
underestimated liquid densities
densities calculated
calculated by
by the
the PR
PR
slages ed liquid
L: Ifl fli.,,,
mgt +m slo equation.
equation.
BB" =
, =
1=I
_.:...i=_t=--______ _
, .. . .. . .. . . ... . ... (20)
(20)
10 PL
V.,
V'IO 'PL Application of
Application of the
the Peng-Robins
Peng-Robinson
on
where
where V 5 0 isis stock-tank
V,l stock-tank oil oil volume
volume [e.g.,
[e.g., I I bbl (0.16
bbl (0 16
Equation of State
Equation of State
3
m 1It, and
m )]. and n m g and
and m slO are are masses
masses of oftotal
total surface
surface gases
gases Measured
Measured CVD CVD data
data and
and material-bala
material-balance-derived
nce-derived propprop-
and
and stock-tank
stock-tank oil,oil. respectively.
respectively. Liquid
Liquid density, P L, can
density, PL. can erties
erties were
were controlled
controlled using
using aa fluid
fluid properties
properties package
package
be
be determined
determined eithereither from
from material-bala
material-balancence calculations
calculations based on
based on the
the PRPR FOS.
EOS. Pure Pure component
component properties
properties
(mL from
(rnL from Eq.Eq. 14 14 and
and VL V L from
from Eq. or from
Eq. 6)6) or from one
one ofof (critical pressure,
(critical pressure, critical
critical temperature.
temperature, acentric
acentric factor.
factor,
several
several compositiona
compositional l density
density correlations available9.10
correlations available 9. 10 andmolecular
and molecularmass)
mass)were
wereused
usedforfornonhydrocar
nonhydrocarbons
bons andand
using
using material-bala nce-derived liquid
material-balance-derived liquid compositions
compositions. . hydrocarbons
hydrocarbon from methane
s from methane toto n-pentane.
n-pentane. OnlyOnly
At
At the
the same
samedepletion
depletion stagestagek.k. vapor
vaporphase
phasewithwithcomcom- n-hexane was
n-hexane was considered
considered forforthe
the C
6C 6 fraction.
fraction. Heptanes
Heptanes
position
position v1Yj isisseparated
separatedthrough
throughthe the flash
flash simulator
simulatorusing
using and heavier
and heavier properties
properties were
were estimated
estimated using
using the
the pro
pro-
identical
identical K-values.
K-values. The The resulting
resulting surface
surface gasgas volumes
volumes cedureand
cedure andequations
equationssuggested
suggestedby byWhitson.
Whitson. 11
divided
dividedby bystock-tank
stock-tankoil oilvolume
volumedefines
definesthethevapor
vaporsolusolu- ToTomanipulate
manipulatethe theretrograde
retrogradeliquid-volum
liquid-volume curve,the
e curve, the
tion
tion GOR.
GOR. R,,. R.,g' Gas
Gas FVF.
FVF. on on the
the other
otherhand,
hand, cancan bebe Watson
Watson characterizat
characterization factorofofthe
ion factor the heaviest
heaviest compo
compo-
calculated
calculated fromfrom thetheCVD
CVDcompressibil
compressibilityity factor.
factor, Z,Z, us
us- nent
nent was
was adjusted,
adjusted. making
making suresure that
that adjusted
adjusted critical
critical
ing the real gas
ing the real gas law:law: properties
propertieswere
werephysically
physicallyrealistic.
realistic.
Binary
Binary interaction
interactioncoefficients
coefficientswerewereset setequal
equaltotozero
zero
BZ p ,,. . Z . T (
_
1
( L) II sl ) - 1
~ - N 2 == 0.02, CO~ - hydrocarbon
B~ = I - -- -l . .. ... .. . . . ..(21)
.
(21) :
2
except
except 12 :N
-N-N
2 -0.02,CO
hydrocarbonss =
p T,
p . TJ , /Iteed
feed 0.15,
0. 15,NN~ - hydrocarbon
hydrocarbons s =0.12.
0. 12.and
andC1 -CII'n n =6.6.
C 1C,,.
6l4
614 JOURNALOF
JOURNAL OFPETROLEU
PETROLEUM TECHNOLOGY
M TECHNOLO GY

--H
A.3-6
A.3-6
TABLE2-COMPOSITIONAL
TABLE PROPERTIES DATA
AND PROPERTIES
2COMPOSITIONAL AND DATA OF FLUID NS-1B
OF FLUID NS-1B
SAMPLED FROM AA WELL
SAMPLED FROM WELL OFFSETTING
OFFSETTING NS-1
NS-1 COMPARED WITH CALCULATED
COMPARED WITH CALCULATED
DATA GENERATED
DATA GENERATED USING THE METHOD
USING THE PRESENTED IN
METHOD PRESENTED IN REF.
REF. 11
11

Measured
Measured Calculated
Calculated
Single
Single Boiling
BOiling Upper
Upper
Carbon
Carbon Molal Specific
Mole Molal
Mole Specific K
5 0
Kuop Point Mole Molal
Point Mole Molal Molat
Molal
Number Percent
Number Mass Gravity
Percent Mass Gravity Factor
Factor ~(SR) Percent Mass Mass
Percent Mass Mass
77 0.94
0.94 95
95 0.7158
0.7158 12.05
12.05 641 .7 0.935
641.7 0.935 95.1
95.1 99.6
99.6
88 0.84
0.84 104
104 0.7365
0.7365 111 .93
1.93 678.3
678.3 0.838
0.838 105.4
105.4 111.9
111 .9
99 0.74
0.74 118
118 0.7557
0.7557 11 .90
11.90 727.3
727.3 0.739
0.739 118.9
118.9 126.8
126.8
10
10 0.60
0.60 132
132 0.7639
0.7639 11 .99
11.99 768.4
768.4 0.600
0.600 134.2
134.2 142.4
142:4
11
11 0.41
0.41 144
144 0.7723
0.7723 12.04
12.04 804.0
804.0 0.410
0.410 148.7
148.7 155.5
155.5
12
12 0.34
0.34 154
154 0.7814
0.7814 12.04
12.04 832.7
832.7 0.340
0.340 161.7
161.7 168.4
168.4
13
13 0.31
0.31 167
167 0.7939
0.7939 12.03
12.03 871.2
871.2 0.310
0.310 175.0
175.0 182.2
182.2
14
14 0.26
0.26 180
180 0.8053
0.8053 12.02
12.02 907.0
907.0 0.260
0.260 188.7
188.7 195.7
195.7
15
15 0.22
0.22 197
197 0.8096
0.8096 12.13
12.13 947.1
947.1 0.220
0.220 202.1
202.1 209.1
209.1
16
16 0.19
019 212
212 0.8152
0.8152 12.30
12.30 1008.1
1008.1 0.190
0.190 215.4
215.4 222.4
222.4
17
17 0.17
0.17 226
226 0.8255
0.8255 12.19
12.19 1019.0
1019.0 0.170
0.170 228.9
228.9 236.1
236.1
18
18 0.15
0.15 234
234 0.8303
0.8303 12.20
12.20 1039.4
1039.4 0.150
0.150 242.8
242.8 250.1
250.1
19
19 0.13
0.13 250
250 0.8341
0.8341 12.26
12.26 1069.4
1069.4 0.130
0.130 256.8
256.8 264.1
264.1
20
20 0.11
0.11 262
262 0.8400
0.8400 12.28
12.28 1097.6
1097.6 0.110
0.110 270.6
270.6 277.8
277.8
21
21 0.08
0.08 277
277 0.8477
0.8477 12.29
12.29 1130.8
1130.8 0.080
O.oeo 283.0
283.0 289.0
289.0
22
22 0.07
0.07 292
292 0.8531
08531 12.32
12.32 1161.0
1161.0 0.070
0.070 294.1
294.1 299.9
299.9
23
23 0.06
0.06 308
308 0.8577
0.8577 12.36
12.36 1191 .4
1191.4 0.060
0.060 304.8
304.8 310.3
310.3
24
24 0.06
0.06 329
329 0.8666
0.8666 12.38
12.38 1234.9
1234.9 0.070
0.070 316.7
316.7 324.0
324.0
25 +
25+ 0.51
0.51 471
471 0.8826
0.8826 12.87
12.87 1465.6
1465.6 0.508
0.508 439.1
439.1 00

6.19
6.19 177
177 0.8061
0.8061 12.25
12.25
------
6.190 17T0
6.190 177.0
(12.02)
(12.02)

The
The gamma
gamma dislribution
dlstrlbullon (Rel
(Ref 11)
11, was
was used
used where
where an
an optimal
opllmal alpha
afpha 010 712 was
of 0 712 found lot
was found eta (minimum
for eta (minimum
molecular mass
molecular mass in the c
In the C 7 . traction)
fraction, 01
of 92
92 Upper
Upper molecular masses were
molecular masses found by
were found fillIng lhe
by lilting the measured
measured
compositions
ComposItions
The hIgher
The higher average K uop value
average Kvp value was
was calculaled
calculated uSIng welghtaverage mixing
using aa weight-average rule, whereas Ihe
mixing rule. the lower
lower
value was
value was eslimaleci
estimated using
uSing Ihe
the Whitson correlallon
Whitson correlation

77,.., linear fit of the Katz


. .. which were estimated using a linear optimal alpha was 0.7
molecular masses. The optimal
molecular 12 for
0.712 for eta
eta
and Firoozabadi 112 data (their Table 2).
2), (minimum molecular mass in the 7
CCp fraction) of 92.
of 92.
match.. Molar distribution
Table 22 gives results of the match of
distribution of
DC I -c =0.14',." -0.0668 . .... . . .... .... (22) NS-l C
the NS-I 77 + fraction then was calculated using
C using a = =
II
0.712, ." =
0.712 92, and MC7+
= 92. compared to
+ = 184 (as compared
7
Mc to 177
177
fluid).. Results are presented in
NS-lbb fluid)
for the NS-I Table 3.
in Table 3.
The interaction coefficient between methane and the
heaviest component then was adjusted until a match of
the measured dewpoint pressure was obtained.
obtained. State
Tuning the Peng-Robinson Equation of State
Single carbon number groups were combined into five
into five
Fluid Description: Rich Gas Condensate NS-l
NS-1 multiple
mUltiple carbon number (MCN) groups: 7
C through
C 7 through C 9 . ,
9
C
NS-I
NS-l is is aa rich gas
gas condensate tirst
first tested GOR of
tested at a GaR 10
C
C 10 through C , 3 C
113.
C 14
C through C
14 through 7 C
117.
C
. 18
C through C
18 through ,
4
C, 24.
3 ) from an in- properties
5.500
5,500 scflSTB
scf/STB (980(980 std
std m" /stock-tank m
m/stock-tank )
3
m in and C 5
C, 25 +.+, as suggested in Ref. II. 11. Group properties
itial
itial reservoir pressure of
reservoir pressure of 7.300
7,300 psia
psia (50
(50 MPa) and and were calculated using Kay's Kays mixing rule Methane in-
rule.. Methane in
temperature of
temperature of 280F
280F (138C).
(138C). Stock-tank
Stock-tank oil gravity
oil gravity estimated using
coefficients were estimated
teraction coefficients using MCN MCN
was
was 44
44API (0.8055 g/cm
API (0.8055 ).
3
g/cm -'). Separator samples were
Separator samples and Eq. 22
gravities and
specific gravities
specific 22 .
taken
taken whilewhile tlowing
flowing the well well at at 16.3 MMscf/D
16.3 MMscflD Using these
Using these data.
data, thethe PRPR EOS yielded dewpoint
yielded aa dewpoint
3 /d) and a flowing bottomhole
(460
460x x 10" std m
l0 std m/d pressure
and a flowing hottomhole pressure much lower than measured
pressure much lower than measured. The C I through
pressure The C through
of
of 7.260
7.260 psia
psia (50
(50 MPa).
MPaI. Table
Table I1 presents constant-
presents constant- 225
C
C then was
coefficient then
interaction coefficient
5 + interaction increased until
was increased until
volume
volume depletion
depletion datadata measured
measured on recombined
on the recombined pressure was matched.
dewpoint pressure
reservoir
reservoir flu id.
fluid. The CVD
The CVD program was run run using
using the properties
MCN properties
the MCN
(Table .3). The overall match was good to
(Table 3) . The overall match was good to excellent. ex- excellent., cx
Heplanes-Plus
Heptanes-Plus Characterization
Characterization cept
cept for volumes, which
liquid volumes.
fbi liquid much too
were much
which were high (32
too high (.32% %
Extended
Extended compositional
compositional data data ofof the
the C were
fraction were
77 . fraction
C simulated maximum vs
simulated maximum vs. 22% maximum). To
measured maximum)
22% measured To
not molecular massmass whether measured
check whether
check were low
volumes were
measured volumes low,. we corn-
we com-
not available
available for
for the
the NS-INS- I fluid
fluid,. only
only molecular
and (TBP) pared material-balance liquid
pared material-balance densities with
liquid densities Alani
with Alani-
and specific
specific gravity
gravity.. Complete
Complete true-boil ing-point (TBP)
true-boiling-point
data These
well.. These Kennedy 10 densities
Kennedy (using material-balance
densities (using composi-
material-balance composi
data were.
were, however.
however, available
available fromfrom an an offset
otiset well
data were
were adapted to
to the
the NS-I
NS- I tluid
fluid using
using the
the methods
methods tions
(ions and molecular masses)
and molecular Table 44 shows
masses),. Table results of
shows results of
data adapted
pre!oented the comparison.
the indicating that measured
comparison, indicating that measured volumes are volumes ame
presented in in Ref.
Ret. I11.I.
Molar vs. molecular mass) consistent lor perhaps
except for
consistent except ermrs in
small errors
perhaps small in the first two
the tirst two
Molar distribution
distribution (mole
(mole fraction
fraction vs. molecular mass)
of
of the
the offset well flu
offset well id was
fluid was tit
fit using
using the distribu
gamma distribu-
the gamma volume measurements
volume measurements.
tion
tion parameter
parameter alpha
alpha and and variable upper-boundary
variable upper-boundary On basis of
the basis
On the we decided
results, we
these results.
of these decided to lower the
to lower the

MARCH
\tAR(H 1983
981 h,l5
615
A.3-7

3PHYSICAL PROPERTIES OF
TABLE 3-PHYSICAL OF THE
THE C.
7
C SINGLE AND MULTIPLE
7' SINGLE MULTIPLE CARBON
CARBON
NUMBER GROUPS USED IN PENG-ROBINSON EQUATION
IN THE PENGROBINSON EQUATION OF
OF STATE
STATE
TO DESCRIBE
TO DESCRIBE RESERVOIR
RESERVOIR FLUID BEHAVIOR
BEHAVIOR OF THE
THE NS1
NS-1 FLUID
FLUID

Critical
Single Boiling Temper- Methane
Carbon Mole
Mole Molal
Molal Specific Point ature Pressure Acentric Interaction
Interaction
Number Percent
Percent Mass Gravity _-,--
(R)
(O_R...:.)_ mnB)
_ ....:(,-O_R:...)_ (psia) Factor Coefficient
----- 77
-

1.2136
1.2136 95.3 0.7177
95.3 646.8
646.8 971.6
971 .6 457 .5
457.5 002742
.2742
8 1.1730
1.1730 106.5
106.5 00.7409
.7409 690.6 1021
1021.4 .4 423.4 00.3056
.3056
9 0.8600 120.7
120.7 0.7599 739.4 1073.4 383.2 00.3454
.3454
10
10 0.6872 134.7 0.7682 781.4
781 .4 1112.9
1112.9 345.9 0.3861
11 0.5681 148.7 0.7781
148.7 822.2 1152.1
1152.1 316.8 0.4251
12 0.4783 162.7 0.7908
162.7 863.1 1192.3 294.0 0.4622
13 0.4074 176.7 0.8034 902.8 1231.2 274.9 0.4984
0 4984
14 0.3498 08153
190.7 0.8153 941.2 1268.3 258.4 0.5342
05342
15 0.3021 204.7 0.8168 972.6 1294.2
12942 240.4 0.5740
16 00.2621
.2621 1029.8
218.7 0.8210 1029.8 1321.5
1321 .5 225.7 0.6127
17
17 0.2282 232 7 0.8310 1039.5
232.7 1354.0 214.6 0.6486
18
18 0.1992 246.6 0.8389
08389 1072.0 1383.6
13836 204.3 0.6855
06855
19
19 01744
0.1744 11047
260.6 0.8432 1104.7 14087
1408.7 194.0 00.7246
.7246
20 0.1529 11316
274.6 0.8486 1131 .6 1434.4 185.1
185.1 007634
.7634
21 01343 288.6 0.8554 1161.9
08554 1161 .9 1461.0
14610 177.4 0.8016
22 01182 302.6 11902
302.6 0.8602 1190.2 1484,9
1484.9 170.0
170.0 0.8416
23 0.1041 316.5
316.5 0.8639
08639 1217.4 1507.0 162.9
1629 0.8830
24 0.0918 1245.1
330.5 0.8690 1245.1 1530.2
1530.2 156.8 0.9241
25+ 07054
0.7054 14880
462.3 0.9292 1488.0 1734.6 91
914.4 1.0590
8.2100 184.0 0.8160

Number Properties Used in


Multiple Carbon Number in the Final
Final CVD Simulation
7
7 through 99 3.2466 106.1 0.7385 688.3 1016.5
1016.5 425.5 0.3044 0.03659*
0.03659
10 13 2.1410 152.7 0.7837
10 through 13 07837 835.0 1163.6 313.1 0.4348 0.04292*
0.04292
14 through 17
14 17 1.1421 209.2 0.8205 984.4 1304.5 237.4 0.5856 0.04807"
0.04807
18 through 24 0.9749 281.5 0.8524 1146.9
l8through24 11469 1446.0 182.7 0.7832 0.05254
0.05254
25+ 00.7054
.7054 462.3 0.9192 1276.1
1276.1 1584.2**
1584.2' 168.8
168.8 0.8819
0.8819 00.18400t
.18400t
8.2100 184.0
184.0 0.8160
Calculated
Calculated using
uSing the and F,roozabadl
the Katz and Frroozabadi co"elallon,
correiahon, curve-flllO
curve-lit to Yield
yield the reiationit
relation c -c t 4 'n - 00668
-c == 00 14
-,,, 0 0668 Though
Though nol shown In
not shown in
this table, the methane/hexane
Ihls lab'e, methane/hexane interaction coett,cient also was
Interaction coefficient was calculated
calculated using
uSing this relation
Ihls'refallon
Adlusted ualues representing
Ad,usled values representing aa 1 actor 01
uup faclor
Kuop
< t 1 80
of 11 on91nal values correspond to a
80 The original tudor 01
a Kuop factor 01 t2 42 and ate
1242 are given above
above
14880)
leg . 14880)
(eg
u
1
)Adsted value
tAd,usted 10 match
used to
value used match the measured dewpoinl pressure
measured dewp01n1

TABLE 4CALCULATED
TABLE 4-CALCULATED LIQUID
LIQUID DENSITIES A FUNCTION
DENSITIES AS A FUNCTION
OF PRESSURE FOR NS-I
NS1 FLUID

Calculated Liquid
Calculated liqUid Densities
DenSities (g/cm
)
3
(g/cm 3)
Measured
Measured CVD
CVD Data
Data Simulated CVD
Simulated CVD Data
Data
Alani-Kennedy
Density
Density Alani-Kennedy
Alani-Kennedy
Material-
Material- (Material-Balance
(Material-Balance Density
Pressure
Pressure Balance
Balance Liquid PR
PR (PR Liquid
(psia)
(psia) Density
Density Properties)
Propertles) Density*
Density *
Properties),
Properties)
5514.7
5.514.7 0.670
0.670 0.608
0.608 0.541
0.541 0.570
0.570
4,314.7
4.314.7 0.680
0.680 0.649
0.649 0.554
0.554 0.596
0.596
3114.7
3.114.7 0.688
0.688 0.670
0.670 0.580
0.580 0.632
0.632
2.114,7
2.114.7 0.700
0.700 0.682
0.682 0.608
0 .608 0.664
0.664
1214.7
1.214.7 0.711
0 .711 0700
0.700 0.636
0.636 0.692
0.692
714.7
714.7 0.722
0 .722 0711
0 .711 0.653
0653 0 .707
0.707

The
The Aiani.Kenrreoy
Alam-Kennedy density
denSity correlation
correlation requires
reqUires liquid
liqUid compositions.
composItions total
tOlal liquid
liqUid molecular
molecular
mass
mass heptanes-plus
heplanes-pJus molecular
molecular mass
mass andand specilic
specific gravity au well
gravity (as well as
as pressure
pressure and and
temperature)
temperature) These data were
These data were available torn either
available from enher material-balance
malenalbalance caiculatiorrs
calculations or or PR
PR
smulation
Simulation resultS
resulrs
The PR
PR simulation used properties
Simulalion useo properlles given n Table
Table 33 wiih
The gIVen In with an
an adusted
adrusted 5 p == 11
Kuop 11 88 for the
or the
-

v
C25 traction
025. traction Using
USing the
1he origrnat
onglnal Kvvp actor 01
Kuop laclor 01 1242
1242 gave
gave even
even lower
lower liquid
liqUid densities
denSities than
than
rhove
Ihose given
given above
above with
with aa larger
larger deviation
deviatIon horn
from the
the Alani-Kennedy
AlaMi-Kennedy values
values

bIb
bl6 JOLR,AL
JOURf',;AL OF
OF PETROLEUM
PETROLEUM TECHNOLOGY
TECHNOLOGY
A.3-8
TABLE 5SIMULATED CONSTANTVOLUME
TABLES-SIMULATED CONSTANT-VOLUME DEPLETION DATA FOR THE NS1
NS-1
FLUID AT 280F USING THE PENGROBINSON
PENG-ROBINSON EQUATION OF STATE (psla)
(psia)

Compositions
Equilibrium
Equilibrium Vapor Liquid
Experi- Calcu-
Calcu
mental lated
Component 6764.7 5514.7 4314.7 3114.7 2114.7 1214.7
1214.7 714.7 714.7 714.7
----- ----- ----- ----- ----- ----- -----
Carbon dioxide
dioxide 2.370 2.403 2.447 2.497
2.497 2.541 2.576
2.576 2.583 0.590
0.590 0.S95
0.595
Nitrogen 0.310 0.323 0.336 0.344 0.343 0.334
0.334 0.321 0.020
0.020 0.029
Methane 73.190 75.549 77.644 79.135 79.712 79.242 77.772 12.420
12.420 11.939
11.939
Ethane 7.800 7.779 7.793 7.878 8.057 8.372 8.711
8.711 3.360
3.360 3.623
Propane 3.550 3.474 3.405 3.383
3383 3.444
3.444 3.660 3.989
3.989 2.920
2.920 3.133
isobutane 0.710
0.710 0.686 0.660 0.644 0.647 0.691 0.778
0.778 0.910
0.910 0.967
n-butane 1.450
1.450 1.390
1.390 1.326
1.326 1.281
1.281 1.282
1.282 1.375
1.375 1.567
1.567 2.090
2.090 2.314
isopentane
opentane 0.640
0.640 0.604 0.564
0.564 0.530 0.516 0.548
0.548 0.638 1.400
1.400 1.509
1.509
n-pentane 0.680
0.680 0.639 0.592
0.592 0.550 0.532 0.563 0.659
0.659 1.600
1.600 1.770
1.770
Hexanes
Hexanes 1.090
1.090 0.996 0.889
0.889 0.789 0.727 0.744 0.877 3.680
3.680 4.223
Heptanes-plus
Heptanes-plus 8.210 6.157 4.343 2.969
2.969 2.198
2.198 1.895
1.895 2.105
2.105 71.010 69.897

Totals 100.000
100.000 100.000
100.000 100.000
100.000 100.000
100.000 100.000
100.000 100.000
100.000 100.000
100.000 100.000
100.000 100.000
100.000

0C7
M
M
184.0
184.0 161.0
161.0 142.7
142.7 129.1
129.1 121.2
121.2 116.4
116.4 114.5
114.5 213.0 209.1
'Yc p 0.816 0.799 0.783 0.770 0.762 0.758
0.758 0.757
0,757 0.833 0.843
zZ 1.203
1.203 1.037
1.037 0.937 0.890
0.890 0.886 0.911
0.911 0.936
nn, %
p .% 0.000 9.637 22.581 39.492 56.196 72.413 81.535
SL, O/
SL'% 0.00 19.55
19.55 26.11
26.11 26.65
26.65 25.11 23.00
23.00 21.58

102 ~240rrrr~~~~~~~~~~~rrrr~~~
0
C III -0- PENG-ROBINSON MATCH
III
, -C ...... MATER lAL BALANCE RESULTS
III PENG-ROBINSON
PINGROBINSON MATCH
MATCH
'"E USING MEASURED DATA
z
Z

220
~ 220
o0
oa MEASURED (ACTUALLY THE DATA HAVE BEEN ...J
=
~ :>
"SMOOTHED"
SMOOTHED AND ADJUSTED ACCORDING u
III w
o0
a.
TO CORE LABORATORIES PROCEDURE)
PROCEDURE) ...J
11.
E
5: ~ 200
o0 TOTAL
u 10 III
:>
...
...J
...J
...J
a
11.

~ 180
0
5: .:.
w
180
IE
o0 ...
zz
~

,....
a.
11. 0
11.
> w
:z:
= 160
160
n-C

nii_:i00
140
140

N,o-o---'c----<>----c-------o----
N O
VAPOR
120
120
NS-1
NIi NS1
NS-1
280F
280F MEASURED
MEASURED (--)
C......) 2800 F
2800 F
_ ...............,10.L.0...,0........~20--0..,..0~~3...L00,...0~~4-'00~0..........~5~01....00~-6-0'-00
............~7000 10%~
0 ............~10*OO~~20f.OO~~3~OOO~ 4~0~00~-5~OOO~...,...,~~~0~0~~7000
I,,,, I,,,
0
1O_
10'0L..... 1000 2000 3000 4000 5000 6000 7000 1000 2000 3000 ..........4000 5000 6000 7000
PRESSURE, psia PRESSURE, psia

Fig. 6-Calculated
6Calculated and measured vapor compositions vs. Flg.7-Calculated
Fig. 7Calculated heptanes-plus molecular masses vs.
vs
pressure for NS-1 at 280F. pressure for N5-1
NS-1 at 280F.
280F

PR liquid volumes by adjusting the characterization fac fac- adjust dewpoint pressure. Complete results of the CVD
torofthe
tor of the C115
C 5+ fraction. Lowering the factor from 12.24 simulation are presented in Table 5. PR liquid densities
to 11. 80 resulted in an 88%
11.80 % decrease of the liquid are compared with Alani-Kennedy estimates in Table 44..
volumes for the maximum drop-out (from 32 32%% to 26 %).
26%). Many other adjustments of the C 77 + characterization
C +

other estimated data.


The adjustment had little effect on other procedure were tried. None of these were particularly
To have lowered the K 0
K uop factor more would have
extend
helpful, though some are worth mentioning: (1) extend-
helpful.
created a physically unrealistic system. system. Adjusted ing the C+
7
C 440
C
7+ split to C 0+ such last component
such that the last
physical properties for the C 15 15~ fraction are found in
heavy, (2) increasing the number of MCN
was very heavy.
Table 3.3, as is the methane interaction coefficient used to groups used to nine. C 5
C inclusive, (3) splitting the
2 s+ inclusive. +

MARCH 1983 617


A.3-9
A.3-9

10
~ 10
a
Q'" PRESSURE o0 MATERIAL
PRESSURE
(ps i; a)
IDS a)
MATERIAL BALANCE
BALANCE RESULTS
USING MEASURED
USING
RESULTS
MEASURED DATA
DATA .... 4.0;-~-T-~,--r~-~-r~-~~-r~~~~-'
~ 1- 5514 _7 ........,LEAST
15514.7 _ LEAST SQUARESSQUARES LINEAR
LINEAR ~ - PENG-ROBINSON MATCH (Z800n
u
'"
s
, 2-4314.7
24314.7 REGRESSION
REGRESS ION
'"....w _.- PENG-ROB INSON MATCH (340 ' n
........ 3-3114.7
33114.7 (N , AND
(N, AND C..
C" DATA
DATA EXCLUDES)
EXCLUDED)
o MATERIAL BALANCE RESULTS
:::>
D
4-2114.7
42114.7 3
lO- 5-1214.7
a 10 -51214.7
a<>
0
0
a:
a
~
6- 714.7
6 714.7 z
c 3.0 ~
.'"
w . ~. 0
w a
11.
a: o
0 ~

.,,'o
:::>
S ...J
V! VI
V!
W
~
'"
~
0
10'
10
VI
:> ~.

a ~
a 2.0 ~ l l'I.l~A'rD
0 Ui o ';NTERCEPT Y (p)
z U, Z
""....
V!
Z a-a
0
....
0
a -i a
a
C
a-
E
10
10
Ui
:::> (7
'"aCD aaz<
<Ui
<Ui <U,
S
...J
<ni <Vi
:::>
S
0.Ui

a
'"
w Ui <O
NS-l
Z80 "f 340 "f
1 2
2 33 64 5 0.00 2000 3000 6000 8000
FVb(1/Tbb -
COMPONENT CHARACTERIZATION FACTOR, F=b(l/T lIT) PRESSURE, ps;a

Flg.8-NS-1
Fig. 8NS-1 K-values at 280F calculated using
using the material- Fig.
Fig. 1
10Slopes vs. Fplots vs.
O-Slopes and intercepts of log Kp vs. pressure
vs. pressure
balance approach.
approach. for NS-1 340F.
NS-1 at 280 and 34QoF.

~ 10
,lO ,.. xx 1022 ~-r~-r~~~-----r--~--~~~rT~
10
'"
Q
11 5514 .7
5514.7 ps ;a
psia
0 PENGROBINSON MATCH
PENG'ROBINSDN NS1
NS-l ...... -COSTANT CO1P0SITION
COSTANT CO POSITION NS1
NS-1 -

Z 4314.7 -"- - LSLR WITHOUT 280 OFF >


F
280 OF
a 10'
10
3 3114.7
4 , 211 4. 7
55 1214.7
.".

.".
N4
N ANI> C"
s
"
>..

:..: 10
10
--CONSTANT
----CONSTANT VOLUME DEPLETION

....
1214.7
6 714.7

,
g 10 ' 1
I
I-
Z
<
'"
11. I-
en
C,,

~ 10 zz
V!
...
V!
-

/
,
- inC
nC
_/
...o
0
C)

~
- -

'" 1 O1
10"
11.
10
10
C /
....
a:
.Z
~
II> 1
7 / C-C /. .~-
....
III
-J
...J
102
:;.10'2
Z
0 /0/ CC - as
u " ' ''PO\AI IOfI 0 ' S l ~ B w
w
E
10 "
: 0 :( 10 'Hl'~
" - .. ( ", , ( Otn U.,l11C t
" ( \ Su l ~ 'IOO D\ ' " .. ffi
w
w

'"=
v

~ :i!

~ CC.
=
::::J
...
10
10-'

z i
'" \
cC--....
,
. I.,
1 o- ~
"ADJUSTED
ADJUSTES CC,..
, . FF VALUES
vALUES 5
10 ' L...~-~..l:-~~~+-~-~""'~~.o......:'-'-~~~ ~
: 4 2
COMPONENT
- 0 6
COMPONENT CHARACTERIZATION
2
CHARACTERIZATiON fACTOR
4
FACTOR,, F=b(l/T
o(l/Th b - lIT)
1/TI
66

i
10-I C25
'2'4.7
Fig. 9-NS-1
Fig. 9NS-1 K-values
K-values at
at 280F
280F calculated
calculated using the PR
using the PR EOS.
EQS.
PRESSURE I
Cps; a) 714. 7
106
10'6~~~-'-~~~--~--~--~~~~
2 3
3x10
2
3x10 io 3
i0
10 10'
PRESSURE,
PRESSURE, psia
ps ia

Fig. 11-PR
Fig. 11 PR K-values for NS-1
K-values for NS-1 at
at 280F two deple-
representing two
280F representing deple
tion processes.
tion processes.

b617)
lK JOURNAL
JOUR:"I OF PETROLEUM
AL OF PETROLEUM TECHNOLOGY
TECHNOLOGY
A.3-10
A.3-1O
7+ fmction
C
C7 fraction into
intoeight
eight SCN
SCN groups
groups and
and aa CC fraction.
15'" fmction. of lean
of lean and
and rich
rich gas
gas condensates
condensates using
using the
the EOS
EOS indicate
indicate
and (4)
and using TBP
(4) using TBP KiloI' instead of
factors instead
K,,, factors those
of those that K-values
that K-values are
are independent
independent ofof the
the depletion
depletion process
process..
estimated from
estimated from Eq.
Eq. 23.
23. 44.. Equations
Equations of of state
state usually
usually overestimate
overestimate liquid
liquid
volumes of
volumes of petroleum
petroleum reservoir
reservoir fluids.
fluids. The
The problem
problem was
was
Results and
Results Discussion
and Discussion improved by
improved by reducing
reducing the
the Watson
Watson chamcterization
characterization factor
factor
Fig. 66 compares
Fig. compares measured measured (or (or moremore correctly.
correctly. of the
of heaviest component.
the heaviest component.
smoothed) vapor
"smoothed") vapor compositions
compositions with with those simulated
those simulated
using the
using the PR
PR EOS.
EOS. The The match
match isis excellent.
excellent, showing
showing only only Nomenclature
Nomenclature
slight deviation
slight deviation for for the
the CC . and CC,
77' and components. Devia-
b components. Devia AA or
or A(p)
.4(p) = slope
= of 10gKp
slope of vs.. FF plot
logKp vs plot
tion of
tion the hexane
of the hexane component
component isis probably
probably because
because of of its
its bb = slope
= slope of
of the
the stmight
straight line
line connecting
connecting
incorrect chamcterization
incorrect characterization as n-hexane.
as n-hexane. the
the critical
critical pointpoint and
and atmospheric
atmospheric
Fig. 77 presents
Fig. presents heptanes-plus
heptanes-plus molecular
molecular massesmasses of of liq-
liq boiling
boiling point point on
on aa log
log vapor
vapor pressure
pressure
uid
uid and vapor phases
and vapor phases and and the
the total
total system.
system. Simulated
Simulated and and vs.. liT
vs l/T plot.
plot. cycle-OR
cycle-R (cycle-K)
(cycle-K)
material-balance-derived values
material-balance-derived values match
match well.well. OurOur ex-ex BB = formation
formation volume volume factor,
factor. bbllSTB
bbl/STB
perience has
perience has shown
shown that that aa good
good match
match of of CC 7 - molecular
molecular (m 3/stock-tank m 3)
/stock-tank
3
(m )
3
m
mass using
mass using the the PR PR EOS EOS isis usually
usually difficult
difficult and very
and very
dependent on For F(T) =
F or F(n = component
component chamcterization
characterization factor.factor.
dependent on proper proper chamcterization
characterization of of the plus
the plus
fraction.. cycle
cycle
fmction
Calculated equilibrium
equilibrium constants
constants werewere correlated
correlated using
using K = equilibrium
equilibrium constantconstant (K-value)
(K-value)
Calculated
the Hoffman et
the Hoffman al. b6 method.
er al. method. Fig. Fig. 88 presents
presents NS-INS-l K- K- K uIJP = = Watson
Watson chamcterization
characterization factor factor
values calculated
values calculated using using material-balance
material-balance relations
relations.. The
The In = mass,
mass, Ibm (kg)
Ibm (kg)
log Kp
log Kp vs vs.. FF plots
common point.
plots are linear and
are linear and appear
appear to approach a =
M = molecular mass, mass, Ibmllbm-mol
lbmllbm-mol
common point. The convergence point can
The convergence can give an (kg/kg-mo!)
(kg/kg-mol)
estimate of
estimate of the
the apparent
apparent convergence
convergence pressurepressure.. Actually
Actually,. n = = moles.
moles, Ibm-mol
lbm-mol (kg-mo!),
(kg-mol). exponent in
the most
the most accumte
accurate value value is obtained by extmpolating
extrapolating the K-value correlation
slope vs
slope vs.. pressure
pressure curvecurve to to zero.
zero, asas done in Fig. 10. 10. The
resulting estimate
estimate of ofpK 8,000 psia (55 MPa) MPa)..
p = pressure. psia (kPa)
resulting p K is 8.000
Fig. 9 presents NS-I
Fig. NS-l K-values calculated from the =
R = universal gas constant, 10.732
EOS.. Once again linear plots of log Kp vs
EOS vs.. F
Fconverge
converge to psia-cu ft/mol-oR
ft/mol-R (9.3143 J/mol-K)
aa point.
point. FromFrom the extmpolation
extrapolation of slope to zero in Rsg =
R = vapor solution GOR, scf/STB

Fig. 10. (std m 3 /stock-tank m 3 )


Fig. 10. p 7,500 psia (52 MPa). Another interesting
p K ::: 7.500 /mstock-tank
3 )
3
m
feature shown
feature shown Fig. 9 is that heavy components are bet-
in bet Rso =
0
R = liquid solution GOR, scf/STB
ter correlated
ter correlated using the log Kp vs vs.. F methods
methods at higher (std m 3/stock-tank m
/mstock-tank
3 m3)
)
3
pressures.
pressures. S = = saturation,
satumtion, fractionfmction or or % %
Temperature effects on the log Kp vs. P
Tempemture F plots of of NS-l
NS-I
were investigated by running the EOS EOS simulator
T == absolute tempemture
temperature., OR R (K)(K)
were simulator at at
340F V = volume,
volume. cu cu ft (m (m 3 )
)
3
340F (171.1C),
(\71. 1C). about 60F (15.5C) (l5.5C) higher than
reservoir temperature.
reservoir tempemture . Results indicate that temperature tempemture x = = liquid composition.
composition, fraction fmction or or %
influence
influence is (I) largest for heavy components
is (1) components at at large
large y == vapor
vapor composition. fraction fmction or or % %
pressures,
pressures. (2) negligible at low pressures pressures (as was found
(as was Yep) == intercept
Yor Y(p) intercept of of log Kp vs.
log Kp vs . F plot
plot
in
in Ref.
Ref. 8). (3) relatively
8). (3) relatively small
small compared
compared to to the
the influence
influence
of
z = total
total system
system composition
composition
of pressure,
pressure. and and (4) not significant
(4) not significant in in changing
changing the the apap-
parent
parent convergence
convergence pressure pressure of of the
the system.
system.
Z = = vapor
vapor compressibil
compressibility factor
ity factor
For
For lighter
lighter systems,
systems. there there does not not always
always appear
appear suchsuch = specific
"y = specific gravity
gmvity relative
relative to to air
aIr or
or water
water
aa unique
unique convergence
convergence point point for log log Kp vs. FF plots.
Kp vs. plots. We We (60/60)
(60/60)
thought
thought that that this
this perhaps
perhaps resulted
resulted fromfrom aa change
change in in the
the =
o = interaction
intemction coefficient
coefficient
total
total composition
composition of of the system or
the system or from
from alteration
altemtion in in the
the incremental
d == incremental
heptanes-plu
heptanes-plus s properties.
properties. We We investigated
investigated these these pp = density.
density, Ibm/cuIbm/cu ftft (kgim
(kg/m3) I
possibilities
possibilities by by running
running aa constant-com position simula
constant-composition simula-
tion
w = = acentric
acentric factorfactor
tion of of NS-
NS-I.I . Resulting
Resulting K-values
K-values were compared with
were compared with
CVD
CVD K-values
K-values and and areare presented
presented as log KK vs.
as log log pp plots
vs. log plots
in
in Fig.
Fig . 11.
II. This
This plot
plot indicates
indicates thatthat compositiona
compositional l change
change Subscripts
Subscripts
during
during constant
constant volume volume depletion
depletion isis not not significant
significant aa == atmosphenc
atmospheric
enough
enough to to influence
mfluence K-values
K-values or or convergence
convergence pressure.
pressure. bb = bubble
bubble point
point (Pt,)
(Pb) oror boiling
boil ing (Thl
,)
1
T
cc = critical
critical
Conclusions
Conclusions cell == cell,
cell cell. pertaining
pertaining toto PVT
PVT cell
cell volume
volume
I.I . Measured
Measured CVD
CVD data
data ftr gas condensate
for aa gas condensate werewere dd == dewpoint
dewpoint
analyzed
analyzed using simple material
using simple material balances and the
balances and the PR
PR gg = gasgas
EOS
EOS. i == index
index forfor summation
summation
2.2 . AA simple
simple method
method waswas proposed
proposed flrfor calculating
calculating
black-oil j = component
component identifier
ident ifier
black-oil PVTPVT properties
properties (FVFs
(FVF"s and
and solution
solut ion GORs of
GOR ' s) of
gas condensates
gas and volatile
condensates and volatile oils.
oils. kk == depletion
deplet ion staize
stage
3.3. Simulated
Simulated constant-com position and
constant-composition and CVD
CVD studies
studies KK =convergence
convergence
\IAR(H 983
MARCH 1983
A.3-11
A311
LL = liquid
liquid phase
phase 5.5. Standing,
Standing, M.B.:
M.B. : Volumetric
Volumetric and Phase Behavior
and Phase Behavior of of Oil
Oil Field
Field
Hydrocarbon Systems,
Hydrocarbon Systems. SPE,
SPE. Dallas
Dallas (1977).
(1977).
nn = carbon
carbon number
number Hoffmann. A.E.,
6.6. Hoffmann. A.E., Crump. 1.S. , and
Crump, J.S., and Hocott,
Hoeon. CR.:
C.R.: Equilibrium
"Equilibrium
oo = oil
oil Constants
Constants forfor aa Gas-Condens
Gas-Condensate ate System,
System," Trans.,
Trans . AIME
AIME ([953)
(1953)
198. 1-10.
198, 1-10.
pP = produced
produced GlaSG!. (3.
7.7. Glaso. and Whitson.
Q. and Whitson. C.H.: "The Accuracy
C.H.: The ofPVT
Accuracy of PVT Parameters
Parameters
rr = reduced
reduced Calculated from
Calculated from Computer
Computer Flash
Flash Separation Pressures Less
Separation atat Pressures Less
1.000 psia.
psia," I.J. Pet.
Pet. Tech. 1982) 181113.
ss == saturated
saturated (bubble-
(bubble- or
or dewpoint)
dewpoint) Than 1.000
Than Tech. (Aug.
(Aug. 1982) 1811-13.
Standing. M.B.:
8.8. Standing. M.B.: A Set of
"A Set Equations for
of Equations Computing Equilibrium
for Computing Equilibrium
sc
sc = standard
standard conditions
conditions Ratios
Ratios of of aa Crude
Crude Oil/Natural
Oil/Natural GasGas System
System at Pressures Below
at Pressures Below
sto == stock-tank
sto stock-tank oil
oil 1000 psia." J.J. Pet.
1.000 psia, Pet. Tech. (Sept. [979)
Tech. (Sept. 1979) 119395.
1193-95.
Standing. MB.
9.9. Standing, M.B. and and Katz,
Katz. DL,:
D.L.: Vapor/Liqu
"Vapor/Liquid id Equilibria
Equilibria ofof
t = total
total (two-phase)
(two-phase) Natural Gas-Crude Oil
Natural Gas-Crude Systems," Trans.,
Oil Systems, Trans., AIME (1944) 155,
AIME (1944) ISS.
vv == vapor
vapor phase
phase 23245.
232-45.
10.
10. Alani, G.H. and
Alani. G.H. and Kennedy,
Kennedy. H.T.: "Volumes of
H.T.: Volumes of Liquid
Liquid Hydrocar
Hydrocar-
bons atat High
bons High Temperature
Temperatures s and Pressures," Trans.,
and Pressures, AIME (1960)
Trans . AIME (1960)
Acknowledgments
Acknowledg ments 219. 28892.
219. 288-92.
We thank
We thank H.H. Norvik,
Norvik, H.H. Asheim,
Asheim, D. Murphy, V.
D. Murphy, V. II. Whitson,
II. Whitson. C.H.:
C.H.: Characteriz
"Characterizing Hydrocarbon Plus
ing Hydrocarbon Plus Fractions,
Fractions."
paper
paper EUR EUR 183 183 presented
presented at at thethe 1980 European Offshore
1980 European Offshore
Dalen. and
Dalen. G. Nielsen
and G. Nielsen for
for useful comments concerning
useful comments concerning Conference and
Petroleum Conference
Petroleum Exhibition. London,
and Exhibition. Oct. 2124.
London. Oct. 21-24.
this paper.
this paper. We
We also acknowledge
acknowledge computer time and
computer time and 12.
12. Katz, D.L. and
Katz. D.L. Firoozabadi. A.:
and Firoozabadi, Phase Behavior
"Predicting Phase
A.: Predicting Behavior of of
facilities provided
provided byby Rogaland
Rogaland Dist. c., Norwegian
Dist. C.. Norwegian Condensate/C rude-Oil Systems
Condensate/Crude-OiI Using Methane
Systems Using Interaction Coeffi
Methane Interaction Coeffi-
Inst. of
Inst. of Technology,
Technology. and Continental Inst. We
Shelf Inst.
Continental Shelf We cients." Trans.,
cients, Trans .. AIME
AIME (1978) 265. 164955.
(1978) 265. 1649-55.
thank Phillips
thank Phillips Petroleum Co. Norway for contributing
Petroleum Co. contributing
needed fluid data
needed data to
to the
the petroleum literature. Support
petroleum literature. Support
from Frying
Frying Pan Publications
Publications Inc.
Inc. is appreciated.
appreciated. SI Metric Conversion Factors
References API
API 14l,5/(131,5+ o
141.5/(l31.5+API)
APO = g/cm
= g/cm 3
3
Reudelhuber., F.O.
1. Reudelhuber
I. F.O. and
and Hinds,
Hinds. R.F.:
R.F.: "A Compositional
A Composition al Matenal
Material bbl
bbl x 1,589 873
1.589873 E01
E-Ol =m
= m3
3
Balance Method
Balance Method for Prediction of RecoveryRecovery from Volatile Oil
from Volaule Oil cu
cu ft x 2.831 685
2,831 685 E02
E-02 =m
=m3
3
2. Dodson,
Dodson. CR.,
Reservoir." Trans
Depletion Drive Reservoir,
C.R . Goodwill,
Goodwill. D.,
. AIME
Trans., (1957) 210,
AIME (1957) 1926.
210. 19-26.
"Application of
Mayer. E.H.: Application
D .. and Mayer.
OF
F (OF-32)/1.8
(F32)/l.8 = OC
= C
2.
Laboratory PVT Data to Reservoir Engineering Problems, Problems." psi x 6.894 757
6.894757 E+0O
E+OO =
= kPa

Trans . AIME
Trans., (1953) 198.
AIME(L953) 198, 287-98.
28798. scf x 2.863 640
2.863 640 E02
E-02 = std m
m3
3
3. Firoozabadi. A
3. Firoozabadi, A.,. Hekim.
Hekim, YY.,. and Katz, D.L. "Reservoir Deple
DL.:: Reservoir Deple JPT
tion Calculations for Gas Condensates Using Extended Analyses in
the Peng-Robinson
Perig-Robinson Equation of State." Cliem. Eng. (Oct.
State, Cdn. J. Chem. (Oct.
1978) 56.
56, 610-15
61015.. in Society office July
Engineers olliee
Petroleum Engineers
of PetrOleum 22, 1981.
1981.
Original manuscript received in
Original manuscript Society of July 22.
4.
4. Conrad, P.G.
PG. and Gravier.
Gravier, 1.F.: Peng-Robinson Equation of
iF.: "Peng-Robinson Papar accepted for publiCBlion
Paper accepled Sept. 5,
publication Sapt. 5. 1982. Revised manuscript
1982. Revised manuscript received 15,
Dec. 15.
received Oac.
Experiments, Oil and Gas J.
State Checks Validity of PVT Experiments." I. 1982.
1982 Papar 10067) first presented 81
Paper (SPE 100(7) SI the 1981 SPE
the 1981 Annual Technical
SPE Annual Con
Technical C0n-
(April 21. 1980) TI-86. Eshibilion held in San Anlonio
ference and Exhibition 57
Antonio Oct. 5-7.
7786.

620
620 JOURNALOF
JOURNAL TECHNOLOGY
PETROLEUM TECHNOLOGY
OF PETROLEUM
A.4-1
A.4-1

SPE
SPE
Socettj of Pet,olet,n Fnea of AIME

SPE 11200
SPE 11200

Effect of
Effect of Physical
Physical Properties Estimation on
Properties Estimation on
Equation-of-State
Equation-of- Predictions
State Predictions
by Curtis
by Curtis H.
H. Whitson, Rogaland Regional
Whitson, Rogaland Regional College
College
Member SPE
Member SPE

Copynght 1982.
Copyright 1982. Society
Society of
of Petroleum
Petroleum Engineers
Engineers of AI ME
01 AIME
This paper
This paper was
was presented
presented atat the
the 57th Annual Fall
57th Annual Technical Conference
Fall Technical Conference and Exhibition of
and Exhibition of the Society of
the Society of Petroleum Engineers of
Petroleum Engineers of AIME,
AIME .
held in
held New Orleans.
In New Orleans. LA.
LA. Sept
Sept 2629. 1982 The
26-29. 1982 matenal isIS sublect
The material to correction
sub,ectto by the
correcllon by author Permission
the author Permission to copy isis restricted
to copy restricted loan
to an
abstract of not more
abstract of not more than
than 300
300 words
wordS Wnle
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75206

ABSTRACT
ABSTRACT INTRODUCTION

The aim
The aim of
of this
this work
work was
was to
to document
document the
the In recent
In recent years, there has
years, there has been
been an an increasing
increasing
influence of
influence of various
various hepatanesplus
hepatanes-plus characterizat
characterization
ion in enhanced
interest in
interest recovery (EOR)
oil recovery
enhanced oil (EOR) methods.
methods.
schemes
schemes onon equation-of-state
equationofstate predictions. Both the
Both the One result has
One result has been need to
the need
been the develop more
to develop more advanced
advanced
Peng-Robinson and aa modified Redlich-Kwong
Peng-Robinson Redlich-Kwong cubic
cubic numerical simulating EOR
for simulating
numerical models for EOR processes.
processes.
equation
equation were used.
used. Numerous characterization
characterization Some of these
Some models use
these models use an an equation
equation of state (EOS)
of state (EOS)
procedures were
procedures were chosen
chosen from
from the literature. Six Six to predict vapor-liquid equilibrium
to predict equilibrium (VLE) (VLE) and and
reservoir fluids
reservoir fluids with detailed heptanesplus
heptanes-plus analysis
analysis volumetric phase behavior.
volumetric phase behavior. The The validity
validity of of EOS
EOS
were
were chosen
chosen to
to represent a broad range of fluid types. EOR processes has
to EOR
application to has been
been well- well
documented elsewhere. 1,2,4, 5, 30, 14, 35, 21, , 27, 4545
Pressure-volume-temperature
Pressurevolumetemperature measurements for these documented elsewhere. 1. 2, It, 5, !D, 0, 15,21., 25, '0, '<6, '<6
fluids
fluids were performed over
were performed over a relatively wide range of
conditions.
conditions. One significant with using
problem with
significant problem an EOS
using an EOS is the the
difficulty in describing heavy found in
heavy fractions found
One
One part
part of the study dealt with methods for usually
fractions, usually
reservoir fluids. These fractions,
estimating
estimating specific
specific gravities and boiling points of +) fraction,
7
(C
heptanesplus (C7+)
constituting a heptanes-plus fraction, have have a aJ
37,45.45
I
petroleum
petroleum fractions.
fractions. These two properties are usually significant effect on EOS predictions.
5
4
2
predictions),
3
,
2
1,2, It, 5, 15, ]6,'0, !7,ooItG
5
0
7
required
required byby critical
critical property correlations. Four the heavy fractions.
Few data may be available for the heavy fractions.
methods
methods were
were studied, including two based on the Watson of critical
Even so, accurate estimates of properties -
critical properties

characterization
characterization factor, one based on the aromaticity critical pressure, critical temperature, acentric
temperature, acentric
factor
factor proposed
proposed by
by Jacoby
Jacoby and Yarborough, and the are required
factor - and molecular weight are

required by by most
most
generalized
generalized properties proposed by Katz
Katz and equations of state.
Firoozabadi.
Firoozabadi. Equation-of-state
Equationofstate predictions
predictions were mace
using
using critical
critical properties based onon the
the estimated
estimated Several methods and correlations exist for
exist for
specific
specific gravities andand boiling
boiling pOints;
points; these
these were characterizing heptanes-plus
characterizing fractions. Some
heptanesplus fractions. of these
Some of these
compared
compared with
with predictions made using critical
critical were developed applications, while
developed for EOS applications, others
while others
properties
properties based
based on
on measured
measured specific
specific gravities
gravities and
and were developed improve or
developed to improve or replace previous methods.
previous methods.
bOiling
boiling points.
points. Most
Most of
of the
the correlations
correlations are or exponential
are polynomial or exponential
equations. were fit
constants were
equations. Equation constants fit to existing
to existing
Another
Another part
part dealt
dealt with
with various
various critical
critical experimental data or correlations based
or graphical correlations on
based on
property
property correlations,
correlations, and
and their
their influence
influence on
on experimental data.
experimental data.
equation-of-state
equation-of-state predictions.
predictions. A A thorough
thorough review
review of
of
commonly
commonly used
used correlations
correlations was
was presented.
presented. Four
Four sets
sets Some
Some of the more
of the more recent methods try
recent methods to provide
try to provide aa
of
of correlations
correlations were
were compared.
compared. Results
Results indicate
indicate that
that better characterization by
better characterization by estimatin~
estimating the chemical
the chemical

relatively
relatively small
small differences
differences in
in critical
critical properties
properties and
and "make-up"
makeup of
of petroleum
petroleum fractions.
12
fractions. 1,2, .It The most
The most
acentric
acentric factor
factor can
can result
result in
in significant
significant differences
differences common approach has
common approach been to
has been to assume fractions are
heavy fractions
assume heavy are
in
in equation-of-state
equationofstate predictions.
predictions. composed
composed ofof three hydrocarbon groups:
three hydrocarbon paraffins (P),
groups: paraffins (P)
naphthenes
naphthenes (N)(N) and
and aromatics
aromatics (A). (A) Several . schemes
Several schemes
Finally,
Finally, aa study
study was
was performed
performed toto document
document the
the have
have been
been proposed
proposed for determining the
for determining the PNA content of
PNA content of
influence
influence of
of adjustments
adjustments in
in heptanes-plus
heptanesplus critical
critical petroleum
petroleum fractions,
6

2
fractions, 1, 2, 6," though
though itit is shown in
is shown this
in this
properties,
properties, equation-of-state
equationofstate constants
constants (a(a and
and b)
b) and
and work
work that
that only
only aa few of these
few of these are reliable.
are reliable.
binry interaction
bin~ry interaction coefficients.
coefficients. Graphical
Graphical
presentations
presentations illustrate
illustrate the
the influence
influence of
of individual
individual All
All of
of the
the above are aimed
correlations are
property correlations
above property aimed
and
and combined
combined adjustments
adjustments of
of these
these parameters.
parameters. They
They at
at obtaining
obtaining accurate
accurate estimates of critical
estimates of properties
critical properties
provide
provide aa guide
guide toto engineers
engineers involved
involved with
with matching
matching required
required by
by equations-of-state. However, each
equationsofstate. However, method
each method
experimental
experimental data
data measured
measured on
on reservoir
reservoir fluids.
fluids. is
is based
based on
on one
one or properties which
more properties
or more cam be
which can be
measured
measured directly.
directly. The common
most common
The most
References
References and
and illustrations
illustrations at
at end
end of
of paper.
paper.
A.4-2
A.4-2

22 EFFECT
EFFECT OF
OF PHYSICAL
PHYSICAL PROPERTIES
PROPERTIES ESTIMATION
ESTIMATION ON
ON EQUATION-OF-STATE
EQUATION-OF-STATE PREDICTIONS
PREDICTIONS SPE
SPE 11200
11200

"correlating
correlating variables"
variables are
are specific
specific gravity
gravity and
and All
All results
results from
from this
this work
work suggest
suggest that
that the
the C,+
+
7
C
boiling
boiling point,
point, originally
originally proposed
proposed by
by Smith
Smith and
and characterization
characterization has
has aa significant
significant influence
influence onon EOS
EQS
Watson.]!
Watson. predictions
predictions for
for reservoir
reservoir fluids.
fluids. The
The numerous
numerous
examples
examples presented
presented and
and systematic
systematic approach
approach followed
followed
Fractional
Fractional distillation
distillation is is the
the only
only reliable
reliable allow
allow the
the reader
reader to
to observe
observe the
the degree
degree ofof influence
influence
method
method for
for obtaining
obtaining direct
direct measurements
measurements of of both
both each
each property
property and
and estimation
estimation procedure
procedure has.
has. It
It was
was
correlating
correlating variables.
variables. In
In recent
recent years,
years, however,
however, suspected
suspected at
at the
the beginning
beginning of of the
the project
project that
that no
no
advances
advances inin chromatography
chromatography have
have made
made distillation
distillation single
single characterization
characterization scheme
scheme would
would prove
prove to
to be
be
less common. As
less common. As aa result,
result, it
it was
was necessary
necessary to
to substantially
substantially more
more accurate
accurate than
than all
all others.
others. This
This
develop
develop methods
methods for
for estimating
estimating specific
specific gravities
gravities proved
proved to be
be the
the case.
case.
and boiling points
and boiling points ofof petroleum
petroleum fractions
fractions without
experimental
experimental data'!','<6
data Unfortunately,
Unfortunately, these
these methods
methods In general,
general, there
there were too
too many degrees of
do
do not
not meet
meet standards
standards ofof generalized
generalized correlations
correlations freedom
freedom - too
too many
-many unknowns - to make
make concrete,
concrete,

since
since they are based
they are based onon specific
specific fluids
fluids and
and have objective conclusions
conclusions from
from this
this study. Also,
Also, it
it
not been compared
not been compared with
with data
data from
from other
other sources.
sources. should be noted that some
some of
of the
the guidelines and
and
conclusions presented are based
based on my
my experience
experience with
with
2
Several
Several investigators
have
2
investigators , !Shave presented results a larger number of fluids than
than are presented in this
which indicate
which indicate that
that the
the choice
choice ofof critical
critical property work. They
They are therefore subject to criticism.
correlations may be
correlations as important
be as important asas the
the choice
choice of II feel, however, that practicing engineers confronted
confronted
EQS.
EOS. The present
The present work was designed
designed to investigate with the problem of "which
which characterization scheme
this hypothesis for reservoir fluids at reservoir
this hypothesis to use"
use should have some guidelines, however
conditions. Another purpose was to investigate
investigate subjective, with which to make their final decision.
influence of
the influence manual adjustments
of manual adjustments to properties,
and interaction coefficients commonly used
constants and
match measured PVT data.
to "match" PHYSICAL PROPERTIES CORRELATIONS: A
A REVIEW

To perform a reliable comparative study,


study, it was The critical point of a pure compound is defined
necessary to isolate the effects of each factor. as the pressure and temperature at which the vapor
The three factors chosen in this investigation were phase has properties identical with ~he
he equilibrium
(1) methods for estimating correlating variables liquid phase. These conditions also define the end
(specific gravity
(specific gravity and boiling point) of SCN groups, pOint
point of the vapor pressure curve. All equations of
(2) correlations or procedures for estimating state require critical pressure and temperature of
critical properties (pressure and temperature, and individual components in a mixture.
acentric factor), and ()
acentric (3) manual adjustments of
EQS constants (n and ~)
critical properties, EOS Most equations facto~
equations also require the acentric factor
a
and binary interaction coefficients (particularly Molecular weights are needed to convert
convert molar volumes
volumes
between
between methane/C02
2 and heavy fractions).
methane/CO fractions) to densities. Some recent
recent cubic
cubic equations have
have
inclu~,d critical compressibility factor as a para
includd para-
The primary basis for choosing reservoir fluids meter.
for this study was the availability of distillation
data for the C+
7
C,+ fraction. PVT measurements
measurements There are numerous correlations for estimating
estimating
performed at
performed at reservoir conditions were also
also a physical properties
properties of
of petroleum
petroleum fractions. Most Most
requirement. Based
Based on these criteria, six
six fluids of these use specific gravity, y, and
of and boiling
boiling point,
point,
literature~U'~~The types
were chosen from the literature,O,,UThe types of Tb' as correlating variables.
Tb, variables. Correlations commonly
commonly
ranged from a lean gas
fluid ranged gas to a non-volatile oil.
nonvolatile oil. used in
used in the petroleum
petroleum and chemical
chemical engineering
engineering fields
PVT measurements
PVr measurements were performed
performed at several
several are presented
are presented in in Tables
Tables I1 and
and 2.
2. Graphical
Graphical correla-
correla-
temperatures for all L3,47
but one system. This
all but This gave
gave an
an tions ~],~, are
tions are not
not considered
considered inin the
the present
present study.
study.
opportunity to illustrate the
opportunity to the apparent temperature-
temperature-
dependence of methanehydrocarbon
dependence of methane-hydrocarbon binary
binary Most correlations
Most correlations were
were developed
developed when
when English
English
interaction coefficients used
used to
to match saturation
saturation units were
units were the
the industry
industry standard.
standard. InIn recent
recent years,
years,
pressures
pressures of
of reservoir fluids. many engineering
many engineering Societies
Societies have
have converted
converted toto an
an SI
SI
standard. To
standard. To help
help facilitate
facilitate using
using these
these correla
correla-
Two cubic equations
Two cubic equations of
of state
state were
were used
used for
for the
the tions with
tions with SPE
SPE preferred
preferred SI
SI units,
units, the
the following
following
study. The
study. Peng-Robinson~ (PR)
The PengRobinson
29 (PR) EQS
EOS was
was chosen
chosen variables and
variables and correlating
correlating factors
factors are
are used:
used:
because
because of its widespread
of its wide-spread industrial use. It
industrial use. It also
also
yields better
yields better liquiddensity
liquid-density estimates
estimates than
than the
the
comparable Soave-Redlich-Kwong
comparable Soave-Redlich-Kwong equation.
equation. As As aa TT ~T*
=T* (la)
. (la)
representative
representative of of the
the RedlichKwong
Redlich-Kwong family, cc 99 c
Yarboroughs
Yarborough's version
version ofof the
the modified
modified Zudkevich
Zudkevich-
Joffe-Redl~ch-Kwonq* (ZJRK)
Joffe_Redllch_Kwong* EOS~ was
(ZJRK) EOS

4 was chosen.
chosen . Pc = 6.8947S9'p~
6.894/59p .......... .... . . . . (Ib)
(lb)
Although
Although not as widely
not as adopted as
widely adopted as the
the PR
PR or
or SRK
SRK
equations, the ZJRK
equat10ns, the EOS gave
ZJRK EOS gave considerably
considerably better
better
estimates
estimates ofof liquid densities and
liquid densities and saturation
saturation tt 1.8T - 4l9.67
459.67 ..... . .. .. . . .. . . . (lc)
(1c)
= l.B.Tt
b

pressures for reservoir


pressures for reservoir fluids
fluids used
used in
in this
this atudy.
study .

* By
*
convention~ the
By convention the abbreviation
abbreviation ZJRK
ZJRK is
is used.
used. y = C(1S . SoC) // pP
o(155C) t (1S . SoC) . . .... . ... (id)
15.5C) (1d)
Actually,
Actually, RKJSZ
RKJSZ would
would be
be more
more correct
correct since
since the
the RE
RK waI.eer
wa r
modification
modification which
which has
has been
been most
most accepted
accepted was
was proposed
proposed
by Joffe,
by Schroeder and
Joffe, Schroeder Zudkevich~9 This
and Zudkevich
9 This modification
modification
API
=
14~.S _ 131.5
141.5
13 1. 5
................. . .... (le)
(1e)
was an almostinstantaneous
was an almost-instantaneous modification
modification ofof the
the y
Zudkevich-Joffe
Zudkevich-Joffe modification
modification (not
(not referenced
referenced here).
here).
A.4-3
A.4-3

SPE 11200
SPE 11200 C.H. WHITSON
C.H. WHITSON 33

e
8 = T /T
b c
(If)
(if) NOKAy28
28
NOKAY

1/3
In 1959,
In 1959, Nokay
Nokay presented
presented seven
seven simple
simple equations
equations
bl
KK = [1.8-T3
[1.8T.J
7

1 /I yY (lg)
(ig) for estimating
for estimating parachor,
parachor, boiling
boiling points,
points, specific
specific
w
qravity and
qravity and critical
critical temperature. The critical
temperature. The critical
yY - 0.8468
0.8468 + 15.8/N
15.8/M temperature correlation
temperature correlation isis perhaps
perhaps the most important
the most important
= .. . . . . .. . .. (lh)
(lh) because it
because it introduced
introduced aa simple
simple equation form which
equation form which
0.2456 1. 77 1M
0.2456 - 1.77/M was later
was later shown
shown to
to be
be applicable many other
to many
applicable to other
physical properties
physical (see RiaziDaubert
properties (see Riazi-Daubert correlations
correlations
x = O.7(l2.1-K)
0.7. (12.1 K ) (ii)
(11) below)
below).
w

WA w
Nokay's original
Nokays original relation
relation for critical temper
for critical temper-
ature has
ature has been
been improved by Spencer
improved by and Daubert
Spencer and 39
Daubert39 by
by
the three
fitting the three constants to data
constants to for each
data for each
where Tb
where Tb and Tc
Tc have units Kelvin (K) and
and pp has
has hydrocarbon family.
hydrocarbon
units kPa.
units kPa. t,
t, TT~ and pP~ are merely variabls
variabl~s
(though they actually
(though actually represent
represent English unit
English unit
equivalents of
equivalents of Tb,
Tb , Tc
Tc and
and p)
pc)' CAVErI

A short review
A review and discussion of each
each correla
correla- In 1962,
In correlations for
proposed correlations
1962, Cavett proposed for
tion is
tion is provided to
to help the reader decipher differ
differ- estimating temperature of
and temperature
pressure and
estimating critical pressure of
ences between correlations. If several correlations
ences correlations petroleum fractions. The
petroleum were built
The correlations were built
are taken from the
are taken the same source, they are
are discussed
discussed into aa program
into designed to
program designed simulate traytotray
to simulate tray-to-tray
together.
together. The order of presentation is
The is chronoloqic
chronologic distillation up
distillation up to
to pressures of 7000
pressures of 7000 kPa (1000 psia).
kPa (1000 psia) .
to
to avoid the appearance of personal preference.
preference.
II have tried to
have tried to give an objective critique
critique of each correlations have
Although these correlations been widely
have been widely
correlation
correlation based on claims of the original authors without reference
adapted, they are presented without to
reference to
and
and my
my experience
experience with the correlation_
correlation. Limitations development, and
which data were used for their development, no
and no
are
are stated ifif they are available. limitations or comparison with previous
previous correlations
are offered.

ROESS
ROESS 36
3&
HARIU-SAGE
32
HARIU-SAGE 12
In
In 1936, Roess presented correlations for
critical
critical temperature and pressure. They were presented aa method
In 1969, Hariu and Sage presented method
developed from flow data on petroleum fractions in (program) for simulating fractional distillation of
aa pioneering work previous to most correlation crude
rude oils. equation
In their procedure they give an equation
development. The API Technical Data Book has from boiling point
for estimating molecular weight from point
retained
retained the
the original form of the Roess critical and specific gravity (viz the Watson characterization
temperature
temperature equation (the critical
critical pressure equation factor, Kw).
I,.) . surfacefit of the
It represents a surface-fit
is
is not
not generally
generally used).
used) It has been modified using
. usinq Winn nomograph. They claim the equation gives aa
equation gives
recent
recent data
data from
from U.S. and North Sea oils.
oils. over 1090
reasonable extrapolation to boiling points over K.
1090 K.

The
The main limitation of thethe Roess correlation This correlation can be rearranged to solve
is
is that it
it should
should not be used forfor fractions heavier directly for specific gravity. It cannot, however,
than C20'
20
C
. It
It highly underestimates critical
critical point.
be solved directly for boiling pOint. Even though
Even though
temperatures
temperatures for
for heavier
heavier fractions
fractions and
and is not, HariuSage
a trial and error method is needed, the Hariu-Sage
therefore,
therefore, reliable for
for many
many reservoir
reservoir applications.
applications. equation provides a necessary link between three
important properties.
properties. It
It appears to more
to be more
accurate than the Kesler-Lee correla
KeslerLee molecular weight correla-
EDMISTER
77
EDMISTER tion, though
though the difference may result from using
different data equations.
data to develop the equations.
In
In 1948,
1948, Edmister
Edmister proposed
proposed aa simple
simple but accurate
accurate
equation
equation for
for estimating
estimating acentric
acentric factor
factor of
of pure
pure
compounds.
compounds. It
It requires
requires boiling
boiling point,
point, critical
critical BERGMAN 1,2
BERGMAN 1, 2
pressure
pressure and
and critical
critical temperature.
temperature. The The equation
equation has
has
also
also been
been applied
applied sucessfully
sucessfully toto petroleum
petroleum fractions.
fractions. In
In 1976,
1976, Bergman
Bergman presented
presented aa comprehensive study
comprehensive study
If
If acentric
acentric factor
factor is
is available
available from
from another
another source,
source, of the
the retrograde
retrograde condensation
condensation effects natural gas
effects on natural gas
the
the Edmister
Edmister equation
equation can
can be
be rearranged
rearranged toto solve
solve for
for pipelines.
pipelines. One One result
result from
from this study experimen
study was experimen-
any
any of
of the
the three
three other
other properties
properties (assuming,
(assuming, of
of tal
tal data
data which were correlated
which were correlated to molecular
give molecular
to give
course,
course, the
the other
other two
two are
are known).
known). weight
weight and
and specific
specific gravity
gravity asas aa function of boiling
function of boiling
point.
point. Only
Only lean
lean gases
gases and
and gas
gas condensates with
condensates with
Edmister
Edmister acentric
acentric factors
factors tend
tend to be Zowep
to be 1,ower than
than relatively
relatively light
light plus
plus fractions were used
fractions were used in this
in this
Kesler-Lee
KeslerLee values
values for
for fractions
fractions heavier
heavier than
than C20.
20
C
. study,
study, thereby
thereby limiting
limiting the
the general applicability of
general applicability of
The
The difference
difference is
is most
most significant
significant for
for EOS
EOS these
these correlations.
correlations.
predictions
predictions when
when the
the ZJRK
ZJRK EOS
EOS is
is used.
used.
AA.4-4
.4-4

4 EFFECT OF PHYSICAL PROPERTIES ESTIMATION ON EQUATION-OF-STATE PREDICTIONS SPE


SIS 11200
11200

BERGMAN (continued) Two acentric factor correlations are proposed.


petroleum fractions with a
One is designed for petroleum
A
A PNA approach is developed to estimate critical reduced boiling point, e0 == Tb/Tc,
Tb/Tc, less than 0.8, and
and
properties of the heavy fractions. Only some of the other for heavier fractions. These correlations
the other
limitations found in the Robinson-Peng
RobinsonPeng method are usually predict acentric factors larger than the
shared by the Bergman method (see below).
below) The basic Edmister equation.
difference between these two methods is that Bergman
Bergman
assumes all three constituents (PNA) have the same Daubert6 made comparisons of the KeslerLee
Kesler-Lee and
and
boiling point, but different properties otherwise. Edmister equations and found that for pure compounds
Robinson and Peng use carbon number as the linking (of unspecified type and number) that the Edmister
property. correlation performed better. This comparison
comparison should
should
not, however, be considered valid for petroleum
petroleum
The method for estimating PNA content is out
out- fractions.
lined below. Although there is less chance of
obtaining negative PNA compositions, the method The molecular weight correlation was developed
is based on scattered data and has not been tested from data with molecular weights ranging from 60 to
for fractions heavier than C20'
;.
2
C 650. Less weighting was given to isomers not
commonly found in petroleum fractions. There is an
First, the boiling P9int
ppint and specific gravity unexplained difference between the resulting
are used to calculate the Watson characterization correlation and values in the API
API Technical Data Book.
factor, Kw
K (Eq. Ig).
ig). Another relation (Eq. Ii)
ii) is
then used to estimate the weight fraction of the
aromatic component; its value is limited to between STANDING 110
0.03 and 0.3. Paraffin
paraffin and naphthene weight fractions
are then calculated from In 1977, Standing
standing presented equations for
critical* pressure and temperature of
estimating critical*pressure
heptanes-plus fractions. The data of Matthews,
1 1 1 1 1 11
x =[--x()J(-) ...(2a) Roland and Katz were used to develop the correlations.
correlations .
WP
W
N wAYA N Yp YN
weight and specific gravity are the
Molecular weight
correlating variables
variables.

x = 11 - x wP - x
(2b) Although Standing claims the correlation is
wA

WN
wN
for C7+
+ fractions, it appears to be valid
7
C valid for
narrower boiling point cuts as well. The use of
Paraffin weight fraction is limited to a minimum of molecular weight instead of boiling
boiling point could be
0.20. If this criterion is not met, the aromatic an advantage for characterization methods such as
contr.nt
content is increased in increments of 0.03 until proposed by Yarborough. That is, instead ofof using
Xwp >
xWP > 0.20. Bergman suggests that the procedure may molecular weight and specific gravity to estimate
be repeated up to 15 times, and is satisfactory for boiling point, which is then used with specific
fractions up to CiS'
15
C
. gravity to estimate critical properties,
properties, they can be
estimated directly. The correlation should be used
Bergman's
Bergmans logic for using the PNA method is that with caution for fractions heavier
heavier than C2S.
;.
2
C
critical property correlations were originally
developed for wider boiling pOint
point cut fractions.
This reasoning loses some validity when he suggests KATZ-FIROOZABADI n
n
that the traditional correlations be used for
fractions heavier than CiS'
15
C
. It appears, in fact, In 1978, Katz and Firoozabadi
Firoozabadi presented
that the PNA approach may merely complicate the generalized properties of single carbon number (SCN)
characterization process unnecessarily, without fractions. Because it has become popular to use
any noticable advantages. these properties when measured data are not
available,
available, they were correlated in the present work.
Molecular weight and specific gravity were made
KESLERLEED, 5
KESLER-LEE 23, 2'1 functions of boiling point using third and fourth
degree polynomials, respectively.
respectively.
In 1976, Kesler and Lee presented correlations
for molecular weight, critical pressure, critical Molecular weights above C 2 are somewhat lower
222
C
temperature and acentric factor. They were proposed than reported by Katz and FirooZabadi.
FiroOZabadi. This results
for improving enthalpy predictions. Kesler and Lee from the choice to use values presented by Whitson
claim that critical pressure and temperature instead of the original values which were merely
merely
equations yield nearly identical results when extrapolated by adding 14 to the previous molecular
compared with graphical correlations found in the weight.
weiqht.
API Technical Data Book. This claim holds up to a
boiling point of 920 K. Modifications are introduced
introduced Specific gravities fit the original
original density data
to extend the correlations beyond this limit by
by with an absolute average deviation of 0.19%,
0.19', and a
ensuring that critical
critical, pressure approaches atmospheric maximum deviation of 0.4'
0.4% (for C6).
).
6
C Extrapolation
pressure as boiling point approaches critical beyond C4S
C.; is not suggested.
temperature.

** Actually, the equations estimate pseudocritical


pseudocritical
properties. For
For narrow boiling cuts, however, critical
and pseudocritical
pseudocritical properties are nearly equal.
A.4-5

SPE
SPE 11200
11200 C.H.
C.H. WHITSON
WHITSON 55

ROBINSON-PENG
ROBINS0N-PENG Jt reach a value of 2.0 for C~s.
45
C
. It appears that the
linear extrapolation is not appropriate for heavier
In
In 1978,
1978, Robinson and
and Peng
Peng proposed aa detailed
proposed detailed fractions. An indirect result is that
that critical
procedure
procedure for characterizing
characterizing heavy
heavy fractions.
fractions. It
It was temperatures are too low.
to be
be used
used in conjunction
conjunction with
with the GPA
GPA Peng-Robinson
PengRobinson
Programs,
Programs, though
though its
its applicability is obviously
applicability is (6) The assumption that
that naphthene and aromatic
not restricted
restricted to
to the
the Peng-Robinson EOS.
SOS. fractions have one less carbon number than paraffins
is only
only approximate
approximate and loses credibility
credibility at
at higher
higher
The proposed
The proposed property correlations
correlations are
are based on boiling points.
the
the paraffin-naphthene-aromatic
raraffinnaphthenearomatic concept.
concept. Equations
for
for PNA
PNA properties
properties are
are provided, including boiling
provided, including Because of these limitations,
limitations, the Robinson-Peng
RobinsonPeng
point, specific
specific gravity,
gravity, molecular
molecular weight, critical method is not suggested for reservoir fluids containin~
containin
pressure, critical
critical temperature
temperature and
and acentric
acentric factor fractions heavier than Czo
20 (about the same limitation
C limitation
(amoung
(amoung others).
others). critical pressure correlation
The critical as imposed on the Bergman PNA method). Unless an
26 critical temperature
is taken from
from Lydersen.
Lydersen. The critical accurate estimate of the PNA content is available
is
is back-calculated factor, boiling
backcalculated from acentric factor, from mass spectrometry or the density-viscosity-
densityviscosity
point and critical
critical pressure. Acentric factor is refractive-index
refractiveindex correlation of Riazi-Daubert,
RiaziDaubert, the
assumed to be a linear
linear function
function of
of carbon number. method should probably not be used at all.

The equations are


The procedures and equations are based on the
requirement that each
each heavy fraction
fraction represent a ROWE 37
single carbon
carbon number (SCN). Vaphthenes and aromatics
Naphthenes
raraffins in the
have carbon numbers one less than paraffins In 1978, Rowe presented equations for estimating
Robinson-Peng
obinsonPeng correlations. This assumption is boiling point, critical pressure and critical
built into the equations in Tables 1I and 2. Do not temperature of paraffin hydrocarbons. Be
He suggested
naphtheoes and
reduce the carbon number by one for naphthenes that the correlations could be used to characterize
aromatics when
hcn using these equations. C7+
+ fractions found in reservoir fluids.
7
C Although
it is not clear that his assumption is correct, the
No indication of the maximum carbon number is correlations are presented because of their
given.
given. Robinson indicated
indicated in
in aa verbal communication simplicity. Carbon number is used as the only
that the maximum value was "Czs.
.
25
C No, I wouldn't
wouldnt correlating variable, and Rowe suggests it be
stop there if I had to get an answer. Because I =
calculated from molecular weight, CN = (M-2)/14.
(M2)/14.
wouldn't
wouldnt know any 30 or
any better way to go if I had C10
C
0 than to just go ahead with the same scheme.
C~O
C I
would recognize that the backup gets shakier and YARBOROUGH '<6
shakier."
shakier. 35
In 1978, Yarborough presented a method for
Experience with the Robinson-Peng
RobinsonPeng method has characterizing the heavy fractions of reservoir
led to the following observations: fluids. AA graphical correlation relating specific
gravity to carbon number for various aromaticity
1, SCN specific gravities can
(1) As shown in Fig. 1, factors~ is the basis for this method.
factorsm These curves
not exceed 0.875, the aromatic value for C7.
.
7
C This
This have been fit by a four constant equation. The
is, of course, unacceptable. constants are a function of aromaticity.

(2) Boiling point data must be converted to cuts The Yarborough method assumes that the C7+
+
7
C
with paraffin boiling point intervals. This is
is often molecular weight and specific gravity are measured.
both time-consuming
timeconsuming and unnecessary. An example is It also assumes that mole fractions are measured
the Hoffman, et ale
al. fluid. from chromatographic
chromatographic analysis (paraffin
(paraffin molecular
weights are assumed to convert weight to mole
(3) The use of a mass accumulation curve to
to determine
determine fractions).
fractions)
SCN densities (from its tangent)
tangent) is highly
unreliable. The procedure
The procedure begins
begins by
by assuming
assuming an
an aromaticity
aromaticity
factor. A good
A good estimate
estimate can
can be
be calculated
calculated from
(4) Methods
Methods proposed for estimating the PNA content
the PNA content Eq. lh
Eq. Ih using
using CC7+ properties.
+
7 properties. SCN
SCN specific
specific gravities
gravities
point, molecular weight and
from boiling point, and specific are calculated
are calculated from the
the specific
specific gravity
gravity - carbon
- carbon
gravity are easily
easily subject to error, resulting
resulting inin correlation. The
number correlation. The plus
plus specific
specific gravity isis
negative
negative compositions.
compositions. Fig. 11 illustrates the the then calculated
then calculated using
using the
the proper
proper mixing
mixing rule.
rule. This
This
problem regions which
problem by showing the regions yield non
which yield non- value is
value is compared with
with the
the measured
measured value,
value, and
and the
the
negative PNA
negative PNA compositions. TheThe problem worsens
worsens when
when aromaticity factor
aromaticity factor adjusted
adjusted until
until a match
match is
is achieved.
achieved.
we note
we note that boiling points
pOints found using the
the proposed
proposed
method will almost always equal the arithmetic SCN specific
Using SCN specific gravities and
and assumed
assumed
average of neighboring paraffin boiling points
pOints weights, boiling
molecular weights, boiling points
points are estimated from
are estimated
(exactly
(exactly if
if the distillation linear between
distillation curve is linear between the charts
the charts in
in Ref.47,
Ref.47, or
or an
an appropriate
appropriate correlation.
correlation.
two values).
these two values). This
This makes
makes the
the region
region (Or
(or line)
line) Critical properties
Critical properties are
are estimated
estimated using
using boiling
boiling
in realistic non-negative PNA compositions
in which realistic compositions points and
points and specific
specific gravities.
gravities. Acentric
Acentric factor is
is
be obtained very
can be small, and in
very small, in many
many cases
cases non
non- estimated from
estimated from the
the Edruister
Edmister equation.
equation.
existent.
existent.

(5) Acentric factors for fractions heavier


(5) heavier than
than CCzo
2 0
considerably higher
are considerably higher than when
when estimated
estimated from
from
either the
either the Edmister
Edmister or
or KeslerLee
Kesler-Lee equation.
equation. They
They
A.4-6
A.4-6

EFFECT
EFFECT OF
OF PHYSICAL
PHYSICAL PROPERTIES
PROPERTIES ESTIMATION
ESTIMATION ON
ON EQUATION-oF-STATE
EQUATION-OF-STATE PREDICTIONS
PREDICTIONS SPE
SPE 11200
11200
66

RIAZIDAUBERT
RIAZI-DAUBERT KK IK 1.1010 for
12 /K
7
C = -O.OllOCN
O.OllOCN ++ 1.1010 for CN
CN = 66 11
Il
CCM
N C7+
In 1980,
In Riazi and
1980, Riazi and Daubert
Daubert presented
presented simple
simple 0.0025.C
equations for
for estimating
estimating numerous
K IKc
KC /K
N C
CM 7
7+
= SCN
2
O.OO N ++ 0.9525
0.9525 for
for CN
CN = 11-19
1119
equations numerous physical
physical properties
properties
of pure
of pure compounds
compounds and
and petroleum
petroleum fractions.
fractions. The
The same
same KK /K 0.OO14.C
equation form
form is used for CN
/K
CM C7+
7
C = CN
4
O.OOl N + 0.9734
0.9734 for
for CN
CM = 19-24
1924
equation is used for all
all properties.
properties. ItIt is
is
identical to
identical to the
the equation proposed by
equation proposed by Nokay
Nokay for
for K IKc
/K = 1.0070
1.0070 for
for C = 24 ......
KC N
CN 24-
critical temperature.
critical temperature. CMN C
7
7+

The correlations
The correlations areare compared
compared with
with the
the Winn
Winn
nomograph and
nomograph and Mobil
Mobil nomograph
nomograph forfor critical
critical pressure
pressure SCN
SCN specific
specific gravities
gravities are
are calculated
calculated from
from SCN
SCM
and critical temperature,
and critical temperature, respectively.
respectively. TheThe characterization
characterization factors
factors and
and molecular
molecular weights
weights using
using
original claim
original claim was
was that
that the
the correlations
correlations gave
gave the
the Hariu-Sage
MarioSage equation
equation (originally
(originally Eq.
Eq. 33 was
was
equivalent results.
"equivalent" results. A A later
later publication
publication by
by Daubert
Daubert suggested).
suggested). Average
Average C7+
+ specific
7
C specific gravity
gravity is
is
gives more
gives more detailed
detailed comparisons
comparisons with
with nomographs
nomographs andand calculated
calculated using
using the
the proper
proper mixing
mixing rule
rule and
and compared
compared
other correlations.
other correlations. In the boiling
In the boiling point
point range
range with
with the
the measured
measured value.
value. If
If the
the two
two do
do not
not match,
match,
255590 K,
255-590 K, the
the Riazi-Daubert
RiaziDaubert correlations
correlations perform
perform aa new
new estimate
estimate of
of K(C7+)
) is
7
K(C is made.
made. This
This procedure
procedure isis
better (though
better (though only
only slightly)
slightly) than
than other
other "best"
best repeated
repeated until
until calculated
calculated and
and measured
measured C7+
specific
7
C specific
methods.
methods. gravities match.
match.

The most
The most serious
serious drawback with the
drawback with the Riazi-Daubert
RiaziDaubert Boiling
Boiling pOints
points are
are calculated from
from SCN
SCN
correlations is
correlations the limitation
is the limitation of
of boiling
boiling point
point to characterization
characterization factors
factors and
and specific
specific gravities
gravities
730 K
730 K for
for critical
critical pressure and
and molecular
molecular weight. by rearranging Eq.
Eq. Ig:
ig: Tb
Tb == (YKw)3
/
3
(Y.Kw) / 1.8.
1.8. Critical
Critical
Whitson proposed
Whitson proposed an
an extension
extension to
to the
the critical
critical properties are
are estimated
estimated using the Riazi-Daubert
RiaziDaubert
pressure correlation,
pressure correlation, but the
the resulting
resulting constants correlations. The original critical
critical pressure
pressure
create aa discontinuity.
create discontinuity. equation
equation is only used for boiling points less less than
than
730 K. A A revised set of constants
constants are
are used
used for
for
For systems
For systems without
without components heavier than heavier fractions. Unfortunately, the the revision
C
,
C2S, the Riazi-Daubert
25 the RiaziDaubert correlations
correlations are
are probably the causes a discontinuity in critical pressure
pressure andand
most accurate
most accurate and
and easiest
easiest to
to use. acentric factor (the Edmister equation uses uses critica
criticall
pressure) near C30-32.
C
3
_
. 0
2


4
WHITSON
WHITSON'H
SUGGESTIONS AND COMMENTS
In 1981,
In 1981, Whitson
Whitson proposed
proposed aa scheme
scheme for
characterizing heptanes-plus
characterizing heptanesplus fractions found in From my experience, there is
is not one correlation
correlation
reservoir fluids.
reservoir fluids. A method is proposed for
A or characterization scheme which is
is better than all
tham all
estimating single
estimating single carbon
carbon number
number specific
specific gravities
gravities others. Observations made from
others. from EOS predictions have
EOS predictions have
using SCN molecular
using molecular weights and a generalized led me to make the following general, albeit subjec-
subjec
function for
function for the Watson characterization factor, Kw.
the Watson K. tive conclusions about physical properties estimation:
estimatico
The method is
The method similar to
is similar to the Yarborough
Yarborough scheme,
scheme,
except that
except that the
the characterization
characterization factor
factor is
is directly
directly CRITICAL PRESSURE
CRITICAL PRESSURE - The Kesler-Lee correlation
- correlation
related
related toto boiling
boiling point.
point. The aromaticity factor is
The aromat~city is suggested.
is suggested. Nearly identical
identical results
results are
are obtained,
obtained,
not.
not. the RiaziDaubert
however, from the Riazi-Daubert equation
equation~ Cavett's
Cavatts
correlation deviates
correlation deviates slightly
slightly from
from these
these two
two at
at
The equation proposed
The equation proposed for relating Kw,
relating K., specific
specific higher boiling
higher boiling points.
points.
gravity
gravity and
and molecular
molecular weight
weight is
is
TEMPERATURE - The
CRITICAL TEMPERATURE The Kesler-Lee
Kesler-Lee correlation
- correlation
is suggested.
is suggested. The
The Riazi-Daubert
Riazi-Daubert and
and Cavett
Cavett
KK 4.5579.MO.15178.. 84573
= 5178
4.5579.M y-0.84573
y (3)
(3) correlations are
correlations are nearly
nearly identical,
identical, with
with estimates
estimates
w
slightly higher
slightly higher than
than KeslerLee.
Kesler-Lee.

Unfortunately, Eq. 33 is
unfortunately, Eq. is only
only valid
valid up
up to
to a boiling
boiling ACENTRIC FACTOR
ACENTRIC FACTOR - The
The KeslerLee
- Kesler-Lee correlations
correlations arc
are
point
point of
of 730 K. The
730 K. The Hariu-Sage
Hariu-Sage correlation
correlation is
is suggested, though
suggested, though with
with acknowledged
acknowledged reservation.
reservation. II
preferred
preferred for
for heavier
heavier fractions.
fractions. The
The Whitson
Whitson have observed
have observed that
that the
the higher
higher acentric
acentric factor
factor
equation
equation is
is probably
probably more
more useful
useful for
for correlating
correlating estimations help
estimations help density
density estimates
estimates when
when using
using the
the
C7+ molecular

7
C molecular weights
weights and
and specific
specific gravities.
gravities. ZJRK EOS.
ZJRK EOS. It It can
can also
also be
be reasoned
reasoned that
that since
since the
the
Such aa relation
Such relation has
has been found very
been found very useful
useful for
for aa Kesler-Lee equations
KeslerLee equations were
were developed
developed specifically
specifically for
for
variety
variety of
of reservoir
reservoir engineerino
engineering applications.
applications. narrow boiling
narrow boiling petroleum
petroleum fractions
fractions (first
(first relation)
relation>
and unusually
and unusually heavy
heavy petroleum
petroleum fractions
fractions (second
(second
The
The Whitson
Whitson procedure
procedure begins
begins by
by assoming
assuming an
an relation),, that
relation) that they
they should
should perform
perform better
better than
than the
the
average
average KwKw for
for the
the plus
plus fraction.
fraction. Eq.Eq. 33 can
can be used
be used Edmister equation.
Edmister equation. This
This is
is only
only aa hypothesis.
hypothesis.
with
with C+
7
C7+ molecular
molecular weight
weight and
and specific
specific gravity.
gravity.
SCN characterization
SCN characterization factors
factors are
are then
then estimated
estimated MOLECULAR WEIGHI
()LUTAR WEIGHT - The
The MenuSage
Hariu-Sage correlation
- correlation is
is
using the
using the following
following correlation
correlation developed
developed byby suggested. AA comparlson
suggested. compar1son should
should probably
probably be
be made
made
Haaland, U
Haaland, between this
between this correlation
correlation and
and the
the one
one proposed
proposed by
by
Kesler and
Kesler and Lee
Lee using
using experimental
experimental data.
data.
*
* Recall
Recall the
the Riazi-Daubert
Riazi-Daubert p Pc correlation
correlation has
has aa
discontinuity because
discontinuity because two
two sets
sets of
of constants
constants are
are
required to
required to cover
cover the
the entire
entire boiling
boiling point
point range.
range.

1;; ::--;
AA.4-7
.4-7

SPE 11200
SPE 11200 C,H. WHITSON
C.H. WHITSON 77

EQUATION OF
EQUATION OF STATE
STATE CONSTANTS
CONSTANTS RESULTS
RESULTS

Several recent
Several publications~Vhave
recent publications 27
suggested that
have suggested that Calculations were
Calculations were performed on six
performed on six reservoir
reservoir
EOS constants a and b (or
EOS constants a and b (or 0 na and
a and 11n b ) can
b can be
be adjusted
adjusted fluids taken
fluids taken from
from the literature~u'~'v
the 4

3 Several
literature
Several
to match
to match experimental
experimental PVTPVT data.
data. ItIt can
can be
be shown,
shown, shcemes were
characterization shcemes
characterization used to
were used describe the
to describe the
however, that
however, that this
this method
method is
is essentially
essentially the the same
same as
as heavy fractions.
heavy fractions. Each example illustrates
Each example the effect
illustrates the effect
the earlier
the earlier practice
practice ofof adjusting
adjusting individual
individual component
component of one
of one or
or more
more physical properties on
physical properties EOS predictions.
on EQS predictions.
critical properties.
critical properties. In all
In all cases,
cases, the
the C fraction was
C7+ fraction
+
7 was split into SCN
split into SCN
groups.
groups.
For the
For the Peng-Robinson
Peng-Robinson and
and Soave-Redlich-Kwong
Soave-Redlich-Kwong
equations,
squat ions The PR
The PR and
and ZJRK equations were
ZJRK equations used exclusively
were used exclusively
R2 T
'T 2 for all
for all calculations. Although detailed
calculations. Although input data
detailed input data
R
2 2
a
a =
= 0nO.
o __ .
cc'[1
.[i + K.(1T
1/22
(1 ........ (Sa)
(Sa) are not
are not presented
presented for each example,
for each can be
they can
example, they be
a Pc r
Pc obtained from
obtained from the
the author.
author
RT
bb = 0 ................. (Sb)
(5b)
b
.
p Eilerts QOL544
Eilerts oo-L-544 Gas Condensate 9
Gas Condensate
9
C

ko +k
kl'W 4-+ 2
k2'WZ The QOL544
The OO-L-544 fluid presented by
fluid presented is aa
Eilerts is
by Silerts
K ka +w
1 .
k i ................. (Sc)
(5c)
=
gas condensate
gas containing 90.162
condensate containing methane and
mol-\ methane
90.162 mol% and
1.51 mol-%
1.51 heptanes-plus. The
mol-\ heptanes-plus. C7+ fraction
The C
+
7 has aa
fraction has
PR
PR SSRK
RK Q (PR)
na (PR) = 0.45724
0.45724 molecular weight
molecular weight of
of 167.3 and specific
167.3 and gravity of
specific gravity of
ng (PR) :. 0.07780
0.07780 0.8051. Fractional
0.8051. distillation data
Fractional distillation are available
data are available
0.37464
ko 0.37464
ko 0.480
0.480 (PR) =
up to
up to C
C2~.
,
2 . These data
These were converted
data were converted to SCN groups
to SCN groups
kl 1.54226
1
k 1.54226 1.574
1.574 no (SRK)
(SRK) = 0.42748
0.42748 according to
according to the
the method of RobinsonPeng
method of (except for
Robinson-Peng (except for
2
k -0.26992
k2 0.26902 -0.176
0. 176 n 8 (SRK) =:. 0.08664
0.08664
b density determination).
density determination). Dew point pressure
Dew point is reported
pressure is reported
to be
to 33.85 MPa
be 33.85 MFa at
at reservoir of 394.8
temperature of
reservoir temperature 394.8 K; K;
~o 0 the reservoir
the reservoir was
was initially undersaturated at
initially undersaturated at aa
~f we
If we define
define adjusted constants a.Qa and
constants na = a.n = pressure of
pressure 35.00 MPa.
of 35.00 MPa.
nb == Bng where
where a and B are correction factors, then
equivalent
equivalent results
results may be obtained using
Dew point pressure
Dew pressure was the ZJRK
with the
was estimated with ZJRK
n EOS at 394.8
EQS Measured specific
394.8 K. Measured gravities and
specific gravities and
ofc -'T
=T
B c
(6a)
(6a) critical
boiling points were used to estimate critical
C
properties from five*
five correlations. Acentric factors
Acentric factors
were estimated from the Edmister equation
equation except when
except when
(6b) correlations.
= KeslerLee and RobinsonPeng
using the Kesler-Lee Robinson-Peng correlations.
For all cases, the interaction coefficients between
interaction coefficients between
.
W
W
-
-kl
1 +
-k i- 1/
V kf
k - 4'k2'
2 (ko-Il!>
4k -)
0
(k

...... (6c)
6
(c)
7
C
methane and all C7+ adjusted to
+ fractions were adjusted match
to match
pressures
2k2
2
2k the measured dew point pressure. Saturation pressures
were then calculated at temperatures from 29Q44Q K.
from 290-440 K.

= K'
K
1 -

.fT7'Tc- . .. . ... .... (6d) Results are presented in Fig. 2a2a.

/ T/Tc
11 - ..; T/T repeated at IC
310 K
-
The matching procedure was repeated at 310
using only two of the property correlations. TheThe
instead
znstead of
of corrections
corrections applied to constants na
123 and nb.
b
0 MPa.
matched dew point was 39.40 MFa. Extrapolation in
Extrapolation in
Eqs.
Eqs. 6a-6d
6a6d illustrate
illustrate that adjustments
adjustments of a and b Results are given
are given
temperature was also performed. Results
can
can be
be directly
directly translated to adjustments of Tc'T, Pc p
in
in Fig. 2b.
and
and W.
w. If a/S =
If alB = 1,
1, only
only Pc
Pc is
is adjusted.
adjusted. If a/B
If 2
0/52= = 1,
1
only
only Tc
Tc and
and ware
w are adjusted.
adjusted. All
All other
other combinations
combinations was made
pressure was
dew point pressure made
of A of dew
A continual match of
of aa and
and B5 correspond
Correspond to
to an
an adjustment
adjustment of
of all three
in
in the
the temperature 290440 K
range 290-440
temperature range K using Riazi
the Riazi-
using the
critical
critical properties.
properties. interaction
resulting interaction
Daubert correlations.
correlations. The
The resulting
coefficients
coefficients are
are presented 2c.
presented in Fig. 2c.
The
The engineer
engineer should
should not
not adjust
adjust aa and
and b more
more than
will
will result
result in
in altered
altered critical
critical properties
properties which
which are
are
calculated as function
as aa function
Liquid-gas
Liquidgas ratios"*were
ratioswere calculated
physically
physically meaningful.
meaningful. Eqs.
Eqs. 6a-6d
6a6d should
should help
of using
temperature using
of depletion
depletion pressure
pressure at reservoir temperature
at reservoir
prevent
prevent misuse
misuse of
of adjustments
adjustments to
to EOS
EQS constants.
constants. the match was
point was
match point
the
the five
five property
property correlations;
correlations; the
They
They were
were used
used in
in this
this study
study to
to investigate
investigate the
the
and 33.85 MPa. Using match,
this match,
Using this
once
once again
again 394.8
394.8 K
K and 33.85 MFa.
the
the influence
influence of
of the
the adjustment
adjustment process
process on
on EOS
EQS performed at
were performed lower
at aa lower
the
the same
same calculations
calculations were
predictions.
predictions. temperature
temperature ofof 310.9
310.9 K. are found
Results are
K. Results found in Fig. 3a.
in Fig. 3a.

Although
Although it
it can
can be
be shown
shown that
that alternative
alternative match
the match
but the
repeated, but
relations The
The same
same procedure
procedure was
was repeated,
relations can
can be
be used
used instead
instead of
of Eqs.
Eqs. 6a-6d,
6a6d, the
the
two of
only two
case, only the
of the
proposed point
point was
was reversed.
reversed. In
In this
this case,
proposed equations
equations are
are considerably
considerably less
less complicated.
complicated. ratios
Liquidgas ratios
used. Liquid-gas
and property
property correlations
correlations were
were used.
and should
should be
be useful
useful interpretive
interpretive tools.
tools.
in Fig. 3b.
are
are plotted
plotted versus
versus pressure
pressure in Fig. 3b.

* The
The first
first correlation,
correlation, labeled
labeled "Eilerts
Eilerts (Paraffin)"
(Paraffin)
** AsAs used
used byby Eilerts,
Eilerts, the the liquid-gas ratio, LGR,
liquidgas ratio, LGR, isis
is
is merely
merely the
the set
set of
of critical
critical properties
properties which
which liquid
liquid volume
volume at
at p,T
p,T divided
divided by volume at
gas volume
by gas standard
at standard
Eilerts
Eilerts proposed.
proposed. They
They represent
represent paraffin
paraffin values
values conditions.
conditions. Its Its relation
relation to to liquid relative to
volume, relativeto
liquid volume,
and
and were
were not
not calculated
calculated from
from aa correlation.
correlation. Acentric
Acentric total
total (L+G)
(LG( volume, vv L'
volume, is:
L is: M M vV rL
factor
factor was
was estimated
estimated from
from the
the Edmister
Edmister equation.
equation. pP (g/cc);
(g/cc) LGR(m 3
/10 6 sm11 ... LGR
LGR(m3/106Sm, LGR =
= 42.26
a. -1""";;';;;"'-
42.26 .....2. rL
g0 0
P
~ lVrL
-~


A.4-8
A.4-8

88 EFFECTOF
EFFECT PHYSICAL PROPERTIES
OF PHYSICAL PROPERTIES ESTIMATION
ESTIMATIONON
ONEQUATION-OF-STATE
EQUATION-OF-STATE PREDICTIONS
PREDICTIONS SPE
SPE 11200
112Q0

Eilerts OO-L-S44
Eilerts OO-L-544 (continued)
(continued)
Jacoby
Jacoby Synthetic
Synthetic Mixtures
Mixturesv
The Peng-Robinson
The PengRobinson EOSEQS was
was used
used to illustrate
to illustrate The synthetic
The synthetic mixtures
mixtures presented
presented byby Jacoby
Jacoby were
were
the effect
the effect ofof adjusting
adjusting the
the methane
methane - C7+
+ interaction
7
C interaction

studied
studied using
using the
the PR
PR and
and ZJRK
ZJRK equations
equations ofof state.
state.
coefficient. Fig.4
coefficient. shows dewpoint
Fig.4 shows dewpoint pressure,
pressure, gas
gas Several
Several critical
critical property
property correlations
correlations were
were chosen
chosen
density and
density and liquid
liquid density
density as functions of
as functions of interaction
interaction to
to describe
describe the
the eight
eight boiling
boiling point
point fractions
fractions
coefficientf Calculations
coefficient~ Calculations were
were made
made at
at 394.8
394.8 K.
K. constituting
constituting hexanes-plus.
hexanesplus.

8,9 Fig.
Fig. B8 shows
shows results
results for for thethe s-3 mixture. The
S3 mix~ure. The
Eilerts CH-P-843
Eilerts CHP843 8,9
phase
phase diagram
diagram was was predicted
predicted by by matching
matching saturation
saturation
pressure
pressure of of 27.4
27.4 MPaMPa at at 370.5
370.5 KK withwith aa methane-C6+
+
6
methaneC
The CH-P-B43
The CHP843 fluidfluid is is aa gas gas condensate
condensate containing
containing interaction
interaction coefficient
coefficient of of 0.0536.
0.0536. Experimental
Experimental data data
76.432 mol-% methane and 2.992
76.432 mol-\ methane and 2.992 mol-\ heptanes-plus. mol-% heptanespl us. show
show aa dew
dew point
point at at this
this temperature.
temperature. AA bubble bubble point
point
The +
7
C molecular weight is
The C7+ molecular weight is 125 with aa specificc125 with specifi was
was predicted
predicted using using both
both PR PR and
and ZJRK
ZJRK equations,
equations,
gravity of
gravity of 0.73BS.
0.7385. Fractional
Fractional distillation
distillation data data diddid independent
independent of of the
the property
property correlation.
correlation. Extrapolation
Extrapolation
not indicat e hydrocarbon s heavier
not indicate hydrocarbons heavier than C13' There than .
3
Cr There inin temperature
temperature was was reliable
reliable for for allall correlations
correlations
are consie rably more
are consierably more intermediates interm ediates in in this
this fluid
fluid than
than (two
(two which
which areare shown
shown in in Fig.
Fig. B). 8). However,
However, the the
OOL-544.
in OO-L-S44. Extensive experimental
experimental data data areare
in Extensive estimated
estimated critical
critical temperatures
temperatures were were always
always 70 70 to
to 100
100
provided by
provided by Eilerts. Eilerts . These include:
These include: the phase the phase degrees
degrees (K) (K) high.
high.
diagram from
diagram from 220-310 K, 220-310 K, critical
critical point, point, cricondenbar,
cricondenbar,
cricondentherm and
cricondentherm and two-liquid
twoliquid phase phase region.
region. Some Some Numerous
Numerous attempts
attempts were were made
made to to predict
predict the the phase
phase
liberty has
liberty has been
been taken
taken in in this
this work
work when
when extrapolating
extrapolating diagram diagram created
created by by recombining
recombining separatorseparator samplessamples at at
the saturationp
the saturation-pressure ressure - temperature
temperature diagram.
diagram.

various
various gas-oil
gasoil ratios.
ratios. For For all
all critical
critical property
property
correlations,
correlations, both both equations
equations of of state
state predicted
predicted
The Peng-Robinson
The PengRabinson EOS EQS was was used
used to predict some
to predict some ofof reasonable
reasonable ( ( 5\)
5%) saturation
saturation pressures
pressures up up to to the
the last
last
the experimental PVT observations, Paraffin critical
critical
the experimental PVT observations. Paraffin two
two gas-oil
gas-oil ratiosratios (S-6(S6 andarid S-7).
S7) .
The
The estimated
estimated
proper ties suggested by Eilerts
properties suggested by Eilerts were used together were used togeth er critical
critical composition
composition (gas-oil (gas-oil ratio)ratio) was was considerably
considerably
with Edmister acentric factors.
with Edmister acentric factors. different
different, thanthan measured
measured experimentally.
experimentally. Bubble Bubble
points
points werewere predicted
predicted until until aa gas-oil
gasoil ratioratio between
between
5a5e show the effect of adjusting C
Figs. Sa-Se
Figs. show the effect of adjusting C7+ +
7 B90-1340
890-1340 Sm /5m
5m
3
3
/Sm 3 (S-4
(S4 to to S-S).
S-5) . Experimental
Experimental data data
critical proper
critical properties. ties. Dew point
Dew point pressure
pressure and and liquid
liquid suggest
suggest thatChat the last bubble bubble pointpoint should
should have have been
been
volume, relativ e to total volume,
volume, relative to total volume, were estimated at were estimated at between 620-710
620710 Sm
3 3
/Sm (S-2
/Sm
Sm
3 (S2 to to S-3).
S3)
310.9 K. Curves labeled 1
310.9 K. Curves labeled 1 and 2 are the same and 2 are the same forfor all
figures.
figures. Curve 1
Curve 1 was determined from
was determined from experimental
experimental u
Hoffman-Crump-Hocott
HoffmanCrujnp-Hocott Reservoir Reservoir Oil Oil
data, whereas
data, whereas CurveCurve 22 is the PR
is the prediction using
PR prediction using
unaltered paraffin
unaltered paraffin properties
properties for for the + fractions.
7
C
the C7+ fractions. Hoffman-Crump-Hocott
The Hoffman-Cru mpHocott (HCH) (HCH) reservo
reservoir ir oil
oil was
was
used to studystudy the the effect
effect of of property
property correlations
correlations on on
The effects of simultaneous ly
The effects of simultaneously adjusting critical adjusti ng critical typical PVT
typical PVT behavior.
behavior. The The oil
oil waswas saturat
saturated at initial
initial
pressu ed at
re and temperature
pressure and temperature are are shown
shown in Figs. 5a
in Figs. Sa and
and 5b.
Sb. conditions of of 26.426.4 MPa
MPa and and 367.0
367.0 K. K. It contains
It contain s
Results
Results of of adjusti
adjusting ng only
only critical
critical pressupressurere areare shown
shown 52.00 rnol-%
52.00 mol-\ methane
methane and and 36.84
36.B4 mol-%
mol-\ heptanespl
heptanes-plus.
in Fig. Sd; us.
results of adjusti
in Fig. Sd; results of adjusting only critical ng only critical The C
The C7+ molecular
+
7 molecular weight weight is is 198.7
19B.7 withwith aa specifi
specific
temperature c
temperature are are shown
shown in in Fig.
Fig.Sc 5c ;; results
results of of adjusti
adjustingng gravity
gravity of of 0.8412.
0.8412. Distill Distillation analysis
ation analys is is is availab
available le
only acentri c factor are shown
only acentric factor are shown in Fig. Se. in Fig. Se. to C
to C3S;
3 boiling point
5 boiling point cutscuts approximate
approximate SCN SCN groups
groups withwith
paraffin
paraffi boiling points.
n boiling points.
Figs.
Figs. 6abc
6a-6c showshow thethe effect
effect of of adjusti
adjusting ng EQSEOS
constants
constants aa and and b.b. BothBoth consta
constants nts areare adjuste
adjusted d inin Several aspects
Several aspects of of C C7+ characterization were
-
7 f charac terization were
Fig. 6a.
Fig. 6a. Only Only consta
constant nt bb is is adjuste
adjusted d inin Fig.
Fig. 6b,6b, investigated
investi gated using using thethe HCH HCH oil.
oil. First,
First, aa comparison
comparison
whereas
whereas only only constant
constant aa is is adjuste
adjusted d inin Fig.
Fig. 6c.6c. was made
was made between
between three three schemes
schemes for for estima
estimating specificc
ting specifi
Note
Note thatthat Curve
Curve 33 in Fig. 6a
in Fig. 6a (decreasing
(decreasing both both aa andand b) gravities
b) graviti es andand boiling
boiling points
points of of SCNSCN fractio
fractions. Fig. 9
ns. Fig.
results
results in an in excelle
an excellent nt predict
prediction ion of of dewpoint
dewpoint compares experimental
compares experimental and and estimated
estimated valuesvalues of of yy and
and rbTb
pressure and liquid dropout. The KeslerLee
Kesler-Lee correlacorrelations were used
used to to estima
estimate
pressure and liquid dropout. The tions were te
critical proper
critical properties ties andand acentri
acentric factors.
c factors .
The saturationp
The saturation-pressureressure - temperature
-

temperature diagramdiagram
was
was predict
predicted ed using
using three
three C +
7
C7+ charac terization
characterization Figs. lflae
Figs. 10a-e presen
present results of of EQS
EOS predict
predictions
t results ions
schemes.
schemes. The The first
first merely
merely used used unalter
unaltereded paraffi
paraffin n for aa simulated
for simulated differedifferential liberation experiment at at
ntial liberat ion experiment
critical
critical proper ties without
properties without adjusti
adjustingng interac
interactiontion 367 K.
367 K. AA swelling
swelling test test (described
(described in in the
the next
next
coeffic ients.
coefficients. The
The second
second was was identic
identical al with
with Curve
Curve 33 paragraph) was
paragraph) was alsoalso simulated.
simulated. There There waswas essenti
essentially
ally
in Fig. 6a.
in Fig. 6a. The
The third
third alterna
alternative tive usedused unaltered
unaltered nono effect
effect on on EQSEOS predict
predictionsions from from thethe various
various methods
methods
paraffi
paraffin n critical
critical proper ties, but
properties, but matched
matched dewpoint
dewpoint for estima
for estimating specific
tnq specifi gravity and and boiling
boiling point.point.
c gravity
pressure
pressure at at 310.9
310.9 KKwith with thethe methaneC
+
7methane-C7+ interac tion
interaction
coeffic
coefficientient of of 0.12.
-0.12. PhasePhase diagrams
diagrams and and critical
critical EOS predict
EQS predictions were alsoalso performed
performed using using
ions were
points are presented in Fig.
points are presented in Fig. 7.7. four differe
rout different critical property
nt critical property correla
correlations.
tions. One
One
case (1)
case (1') used
used variabl
variable e C 2
.
7C7-2l
1 -
- methane
methane interac
interaction
tion
coefficients,
coeffic matching bubble
ients, matching bubble point
point pressure
pressure with with the
the
* AsAs should
*
should be be obvious
obvious from from Fig.Fig. 4,4, deviati ons are
deviations are
1
C
+
2 Cl-C22
C+ coeffic
coefficient.
ient. Results of
Results of differe
differential libera-
ntial libera-
calculated relative to red7mt?d EQS properties
calculated relative to prediated EOS properties - -
tion simulations
ton slmulations are are foind
found inin Figs.
Figs. liaIle.
lla-lle. SwellingSwelling
albeit matched at the measured dew point pressure
albeit matched at the measured dew point pressure. test predirtioime
test predictions are are found
found inin Figs.
Figs. 12a12b
12a-12b and and 13.
13.
Injection
Injecti on gas gas usedused inin thethe swelling
swelling test test isis given
given inin
Table 3.3. ItIt was
Tbl was determined
determined byby optimizing
optimizing a a three three
stage flash
stage flash process
process for for maximum
maximum 6 -C2-C6
2
C C contentcontent inin the the
separator
separa gases.
tor gases.
A.4-9
A.4-9

SPE 11200
SPE 11200 C.H. WHITSON
C.H. WHITSON 99

Hoffman-Crump-Hocott Reservoir
HoffmanCrumpHOcOtt Gas 13U
Reservoir Gas Using the Kato
Using the Kato coefficients (B),, saturation
coefficients (B) saturation
pressures were
pressures were grossly
grossly underestimat ed.
underestimated. Bubble
Bubble point
point
Hoffman, et
Hoffman, et al.
al. also presented
also presented extensive
extensive data
data pressures were
pressures predicted up
were predicted to aa CO
up to 2 concentration of
C02 concentration of
for the
for the gas-cap
gas-cap fluid
fluid loacted
loacted inin the
the same
same formation
formation 70 mol%.
70 mol-\.
as the
as the abovementioned
abovementioned reservoir
reservoir oil.
oil. The
The gas
gas contains
contains
91.35 mol%
91.35 mol-% methane
methane and
and 1.54
1.54 mol-%
mol-% heptanes-plu
heptanes-plus.
s. Using the average
Using the average CO2HC
C02-HC coefficient of 0.175
coefficient of 0.175
The C
The C7+ molecular
+
7 molecular weight
weight is
is 141
141 with
with aa specific
specific (from A)
(from A) resulted
resulted in
in overestimate
overestimates s of
of saturation
saturation
gravity of
gravity of 0.7867.
0.7867. Dewpoint
Dewpoint pressure
pressure equals
equals bubble
bubble pressures. At
pressures. 60 moll
At 60 mol-\ CO2,
C02, no saturation pressure
no saturation pressure
point pressure
point pressure of
of the
the oil
oil (26.4
(26.4 MPa)
MPa) at
at reservoir
reservoir was predicted
was predicted below 30 MPa.
below 30 MPa. The experimental critical
The experimental critical
temperature of
temperature of 367
367 K.
K. pressure at
pressure at this
this concentration was 17.7
concentration was 17.7 MPa.
MPa.

The same
The same comparisons
comparisons made
made in
in the
the previous
previous example
example Phase behavior of
Phase behavior of this system was
this system also predicted
was also predicted
were made
made for this fluid (except
(except the
the case
case with
with using the
using ZJRK EOS.
the ZJRK Only a slight
EOS. Only slighe change
change (from
(from
varying interaction
varying interaction coefficients)
coefficients).. Instead
Instead ofof 0.137
0.137 to in 3
0.147) in
to 0.147)
2
C0
+ C coefficients
C02-C3+ was necessary
coefficients was necessary
simulating a differential liberation
simulating liberation experiment,
experiment, to match
to the entire
match the phase envelope.
entire phase The adjusted
envelope. The adjusted
aa constant
constant composition
composition (mass)
(mass) expansion
expansion (CCE)
(CCE) and
and value
value is nearly identical
is nearly identical with the one
with the found using
one found using the
the
constant volume depletion (CVD>
constant simulated. Only
(cve) were simulated. Only PR EOS
PR EOS (0.145);
(0.145); note that the
note that ZJRK EOS
the ZJRK used slighly
EOS used slighly
some results
some results are included
included in
in this
this work. CCECCE lower values
lower values for
for CO Ci and
C02-Cl

2 and 2
CO C coefficients.
C02-C2 coefficients.
predictions were
predictions were compared with
with experimental
experimental data
data As
As in
in all
all other cases, critical
other cases, C02 concentration
critical CO
2 concentration
reported by
reported by Hoffman, et
et al.
al. was overestimate
was d.
overestimated.

Figs. 14a-14d
14a14d present results of the
the comparisons
made between different methods of
of estimating
estimating specific DISCUSSION
gravities and boiling points. KeslerLee
Kesler-Lee properties
properties
were used in
were in the ZJRK
ZJRK EOS.
EOS. Discussion
Discussion of the results
of the results begins
begins by
by disclaiming
disclaiming
any attempt
attempt to present a conclusive
to present document of
conclusive document of the
the
Figs.
Figs. 15a-15d
15a15d present results of the comparisons
comparisons effects characterization has on EOS
+ characterization
7
C
effects C,+ EOS predictions.
made between different property correlations.
correlations. Both
Both were designed to
examples which are presented were
The examples to give
PR and ZJRK equations were used. an indication of characterization
of the influence certain characterization
schemes may have on EOS predictions. Examples were were
also limited to the examination ofof PVT
PVT properties
properties
Hong Reservo~r
Reservoir Oil A
A - COz System~
2 System
CO-
5 important to reservoir engineering.
important

A
A recent publication by Hong gives experimental Interaction Coefficients
data for a reservoir oil - COz
2 system.
CO
- The oil
contains 31.00 mol-\
mol-% methane and 32.43 mol-% heptanes-
heptanes The effect of increasing binary interaction
plus. C,+
C-,+ molecular weight is 199. No distillation coefficients between methane and heavy
heavy fractions is
data or C,+
+ specific gravity are reported.
7
C Mole to increase saturation pressure prediction. This
fractions and "tuned"
tuned critical properties are given the
observation appears to be general for both the
for C,-CIZ
-C SCN
7
C
2 SCN groups and the remaining C13+
13 fraction.
C
+ bubble point and retrograde dew point regions.
Bubble point pressure of the
the initial oil is 11.4 MPa
at 327.6 K. Fig. 44 presents the general trend expect
trend one can expect
in saturated liquid and gas densities and saturation
The Hong oil - C02
2 system
CO
- system was chosen to pressure when adjusting the CI-C7+
+ interaction
7
CiC
illustrate
illustrate the effect of carbon dioxide
dioxide - hydrocarbon
coefficients. The primary reason for variation in
(C02-HC)
HC) binary interaction coefficients on
2
(CO saturation
saturated densities is the variation in saturation
predicted
predicted phase behavior. The Peng-Robinson
PengRobinson EOS is pressure. At constant pressure and temperature,
used by
by Hong. Both
Both PR
PR and
and ZJRK equations were used interaction coefficients have a small influence on
in
in this
this study.
study. phase densities.
densities.

Using
Using the
the PR
PR EOS,
EOS, four
four methods were used to Pang-Robinson EOS
general, the Peng-Robinson
In general, EDS requires
describe
describe the
the C02-HC
HC interaction coefficients.
2
CO coefficients. The positive coefficients
coefficients to match saturation
to match saturation pressure,
pressure,
first
first method
method used guidelines
guidelines provided
provided byby Hong.
Hong. often requires
whereas the ZJRK EOS often requires negative values.
Coefficients
Coefficients were
were varied
varied from
from 0.14
0.14 to
to 0.20,
0.20, decreasing
decreasing not always
does not
This rule does hold, as
always hold, shown in
as shown 2a.
in Fig. 2a.
as
as aa function
function ofof acentric
acentric factor.
factor. The
The second
second method Apparently the critical
Apparently the critical properties
properties influence the
influence the
used
used the
the empirical
empirical equation
equation suggested
suggested byby Kato~
Kato coefficients needed to
of interaction coefficients
value of match
to match
Fig.
Fig. 16
16 shows
shows the
the graphical
graphical form
form of
of this
this correlation. This observation
saturation pressure. This
saturation observation leads me to
leads me to
The
The third
third method
method used
used aa constant,
constant, molar
molar average
average of conclude
conclude that
that adjusting interaction coefficients
adjusting interaction coefficients isis
coefficients
coefficients from
from the
the first
first method.
method. TheThe last
last method
method more
more a correction due characterization
to inadequate characterization
due to
used
used aa constant
constant C02-HC
HC coefficient
2
CO coefficient ofof 0.145.
0.145. This
This of
of the
the heavy
heavy fractions than aa phYSical
fractions than description of
physical description of
value
value was
was determined
determined by
by matching
matching the
the bubble
bubble point
point interaction between large
interaction between and small
large and compounds.
small compounds.
pressure
pressure at
at 50
50 mol-\
mol- C02'
.
2
CO
It appears that
It appears C interaction
1
C
+
7
that Cl-C7+ interaction coefficients
coefficients
Results
Results of
of the
the first
first three
three cases
cases are
are shown
shown in
in have relatively strong
have aa relatively temperature dependence
strong temperature dependence for
for
Figs.
Figs. 17a
17a and
and 17b.
17b. For
For the
the first
first case
case (A),
(A) many reservoir fluids.
many reservoir fluids. AnAn important consequence is
important consequence is
saturation
saturation pressures
pressures matched
matched experimental
experimental data
data up
up to
to that saturation pressures
that saturation may be
pressures may overestimated if
be overestimated if
COz
CO2 concentrations
concentrations ofof 80
80 mol-%.
mol. TheThe critical
critical C02
2
CO coefficients
coefficients matched
matched at one temperature
at one temperature are used to
are used to
concentration
concentration was
was overestimated
overestimated byby 10
10 mol-to
mol-%. This
This estimate saturation pressure
estimate saturation pressure (VLE) at lower
(VLE) at lower
predicted
predicted phase
phase diagram
diagram isis similar
similar toto the
the one
one using
using temperatures. An
temperatures. of this
example of
An example might be
situation might
this situation be
aa constant
constant COz-HC
CO2-HC coefficient
coefficient ofof 0.145.
0.145. when the dew
matching the
when matching point at
dew point reservoir temperature,
at reservoir temperature,
then
then using
using the
the same interaction coefficients
same interaction to
coefficients to


A.4-10
A.4-1O

10
10 EFFECT OF
EFFECT OF PHYSICAL
PHYSICAL PROPERTIES
PROPERTIES ESTIMATION
ESTIMATION ON
ON EQUATION-OF-STATE
EQUATION-OF-STATE PREDICTIONS
PREDICTIONS SPE
SPE 11200
11200

predict VLE
predict VLE properties
properties at
at temperatures
temperatures expected
expected in
in .. By
By noting
noting that
that maximum
maximum liquid drop-out is
liquid drop-out is
the tubing
the tubing and
and process
process equipment.
equipment. Underestimation
Underestimation strongly, though
strongly, though not
not completely dependent on
completely dependent on liquid
liquid
seems to
seems to be
be less
less significant
significant if
if the
the match
match at
at one
one density, one
density, one can
can draw
draw similar conclusions about
similar conclusions about
temperature is
temperature is extrapolated
extrapolated to
to higher
higher temperatures
temperatures volumetric phase
volumetric phase behavior
behavior of
of reservoir oils. Effects
reservoir oils. Effects
(see Fig.
(see Fig. 2b).
2b). dew point
on dew
on pOint pressure
pressure should be analogous
should be to effects
analogous to effects
on bubble
on bubble point
point pressure for oil
pressure for systems; therefore
oil systems; therefore
Several attempts
Several attempts have
have been
been made
made to
to correlate
correlate term saturation
the term
the pressure has
saturation pressure used above,
been used
has been above.
methane-hydrocarbon interaction
methanehydrocarbon interaction coefficients.
coefficients. 21,25

1
The trend
The trend is
is that
that coefficients
coefficients increase
increase with
with
increasing molecular
increasing molecular size.
size. AA comparison
comparison between
between General Qbservations
General Observations
using aa constant
using constant 7 CI-C7+

1
C
+ coefficient and
C coefficient and using
using
variable (increasing)
variable (increasing) values
values had
had little
little effect
effect on
on The influence
The influence of heptanes-plus characterization
of heptanesplus characterization
most EQS
most EOS predictions.
predictions. Some
Some properties
properties were
were influenced
influenced on EQS
on EOS predictions appears to
predictions appears to be substantial for
be substantial for
however. These
however. These included
included gas
gas compressibility
compressibility and
and reservoir fluids.
reservoir fluids. The choice of
The choice critical property
of critical property
gravity (i.e.
gravity (i.e. molecular
molecular weight)
weight),, swelling
swelling factor,
factor, correlation usually
correlation usually has more influence
has more influence onon EQS
EOS
saturation pressure
saturation pressure increase
increase due
due to
to gas
gas injection,
injection, predictions than
predictions method used
the method
than the used to estimate specific
to estimate specific
and interfacial
and interfacial tension
tension (calculated
(calculated using
using aa gravities and
gravities boiling points
and boiling these properties
(when these
points (when properties
compositional correlation)
compositional correlation). are not
are not available)
available). This
. lias somewhat
This vas somewhat unexpected.
unexpected.
reason may
The reason
The that reservoir
be that
may be reservoir fluids have heavy
fluids have heavy
Concerning the
Concerning the use
use of
of C0
C02-hydrocarbon

2 binary
hydrocarbon binary components with
components properties which
with properties reach the
which reach the limits
limits ofof
interaction coefficients,
interaction coefficients, it
it appears
appears that
that there
there is
is some, if
some, if not
not all correlations. The
all correlations. The methods used for
methods used for
little advantage
little advantage in
in using
using coefficients
coefficients which
which vary
vary as
as estimating specific
estimating gravities and
specific gravities and boiling
boiling points
pOints
aa function
function of
of molecular
molecular size.
size. This
This conclusion
conclusion is
is appear to
appear be reliable
to be reliable for even very
for even heavy fractions.
very heavy fractions.
based on
based on studies.of
studies.of only
only two
two systems.
systems. ItIt may
may not
not
be valid
be valid if
if near-critical phase
phase behavior
behavior is
is to
to be
be Several
Several observations not directly
observations not directly related to 07+
related to C7+
predicted accurately.
predicted accurately. characterization are worth
characterization are noting. The
worth noting. two equations
The two equations
of state
of state used
used in this study
in this always overestimated
study always overestimated
critical temperature
critical temperature (see Figs. 77 and
(see Figs. 8). The
and 8). The same
same
EOS Parameter Adjustments
EQS Parameter behavior been observed
behavior has been for several other
observed for systems.
other systems.
problem can
This problem can be particularly important
be particularly if aa rich
important if rich
Several
Several generalizations appear valid
valid concerning
concerning (near critical
(near condensate is
gas condensate
critical point) gas is being studied..
being studied
the adjustment
the adjustment of heavy fraction critical
critical properties
properties That is,
That is, it may be difficult
it may to predict
difficult to dew point
predict aa dew point
and
and EOS
EQS constants.
constants. They are interpretations of
of at reservoir temperature.
temperature.
results
results presented in Figs. 55 and
and66 for a gas
condensate.
condensate. A
A summary of important observations is Although it is not my intention
intention to suggest one
to suggest one
given
given below:
below: EQS over another, the ZJRX
EOS ZJRK EQS gave an
EOS gave overal better
an overal better
performance than the PR EQS. The major
EOS. The difference
major difference
(1) A
(1) A decrease
decrease in critical temperature results in density (volumetric)
was seen in liquid density predictions.
(volumetric) predictions.
aa decrease
decrease of both saturation pressure and maximum On the other hand, the PR EOS has a
EQS has simple form
a simple form which
which
liquid
liquid drop-out.
dropout. can be
can be readily
readily reproduced. This is not the case
variants.
for most of the ZJRK variants. For example,
For constants
example, constants
(2)
(2) An
An increase
increase in
in critical
critical pressure results in
in an a and b presented by Yarborough have have the shortcoming
the shortcoming
increase
increase in
in saturation pressure and a decrease in that they must be digitized from figures. The The
maximum
maximum liquid
liquid drop-out. method of representing these values values - equations
equations
versus tables - varies from program to

program.
to program. The
The
(3)
(3) Acentric
Acentric factor
factor has little
little or no effect on ZJRK EOS
EQS lacks an essential property of of being
being
is,i9,27,w
maximum
maximum liquid
liquid drop-out.
drop-out. This
This is
is only
only true for the reproducible. ~, 10,19,27, '<6
PR
PR and
and Soave
Soave RK
RE equations;
equations; acentric
acentric factor
factor only
affects
affects EOS
EQS constant
constant a,
a, which
which is
is mostly
mostly related to
VLE
VLE calculations.
calculations. For
For these
these two
two equations,
equations, a CONCLUSIONS
decrease
decrease in in acentric
acentric factor
factor results
results in
in a decrease
decrease
1n
in saturation
saturation pressure
pressure.. Results indicate
Results that equation
indicate that equation ofof state
state
predictions are highly
predictions are highly sensitive
sensitive toto characterization
characterization
Constants
Constants aa and
and bb in
in the
the ZJRK
ZJRK EOS
EQS are
are both
both dependent
dependent of the
of heptanesplus fraction.
the heptanes-plus fraction. This
This observation
observation has
on
on acentric
acentric factor
factor.. For
Fut this
this equation,
equation, values
values of
of also been
also been made
made by
by others.
others. The present
The present study offers
study offers
acentric
acentric factor
factor will
will strongly
strongly influence
influence volumetric
volumetric comparison between
direct comparison
dlrect between various physical property
various physical property
properties
properties such
such as
as maximum
maximum liquid
liquid drop-out.
drop-out. This
This correlations&
correlations & their effect on
their effect on predicted
predicted phase
phase
results
results from
from the
the strong
strong connection
connection between
between band
b and behavior using
behavior using the
the Peng-Robinson
Peng-Robinson and
and Zudkevich-Joffe-
Zudkevich-Joffe
volumetric
volumetric predlctions
predictions.. Redlich-Kwonq equations
Redlich-Kwong equations of
of state.
state.

(4) A decrease
(4) A decrease in
in constant
constant aa results
results inin aa decrease
decrease
1n
in both
both saturation
saturation pressure
prussure and
and maximum
maximum liqu1d
liquid Too many
Too unknown factors
many unknown factors are involved in
are involved in the
the
drop-out.
dropout. TheThe greater
greater influence
infLuence is
is on
on saturation
saturation characterization of
characterization of heavy fractions to
heavy fractions to make
make
pressure
pressure (i.e.
(i.e. VLE
VLE predictions).
predictions), objective conclusions
objective conclusions concerning which property
concerning which property
correlations are best.
correlations are This is
best. This is compounded by
compounded by
(5) A
(5) A decrease
decrease in in constant
constant bb results
results in
in aa relatively
relatively nconsLstencies and
inconsistencies di iferent extrapolative
and different extrapolative
large
Larqe increase
increase in in saturation
saturat ion pressure
pressure and
and decrease
decrease in
in capabiiitces of
capabil1ties of various property correlations.
variuus property correlations.
maximum
maximum liquidLiquid drop-out.
dropout. This This observation
observation suggests
suggests
that
that constant
onatant bL has
has influence
influence on
on both
both VLE
VLE and
and Most engineers
Most will probably
enqineers will probably rely on adjusting
rely on adjusting
volumetric
vol uric t r cc predictions.
pc cdi (t ions EQS
EOS parameters to achieve
parameters to achieve satisfactory predictions of
satisfactory predictions of
PVT
PVT properties
properties. To this
To this end, guidelines are
end, guidelines are provided
provided
for
for making such adjustments.
maKing such adjustments.


A.4-111
A.4-1

SPE 11200
SPE 11200 C.H. WHITSON
C.H. WHITSON 11
11

NOMENCLATURE
NOMENCLATURE REFERENCES
REFERENCES

aa = equationof--state
= equation-of-state constant
constant 1. Bergman,
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"Predicting the
the Phase
Phase Behvaior
Behvaior of
of
Natural Gas
Natural Gas in
in Pipelines,
Pipelines," PhD
PhD Dissertation,
Dissertation, U.
U. of
of
AA = constant in
constant in property
property correlation
correlation Ann Arbor
~lichigan, Ann
Michigan, Arbor (1976)
(1976)
bb = equation-of-state constant
equationofstate constant
2. Bergman,
2. Bergman, D.F.,
D.F., Tek,
Tek, M.R.
M.R. and
and Katz,
Katz, D.L.:
D.L.:
BB = constant in
constant in property
property correlation
correlation
"Retrograde Condensation
Retrograde Condensation in
in Natural
Natural Gas
Gas Pipelines,
Pipelines,"
C carbon number Project PR2669
Project PR26-69 of
of the
the Pipelines
Pipelines Research
Research Committee
Committee
CMN = carbon number
AGA (Jan.
AGA (Jan. 1977)
1977)
C7+ heptanes-plus fraction
+ = heptanesplus
7
C fraction
J Jacoby aromaticity factor
factor 3. Cavett,
3. Cavett, R.H.:
R.H.: Physical
"Physical Data
Data for
for Distillation
Distillation
A = Jacoby aromaticity Calculations - Vapor-Liquid
Calculations Vapor-Liquid Equilibrium,
Equilibrium," Proc.
Proc.
k constants
k = constants in
in Eqs.
Eqs. 5 and 66
S and
27th Meeting,
27th Meeting, API,
API, San
San Francisco
Francisco (1962)351366
(1962)351-366
KK ,K
,K = Watson characterization
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factor
w
3 6 3 4. Coats,
4. Coats, K.H.:
K.R.: Simulation
"Simulation of
of Gas
Gas Condensate
Condensate
LGR
LGR = liquid-gas ratio,
liquidgas ratio, m/10
m /10
3
S
6 m Sm
Reservoir Performance,
Reservoir Performance," paper
paper SPE 10512 presented
SPE 10512 presented
M = molecular
M molecular mass,
mass, mass
mass per
per mole
mole at the
at the Sixth
Sixth SPE SympOSium on
SPE Symposium Reservoir Simulation,
on Reservoir Simulation,
New Orleans,
New Orleans, Jan.
Jan. 31
31 - Feb.

Feb. 3,
3, 1982
1982
Pc = critical pressure,
critical pressure, kPa
kPa
P~
p* = critical pressure
critical pressure variable
variable 5. Conrard,
5. Conrard, P.G.
P.G. and
and Gravier,
Gravier, J.F.:
J.F.: PengRobinson
"Peng-Robinson
Equation of
Equation of State Checks Validity
State Checks Validity of
of PVT
PVT
PNA
PNA = Paraffin, Naphthene,
Paraffin, Naphthene, Aromatic
Aromatic
Experiments," Oil
Experiments, Oil end
and Gas
Gas J.
J. (Apr.
(Apr. 21
21 1980)7786
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RR = universal gas
universal gas constant,
constant, 8.3143
8.3143 J/(moiK)
J/(molK)
6. Daubert,
6. Daubert, T.E.:
T.E.: Characterization
"Characterization Parameters
Parameters for
for
tt = boiling point
hailing point variable
variable
Hydrocarbons for
Hydrocarbons for Physical
Physical and
and Thermodynamic
Thermodynamic
T
T = absolute temperature,
absolute temperature, KK Property Prediction,
Property Prediction," Proc.
Proc. 53rd GPA Convention
53rd GPA Convention
(1979)17-24
(1979) 1724
Tb
Tb = normal boiling
normal boiling point,
point, KK
Tc
T = critical
critical temperature, K
temperature, K 7. Edmister,
7. Edmister, W.C.:
W.C.: Applied
"Applied Hydrocarbon
Hydrocarbon Thermodynamics
Thermodynamics
Part 4:
Part 4: Compressibility Factors and
Compressibility Factors Equations of
and Equations of
T*
T* = critical
critical temperature
temoerature variable
cC State," Pet.
State, Pet. Refiner
Refiner (Apr.
(Apr. 1958)37,173-179
1958)37,173179
Tr
T = reduced
reduced temperature
temoerature (=T/T )
r c Barr, V.L., Mullens,
Mullens, N.B. and
8. Eilerts, C.K., Barr, N.B. and
vvL = liquid
liquid volume,
volume, relative
relative to total volume of a Gas-Condensate
rL Hanna, B.: "Phase
Henna, Phase Relations of GasCondensate
Xw
x = weight
weight fraction Fluid at Low Temperatures, Including the Critical
w State,"
State, The Pet. Engineer (Feb. 1948)154-180
1948)154180
~ = adjusted value of variable x
adjusted value
and Others:
9. Eilerts, C.K. and Phase Relations
Others: Phase of Gas-
Relations of Gas-
Condensate Fluids, Monograph 10, Bureau of Mines
Greek
Greek Symbols
Symbols
American Gas Association, New York (1957)Vol. 11
aa = correction
correction factor
factor for
for EOS
EOS constant
constant a
10. Gray, R.D., Jr.: "Industrial Applying
in Applying
Industrial Experience in
B
6 = correction
correction factor
factor for
for EOS
EOS constant b the Redlich-Kwong
RedlichKwong Equation to Vapor-Liquid
0 Equilibria,"
Equilibria, Equations of of State
State in
in Engineering
Engineering
Y
y specific
specific gravity,
gravity, relative
relative to water at 15.5
15.5C C
=
and Research, K.C. Chao and R.L. Robinson, Jr.
YAPI = liquid
liquid gravity,
gravity, degrees
degrees API (eds.),
(eds.) , in Chemistry
Advances in Chemistry Series 182, Amer.
Series 182,
Chem. Soc.
Chem. Soc. (1978)386-439
(1978)386439
aO = reduced
reduced normal
normal boiling
boiling point
ooint (=Tb/T
-
(=T IT )
b cC
KK = constant
constant in
in Eq.
Eq. 55 11. S.: "Characterization
11. Haaland, S.: Characterization of
of North Sea Crude
North Sea Crude
Oils and MS Thesis,
Fractions, MS
and Petroleum Fractions," Thesis, Norwegian
Norwegian
pp = density,
density, gm/cc
gin/cc
Institute of
of Technology (NTH), Univ. of
(NTH), The Univ.
a = acentric
acentric factor
factor Trondheim, Norway
Trondheim,
= equation-of-state
equation-of-state constant
constant in
in Eq.
Eq. Sa
Se
and Sage,
O.H. and Sage, R.C.: Crude Split
R.C.: "Crude Figured
Split Figured
12.
12. Hariu,
Hariu, O.H.
= equation-of-state
equationof-state constant
constant in
in Eq.
Eq. 5b
5b by
by Computer," Hydro. Proc.
Computer, Hydro. (April 1969)143-148
Proc. (April 1969)143148

13.
13. Hoffman,
Hoffman, A.E., Crump, J.S.
A.E., Crump, and Hocott,
J.S. and C.R.:
Hocott, C.R.:
ACKNOWLEDGMENTS Equilibrium Constants
"Equilibrium Constants for GasCondensate System"
for aa Gas-Condensate System
ACKNOWLEDGMENTS
Trans.,AIME(1953)
Trans. ,AIME(1953) 198,1-10
198,110
ij would
would like
like to
to thank
thank V.
V. Dalen
Zalen and
and G.".
G.O. Nielsen
Nielsen
for 14.
14. Hong, K.C.: "Lumped-Component
Hong, K.C.: Characterization of
LumpedComponent Characterization of
for helpful
helpful comments
comments anj
and criticism
criticism ofof this
this paper.
paper.
The Crude
Crude Oils
Oils for Compositional Simulation,"
for Compositional Simulation, paper
paper
The work
work was
was performed
performed atat the
the Continental
Continental Shelf
Shelf
Institute SPE
SPE 10691 presented at
10691 presented at the SPE/DOE Third
the SPE/DOE Joint
Third Joint
Institute (IKU)
(IKU) during
during 1982,
1982, and
and the
the equation
equation ofof state
state
used Symposium
Symposium on
on Enhanced
Enhanced Oil Recovery, Tulsa,
Oil Recovery, Tulsa,
used was developed under
was develo~ed under aa joint
joint project
project byby IKU
IKU and
and
Norsk
Norsk AGIP
AGIP A/S.
A/S. Continuing
Continuino support
support from
from frying
frying pan
pan April
April 4-7,
47, 1982
1982
publications,
publications, inc. is greatly
inc. 1S greatly appreciated.
appreciated
15.
15. Hughes,
Hughes, D.S., Matthews, J.D.
D.S., Matthews, and Mott,
J.D. and R.E.:
Mott, R.E.:
"Theoretical
Theoretical Aspects
Aspects of Calculating the
of Calculating the Performance
Performance
of 2 as
CO
of C02 as an Process in
EOR Process
an EOR North Sea
in North Reservoirs,
Sea Reservoirs,"
presented
presented atat the
the SympoSium
Symposium onon Enhanced
Enhanced Oil
Oil Recovery
Recovery
Bournemouth,
Bournemouth, England,
England, Sept.
Sept. 21-23,
2123, 1981,
1981, 247-266
247266

I
A.4-12
A4-12

12
12 EFFECT OF
EFFECT OF PHYSICAL
PHYSICAL PROPERTIES
PROPERTIES ESTIMATION
ESTIMATION ON
ON EQUATION-OF-STATE
EQUATION-OF-STATE PREDICTIONS
PREDICTIONS SPE
SPE 11200
11200

16. Jacoby,
16. Jacoby, R.H.
R.H. and
and Berry,
Berry, V.J.:
V.J.: "A Method for
A Method for 31. Reid,
31. Reid, R.C., Prausnitz, J.M.
R. C. , Prausnitz, J.M. and Sherwood, T.K.:
and Sherwood, T.K.:
Predicting Pressure
Predicting Pressure Maintaenance
Maintaenance Performance
Performance For
For The Properties
The Properties of Gases and
of Gases and Liquids, 3rd edition,
Liquids, 3rd edition,
Reservoirs Producing
Reservoirs Producing Volatile
Volatile Crude
Crude Oil,
Oil," Trans.,
Trans., McGraw-Hill, New
McGrawHill, New York
York (1977)
(1977)
AIME(1958)213,59-64
AIME (1958)213,9964
32. Riazi,
32. Riazi, M.R.
M.R. and Daubert, T.E.:
and Daubert, "Simplify Property
T.E.: Simplify Property
17. Jacoby,
17. Jacoby, R.H.,
R.H., Koeller,
Koeller, R.C.
R.C. and
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Berry, V.J.:
V.J.: Predictions," Hydro.
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Proc. (March 1980) 115-116
"Effect of Composition
Effect of Composition and
and Temperature
Temperature on
on Phase
Phase
Behavior and
Behavior and Depletion
Depletion Performance
Performance of
of Rich
Rich Gas
Gas- 33. Riazi,
33. Riazi, M.R,
M.R. and
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T.E.: Prediction of the
the
Condensate Systems,
Condensate Systems," Trans.
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,AIME(1959)216,406411 Composition of
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D.-Y.: The characteriza-
tion of
tion of the Heptanes and
the Heptanes Heavier Fractions,
and Heavier Fractions,"
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GPA Convention 102104
(1977)102-104

20. KatO,
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36. Roess, L.C.: "Determination of
L.C.: Determination Critical TemperaturE
of Critical Temperature
"Generalized Interaction
Generalized Intera"tion Parameter
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Fractions by Flow
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2 and
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Phase Phase Compositions
Predicting Phase
Predicting for Use
Compositions for in Reservoir
Use in Reservoir
Behavior of
Behavior of Condensate/Crude-Oil
Condensate/Crude-Oil Systems Using
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paper SPE
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presentee
Methane Interaction Coefficients,
Methane Coefficients," J. Pet. Tech.
J. Pet. Tech. at the
at the 93rd Annual Fall
53rd Annual Technical Conference
Fall Technical Conference and
and
(Nov. 1978)1649-1655; Trans.,AIME,228
1978) 16491655; Trans. ,AIME,228 Exhibition, Houston,
Exhibition, Oct. 13,
Houston, Oct. 1-3, 1978
1978

22. Kay, W.B.: "Density


22. Kay, Density of Hydrocarbon
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(1936)28,1014 md. and Eng. Chem. (1937)14081414
Ind. (1937)1408-1414

23.
23. Kesler, M.G.
M.G . and Lee, B.I.: "Improve
Improve Predictions 39. Daubert, T.E.:
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T.E.: A Critical
of
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the
the Fluid Properties Required for
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. C.: "A
the
the SPE 54th Annual Fall Technical Conference and State, Chem. Eng. Data
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Exhibition, Las Vegas, Sept. 23-26, 1979 (1976)31,1077-1084
(1976)31,10771084

26.
26. Lydersen, A.L.:
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Estimation of Critical Properties G.B:
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Calculating PVT
PVr Behavior in Gas
Gas Propert:er.
for Approximating Critical and Thermal Properties
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Oil Recovery
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Estimate Petrochemical
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23 1959)147-148
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Oct. 21-24, 1980

29.
29. Peng,
Peng, D.-Y. and
and Robinson,
Robinson, D.B.:
D.B.: "A
A New Two- 45. Whitson, C.H. 5.8.; "Evaluating
C.H. and Torp, S.B.: Constant
Evaluating Constant
Constant
Constant Equation
Equation of
of State,"
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md. and
arid Eng.
Eng. Chem.
Chem. Volume
Volume Depletion
Depletion Data," paper SPE
Data, paper SPE 10067 presented
10067 presented
Fund Vol.
Fund.., Vol. 15,
15, No
No.. 1(1976)59-64
1(1976)5964 at
at the SPE 56th
the SPE Annual Fall
56th Annual Conference
Technical Conference
Fall. Technical
and
and Exhibition,
Exhibition, San Antonio, Oct.
San Antonio, 5-7,
Oct. 5- 1981
7, 1981
30.
30. Pitzer,
Pitzer, K.S.,
K.S., Lippman,
Lippman, D.Z.,
D.Z., Curl,
Curl, R.F.,
R..F.., Jr.,
Jr.,
Huggins,
Huggins, C.M.
C.M. and
and Petersen,
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O.K. : "The
The Volumetric
Volumetric 46.
46. Yarborough,
Yarborough, L.: Application of
L.: "Application Generalized
of aa Generalized
and
and Thermodynamic
Thermodynamic Properties
Properties of
of Fluids.
Fluids. II. ri. Equation of State
Equation of Petroleum Reservoir
State to Petroleum Fluids,
Reservoir Fluids ,"
Compressibility
Compressibility Factor,
Factor, Vapor
Vapor Pressure
Pressure andand Equations
Equations of
of State
State in Engineering and
in Engineering Research,
and Research,
Entropy
Entropy of
of Vaporization,"
Vaporization, J.
3. Amer.
Amer, Chern.
them. Soc.
Soc. K.C.
K.C. Chao
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and R.L.
R.L. Robinson, Jr.. (eds.)
Robinson, Jr (eds.)
(1955)77,3433-3440
(1999)77,3433-3440
47.
47. "Technical
Technical Data
Data Book Petroleum Refining,"
Book - Petroleum
- Refining,
American Petroleum Institute,
American Petroleum Washington, D.C.
Institute, Washington, D.C..
(1976) Chpts. 1-6
(1976)Chpts. 16
TABLE IA - CRITICAL 000.001166 CORRELATIONS
T~ IA - aUTlCAL PRESSUIl& (DU.E.LATUltlS TABLE la(9- ClUTICAL
TULT. CRITICALTEMPERA'nIR
- TEMPERATURECOJUtELAT1OHS
C0000I,ATI090 l'AbU. IL ACEWfk Il' t 'N.":1l )k ( 'UHREI.ATI1lN ::
001.1, IL 0000(1111 FAC)nlA IV:IlO).LA ([((91.

ERSLRR-LLE
~ KESLER-LEE
!!!!:!!:!:!! PIT200 IOt:.FIHI
,ITZIJ' )l(EFINTITWH'
(1)1)
In p 0.3634 O.0066/y 0.24244 2.2690/3 O.lI00
(
6
l .. p~ . 8 . )6)4 O.O!t66/y - (0 . 24244 2 . 2898/y .O . UaS1/y7/l).IO
-
.Il.0.T t
J'.'O'.II.S oT ' T~ 341.3
14), 1 0 alloy'
0lly (0.4244
(0.4244 0 (3.1174(3
. 1174 "'' ' lI((AT
)
6. aoTb) W. - 101 d . l'l / p, I - I
11 P" I ' Tr71(.2I/p,
b 1614(p).,) I I

11.46000 3.6400/3, 1 6
0.4

7 ).lO 727 .I1.R 7/
T
C"46850 3 .'480/, 0 . 47217/.,') 0 10. 7 0 CI .8oTb,1 (0.4669
(0 . 4669 - 1 .626210Ylolo'/u
3.2623
3 . eoTb'

)10/).l.6T
+
(0.420(9 O.0000/( 6
I.69
)
7
3 .I1i 770
.(.LR
.T/
(0.42019 ' 0 . 0000/Y 69770/yl.ourUoU.aoTb)
~
01(M) SF60
CASTrO C60E17
S!Y!!! ' lloq'pc'
laqlp) . 2.2 UW,11
.L0,7(
!:!!!!!! - I
1'7-IT/T
IT I T I)
lag p 2.0290406 O.94I2OI09IRt 760.07121
T- 768 . 01121 0.111ll6'1 o
l W10
0.17133693. , t 6 - OU.ii,Ai4UV3
. I08i400)oI0Jot. ~
6 c b
0.30474749lOt c .I0t
109 p~ 2.8290406 0.94.20109 0 10-- ot - 0.304'4749 0 'O'.t l
-

z YAPlot ' 0 . 18890584-10-'ot 1


. 89212579 0100
- 00.092I2079-l
O.20076ll0IO300I 0.l5104103l

+ 0.30090004I0t

l ot: I
- 0.20816t10 0 10- oYAPl t O. U18.'Ol o I0Ot
0. + 9ont
J:SLER - LEE t tl0 < U . tI,
000600-660
.. 00Sl094920oI0-JoYAPl0r!. 'o t Z 0.3)1
O.llO47O99(0it O.4827l599IO3p(E 0.O3O9092UlD10pIE1 0.127116001O-
0.32711600lOE
O. 11047899oI0'oYAPlot'. 0.48271599010.' Y!.l ot .olnIP(,;' / IOI . 12'iJ - ', ." 2114 , ". I)'J,,4ICU-' 1 . )1111(.,1 /,,0 _ U.lh"H'Jll h
/n)p/I01. (20) 0.32(14 l,.(jVL1l) I boi).3
0.139496(9

.
IO31t
0 . 13949619 IO"Y!.Itl 11) .:1 ':118 - I r htll', n- I - ) 1. 4',:'1 /,,11 , CI.4I',nll r.
RIAZI-D600
RIAZI ... DAUBERT
EAT 10.2010 10.1/1700 . I I_Il_Il (I/I (I.4l07V(
OlAZI-00090AT IWOIITOON EXTENSION)
.IUI-DAUBERT IWHI'I'SON EXTENSION)
T; 24 027a7_u.eoTb)0.SB848 0.3096
24.279
(
6
000 7)l.O
40 T eyO
.9
. 3596 Kt:SLER-LEE ,0 U.tli
3.I22A1IO (lOT -2.31200 . )I FOULERL EE 30 0.03
)
6
P~ .. J.1228,0IO'ol1.80Tbl-l . 112S0
-

i 1201 ool
T
Tb UO < 47S
A 470

306610 U -7
791(4 . IJ520)( - CI . UlJ"l4h'j IC J
.'104 .10I).1352K O
.. II . , 'I'J' U (1 .,lUn _ ,1 .II IObltIi l i n
(
6
2.4149U(O 900.00 W W
(l.)110C30W
-)l.AT
P~ 2.414900I0hofl.a . Tb,wl . B66la oy4.2448
4.2440
T
I
6 KI 0470 !!l2! Ll:C(4,:n , II. 30), (LUll /0
TbOq > 47S

T~
T 19.U180
19.V70
6

0
6 2160'LS0)l.0.T
oTb,O
I . 62164
4 2.,00.2900
. 2985
ROBINSOH-PEHG
1.0110.000.4 I009I900IL0670: 000I1I009-PE1IC (PhM 301103
01101
l:tuERSE" (R081NSON - PENG, 'HAl

4.72609 a 2.016 PP ; ~ 0.04 1 2 o CN to O. 04'i7


0
0.0432C
P1 PARAFFIN-
, : 'AR.vFIN: p:. 14.69600
p - (4.69600 .4 . 0n CN 2.016
0.22709 + 0.340(1
00000
!2!!!
a 0.0457

(0 . 227oCN 0.)40) J
N
0:: W
A . 011.11432
. 0412"CN"
9 - 00.0000
C . 0880
4.02609 - 14.026 T~ 645
640.03 l.6667(3)l.BT - )59.61)
6
. 83 .. 1.66610hll.8-Tb 309.67(1 -

0, 060934000: p 14.69600 14 . 0~6 0 CN - 14.026


N: NAPH1'HENE : P~ 14 . 69600 0T - lS9 .6lIJZ l0- 1 )::s
9
(0.227C _0.7127.1l3l
0 . 1I:nhU08 359.67)l.)O 0 . (441) e
.0.To A: N - 0 . 099 1)

5,1371 A: w

(0 . 227.CN O. lll) a b A -
L.0440Co - 0.0930

14.026C 20.074
.;:.
A: AROMATIC: p 14.69600 .
,,__ N
.4 . 026C - 20 . 014
N I
A: ARQtlATIC ; p~. 14 . 69600 630ISTER IROaINSON-PENG
EDMISTER IROBINOONPENG;, PNA)
(0.22709 0(46) BERGKAH
0.720) 0000)50)1 I PHA)

fO o221oCN 0 . 12S) I IPSO) W


0
T~
T I.
aoTb
6
(.0T
(.I (I..
Jlng)p /101.320)
3 109 (pc / IO lo l2S)
A P : 101
0: A
b . 140 0 . 900 10- 1 t 0. 2 )) 010-' l 1
~ :1(40 0

000090)1 10110) 70
((lou)
(J.w) 0.9U0l0t+ 0.273IO t
BERGMAN (rNA)

0: p = 073.011 BERGMAN II: PARAFt'IH VALUE - O.Dle;


N; A~ ~. PARAFFIN
I. 13707E 0. 13162 l0t

0.80(03 (01,EI BEAGHAN 3096)
(PH" I VALUE 13.375 -

P : p~ 51) . 011 - l . l)107 0t O.1l16Zo10-loC2 .O.8510) o lO-I ot J


0- A : Au
M PAltAFFItI VALUE
0000FFIA VALUE - 0.100
N: L 726.414 I.32700n 0.90460 10n

0.40(A9lOt P : TT- - 734.06
734.86 0.. 1.21616
J . 2061ot 0.32984(G
0 . 329B40tO-Iotl
t 0.100

N : P~ - 726 . 414 - 1. 12150 0 t + OoIJa460 0 10-' o t 2 0 . 45169010'0t:'




o

N: 1 and (Ar
and for (1000T00005
IIAPHTHEHES IN'.
0: 0 1104.014 3.44680.
0.40312 l0 ( 0.234(6 10 E
. N ~ TT- 616.56
616056 0.. 2.6O77t
2 060110t 0.3oolA.1o-- e o+ 0.25440.1U
0.3aOIO-10-10t' D. 2S440-IO"'!lot
L
IN)
0\ : P~ -1184.514 1 . "4681 0t O. 45312.10 l o t l 0 . 21416010'ot1
-

C

IoIles ) 0.26
O.2b, W(C ) 0 . 27, "'le W' O. J"
AI TT~ 740.20
A: A)C_) 0
749.20 0.. 1.7017.0
1.'0l1ot - 0.l0B43I0n
0.t584JeI01.t'
.. U.823S
D.B23SBoIO'otl 61(09)
Q 0.27; )
0
alC 0.35
STANDING 657)59605, ROLAND, KATZ)

Rll.t
STAND .... UIATniEWS. ROLAND . U.TZ'

= 1100 43! log (661.)) + 12314 002 lag (603


100N0603 00000T (005)
SPENCER ... DAUBERT .!!!!!L
p~. 1188 - 4)1 1091"-61.1) (2119 - 852109("-5).711)90.8 )

. 7) ) . (y-0 . 8)

0: T~ l.R.(22
p , T* t.8_12208l689oT~
562 .B76B
24 562244 50436857J
9.T _y00436841)
ROWE
!!!2!!!
N:
HI TT; (.81
1. S-( 09
4 055116_T:811961
4,55II6 .-O.O7l646
oy0 . 071646)
0,01)7726626 09 6T
(XI IX 0 0.680140160(
p 10'010-0 . 01l7726826 oc,. 6T)
0.680'4aI651 /I II(LBoT
c c
1.80[11040300_T~
A,Az TT; I.AfII
669 .403Z0
28 o 669286
T O.227320j
oyO . 227l20)
EDMISTER
!2!!!!!!!!
futi
7 ( Ii
6
)l)T/T BOND
!!!!!!
p; (4.69600.10
14.69600.10 ,(W+I)( ITc/Tb'-I)
(2.90597 0 . 090597.C~/l
12 . 95597 - 0.l9l59

7C) 1
T
T~ 1.61961
I . S[961 - III10

)

STANDING
STANDING INATZH005 , ROLAND,
CMA'l"nIDlS, MOLAND, KATZ)
KATZ)

STT~ 628
-
608 6A300)I4
J6 109 (....7!,2)
-
71. 2) + 2400-3oa(M(
[2.50109(") - 30201.Iog:.y
JBOOJ. 1091 YI

A.4-14
A.4 -14

: MiU TABLE
T,\BLE A B VOILFl,1
.
POUr.CORRELVT
BOILPKi POINT IOFT
CCf;.RELATIO~S
-

261.1 .FF FPCF I C I F-;FF VT TV C FVVELVT IV1FT

PONINVFTF -PENG FPN4F


POBIHSONP[~JG liJNAI

/0)05- IF,F

,
~ . '
P'T::.) . ' E I , .II
0p. FSF (eN
N
T
,.,
,.

., , '- '

I1
, ,-,
I -.1F- ' "F I *

, I ,, c.

F, h lTbF l
:1 : SoFT SI /9

.,
,,

-F

" '\. r-. ,.,.


,FF

.,, ~
,, 0,,,; A

2

A t '
A !~ 1'0'
o/T,,/
b

-,-,I , . C
N
_, ,-I
.'
..
"l1't Fl

.. , 1.,.7, . ,. A
I.
A
A
CONUIAIFT PMAF'r,,,
PARAFFIN FAPFFTNE NE VAOMVOFE
~ 'fAPH'mN[ AROMATIC

.,
F -5,3F401-13
; . ~U~I~ J,'" .0. 15FF. F
. ~, -1 '\ ' UJ.! ' *0,0611 1600
.r, . Rb7J1bon
F- ..3FFF,
) .8 .a~otJO1,13
Y) 'I IJ'1 1
F.F48F0FI0 .lF
. ';' .l CJ9 ' SIl9S " ' - , 1
-.FFF416F 4F0
'l).U04JbI)47'IO
- ..,
1 ~ l J..N~h.ll ,- ~
"1
n. ~.~& J .... .t

" 1"l . ~ I _',.?<I ,''' ' 10 ' J


~~ .

:.-.:::[
. . 1.a1f031:). 10. 3
-\l HI J{,SOb'IO ..!

"."
F - F: F . 0 c, B, F.,, :
VIII
0. 1621HbCj.1O -3
;


-I. 14 '))J)bl. h:
J. F4FF/167/ l - :i
..
-- .3F,FFFS3IG
' u.
.IFF
:,.~qSll(' . Il' -" -0 . FR
-F, 12721F.IFI
J8J27239'10'

A
., "
0 8
1
F
'. .. 0 . p ~ aljJh .,.1,:
-.1F3404F- -- . OFF F
-l.1991J77C)4' Hi-
7
O1.12501100 6IO 7
..O. 1lIjSOS1Et'IO

~'."IW.r,II-)
/4 150.1 -1. 1:.oN,, " ,., ) ",(. I ': ~
F,FSIT,FY -L J41o-}I(,"
,7-IIFi.IFF
'1.1 1. ~ r.lll lih 1,,-1 .1. ,1,FF7.
-7, 'lrh I71 jF
1" - ).] ') ,47 ' 1
1.13,47.1 F'i.6'54alj. 1')'-
.F,54,5 lT
F,
-4. ,17' 5 ]'11,-1 0" ,l,r,lll o try-' 1o
I .F77-Fh
)11 4&, lT
10- 1
('. 2 1."7!}ijloIlJ'

...
F.IFOll I.
\,.,
.
.2 1
1. I II , .10- 1 F1
.,
o
- F,I. '.' 3
1. FFF,.IFY I FI.IU, 10.
,F .
.; . F77,O.lF
F. J)1mtlO- I 1 .192&7.10-
7-7267
-

H/)',oIU- l --t.IJ%C,
F Fbi,. "
F , 1.~ O I)'I-t' l n-l
-51,4.1 F .02005.
fl .920nsw-'
FF
3.70 1FF IF, F -

-7 l'J.1 I.lIO- , -1. ')7 ' .{,I t t \.~ 131/lW


1- 271IO- -J..f.7'4tIJ'
-1,67141.1
-7, FF41 31FF
11.11 _ 1.171)1 11 .10. 1 -7.71 t41 2F 10
1 ': ,I" nfllf. 10" I I. F3 l
0 9182l'r
.711FF2
F, F7F,F F F -7, JFF4 IONS
TABLE IC WEllo"HT TOARELAT
R WEIFAFT
-
TABLE lC - MOLECULA
MOLECULAR CORRELATIONS
-

FFARIIF-,AGE
tU:RCiHA,N (GENERAL)

0 V,, FV
TFqFMF
loqlK'
, n

- 7,-F: lW .1 I / FF-FF1
, V, .4 5A1IN5OIV
1
A 0 -269A6910IA

1
V
A,)1F O . lOWS):
F. hF
jC;lj211)11") AllF
F
4 5. F055FFS0 IV;
C;.7'5'j1j850IO -": A
A:Ol F 0704FFIV 1W
.1.87Sf)SOO-IO-'
MTZ - t'lROOZABAUI
ZAN0FFi (GENERAL.
IGENERALI
KA1Z-FFA lV
F l" 2.0100A40 FV.: A, -I.0A622AO
Ao ,
AF .Cj IFF3FFOF
-0 J1t14C)60'h ; AFF
F AI ::' .2.S0011)84010" An 1.566228010'-
,
6 ,
F,,
8 F. 2011 F Fr, - 2.2110
FF,.,,] FEE
/FF,FQFI BEFFLEA

14,16 . 4' F F . &1j


6021 F F I. ATl
I 1101' ,'I
~ . --12172, F,
12272 . L 9486 4
" 1~ 2 J -
-
1.12R7 I . B T '
b
MOBINF,VN- FF,NG FiNAl
F Ii.. J4Jl
FR Fl 720.1Cl/It 1
6
FFT loj II F FF
... ~III 79/Il . 8.Tb,I-IO"/ n .R.T '
F F - U. / /304,
I 77084 FF1100.0 F 720.
II 020r,R
.
, -

14.U.lh'CN F 1. b
3- 11 1/,
f>:
B,
I
-
FIFF.CFTF
(
[ ----
- --I
1I1,,,
. .!IIUoCN
FF11,
- - 1 ,/F1.lFFI
U. lrJ<)1
11.
* Fl
(1
, .72226-,F]I
OFFIF .,. .0.02226,
'.dOHIU ARIA - 18
/ )( 1. 8'128 IAl8A/il.0TN
I. Q8/t1.0-T ,II0
b
F)
11/11.8
F1lA/ .T
b
,1
FFF_,F F II 11)11
IF F F

Fl FF11, N -1ol . n}'.


'-1.117h'C
N:
F,
I
F

-
1- - --
(.
- - - - -I
1 I/ fL
a
,')111
F,,, A IAZI-DAUAEAT
RIAZI-DAUBEIIT
I',
IF, . tU,'C t, -
,IF,F,,
1,",11401
F, Ill-F
- 67 ,, -1,0164
14 ) l'j" ('N .. 211.0'14
14. F-h, N 20
B 4,,F,lF r OF

1- - -- -___I
---1 III,"'J'II
0 , I
II. 111l rN -
I FFFFN
o


Po
25.. 'f,'"
OF/Fl
/ FFCFfl

FVENERALF
FFEAEMAN tGEHEIIAL'
BERCHAN

F,, F
9 - 5/. IF, IF . I - FFFlF.FF,FFFFrt Fl-CF IV

p ],;. IFFF.FFF4FFFT. F
. F.
F, Fl//F F 1FF. F. . 12 FF,./F.,F 0 F9F
,

NAT,F-FIRO
KA1'7. OZARAEI IGENRAL
" FIIiOOZABADI GENERAL,I
F
.f. H ) fllI I l ' MI"1 ,.
..FFF,.FFFFF . f" .,
IFFF _..,,.
.f ' 11 ' I I' ' " *
, ,FFIF,F,F. II
I ,FF,- ~ ., ( , J
" .... . I F.-,]FF. FFFJ

.,
0
. . ]; FF. F FF..-F,i lrFF .170...F F: I F
02,0?. . F/F - F 5,,FOFFFOt F. CF, FFF

OOFFFNGU
ROB I NSON-Pi':Hr. F PNAF
NPFFNF, CPHA'
F :.I.FR OFT

pp : FF1
1.a F.Ol(o' e 2. IF
2.'11 1.
F
I F.,,F,
:', lfotf I ,i. .
I.F,1:F,.FFF,r
III " , ' ,. ' I , ''' ' ,"
.FOF-F.F.E 'r F,T
I II ' T ".q .
N

" " N.M. 1 44.('I~ {,C N


F
4.226
14.0110

" A 0 ,.FF-C
HII.U)b C" 20.IFFA
:!f)'CI/4
A.4-15
A.4-15

TABLEJ 3-
TABLE - INJECTION-0A5COMPOSITIO~
I~JECTI0N-GAS COMPOSITIONFORFOR
9OFFMANETETAL.
HOFFMAN AL. SWELI.ING
SWELI.INCTEST
TESTEXAMPLE
EXAMPLE

COMPONENT
COMPONE~ MOLEPERCE~
MOLE PERCENT

C.C
1 90.29
90.29

C,Cl 5.14
5.14

C,Ci 2.24
2.24
i-C
l-C .. 0.48
0.49
n-C
n-C .. 0.52
0.52
iCj
i-C, 0.22
0.22
5
n-C
n-C~ 0.14
0.14

C.Ci 0.29
029
CC-
, 0.51
0.51
Co
C. 0.11
0.17

100 . 00
100.00

A
zN
0.10
0.10
CONTINUAL
CONTINUAL MATCH
MATCH
oh 0.08
008

r~
0w -
miAzi-Daul.
CIIIAlHlAUIIDT "R~.'
N
zc) 0.08

0 0.04
0.04

Z 0.02
0.02
0
i
0 .....
mi
DUU- I I
800 49-
S8
PROPERTY COMBINATIONS
PROPERTY COMBiNATIONS OUTSIDE
OUTSIDE
U) 80
50
500 PNA TRIANGLES YIELD
U) soo PNA TRIANGLES YIELD
a
4
400
NEGATIVE COMPOSmONS
NEGATIVE COMPOSITIONS

P ~2
0. a 4S
45 MATCH
MATCH
POINT
POINT

~~
400 0.02112
0.0252- _
40 -0.011711 ~ :I 1 J

I
0 N -0.0575
0 300
N 300
-I
..a
0
0
ff25 U)
U)
N
38
35 ,

~..
Z 200-
200 II.
0.
30
30 S&
15 C'~7.
.
7
cl
p-,.c,t-Y
100 N,s 10 28
25
A

0 (a) 20
20
0 88
55 0.0_2:1 ._
0.95 0.0522 -
0.98 KATZ-FIROOZABADI 0.04110 -~ 4
KATZFIROOZABADI
GENERALIZED
o.~"" 80
50
0.0490
GENERALIZED PROPERTIES .0
0.90 PROPERTIES
0.90 AA
0.0'17 _:I
0.0lfl_

;;rili\ \~\\\\\\~
00 -0.0'. _ II
-0.0129
4S
45
I a. a -

.... 0.85
-0.04811- :I
2~
u I I -0.0455
Ci 0.88 1
-

N i
6.....

..
40
S
0.8O-
III !II IJ,I 1\ N

U)
40
MATCH
F~0.80
'.
0 POINT
>0
U)III 38
35 I ' -IXPSRIflNTAI.
- .x,......"....
Co

a.U)S
UI N I \ 20 IIIURTIIIPARAPFIN)
CPAIlAPPIIII
N \ \
N 2:I - EILSWVS
-

0.75
i5 0.7S
C I
I
til
II. 30
30 3
:1- RCIlI _ _ CPIIAI
- RQBINSOM-flNG LPNA)
Q I 10 44-CAnTT
CAVITY

.,
-

0.70 28
25 51 1-1('-
0.70 -KflLER-lfl
_ -RIAZI-DAUIER1
IllAD-DA""'"
P S -

(a) IaJ
20
20 -m (a)
0.88 380 400 480
300 400
400 500
SOO 600
800 700
700 800
800 280
250 300
300 350 400 450
300
BOILINGPOINT,
BOILING POINT.KIt TEMPERATURE.KIt
TEMPERATURE,

Fig.
Fig.1Flobinson-Peng
1-RobinsonPBngPNA molecularweight
PNAmolecular weIghtand
anddensity
denSItyvs115. Fig.2ZJRK
Fig. 2-ZJRKSOS EOSpredictions
predictionsofofSilerts
EilertsOO-L-544 gasconden
OO-L544gas conden
boiling point. sate:phase
asia phasediagram
diagram
boiling point.
A.4-16

I n-- -1-.~",,_AL' ~
2 - muIITS !PAIIA_

100
.2 - R a . I I I . _ CPIIA'
4 - CAYIITT

I-K UIH.D
1- RIAZHlA .....,
I
COo

x 106
LIQUID-GAS RATIO m/Sm
3

.,

100

O~____~__~~~~~~~~~~~~w~
o 10 20 30 40 80
PRESSURE, MPa

FIg. 3-ZJRK EOS predictions of Eilerts OO-L544 gas conden


C
1

ccC 0
9

sate: liquid/gas ratio.

PENG -ROBI NSON EOS "


EILER TS (PARA FFIN' PROP ERTIE S
5
PERCENT DEVIATION

o
-5

-10
0

-IS
Ci]
I-I
I

384.8 K
-20 ;-.-r.............I"'I""I'T"........................'Trr"'I............I"'I""I'T",...,..,..,,...,..,..,..,........,...,..,..,~
L4)
0
I

o 0.02 0.04 0.06 0.08 0.10


MET HAN E - Cl .
0 ci
CD t:i
z z
1

INTERACTION COEFFICIENT
CD
hi
hi
0
I
-3
ci
tTl
z
I

C , - C 7 ..
0

Fig. 4-PR EOS predictions of EI'erts OQ.L544 gas condensate'


+
9
a,
0

0
DC
CD
0

CD
CD
CD
CD

CD
m
CD
0
00
CI

-Co
CD
ri1

CCCD
DO
TI
9

InteractIon coefficient.
CD
A.4-17
A.4-17

EXPflThWITAL
I EllPDDlEllTAL
,- - a2 NO xomrMnrr
NO ADrusna:HT
0.20
o.ao

0.l5.
o.lS
I
3 To
3' Id-UO/IITc
P
2
10/St 7:
Pd11O/9j
Pc -IIO/e,:!p.

4Tdt9/1olTc
c
3
...
3.Te
...
Td - 181101
Pd
Tc
19,101 To
Pc

~
.. -Tei -(8/101 T. 4. ra=liool Tc

z
pa 18/101 2 po
PC Pd :Pc, ,
0 \
\ !
iJ
/71
0
0 0 4 I 2 3 I-) ....~__................~~1~2
~__....~.~~1_~~ ____~~~ j51,2__~4
I____~
S
0
S
0T-................
0.20
0.20
WI

!
'"
3-Td19/lOtTc
13To'B/10l'l'e: 3TdTc
0

~
-19,101 p~

I!
; Pd -(8/101
Pc Pc pd: 10/si Pc
0.19
~~
S
4.7/:Tc
~ 4'
4-Tdiiol9ltc
Tc -!lO/BITo ... Ta I To t
1 Pc :110,91 Pa
Pd =(10'81 Pc Pc =191101
Pci' Pc
11/101 Pc -

010-
o.lOj I / / r
/ [
0.05
O'OSl /
F-
7
_I . rf 11- EXPERIMENTAL
EXPERIMENTAL
22- NO
NO ADJUSTMENT
ADJUSTMENT
0L--...
0
o0
3t2t
95 10
10
--
_ _ _ _ _ ~.::.3....:..I-a:;._-_+'--....;:.-'1I---~---
15
IS 20
20 25
28 300
30 0 '0 10
10 1
10 20 35
A30
0.30
z
~
o.2o--------
020'i'1--~----~--"""----"'"

0
fi
e!:I 0.19
0.18
1: 3
.
3 ' .... (81101 ,
.4.. /9[ -'
.... '110/81
c
[
0.15-
0.18
3.. [9/10)~.
b' a [9/10H
! [ 4' .. 110/9)~.
g~ 0.10
001
1!
./
r
.
0.10 - b' =[10/9)'b
g0.o9 I !
~ 05
0. 1 /
f
a
m
0
!
0+0----C---10C--~lcS~~20~---2-S----30~
0 5 10 19
i loOt
Si:
0.05
0.08 -

20 25 30
P9SUTlE. ICP.
PII88UIII: NP.
0 31 ~ 4
Fig. 5-PR
Fig. EQS predictions
5PR EOS predictions 01
of Eilerts
Etlerts CH-P843
CH-P-843 gas condensate: critical pro
pro-
z
:I:
0
0.20
I
I!
perties adjustment.
perties adjustment.

0.15-
0.18
3
3'.0.
ac a
bb' o [9/10h
[9/bIb
I
II
44 ....
..:I
0.10-
0.10
~ I.
g
~ 0.05.
0.08

00 ID)
0.20
0.20

3-ac[9/1OI.a
3 [9/10).
0.15
0.18 b'o b

44' ;0/9IaT
[10/9). h\
0.10
0.10 b' b

0.05J
0.08

0
..,
0 IS 10 18 20 28 30
PRESSURE. MPa
PRESSURE MP.
Fig. 6PR
Fig. EOSpredictions
6-PR EQS predictionsof01Eiierts
EilertsCH-P-843
CHP-843gas
gascondensate:
condensate:
EQS
EOS constants
constants adjustment
adjustment
A.4-18

20

I-
m
m

-I
z
m
x
2 - NO AD.JUSTMENT

Io
Z
I
18

Co
I-.
3 - a' =(9/10'~ a

D)
I
b' =(9/1 O'b

N
0
a.
H
"'
PRESSURE, MPa 16
0)
I.
C1t
:s 4 - 8 = -0.12

-c
+ II
C,C7+

0
-4
W 14

7
p:; match
::l point
CIl for
CIl
12
I-

go
W 3&4
p:;
C1t
10
0
I-

8
C
ITt
0

6~~~~~~~~~~~~~~~~
0)

0-
0)-
0

0
C)
200 220 240 260 280
LZ 300 320
0

0
CA)
0
0
r:)
0
0

TEMPERATURE,1t
Lii
a

Fig. 7-PR EOS predictions of Eilerts CHP-843 gas condensate: phase diagram.
-p
I
C-)
m
a
a
m
0
a

a
CC)
-n

CD
CD
CD
CD

28~~~~~~~~~~~
ESTIMATED ~
CRlnCAL
26 POINTS
0)

POINT
"
",
, .
PRESSURE, MPa

24 MEASURED DEW POINT \.,


MEASURED BUBBLE POINT \ .
- RIAZI-DAUBERTIEDMISTER \,
22 --- CAVETTlEDMISTER
, ,,
,,
,,
,,
20 .
L)
0

18
I
a

PREOS
16~~~~~~~~~~~~~.~-
I-
0)

0
CI]

300 350 400 450 500


0
0
0

JI

0
CD)
0

CI]
Ci)
0
0

TEMPERATURE, K
Lii
c
-3
-3
tTl

ru

a
CCC

Fig. 8-PA EOS predlcllons of Jacoby 5-3 mlxlure. phase diagram


CC)

-o

CD
a

CD

CD
CD
DC
CD
m
a
0
CC)

CD
9
-o

C
-Ti

C
CD
CD
0
CD

C
-C
A.4-19

SOO
lid

NOMAL BOILING POINT, K


~
0
700
110
t!I

~
600

0
III 2 - CONSTANT Ituop

~
500
3 - ItATZ-FIROOZABADI
4 - YARBOROUGH
0 (AROMATICITY)
Z 400

300 w
1.00

iD
SPECIFIC GRAVITY (15.5/15.51

0.95
cD
.......
II)
cD 0.90
-=
~
0.S5

t!I O.SO
C)
E
~ 0.75
110
III
0.70
5 10 15 20 28 30
.38
CARBON NUMBER
1

Fig. 9-Experimental vs. estimated boiling points and specific


0
ID

0.
ID

CD

CDI

S
O

ID

0
DC
CD
3<
DC

PC
S

C)
C)
ID
CD

gravities: Hoffman oil.


I

aoo
3.3.11
~
CUMULATIVE GAS REMOVED.

11 ____ a

-
lI..CdCC.1I

DIBODroaOft. . . . .

" ...1
-
:I
..............
.. "COIIft"""_
!:!!!!

P
5CD
/5
3

I' -AI.
t
1 .. ........
3'

e
....1HIIIOOUMIII
T_
... 0.88

0.811 .
{ o.ao ~
~ t
LIQUID DENSITY,

0.711
i5 :I
Q 0.70 "EI
~
:I
0.1111 3

0.110
i
0.1111 III O.BS
1.11 0.811
0.80

. j
1.11
-:;
iSm I..idCI.l

~
0.811
1.4
j
... , ~ 0.811

i 1
IL FVF, 3

1.31 f
... ~
~ 0.
7s

~
~
ul
1.1 ~
~
!
0.
Mil
70
1 f
II
a
3
4
I

1.0 i
0 8
,
10 IS 3D as
wi
30
0.110
0 8 10 18 3D as
to!
30
0

PIIEIIIIUlIE. lIP. PIIEIIIIUlIE. lIP.


I
1

m
0
C,)
C

Fig. 10-ZJRK EOS predictions of Hoffman oil: simulated differential liberation tsst.
I
I

I
0
0
ID

C,

S
0

0
CD

CD
DC

CD
CD
0

S
0
3DC

DC
S
0

DC
CD

CD
CD
3C
A.4-20

200 -

_ -_ -_n_._" --====--_
5.

~ mu.
I5o.2
, -
.-....
, _ .-
4

_ . _.a_IIII~""'"
_ ._ la_rm ._efta

I a0 ... 0.88
---_._----
_._-----
tIIIJ.--_._ .. _--

I
0..80
0.80

a.BS
0.88.

,Q.80
I
0.80

~ 0.78
078 -

.
0
ea
0.70
0.70

50 .
0
0..00
:I 050
O.SI
5.85
I16.
o.eeL
0..88
0.11
_0.g5
..
1 0

...""
..
15
U

I.'
.4
~.,
.
/~ !

~/ .I. I' !,
/. . ~
to.eo
:!
~o.BS
oJ;
~
1.3
3
~
~ ".....-'
/"
~'

.
,
::Io.BO
co
=0..78

e
_
:! 1.2
I.a ~ ~,.,,-
0 a.7a
o
1.1
1.1 ,.'
10.111

1.0. :.-_-=-_--:."...._..,.,,_--::-:-_-=-=_-=
I 10 5 II
15 ZO
20 as
25
..30
+1
30
O'BOa---=--~I~a~--I~.~-~OO--"'---~'".....
PRUHE. .....
PIIEIIIIUIIE, NP. PREDSURZ NP.

11ZJRK and PA
Fig. 11-ZJAK PR EOS
EQS predictions of Hoffman
Hoffman oil: simulated differential liberation
liberation
test.
lest.

, .. 56

SOl
~
1 I'~
i lar
'1
Ij~
So
:;! ! I!

.~-~.--~
B
S
45 ! ~ t~
r
~'l
f 40~
rr
40 Oil
~ i ~
2 31 I
...." 30 1I
::I 1 'fP" , !
Ii
O
10
EFFECT OF VARIOUS METHODS FOR
10 ElllDlATDfG
ESTIMATING 801U11G
ROILING PODII8.
SPECIFIC GRAVITIES
"""",""GIUlVl'ftlll
POliCES 4
f
wi
I
,
'"
14
24 !
-~-.;r
- 2.3.481
, 11
10. wt
.. I
I' t
t
a t
...;
j ,r

i .
13 j I

..
0
..
11
i
~

'.
I
t 0..1
0.1--1
:! i
2
r
"Z ,/

a. II 10."
l0

S ---
., r
10.
a0 30
00

ClllWlJlTIYE
40
CUMULATIVE ......
00
80

GAS INIECTZII
BO
80

g..3,?
INJECTED .....
100
200

hoo.I 0011
, ..........
100
120 140
240 100
80
lo3i
25
'"
30
'" auau: 36
30 40
40

48
POINT PUBmH.
RUHRLE PODn' PRURE. ....
NP.
I'
00
80 ..
-of55

12ZJRK and PA
Fig. 12-ZJAK PR EOS oil-
EQS predictions of Hoffman oil: Fig. t3ZJRK and PA
Fig. 13-ZJAK PR EOS
EQS predictions ofoi Hoffman
Hoffman oil:
oil:
simulated swelling test.
lest. Simulated swelling tesfinterfacial
simulated test-interfacial tension
tension.

_a_. . ..,......'......--..
-- ..... ..-
!!!!..!..-.---.
....... --------
.... ..
-
CAR EQUATION or nAn
EQUATION OF ST*fl CORRELATION
CASt

PEIf~.OanmoN
------ -~ ~,..Q ..
2 200RLVITCHlOFfl
ZUDUITCH'Orn:
S

RESEtS-EEL
UlllD-ID
4 .- . 008FNSON PENO1PARAFI1N1
ftOIllJfJM)N'PDlCXPAUlFIIIJ
S -
ROBINSON PENO1AROMATICI
aOIlDdON PDIGtAJI,OMA11C1
A.4-21

IIaIIOD roa OftAllllllO

!Ig
.au.aro PODI'I'II
~

C,
8PECII'IC OU'lmlll
1 EZPEIUIUIITAL
a VAaIAIII.& It. .
3 COJDTAIIT L."

?
. utz....OOZABADJ
I. yu.oaoUGH

h

I.OO-t---.....- ........--~--.......- -.......---t-

.. 0.98

~0'98
LIQUID DENSITY o,o/o

=0.94

iO.1I3
00.90

a 0.88
... eva ...
Cl
I-)
(-I

0.1111 CCE 0.811

l
120 o.oao
,e

"0 13
~IOO 3&4
j....
~80
.... 1 ~~
~80 ~ 5 20 01 ,
LIQUID-GAB RATIO.

,\ i0I !
F .r
I :I tio.oos
f CVD j
C)
I

CCE
C

ao
-c

as 30 S 10 115 as 30

I
PIIEIIIIUJIE, . . .
I

Fig. 14-ZlRK EOS pr8dictions of Hoffman gas: simulated expansion tests.


U)
m
0

I
-n

I
C

0
tO

a,
DI
3

ID

C
-o
ID

ID

Co
0

3
C
C

C
C,

U,
ID

ID
0

a,
C

CD
I,
I

,.
................
....-~

...-..
iIi
H
II
Ii

'

0.811

~l
0.80
8
lO.7&

i5~ 0.7

~ ~
Q

~ O.IIIS
0
'~ -4
:I 0.110
-, , L" .
0.8&
IZO
CCE ... ...
"!a _.' _ 1... __.
100
..... eo
~
I
0
.5 110

g= 40
50
:I
:L~.,~~~~~~~[ 8 10 lIS 30 ao
30
10 lIS
I

PIIESBUIIE. lIP. PIIEIIIIUJIE, . . .

Fig. 1S-ZlRK and PR EOS predictions of Hoffman gas: simulated expansion tests
C-
I
0
(I)
:ij

0
-n

m
U,

CD
3
DC

DC
CD

-D
DC
C
ID

0
DC

CD

C
0

3
4,
C

Co
C

C
C,
ru
A.4-22
A.422

E-e
z~w
....
I-I
0
t)
0.5
TEMPERATURE, K
TEMPERATURE,
I
I4t::
""00w
L4

0
t)
0.4
A- 250
A-250
0.3 B - 300
B-300
~z C- 350
0....
0
I-I
E-e 0.2 - 400
D-400
D
0
t)

:! 0.1 A
~
....~z
-4 0.0
0.0
~ A
~ B
<
I1
-0.1
-0.1 C
....P:a~z -0.2 -
D
C] 0.0 0.2 0.4 0.6 0.8 1.0
1.0 1.2
1.2 1.4 1.6
1.4 1.6
oC\J
0
C)
t)
ACENTRIC FACTOR
Fig. 16-Kato
Fig. 1 6Kato correlation for carbon dioxide-hydrocarbon interaction
carbon dioxide-hydrocarbon interaction coefficients.

U1r-----------------______--,
u.
Oil I
U3
Dii
~ Dii ~I
an
B 0-il
Ut \

UO~-\
iia.,\
! ..,.o ii -
. IIOUL
MOLAL AVEAAGE
AVERAGE

~~.~~I~_.C
OFEEST FIT
iu= 1.11 --'\-- ' - - - - - - - ____

1
;: 015
.,.
~.
::
0.17
0. 1
'.
\
\
\
r

-~
.
. ~ 'UT
lEST FIT"
Fir

- 0.'.014
'" --.~
.---_-_

i. 1.13 '" RATS


UTO
"
;II: DID
"" ..............
;; '.n
~-.7__::___:7"'--_:_:_---_:_-:__-_:_--:_----_:":-:_-----::':,~
DII

....
0_ID

o0 ...
ii u
Di u
03 u
0.4 u u
050.1 vDl u
0.0 u
Ii

AClllTJltC
ACEIITRIC FACTOR.
FACTOR. (oj

30

/7
=1
"I
7
I

=1 "
"I -'
20 l,)1&
,oo .

~. ;]!..
gi ,. ~.::::::-::--~--
II _ ""c ... ...
~.-?"-':'::---f
.L.
_ 11 >
,. ~ --11---- ./
"
5 ~
, ___
l.1!.------
O
TU

_
----- -
--r:;-------

III
20
_

CIAUIO
LIQUID
VOLUME
::i~E-:'\
eE.""IIIEITAL
EXPERIURATAL
.o"n: ..,
CRITICAL
PAIFdT
N'IT
l f
. 2o~I------------------------~
L_..

10
It 20 m
10 q00 M
50 an
SQ 10 _
Ia so ~
.. .

t.
"Co,'flsvmll
S COO lid OUSTER

Fig. 17-PR
17PR EOS
EOS predictions of Hong oil.oil phase
diagram
diagram and Interaction coefficients.
and Interaction coefficients
A.5-1
A. 5 1

A FAMILY OF CUBIC EQUATIONS OF STATE

Curtis H. Whitson
Rogaland Regional College
Ullandhaug
4000 Stavanger, Norway

January, 1983
A.S-2
A.5-2

INTRODUCTION
INTRODUCTION

The Usdin-McAuliffe1 (UM) and 2


The Usdin-McAuliffe
1 Peng-Robinson 2 (PR)
Peng-Robinson
equations of state
state (EOS)
(EOS) are two
two of
of the more useful cubic
cubic
equations available
equations available for predicting
predicting volumetric
volumetric and phase
of fluids.
behavior of is a three-constant equation
The former is
Redlich-Kwong 3 (RK) EOS, van
which reduces to the 3
Redlich-Kwong van der
Waal s 4 EQS
4
Waals EOS or
or the real gas law. P R EOS,
The PR EOS, aa
two-constant equation,
equation, has gained wide-spread acceptance
in the petroleum
in petroleum industry because of
of its simplicity and
improved liquid-density estimation.
improved estimation.

A family of
A of cubic equations
equations of state is proposed which
incorporates both
both the UM and PR equations. It stems from
5S general two-term,
the development of Martin's
Martins
EOS. Thermodynamic expressions presented
four-constant EQS.
for the general equation are not limited by restraints which
define the proposed cubic family
family.. They are shown, for
example, to be applicable to the recent Schmidt-Wenzel (SW)
EOS~
EOS

The UM EOS
EQS has been modified by matching vapor
pressures and saturated liquid densities with correction
factors for EOS
EQS constants. The resulting expressions for
these factors are not complicated like some which have been
proposed for the RK EOS?-10
Only acentric factor is used
1
EQS!
as a correlating variable, making the modified UM EOS
EQS
11
comparable in simplicity to the PR and Soave-RK 11 (SRK)
equations. The new equation should also give better
predictions of liquid densities for petroleum reservoir fluids
containing considerable amounts of heavier fractions.
A.5-3
A.5-3

MARTIN FOUR-CONSTANT
MARTIN FOUR-CONSTANT EQUATION
EQUATION OF
OF STATE
STATE

The basis
The basis for
for EOS
EQS development
development in
in this
this study
study is
is the
the
general four-constant,
general four-constant, two-term
two-term equation
equation proposed
proposed byby
-5
Martin~
Martin,

RT
RT aa
=- - -
pp= - . . . . . . . . . . . . . . . . . . . . . (1)
(1)
(v-b)
(v-b) (v-b+c)(v-b+d)
(v-b-i-c)(v-b+d)

which has
which has been
been translated inin volume by
by constant
constant b.
b.
Eq. 11 is
is a special
13
Actually, Eq. special case of
of the
the Abbott
13 equation,
Abbott
the denominator of
where the of the
the second
second term
term (v-b+c)(v-b+d)
(v-b+c)(v-b+d)
replaces the more
more general quadratic form. Using
Using the
compressibility factor, Z=pv/RT,
definition of compressibility Zpv/RT, allows Eq. 11
to be rewritten as

Z3 ++ Z2[-3B
[-3B +
2
Z + (C+D-1)]

3B2 - 2B(
+ Z [ 3B 2B(C+D-1)
C+D-1) +
- + (A+CD-C-D)]
(A+CD-C-D)J

+ 33 + B
[-B
[_B 2
B 2
(C-I-D-1)
(C+O-1) - B(A+CD-C-D)
B(A+CD-C-D) - CD]
- - =
= 0 ... (2)

Using the definition of fugacity, f, for a


a single component,

ln(f/p)
In(f/p) =fb
=f (v/RT
(v/RT - 1/p)dp
1/p)dp
- ............... (3)
(3)

gives
gives

B
B A B-D
B-D C-B
C-B
in(f/p)
In(f/p) = -ln(Z-B)
-In(Z-B) + - - ++ [ +
+ ]]
Z-B
Z-B D-C
D-C Z-B+D
Z-B+D Z-B+C
Z-B-t-C

A
A Z-B+D
Z-B+D
+
+ --oln(
In( )) . . . . . . . . . . . . .. (4)
(4)
C-D
C-D Z-B+C
Z-B+C
A.S-4
A.5-4

For aa mixture
For mixture the
the fugacity
fugacity relation
relation can
can be
be written
written

ln(f/xp) f [, - - lnZ ........... (5a)

or
or

B.
B.
p
1
In(f/xiP) -In(Z-B) ++ --=-Z--=~~
) = -ln(Z-B)
ln(f/x

A
A B.-D.
B.-D. C.-B.
C.-B.
+ ___ [ I II + II I]
+ +[
O-C
D-C Z-B+O
Z-B-I-D Z-B+C

2Ix.A..
2x.A.. A(O.-C.)
A(D.-C.)
II
Z-B+O
Z-B+D
+ [ _ _...'...;:II.....
+ [
J ++ I ].In(
]1n( )) .. (Sb)
(Sb)
..

(C-O)
(C-D) (C-0)2
(C-D) Z-B+C
Z-B+C

where traditional mixing rules have been used for EOS


EQS
a=IiIj x.x.a..
constants: aL.
ij b=I x
aij=(1-K )(a j a )\ bZ
xixja where a..=(1-K..)(a.a.Y, 1 ,
b
1
xib , ij j i i
c=I jI xic
cL x.c. and d=I
IIi
d. xid
iI x.d..
IIi
.

EOS
EQS constants are defined as follows,

A
A = a.p/R
T
2
ap/R
2T 2 = aO .p /T2 (Sa)
(6a)
acapr/T
= a r r
B bp/RT
B = bp/RT =
= pObp r /T r
QbPr1Tr . . . . . . . . . . . . . . . . . . . . . . . .. (Sb)
(6b)

C =
= cp/RT
cp/RT = tO c .p r /T r
cPrTr . . . . . . . . . . . . . . . . . . . . . . . . .. (Sc)
(6c)

oD = dp/RT
dp/RT = 50
= d .p r /T r
QdPr/Tr (Sd)
(6d)

Q , 0c
Q , 0b'
where numerical constants 0a' Q and 0d Q must be
a b c d
determined, usually by critical-point restraints
restraints.. Liberty
Liberty
has been taken to include terms a, P,, t and 5 in Eqs 6.
Eqs.. S.
These represent corrections
corrections to the numerical constants 0a'
the numerical
temperature
0b, etc. and are typically functions of reduced temperature
and
and acentric factor. The terms t and
factor. The and 56 are
are usually
considered
considered constants
constants (unity)
(unity) or
or can
can be
be written in
in terms
terms
of p.
of .
A.S-S
A.5-5

PROPOSED EQUATION-OF-STATE FAMI LY


FAMILY

MartinS
5 shows that Eq. 1
Martin 1 can be simplified to yield the
RK, UM and PR equations, amoung several others. Table 11
shows the necessary definitions required to make the
simplifications. Since the SRK, UM and PR equations are
amoung the most promising, an EOS
EQS family is proposed
which incorporates all three.

First the constraint

c = Xb
= Ab
or . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. (7)
= XQb

is imposed, where A a numerical constant.


A is a For the UM
A=1,2i for the PR EOS, A2J2.
(and RK) EOS, A1,2; A=2.J2. The
restraints~2
following critical-point restraints
2

z
Z =z
=Zc

(av/ap) = v2/ap
(3
)
2
= (a = 0
v/op2) = at T
at T,c' PC
Pc . . . . . . . . . (8)

or (Z-Z
3
(Z-Z)
c
)3 = 00
=

are sufficient to yield

- -3X-f3Z
2
Q(A ) + cb(A-3xZC-f3Z) - = 0 (9a)

Qd =Qb(3-A)
=
- 3Z c +
-
+ 1
1 (9b)

Qa Qb2X
=2
(
Q (A2-3A+3)
=
3A+3) +
+ Qb(3AZ
cc+
Qb(
Z
6
)
3 Ac
-A-6Z c +3) +
+ (3Z
2-3Z +1)
(3z-3Z+1)
c c
.... (9c)
A.S-6
A.5-6

The smallest real root of Eq. 9a is taken for 0b' while 0d


and 0a follow directly from Eqs. 9b and 9c. ZcZ is a critical
a
compressibility factor to be specified. For the PR EOS, Z Zc
0.307401 ... ; for the RK EOS, Zc is 1/3; for the UM
is 0.307401...;
EOS, Z can be specified individually for each component in
EQS. Zc
c
a mixture.

The restriction that 0c AO , combined with the


= Xb,
c b
critical-point criteria, define the family of equations. Other
choices could have been made, of course, and the Z-chart
Martin~ (I
sum proposed by Martin ( == 0.62) was considered but
eventually rejected during this study. Although Eqs. 7
and 8 constitute a specific family of equations, Eqs. 11 to 6
are completely general expressions.

One observation to be made at this point is that


critical compressibility factor Zc
Z of 0.307401 is not unique
to the PR two-constant EOS.
EQS. Neither is Zc
Z of 1/3 claimed
C
EOS. Any choice of AA leaves the remaining
by the RK EQS.
option to choose Zc.
Z. There is no reason given by Peng
and Robinson, for example, why the value of 2.J2
2 is better
2d
than, say 2. One might contemplate if a specific pair of A
A
and Zc
Z gives better overall predictions of pure component
and mixture phase behavior; the optimal pair would
obviously depend on which physical properties were chosen,
and in which p-T-x.
p-T-x regions they exist.
I

A study was made to determine the pair A*, Z


A Z* * which
c
i-chart defined by Martin~
.5
minimize the I-chart Martin,

= Z
I = (aZ/apr~ =1, P
Zc - 1
(aZ/apr)r
- 0 =0 (lOa)
........................ . . (10a)
r r

which is easily shown to be given by:

I=Z +0
= Zcc + 0aa --Q
0b .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. (10b)
(lob)
b
A.5-7

Fig. 2 shows I versus Zc


Z for four values of 'A (1, 2, 2.j2)
2/2),,
and values defining the SW EOS
EQS (see Eq. 16); curves for
A=1,2 define the UM EOS.
'A=1,2 EQS. An interesting observation is
that the minimum I-chart
-chart value, I:r is always 0.67188, the
same value given by Martin for his "bestll
best three-constant
equation. Fig. 3 shows the variation in optimal 'A*
A with
Z*.
optimal Zc *. All values on the curve give a I* of 0.67188.
Points representing the RK and PR equations are also
noted; IRK =
= 0.67417 and IpR = 0.68684.
RK PR

MODIFIED USDIN-MCAULIFFE EQUATION OF STATE

An effort has been made to improve the UM EOS


EQS by
matching vapor pressures and saturated liquid densities
15
(calculated from correlations15;; see Appendix).
Specifically, correction factors a and P
f3 were adjusted in the
subcritical region 0.4<T
<Tr<l
4
O .0, where
r<1.0,

aa= a(T
ci(T,w)
r'w) (11a)
(ha)

P = (T,w)
P(T r'w)
= (11b)
(hib)

~ = 13(T,w)
P(T r'w)
= (11c)
(hic)

a = 1 (c2b/Qd)[(Tr,w)-1J ....................... (11d)


(lid)

The last expression results from not correcting what is


introduced in the original form of
of the UM EQS
EOS as a third
constant ("d ll as denoted by
constant (d by Usdin and McAuliffe). The PR
The PR
and SRK
SRK equations only
only consider
consider a as a function of
of T
Trrand
and
w, where p=~=o=1
1..

A.S-8
A.5-8

As shown
As shown by Fuller ~6 the
by Fuller
6 and f3P functions are
the a and are more
more
well-behaved for the
well-behaved the UM
UM EQS
EOS than the
the RK EOS (as
RK EQS (as modified
by Zudkevitch and
by and Joffe? Haman~ and
Joffe? Haman Yarborough 10) .
and Yarborough
).
10 This
results from specifying
results specifying Z
Zc for each
each component
component close
close to
to its
its
true value.
true value. Unfortunately
Unfortunately this
this procedure
procedure lessens
lessens the
the
accuracy of
accuracy of EOS
EOS predictions
predictions for lighter
lighter components
components such
such as
as
methane.

The present correlations for a and


The and P differ from
Fuller's and are easier
Fullers easier to apply,

a\
cx = 11 + m(1-T)
+m(1-T ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. (12a)
r
m
m =0.46089 + 1.2032w
= + 0.34548w2
1.2032ui - O.34548w
2 - (12b)

P = 11 + (P*_1){2/[1+e
= +8 T1)]
/[l+e
2
(*l){
( 8(Tr-1)] - 1} 1}
- (12c)
P* = 1.4891 + O.92175w
= 0.92175w + 0.40116w
+ 2
0.4O116w
+
2 ................. (12d)

1 13P is set equal to one. More accurate results


T r >> 1,
For Tr
would probably result if a second correlation were used for
a at supercritical temperatures.

The Pitzer correlation was chosen to estimate Zc


Z,l

Z = 0.291 - 0.08w
Zc 0.08gw- ............................... (13)

Z with w
Fig. 11 shows variation in experimental Zc w for
paraffins. The Pitzer correlation (Eq. 13) is also shown. Its
main advantage in the present context is simplicity and that
its close estimate of true critical compressibility factor
contributes to the smooth
smooth,I simple behavior of a and P
relations
relations..

Figs m and P*
Figs.. 4 and 5 show variation in m 13 with acentric
Figs.. 6 and 7 show variation in a and P
factor. Figs 13 with
reduced temperature for methane and benzene. Table Table 2
reviews properties of compounds used to develop the
modified UM EOSEQS..


A.S-9
A.5-9

SCHMIDT-WENZEL EQUATION
SCHMIDT-WENZEL EQUATION OF STATE
STATE

It might be argued that aa better


It better choice for the
the Z-w
Zc-w
relation would be
relation be one
one which had
had 1/3 as its
1/3 as its intercept,
ensuring RK capabilities for methane and the ligher
components. is used by
This arguement is by Schmidt and
and
to develop specific criteria for determining EQS
Wenzel to EOS
constants.
constants. of the
They try to incorporate characteristics of
PR and Harmens
RK, PR Harmens 17 equations
17 equations by noting that each seems
seems
suited for components
better suited components with increasing
increasing acentric
acentric
factors - specifically, w0.0,
- w=0.0, 0.33
0.33 and 0.67.

previous notation that cXb,


Retaining the previous c=Ab, but now
allowing A
X to vary for each component (i.e. acentric
factor), the SW equation is solved by first calculating the
constant Pc'

(6w+1)P 3 + 3p2 + 3p - 11 =
= 0 (14)
3c +
(6ui+1)13 c + c
3c
-

where Pc is the smallest positive root of Eq. 14. Z is then


Zc
defined by the relation:

1
Z . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. (15)
15
3(l+w)

which is shown in Fig. 11 and can be compared with the


Pitzer correlation. EOS directly
EQS constants follow di rectly from Eqs.
9 where A? is given by:

= (1+w) + [9(1+uj)2 - 811/2 (16)

Note that EOS


EQS constants and Zc
Z are defined explicitly by
acentric factor. Schmidt and Wenzel suggest that only a be
fEoi. The
considered temperature-dependent, where P=t=cS=1.
a(T r'w) function is given by two expressions, one for T
a(Tr,w) r~1
Tr<l
and the other for T r>1 .
Tr>l
A.5-10
A. 5i 0

CONCLUSIONS
CONCLUSIONS

1. General
1. General thermodynamic expressions are
thermodynamic expressions developed for
are developed for
the Martin
the Martin twoterm,
two-term, fourconstant equation of
four-constant equation of state.
state.

2. A
2. A family
family of
of cubic
cubic equations of state
equations of state is proposed which
is proposed which
includes the
includes the Peng-,
Peng-Robinson, Redlich- Kwong and
Redlich-Kwong and
Usdin-McAuliffe equations.
Usdin-McAuliffe equations. It
It is based on
is based the general
on the general
Martin EQS
Martin is simplified
EOS which is by introducting aa
simplified by
having aa specific
A, having
correlating parameter, ,
numerical each equation.
numerical value for each equation.

3. For the proposed


3. EOS family it is
proposed EQS shown that the values
is shown
of X Zc which minimize the I-chart defined by Martin
A and Z
a smooth function and that the minimum I-chart
form a
value is always 0.67188.

4. The Usdin-McAuliffe equation is generalized by matching


vapor pressures and saturated liquid densities. The
EOS-constant correction factors are expressed as simple
functions of acentric factor and reduced temperature.
This equation should predict more accurate liquid densities
of petroleum mixtures containing considerable amounts
of heavy fractions.

5. The Schmidt-Wenzel equation is expressed in terms of the


general
general Martin
Martin EOS
EQS and is shown to be a specialization of
the proposed EQS family where A is
proposed EOS function of acentric
is a function
factor instead of a numerical constant.
A.S-111
A.5-1

TABLE 11 - Definition
TABLE Definition of
- of Martin
Martin EOS
EOS quantities
quantities for three
three common
common
equations of
equations of state.
state.

Redlich-
Redlich- Peng-
Peng- Us din-
Usdin
Quantity
Quantity Kwong
Kwong Robinson
Robinson McAuliffe
McAuliffe

aa aa aa aa

bb bb bb bb

cc bb (2+.j2)b
(2+J2)b bb

dd 2b
2b (2-.j2)b
(2-J2)b b+d
b+d

ZZ
cc
1/3
1/3 0.307401. ..
0.307401... ZZ
cc
'A 11 2+.j2
2+,J2 11

Note: d represents the constant found in the original UN UM EOS.


Definitions of cc and
and ddare
are interchangable
interchangable because of symetry;
this suggests
this suggests that 'A can have
)b can have either of two
of two values - e.g.
e.g.
-

PR: 2.j2, RK: 1,2.


PR: 2J2, RIC: 1,2.

UM EOS.
TABLE 22 - Compound properties used to develop modified UN
-

Critical Critical
Molecular Pressure Temperature Acentric True Rackett
Compound Name Weight (MFa)
(MPa) (K) Factor Z
Z Z
Zra
ra
c
methane 16.043
16.043 4.604 190.58 0.0115 0.288 0.2876
0.2876
ethane 30.070 4.880 305.42 0.0908 0.284 0.2789
propane 44.097 4.249 369.82 0.1454 0.280 0.2763
i-butane 58.124 3.648 408.14 0.1756 0.282 0.2750
n-butane 58.124 3.797 425.18 0.1928 0.274 0.2728
i-pentane 72.151 3.383 460.43 0.2273 0.270 0.2716
n-pentane 72.151 3.369 469.65 0.2510 0.262 0.2685
benzene 78.114 4.898 562.16 0.2100 0.271 0.2696
cycloheaxane 84.162 4.075 553.54 0.2144 0.273 0.2729
2,3-dimethylbutane
2,3dimethylbutane 86.178 3.127 499.98 0.2473 0.269 0.2694
n-hexane 86.178 3.012 507.43 0.2957 0.264 0.2635
2,2-dimethylpentane 100.205 2.713
2.773 520.50 0.2886 0.267 0.2673
n-heptane 100.205 2.736 540.26 0.3506 0.263 0.2611
n-octane 114.232 2.486 568.83 0.3978 0.259 0.2567
n-nonane 128.259 2.289 594.64 0.4437 0.254 0.2547
n-decane 142.286
142.286 2.096 617.65 0.4902 0.246 0.2503
n-dodecane 170.330 1.820 658.26 0.5622 0.237 0.2466
A.5-12
A. 5-12

REFERENCES
REFERENCES

1. Usdin,
1. Usdin, E.E. and
and McAuliffe,
McAuliffe, J.C.: IIA
A One Parameter
Parameter Family of Equations
of State,lI
of State, Chern.
C hem. Eng
Eng .Sci.
.Sd. (1976)31,
(1976)31, 1077-1084
1077-1084

2. Peng,
2. Peng, D.-Y.
D. -Y. and
and Robinson, D.B.:
D.B..: IIA
A New Two-Constant
Two-Constant
Equation of
Equation of State,"
State, Ind.Eng.Chem.Fund.
lnd.Eng.Chem.Fund. (1976)15,1,
59-64
59-64

3. Redlich, O.
0. and Kwong, J.N.S.: "On
On the Thermodynamics
Thermodynamics of
V: An Equation of State. Fugacities of Gaseous Solutions,lI
Solutions. V: Solutions,
Chem.Review
Chern. Reviewss (1948)44, 233-244
4. van der Waals, J.D.: Doctoral Dissertation, Leiden, Holland, 1873

5. Martin, J.J.: IICubic


Cubic Equations of State - Which,,'
Which, Ind.Eng.Chem.Fund.
- lnd.Eng.Chem.Fund.
(1979)18,2, 81-97

6. Schmidt, G. and Wenzel, H.: "A A Modified van der Waals Type
Equation of State,
State,II Chern. Eng . Sci.
Chem.Eng.S ci. (1980)35, 1503-1512

7. Zudkevitch, D. and Joffe, J.: "Correlation


Correlation and Prediction of Vapor-
Liquid Equilibrium with the Redlich-Kwong
Redlich-Kwong Equation of State,"
State,
AIChE J. (1970)16, 112-119

8. Joffe, J, Schroeder, G.M. and Zudkevitch, D.: "Vapor-Liquid


Vapor-Liquid
Equilibria with the
the Redlich-Kwo
Redlich-Kwong
ng Equation of State,
State," AIChE J.
(1970)16,3, 496-498

9. Haman, S.E.M., Chung, W.K., Eishayal, l.M. I.M. and Lu, B.C.-Y.:
Generalized Temperature-Dependent
"GeneralJzed Temperature-Dependent Parameters of the Redlich-Kwo
Redlich-Kwong
ng
Equation of State for Vapor-Liquid Equilibrium
Equilibrium Calculations
Calculations,"
,
lnd.Eng.Chem., Proc.Des.De
Ind.Eng.Chem., Proc. Des. Dev.
v. (1977)16,1, 51-59
51-59
10. Yarborough, L.:
L.: Application
IIApplication of a Generalized Equation of State
State
to Petroleum Reservoir
Reservoir Fluids,
Fluids," Equations
E uations of
of State in
in En9ineering
En ineerin
and Research, K.C. Chao
Chao and R.L.
R.L. Robinson, Jr. (eds.)
eds.
11.
11. Soave,
Soave, G.: Equilibrium
IIEquilibrium Constants
Constants from aa Modified
Modified Redlich-Kwo
Redlich-Kwong
ng
Equation of State," Chem.
State, Chem.Eng.Science
Eng Science (1972)27, 1197-1203
.

12.
12. Martin, J.J. and
and Hou,
Hou, Y.C.:
Y.C.: AIChE
AIChE J.
J. (1955)1,
(1955)1,142
142

13.
13. Abbott,
Abbott, M.M.:
M.M.: Cubic
"Cubic Equations
Equations of
of State,
State,1I AIChE
AIChE J.
J. (1973)19,3,
(1973)19,3,
596-601
596-601
14.
14. Martin,
Martin, J.J.:
J.J.: Equations
"Equations of
of State,
State," Applied
Applied Thermodynm
Thermodynmaics Symposium
aics Symposium
(1967)59,12, 34-52
34-52
A.5-13
A.5-13

15.
15. Technical
Technical Data Book - Petroleum
Petroleum Refining, American Petroleum
-

Institute,
Institute, Washington, D.C. (1976)VoI.1,
(1976)Vol.1, 3rd ed.;
ed.; Procedures
5A 1 .10 (Lee-
5A1.1O Kesler) and 6A2.
(Lee-Kesler) 6A2.1313 (modified
(modified Rackett)

Fuller, G.G.: "A


16. Fuller,
16. A Modified
Modified Redlich-Kwong-Soave
Redlich-Kwong-Soave Equation of State
State
Capable of
of Representing the
the Liquid State,"
State, Ind.Eng.Chem.Fund.
lnd.Eng.Chem.Fund.
(1976)15,4, 254-257

17. Harmens, A.: Cryogenics (1977)17, 519


17.

NOMENCLATURE

a, b, c, d = EOS constants
A, B, C, D D = EOS
=EQS constants
f3, t,
a, p, , cS6 = EOS
=EQS constant correction factors

d = EOS nUf'!"'C!rical
0a' EQS numerical constants
a 0b'
b 0c' 0d
f = fugacity
=

K
K = binary interaction coefficient
=

m = correlating parameter for a


m =

MM = molecular weight
=

p = absolute pressure
pressure
Pc = critical
critical pressure
=

Pv = vapor pressure
=

R = universal gas constant


R =

T = absolute temperature
=

T c = critical temperature
Tc = temperature
v = molar
molar volume
volume
x. = mole
x mole fraction of of component
component Ii
I
ZZ = compressibility
compressibility factor
Zra = Rackett
Zra= Rackett correlating
correlating parameter (~Zc)
parameter (Z)
Zc =critical
critical compressibility
= compressibility factor
factor
Pc =correlating
=correlating parameter
parameter for SW
SW EQS
EOS
P* =correlating
=correlating parameter
parameter for P
1
K 1 =binary
Kij binary interaction
= interaction parameter
parameter between
between I and jj
and
XA = = correlating
correlating numerical
numerical constant
constant
PsL
sL =saturated
=saturated liquid
liquid density
density
I =Z-sum
Z-sum chart
chart
ww = =acentric
acentric factor
factor
A.S-14
A.5-14

APPENDIX
APPENDIX

The
The correlations
correlations for
for vapor pressure and
and saturated
saturated liquid
density
density were taken
taken from
from Ref.
Ref. 15,
15, procedures 5A1.10
5A1.10 and
and
6A2.13. They
6A2.13. They are repeated here because Ref. 15
15 is often
not available.

Vapor pressure, Pv'


p,, is estimated from critical
properties and acentric
acentric factor (see Table 2):

ln(p/p) = 0
A + w
1
A (A-1)
(A-i)

where

0
A
AO = 5.92714 6.O9648/T r - 1.28862lnT
- 6.09648/T
-
28862r +
l
!Tr 0.169347'T~
O.169347T
6 ... (A-2a)
1 =
A
A1 = 15.2518 - 15.6875/T
l5.6875/T r - 13.4721lnT
- + 0.435770'T~
i3.472llnT r +
- O.43577OT ... (A-2b)

and T r=T IT c' Units are arbitrary, though temperature and


Tr=T/Tc
pressure should always have absolute units.

Saturated liquid density, sL


PsL ' is estimated from a
modified Rackett equation using critical properties,
molecular weight and a correlating parameter Zra Z (closely
ra
approximated by
by true critical
critical compressibil
compressibility
ity factor):

-[1.0+(1.0-T )2/7}
-[1.0+(1.0-T )2/7]
P
sL
sL
=M[p/RT]Z
=M'[p IRT ].Z
c c ra
r
r . . . . . . . . . . . . . . .. (A-3)
(A - 3)

where thethe units of


of sL
P depend
depend on
on the
the units
units of
of RRand
and
sL
critical
critical properties.
properties. Values
Values of
of Zra
Zra are
are given
given in
in Table
Table 22 for
several
several compounds.
compounds.

It
It is
is only
only suggested
suggested to
to use
use these
these two
two correlations
correlations for
for
reduced
reduced temperatures
temperatures greater
greater than
than 0.4
0.4 and
and less
less than
than oror
equal
equal to
to 1.0.
1.0. The
The accuracy
accuracy should
should be
be less
less than
than 0.5%
0 . 5% in
in
this
this region
region and
and only
only applies
applies to
to pure
pure hydrocarbon
hydrocarbons.
s.
A.5-15

0.34 I I I I I I I I

.. RK
' ... ......
%
..... .....
a:: 0.32
:

..........

...... .....
o S...

U PR
...... ....
... ......
...........
0.30
..... .........

u. .............
> ...... S
I- A . . . . . . . . . . . . . . . . . . ~ I:O~
::i 0.28
-m
...... ....... g
..............
.........
~ 0.26 . AAO
oo

I
-00 00


0.24
o
...J - - normal
.-

(5 0.22
AiSO
ISO.:.
~o0 -.
0- other
0.20


0.18 I I I I
0.18 ' - - - ' - _ - ' - - _ ' - - - - - ' - _ - L - - - - I L . . . . - - - - ' - _ - - L - _ L - - - I
I I t I I

o0 0.2 0.4 0.6 0.8 1.0


ACENTRIC FACTOR

Zc-w data for paraffins;


FIG. 11 - Experimental Zc_W

Pitzer Z Z w
-w correlation and Z
Z w -w correlation
c
C cC
Schmidt-Wenzel EQS.
defining the Schmidt-Wenzel EOS.
A.S-16
A.516

0.73~--~----~----~----~----~--~
0.73
2(RK)
1
0.72
0.72- -

0.71
~'
1t:'
U) 0.70 A =2+12
2+/i (PR)
..
1 (RK)

c(
:c
0 0.69 - -

I .
~

0.68

2/(PR)
A
0.67
0.67- -

0.66 ____~____~__________~____~____
0.66
0.25 0.30 0.35
0.35 0.40 0.45 0.50 0.55
CRITICAL COMPRESSIBILITY FACTOR
FIG.
FIG. 22 -
- Behavior of
Behavior of the
the I-chart
E-chart sum
sum as
as a function of
of ZZc
several values
for several values of
of correlating
correlating parameter
parameter A.
A.
A.S-1B
A.5-18

I I


1.0
1.0
EE
...
a:
cr
w
Lii -

I-
I
.W
Lii
:s
<C
a:
<C
a..
0.
~
C!,
-Iz<Cziz- -

..J
-j
w
W
a:
a:
o0
oC.)
-

0.5
0.5-

I I

o0 0.5
0.5
FACTOR
ACENTRIC FACTOR
ACENTRIC
FIG.
FIG. 44 - Relation
Relation between
between correlating
correlating parameter
parameter mm and
and
acentric
acentric factor
factor for
for the
the modified
modified Usdin-McAuliffe EQS.
tjsdin-McAuliffe EOS.
A.S-17
A.517

3.5 I I

*~
\ *-i
*-PR

~- 3.~
3.0 *-RK

.:en
Co
z 2.5
02.5
0C.)
0
(!l"

-.Z...
z
2.0
-I
w
a:
a:
8' 1.5
..I'
i-....
a. 1.0
0 *
0.50,
0.25 0.30
* 0.35.. :
0.40 0.45 0.50
CRITICAL COMPRESSIBILITY. FACTOFl,
OPTIMAL CRITICALCOMPRESSIBILITV
,
zd
FACTOR, Zc*

FIG. 3 - Optimal parameters A*and


- Z*for
A*and Z *for minimizing the
c
schart sum (to its universal value of 0.67188).
E-chart 0.67188)
A.5-19
A.5-19

I I

*
*
c:CL
ccL .
r:i 2.0-
2.0
w
LU
I
I-
LU
W

:! .
a:
e(
c.
C!l F

z
-
Z
l-
e( .
.
_.I
...I
LU
W
a: .
a:
o
0
o
0 -

.
1.5

p I I

oo 0.5
0.5
ACENTRIC FACTOR
FACTOR

FIG. 55 - Relation
FIG. Relation between parameter S*
correlating parameter
between correlating 8* and
and
acentric factor
acentric factor for
for the
the modified Usdin-McAuliffe EQS.
modified Usdin-McAuliffe EOS.
A.5-20
A.520

I I I p

methane
en
Cl)
a:
o
0
I-
I
o
C.)
<C
LL.
LL
z
Z
o
21 P
i= 1.5
i-I.
oC-)
w
LU
a:
a:
o0
o
0
I
I-
z
Z
<C
I-
en
Cl)
z
Z
o
o
C-)
en
Co
o
0
w
LU

1 .0 ----~------------------------~----~
1.0
0.5 1.0
1.0
REDUCED TEMPERATURE, Tr

FIG.
FIG. 66 -
- Relation
Relation between
between EQSconstant
EOS-constant correction
correction factors
and SS and
ca and and reduced
reduced temperature for methane.
A.S-21
A.5-21

benz ene
benzene
.E
UJ
Cl)
a: -

oI- -

I
o
C.)
<
u.
U
z
Z
o
-o
0
I-
C.)
w
Ui
a:
a:
o
0
o
C.)
I- 1.5-
Z
<
I-
I-
UJ
Cl)
z
Z
o0
oC-)
UJ
Cl)
o0
wUi

1.0
1.0
0.5
0.5 1.0
1.0

REDUCED
REDUCED TEMPERATURE, Tr
TEMPERATURE, Tr

FIG. Relation between


FIG. 77 - Relation between EOS-constant
EOSconstant correction
correction factors
factors
and BS and
ac and and reduced
reduced temperature
temperature for
for benzene.
benzene.
A.6-1
A6-1

PRPCTICAL ASPECTS
PRACTICAL PSPECTS OF
OF CHARACTERIZING
CH
R
1 ACTERIZIN
P O PETROLEUM
PETROLEUM FLUIDS
FLUIDS

by

Austad1
Tor Austad
22
John Hvidsten
Hvidsten

22
Haakon Norvik
Norvik

Curtis H. Whitsonl
Whitson

1 Rogaland Regional College


2 Rogaland Research Institute
Institute

presented at the conference on


presented on

North
North Sea
Sea Condensate
Condensate Reservoirs and
and Their
Their Developmen
Developmentt
May 2425,
May 24-25, 1983
1983
London
London
INT HO(XJCT lON
iNll-fO[juQTidN depletion procedure
aepletion proceckJre is
is considered in more
considered in detail since
more detail since it
it - 3-
-2 -
-2-
closely
closeiy simulates the
simulates physical process
the physical gas condensate
process aa gas condensate
This
This paper
paper describes the
the essential
essential aspects
aspects of
of chemical
chemical and
and undergoes during
undergoes during depletion.
depletion.
pressure-volume-temperature
Pressurevo lumetemperature (PVT)
(PVT) analysis
analysis of
of gas
gas
condensates.
condensates. It also discusses
It also discusses the
the use
use of
of cubic
cubic equations
equations Finally, we
Finaily, we describe
describe the use of
the use cubic equations
of cubic equations of
of state
state
ut
of stale
state tEDS)
(EOS) for modelling
modelling gasconden
gas-condensate phase behavior.
sate phase behavior. (Peng-Robinson's
(PengRob equation in
insons equation in particular) for modelling
particular) for modelling phase
phase
r-articmmiar e~hasis is
Particular emphasis is placed
placed onon characterizat
characterization
ion of
of behavior.
behavior. lus characterizat
Heptanes-plus
Heptanesp ion is
characterization reviewed and
is reviewed and
petroleum defining the
petroleum fractions defining the heptanespi
heptanes-plus (C7+) group.
us (Cj+) group. its
its importance
importance to
to EOS
EDS predictions
predictions is
is emphasized.
emphasized. 0A
Rlthnuqh
AltMugh wewe have chosen
chosen to
to concentrate
concentrate our
our discussion
discussion on
on gas
gas procedure for
procedure matching experimental
for matching PVT data
experimental PVT is given,
data is given, and
and
condensates,
wrmdermsates, sn keeping with
in keeping wi th the
the conference
conference theme,
theme, most
most it
it is
is tested on
tested on aa North
North Sea
Sea condensate previously
gas condensate
gas previously
Pdrt s of
parts of the
the paper
paper are
are equally
equally applicable
applicable to
to black
black oils.
oils. published in the
published in the literature.
literature.

iiA gas
gas condensate is, by definition,
is. by definition, aa naturally
naturally occuring
occuring AA convenient li terature
literature guide
guide is
is given
given following
following the
the
petroleum mixture
pesielcusm found at
founo reservoir temperature
at reservoir temperature greater
greater References section.
References section. These sources
These give access
sources give to aa wide
acces~ to wide
than the mixtures
than te~erature and
mixture's critical temperature and less than its
less than its range of
range of information on gasconden
information en sate fluids.
gas-condensate fluids.
cricondentherm
cricondentherm (see Fig. FIg. 1).
1). The most
The most distinguishing
distinguishing
feature of
feature of a gas condensate is retrograderetrograde condensation,
condensation, CHEMICAL ANALYSIS
defined In
oefined in the present context as an an increasing
increasing arclImulation
arcmmulation
of liquid
of liquid (condensate) during isothermal pressure reduction.
isothermal pressure reduction. Analytical
Anaiyticalinformation yielding
information yielding compositional data for
compositional data for
cther typical characteristics
Gther characteristics of gas gas condensates
condensates include petroleum
petroleum reservoir useful during
fluids is useful exploratier,
during exploration,
include
producing gas-oilgasoil ratios greater
greater than
than 3000
3000 scf/STB gas-cycling phases of
production and gas-cycling of a gascondensate
a gas-condensate
scf/STB
(555 Sml
(535 / 5m l ), stock-tank
/Sm.t,
3
Sm stocktank oil gravity greater
greater than
than 4S45 degrees
degrees reservoir. Analytical oata,
Analytical combination
data, in combination with PVT
with PVT :x::o
-tPi (0.8 g/cc), and reserlloir
API reservoir temperatures often
often greater describe phase
analysis, can be used to accurately describe behavior
phase behavior 0'\
greater I
t.han
than 200 Of (9S schematically
illustrates schematically r3
N
200 OF (95 0C).
C). and physical properties. Fig. 22 illustrates
highly dependent
several processes which are highly dependent on on pruper fluid
proper fluid
The tirst part of the paper concerns chemical
The first chemical analysis
analysis of
of nearwellbore effects,
characterization - near-wellbore eftects, vertical flow,
vertical flow,
characterization

separator
separator samples. Description of experimental
experimental techniques
techniques platform or weilsite processing,
surface separation, platform or wellsite processing,
ms supplemented
is sump]emented with North Sea gas-condensate
gascondensate data
data measured
measured miscible/immiscible gas
transportation,
transportation, refining,
refining, and
and miscible/immiscible gas
at
t Rogaland
Roqalann Research Institute (RRI).
(PHi). These
These data
data typify
typify the
the displacement.
displacement.
fluid
fictu character of richer North
North Sea
Sea fluids.
fluids.
The obvious first step in properly characterizing characterizing aa
The
the chemical
chemical characterization
characterization of
of heptanes-plus
heptanesplus is
is Petroleum
composition. Petroleum
reservoir fluid is to determine its composition.
discussed in detail. Numerous experimental
discussed in detail. experimental procedures
procedures are
are specifically, are
in general, and gas condensates specifically, very
are very
reviewed
reviewed and data from from North Sea
Sea condensate
condensate samples
samples are
are hydrocarbons and
complex mixtures of hydrocarbons and light nonhydrocarbons.
light non-hydrocarbons.
presented. Rise, aa co~lete
precented. Also, complete distillation analysis
analysis upup to
to C20
20
C is only possible to
only possible define the
to define molar
the molar
On a routine basis
basis it is
is presented for for a mixture of of North
North Sea
Sea heptanes-plus
heptanesplus quantities
quantities of
of aa few relatively light including
components, including
light components,
fractions
ractions representing
representing black-oil
blackoil and
and gas-condensate
gascondensate systems.
systems. suiphide (~S),
hydrogen sulphide S), carbon dioxide
2
(H dioxide (C02),
(CD )
2
(N
nitrogen (N2)
), nitrogen
2
Properties
Properties of of carbon-number
carbonnumber groups
groups should
should give
give useful
useful
nonhydrocarbons
the most common non-hydrocarbons
methane ),
1
(C
methane (Cl),
estimates for normal
estimates for normal boiling
boiling points,
points, specific
specific gravities,
gravities, and
and ethane
ethane (C2),
),
2
(C propane (C}),
),
3
(C iso-butane ),
0
(iC
isobutane (iC4), normal
normal
molecular
molecular weights
weights when
when experimental
experimental distillation
distillation data
data are
are butane )
4
(nC
butane (nC4),
, isopentane normal pentane
iso-pentane (iCs), normal pentane (ncs),
)
5
(IC , ),
5
(PC
not
nut available.
available. grouped hexanes and similarsize compounds )
6
(C , and the
grouped hexanes and similar-sized compounds (C6), and the
d
heptanes-plus
heptanespius fraction (Cj1-) combining all
fraction (C7+ ) combining all remaining remaining
Next
Next we we review
review the
the most
most common
common PVT
PVT analyses
analyses offered
pfcered by
by
commercial
n:mpcrc :t1 and
and in-house
inhouse laboratories
heavier constituents.
heavier constituents.
leocratories,. The
The constant-volume
constant volume
The neptanespl
The heptanes-plus
thousands of
fraction may
us fraction may consist
consist of
paraffinic, naphthenic
of paraffinic, naphthenic and
of hundreds
hundreds or
and aromatic
or
aromatic compounds.
compounds.
-4-
4 as Analysis
Separator-Gas
SeparatorG Analysis -5-
- 5- I
thousands
The C
The C7+
+
7 fraction is
fraction is commoniy
commonly described
described by
by experimentai
experimental Prior to
Prior GC analysis,
to GC cylinder is
gas-sample cylinder
the gassample
analysis, the is heated
heated
molecular weight,
weight, density (Le, specific
density (i.e, specific gravity,
gravity, relative
relative to
to about 10
about 0C above
10 C temperature. Instrumentat
sampling temperature.
above sampling ion
Instrumentation
solecular
water) srid
water) and sulfur content.
sulfur content. Other properties
Other properties used
used to
to includes an
includes level four
HP-5B80, level
an HP-5880, four CC with two
GC with detectors. The
two detectors. The
characterized the lumped C7+ fraction include viscosity,
characterized the lumped Cj+ fraction include viscosity, GC run
CC run is made using
is made thermal conductivity
using aa thermal detector (TCD)
conductivity detector (TCO)
retractive index
retractive index and
and Watson
watson characterizat
characterization factor.
ion factor. to determine the
to determine content of
the content of nonhydroc
non-hydrocarbons and paraffin
arbons and paraffin
constituents from
constituents from methane to butane.
methane to second CC
The second
butane. The run is
GC run is
Fluid
Fluid samples
samples used
used for
for chemical
chemical analysis
analysis during
during made using flame ionization dector (FlU). run
made using aa flame ionization dector (FlO). This run first
This first
exploration and
exploration and production
production phases
phases are
are normally
normally sampled
sampled from
from determines pentanes
determines and hexanes
pentanes and content, then
hexanes content, uses backflush
then uses back flush
aa test
test separator.
separator. The The well
well is
is produced
produced through
through separator
separator to quantify
to quantify heptanes-plu s. Fig.
heptanes-plus. 3 illustrates the procedure
Fig. 3 illustrates the procedure
equipment at monitored pressure and temperature
equipment at monitored pressure and temperature (e.g., 1500 (e.g., 1500 analyzing separatorg
for analyzing
for as samples.
separator-gas samples.
ps ia and 100 OF I 10000 kPa and
paia and 100 F; 10000 kPa and 40 C). 40 OC). After producing
After producing
gas-oil ratio
gasoil ratio (COR)
(GOR) stabilizes,
stabilizes, equiibrium
equilbrium is is assumed
assumed and
and The chromatogra
The chromatograph detects mass
ph detects of certain
mass of substances and
certain substances and
samples are
samples are collected.
collected. Gas Gas and
and oil
oil samples
samples are
are taken
taken in
in responds by
responds drawing aa peak
by drawing on the
peak on the chromatogra
chromatogram (see Fig.
m (see Fig. 4).
4).
under the curve for a given peak indicates
The area under the curve for a given peak indicates the
The area the
stainless steel
stainless steel cylinders
cylinders to to prevent
prevent leakage
leakage and and
contamination.
contaminatio n. Usually 200
Usually to 300
200 to cc samples
300 cc samples ofof both
both oil
oil mass of
relative mass
relative of that substance (weight
that substance fraction). From
(weight fraction). From
and gas are available (measured
and gas are available (measured at at separator
separator conditions).
conditions). calibration it is known when a specific compound
previous calibration
previous it is known when a specific compound
will detected by
be detected
will be the chramatograp
by the h.
chromatograph. Assigning the
Assigning the area
area
Rogaland Research
Rogaland Institue (ART)
Research institue (RRI) has developed aa routine
has developed the specific
to the
to is then
it is
compound, it
specific compound, possible to
then possible define the
to define the
procedure
procedure forfor analyzing
analyzing separator
separator oil
oil and
and gas
gas samples. composition
composition of
of the
the gas.
Identical
gas. injected quantities
Identical injected quantities
Having determined respective
Having determined respective compositions
compositions on weight and (moles) of
of gas
gas is
is for each
ensured
ensured run by temperature
for each run by temperature
molar
molar bases,
bases, the
the wellstream
welistream composition
composition isis calculated
calculated using and a
control and
control backpressure gauge.
a back-pressure gauge. 0'\
I
CA)
separator
separator GOR,
CUR, temperature
temperature and
and pressure.
pressure. The
The following
following is a W
Results
Results from
from each
each run
run are
are stored
stored on
on tape
tape and
and then
then
discussion of RRI's procedure.
discussion of RRTs procedure.
automatically
recombined automatically to
to yield
yield weight
weight and
and molar
molar
compositions. Molecular weight
compositions. of hexanes
weight of hejtanespi
and heptanes-plus
hexanes and us
Laboratory Equipment
Laboratory Equipment are 86.0
basis are 100.0,
and 100.0,
86.0 and
convert to
used to convert molar basis
to molar
respectively,
respectively; these values represent
these values the molecular
represent the weights
molecular weights
The
The laboratory
laboratory isis equipped
equipped with
with standard
standard equipment
equipment such as
hexane and heptane. Table 1 gives
of normal hexane and heptane. Table 1 gives an example
of normal an example
lowtemperature distillation
aa low-temperature apparatus, gas
distillation app~ratus, gas chromatograph
chromatograph
report
report separatorgas
of separator-gas
of analysis
analysi~ from aa North
from Sea
North Sea
(GCl,
(CC), density
density meter
meter (atmospheric
(atmospheric pressure),
pressure), freezing-point
freezingpo int
oepression molecular weight apparatus, and X-ray
Xray gasconden sate
gas-condensate sample.
sample.
depression molecular weight apparatus, and
fluorescence
Fluorescence used
used for
for determining
determining sulfur
sulfur content.
content.
SeparatorOil Analysis
Separator-Oil Analysis
Addi tional equipment
Additional equipment usedused forfor detailed
detailed analysis
analysis ofof the
the
heptanes-plus
heptanesplus fraction
fraction include
include aa high-temperature
hightemperature The pressured-oil
The sample is
pressuredoil sample distilled roughly
is distilled three
into three
roughly into
distillation
distillation column,
colurmi, high-pressure
highpressure liquid
liquid chromatograph,
chromatograph, GCCC batches.
batches. rirst,
First, the
the lighter
lighter components
components including
including
equipped with a capillary column, and a mass
mass spectrometer
spectrometer nonhydrocarbons and methane to
and methane separated hy
are separated
butanes are
to butanes by
equipped with a capillary column, and a non-hydrocarbons
facility
facility based
based on on GC.
CC. Necessary
Necessary data
data processing
processing equipment
equipment boiling the separator oil to about
boiling the separator oil to about 23 0C. 23 C. Pentanes
Pentanes and and
includes micro- and mini-computers.
includes sicro and minicomputers. hexa,.es are then
hexaies are separated by
then separated up to
boiling up
by boiling 94 0C.
to 94 C. The
The
remaining mixture is
remaining mixture considered heptanes-plus. Fig. 33
is considered heptanes-plu s. Fig.

illustrates the distillation


illustrates the procedure.
distillation procedure.
Tie first
Tile first disti
distillation batch iis
llation batch s collected
collected inin preevacuated
preevacuated -6-
-6- The
The temperature
temperature function
function fF is is di fferent for
different for each
each -7 -
1
receivers.
recei vers. ByBy recording
recording temperature,
temperature, pressure
pressure and
and volume it is
volume it is component.
component. It is
It is defined
defined as as thethe product
product of of bb and
and the
the
possible
~u s siule to to calculate
calculate thetne mass
mass ofof gas
gas collected.
collected. The
The quantity (l/Tb-l/T),
quantity (l/Tbi/T), where
where Tb Tb isis the
the normal
normal boiling
boiling point
point of of
pontanestoriexanes batch
pentanes-to-hexanes batcn is is weighed
weighed directly,
directly, asas is
is the
the the
the component
component and and bb isis aa composite
composite function
function of of critical
critical
rr-siaininq
remai neptanesplus fraction.
ning heptanes-plus fraction. pressure
pressure andand temperature
temperature and and normal
normal boiling
boiling point.
point. Standing
Standing

CL analysis
analysis i!, used to
is used
gives
gives modified
modified values for band
values for b and TbTb for
for light
light compounds which
compounds which
GC to determine
determine weight
weight fractions
fractions ofof
-ospoiierits bond in the
should
should bebe used instead
instead ofof the true values. Table
the true values. Table 33 shows
shows anan
cumponents found i n the firstfirst two distillation batches
two distillation batches (see
(see
Fig .5i; batch is
example
example calculation
calculation of of KpKp vsvs fF for
for the
the same
same gas
gas condensate
condensate
Fig. each batch
3); each is analyzed
analyzed separately
separately and
and results
results are
are
Joreo on
fluid
fluid analysed
analysed earlier.
earlier. A A plot
plot ofof the
the function
function is is given
given inin
stored on tape.
tape. The C7+
The t fraction
7
C fraction is is characterized
characterized byoy
xieasuriiig its specific
specific gravity,
fig.
Fig. 6. Note that thethe C7+
- f-value
7
C Fvalue is is not
not well-detired,
welldetired, so so
lIIeCisur illg its gravity, molecular
molecular weight
weight and sulfur
sulfur
cool ent
not . When combi
it
it can not be included
included inin the
the consistency
consistency checkcheck directly.
dii ectly.
conl. .
When combinep
ned with the CC results for
the GC for the two
two
lighter Latches. toe total
l i ghter uatches, the total separator oil composition is
separator oil composition is Inconsistent compositions
compositions we
due to
to leakage,
leakage, improper
ilipropor
rir-tormined. Compounds with seven
liE-termi ned. Compounds with seven carbon atoms atoms which areare analysis or lack of equilibrium
equilibrium during
during sampling
sampling may
may b<.
he
can ied
carr icc overover iinn the the pentanes-to-hexanes
pentanes-tohexanes batch are detected spotted on a log
log Kp
Np vs
vs FF plot
plot which
which is
is nonlinear.
nonlinear. Suct.
Such an
an
ry tile
by the GC CC.. The
The measured
measured C7+t molecular weight and speci
7
C fic
specific example is given in Fig.
Fig. 6.
gravity
grav i ty isis corrected
corrected for for these
these constituents by assuming they
eve properties
I.ave piuperties of of normal
normal heptane. Table 2 gives
heptane. Table gives an example Another helpful consistency
consistency check
check isis to
to estimate
estImate the
the
ot separatoro il analysis for North
of separator-oil analysis for a North Sea gas-condensate
a Sea gascondensate Watson characterization
characterization factor
factor using
using measured
measured C7+
t molecular
7
C molecular
i
0 xpIe.
~ample. Hg. 5 shows chromatogra
Fig. 5 shows chromatograms for runs 1I and 22
ms for runs weight and specific gravity.
gravity. The
The correlation
correlation given
given by
by
dietiliation
(di st ill ation batches batches II and and 2) of a North Sea gas Whitson is, ):0
condensate.
conoensate . m
I
.j::>
Recomoinat
Recombi ion and
nation Consistency Check
and Consistency Check Kw == 457
4.5579'MO.15l7B'y-O.84573
L
557
.MD
B
7 nU. i.
.lSl 9
3
B
Kw .................. (1)

It is
It is usually pt interest
usually of interest to
to recombine
recombine the separator gas
arid oil compositions to yield
ano oi l compositions to yield aa composite
composite wellstream
wellstream
cnxposit
We have
We have found
found that
that the
the Nw
Kw value
value for
for aa given
given oiloil or
or
ion..
CUIllPOS it ion This
This is done by
is done by aa simple
simple material
material balance if
balance if
eparator
gas-condensate
gasconden field varies
sate field varies only
only slightly
slightly (e.g.,
(e . g., 12.hiib.112
12.uO!O.02)
separator COR, pressure
GOR, pressure and and temperature are known.
temperature are known. An
An
example
the 7
for the C7+ fraction.
C
+ This is
This is illustrated
illustrated in
in Table
Table4 for
for Li
example of recombinatio
of n is
recombinat i on is given
gi ven 1n Table 33 for
in Table for the
the
several North
several Sea gasconden
North Sea gas-condensate and blackoil
sate and black-oil reservoirs.
reservoirs.
ieparator
~ eparatnr camples
samples given
given above.
above.
Fig. 7a
Fig. 7a shows
shows the
the very
very slight
slight variation
variation in
in Kw
Kw value
value for
for aa
To
To check
check the
the consistency
cons i stency of
of separatorfl uid compositions
separator-fluid compositions North Sea gasconden
North Sea gas-condensate reservoir. Fig.
sate reservoir. fig . 7b
7b shows
shows anan
it may be helpful to use method
it may be helpful to use a method proposed by Hoffman,
a proposed by Hoffman, Crump
Crump anologous plot
anologous plot for
for aa North
North Sea
Sea blackoil
black-oil reservoir.
reservoir.
aid
and i-bocott
Hocott tar
for correlating
correlating equilibrium constants (Kvalues).
equilibrium constants (K-values).
If aa laboratory
If laboratory cancan establish
establish the
the characterizat
characterization factor
ion factor
ns
8y oe
i
1 nitiun.
defi ni tion, Kvalue
K-value is
is the
the ratio
ratio of
of normalized
normalized mole
mole
Kw
Nw for
for a
a given
given field
field (or even a given well), then each
(or even a given well), then each time time
t
r
fraction
action in
i n the
the vapor (gas ) phase
vapor gas) phase to the normalized
to the normalized mole
mole
new measuremen
new measurementsts ofof C C7+ molecular
+
7 molecular weight
weight and
and specific
specific
fraction
fract ion in
in the
the liquid (oil or
l i quid (oil or condensate) phase. Hoffman,
condensate) phase. Hoffman,
gravity are
gravity are made,
made, the
the resulting
resulting NwKw value
value can
can be
be checked
checked to to
Cruep
Crump and Hocott rioted
anu Hocott that if
noted that the product
if the product Np is plotted
Kp is plotted
see if
see if it is close
it is close to to the
the field
field average.
average. If the value
If the value
sersus
versus aa temperature
temperature function,
function, F,
f , on paper , then
semi-log paper,
on semilog then
deviates more than
deviates more than ! 0.01 to 0.02
0.01 to then the
0.02 then the molecular
molecular weight
weight
the
the resulting
result i ng curve
curve is
is linear.
linear. This
This relation
relation is
is
measurementt (which
measuremen (which isis much
much more
more difficult
difficult toto perform)
perform) should
should
nanticularly
particularly accurate
accurate at
at pressures
pressures and
and temperatures
temperatures
be questioned;
be questioned; aa newnew measuremen
measurementt ofof both
both specific
specific gravity
gravity
encountered
encountered atat separator
separator conditions.
conditions .
and molecular weight
and molecular weight should
should probably be made.
orobabiy be made.
The research laboratory
The research RRI has
at RRI
laboratory at developed aa special
has developed special -9-
III the
lii the last
last column
colunn of
of Table
Table 44 we
we have
have calculated
calculated C-j*
C7+ analysis procedure for characterizin g heptanespl um
-8-
-5- analysis procedure for characterizing heptanes-plus
molecular
molecular weight
weight using
using Eq.
Eq. 11 with
with measured
measured specific
specific fractions.
fractions. with the
Starting with
Starting mentioned procedure
previously mentioned
the previously procedure
gravity
gravity and the
and the fieldaverag
field-average characterization
e characterizat factor.
ion factor. for analysing separator
for analysing oil, the C7+ mixture is
separator oil, the +
7
C mixture subjected to
is subjected to
It is
it is seen
seen that
that the
the range
range in
in Kw
Kw of
of 1! 0.02
0.02 suggests
suggests aa maximum
maximum one more of
or more
one or following analyses:
the following
of the analyses:
error in
error molecular weight
in molecular weight ofof approximatel
approximatelyy 22 to
to 33 (usually
(usually
0 with a
less than
less than 1.5%).
1.5%). carbonnum
carbon-number distillation from
ber distillation from C C7 to
7 to C2
C20 with a
remaining C21+ residue; normal paraffin boiling points
remaining +
2
C 1 residue; normal paraffin boiling points are
are
used to define
used to single carbonnum
define single carbon-number groups (ASTH
ber groups (ASTM 00 289278).
2892-78).
SPECIAL ANALYSIS
SPECIAL ANALYSIS OF
OF HEPTANES
HEPTANES-PLUS FRACTION
-ft05 FRACTION
TSP distillation using
TBP distillation predefined volumeper
using predefineo volume-percent cuts to
cent cuts to
Characterizing
Ctiaracrerizin all compounds
q all compounds with
with more
more than
than six
six carbon
carbon fractions e.g., 3% per cut.
separate the petroleum
separate the petroleum fractions - e.g., 3% per cut.

rumbers
iuebers asas aa single
single component
component is is acceptable
acceptable for for many
many
ion
engineering applications.
engineering applications. It It may
may be
be necessary,
necessary, however,
however, to to simulated distillation
simulated with highprecis
GC with
using CC
distillation using high-precision
better define
better define the
the constituents
constituents making
making up up heptanespl
heptanes-plus. One
us. One slice widths
slice detector readings
(240 detector
seconds (240
of 66 seconds
widths of per
readings per slice).
slice).
example would
example would be
be for
for the
the pricing
pricing of of oil
oil or
or condensate;
condensate; i.e,i.e,
it
it is
is necessary to determine the relative quantities
necessary to oetermine the relative quantities of fuel of fuel aromatic of carbonnum
analysis of
aromatic analysis ber fractions
carbon-number up to
fractions up to C
2 0
(20
using high-pressure
using liquid chromatogra
high-pressure liquid phy.
chromatography.
oils, gasolines, etc. which can be refined from
oils, gasolines, etc. which can be refined from the produced the produced
fluid. Another
fluid. Another example would be
example would be if
if anan equation
equation ofof state
state isis ber
paraffinna
paraffin-naphthene-aromatic of carbonnum
analysis of
phthenearomatic analysis caruon-number
used for
used for predicting
predicting phase
phase behavior
behavior at at conditions
conditions other than
other than using mass spectrometry based on CC.
10 using mass spectrometry based on GC.
C
fractions up to
fractions up to CIO
those
those measured
measured experimentally.
experimentally. The The predictive
predictive capability
capability of of
all
all equations of gravity measuremen ts of
equations of state
state is
is severly
severly limited
limited if if only
only molecular weight and
molecular weight specific gravity
and specific measurements of
lieptanea-plus properties
heptanes-plus
necessary to
properties can
split
necessary to split C C7+
can be
into
be defined;
defined; in
at least
in general
into at least three to five
7
general it
three to
it is
is
five distillation.
distillation.
determined by
fractions determined
petroleum fractions
all petroleum carbonnum ber
by carbon-number or TSP
or TBP
.
):0

0'1
aI
pseudocomponents.
pseudocomponents. U1
Oepending on
Depending on the need, some
particular need,
the particular all of
or all
some or the above
of the above

There are many ways to justified. Usually, however, only


There are many ways to extend
extend the
the analysis
analysis of of may be
procedures may be justified. Usually, however, only
heptanes-plus can be ron on a routine basis. This
heptaneapius fractions.
fractions. Perhaps
Perhaps the
the oldest
oldest and
and most
moat common
common distillation can be run on a routine basis. This
simulated distillation
is analysis of
for analysis production fluids
of production fluids where where
is true
true boi ling point
boiling point (TBP)
(TSP) distillation.
distillation. Because
Because this
this might be practical for
be practical
technique based on
determined based
been determined on more
technique isis both
both time
tiae consuming
consuming and
and expensive,
expensive, it
it may
may bebe calibration of
calibration the GC
of the has been
CC has more
replaced by simulated distillation using gas chromatography. TSP or
reliable TBP carbonnumber distillation
or carbon-number results. The
distillation results. The
replaced by simulated distillation using gas chromatogra phy. reliable
Although need to
would need be justified
to be for aa specific
justified for use
specific use
simulated distillation
Although simulated distillation may may only
only require
require aa small
small other analyses would
other analyses
fraction detailed description of the C+
7
fraction of the time and expenses required by TBP
of the time and expenses required by TSP analysis,
analysis, requiring particularly
requiring particularly detailed description of the C7+
it from experimental work on North Sea
it does
doea not
not provide
provide thethe engineer
engineer with
with the
the same
same data
data base
base forfor fraction. Some results
fraction. Some results from experimental work on North Sea
each are presented in the following
each fraction.
fraction. Instead
Instead of of measuring
measuring boiling
boiling point,
point, volume
volume heptanes-plus mixtures
heptanesplus mixtures are presented in the following
distilled,
distilled, specific
specific gravity
gravity andand perhaps
perhaps molecular
molecular weight,
weight, discussion.
discussion.
viscosity
viscosity andand refractive
refractive indexindex ofof each
each fraction,
fractIon, thethe only
only
real
real data simulated distillation gives
data simulated distillation gives is weight is weight fraction
fraction
and
and aa calculated
calculated estimate
estimate of of boiling
boiling point.
point.
balances.
balances. Unfortunately,
Unfortunately, small
small errors
errors in in C7+
07+ molecular
molecular -11-
-11-
arbonNumber Distillation
Carbon-Number Distillation --to-
10- weight
weight may
may result
result in unphysical values of residue molecular
in unphysical values of residue molecular
weight.
weight. Engineering
Engineering judgement should be
judgement should be used,
used, though
though direct
direct
Results of
Results of aa carbon-number
carbonnumber distillation
distillation based
based on
on the
the
estimation
estimation of
of residue
residue molecular
molecular weight
weight is
is desirable.
desirable.
RSTM 0D 2892-78
ASTM 289278 method
method isis presented
presented in in Table
Table 55 and
and fig.
Fig. 8.8.
itiere are
lhere are several
several aspects
aspects ofof interpreting
interpreting distillation
distillation data
data The
The example
example distillation
distillation presented
presented inin Table
Table 55 and
and Fig.
Fig. 88
worth noting.
worth noting. First
First let
let us
us start off by
start off by asking
asking Nwhat
what is
is the
the represents
represents aa mixture
mixture of
of numerous
numerous C7+07+ fractions
fractions separated
separated
normal boiling
normal boiling point
point of
of aa given
given fraction?"
fraction? first,
First, by
by normal
normal using
using the procedure outlined in in the
the previous section.
section. Both
Both
t is
it is inferred
interred that
that the
the boiling
boiling point
point corresponds
corresponds to to black-oil
dlackoil and gas-condensate
gascondensate samples were mixec, U,ough
samples were mixeo, ttouah the
the
atmospheric (normal) pressure
atmosphE'r ic (normal) pressure - i.e., i.e., the
the vapor
vapor pressure
pressure properties
properties of thethe mixture
mixture suggest aa moremore gas-condensate
gascondensate
equals atmospheric
equals atmospheric pressure
pressure at at its normal boiling
its normal boiling point
point character.
character. Carbon-number
Carbonnumber boiling points, spec if ic gravities
specific gravities
eiiiperature.
l emperature. and molecular weights up to C20 020 can probably
probably bebe used
used as
as
estimates for most North Sea fluids if measured
measured data
data are
are not
not
Suppose the
~uppose the distillation
distillation cut cut wewe are considering starts
are considering
available.
tinil inn at
voiling at 68 68 0CC and
and stops boiling
boiling at at 98 0CC (boiling
(boiling points
of normal paraffins 6
C and C]).
ut lIormal paraffins C6 and C7)' If 8 volume percentIf 8 volume percent of
of the
the
initial C-,i+ mixture boils off in
Simulated Oistillation
Distillation
lnUlal C7+ mixture boils off in this interval, then one
point on
point on thethe distillation
distillation curve curve would be 0% and 68 0C C and
A
P chromatogram for simulated distillation by GC CC Isis shown
shown
snottier would be
anott,er would be 8%
8% aMand 9898 0C.
00. Suppose that 6 volume percent
in fig.
Fig. 9. It is for the same C7+
+ mixture analyzed
7
C analyzed in in the
the
rioliss between
boil between 9f1 98 oC
00 andand 126126 0C.
C. The next point on the previous section. Normal hexane
hexarie is usell
useu asas tt,e internal
the internal
distillation
disti curve would
l lat i on curve would be De 14%
14% (8% + 6\)
6%) and 126 0C. C.
standard. For paraffinic
paratfinic oils it is easy to locatf.'
locate nonnal
normal
Mavinp three points on me distillation
HavinQ three points on the distillation curve, curve, a smooth line ):0
paraffin peaks on the chromatogram. Instead
Instead of using
lJ';ing peak
peak
can be
can b drawn.
drawn. The normal
The normal boiling
boiling point
point for
for the first
first (C7)
)
7
(C en
integration mode, area slice mode is chosen. This sole is
This mode is I
cut would lie read from the curve
cut would be read from the curve at the mid-volume at the midvolume point - en

useful because
because simulated
simulated distillation analysis depenos
analysis depends on on
.e., at
1 .e., at 4:1..
5%. The normal
The normal boiling
boiling point for the second cut the distribution of area under the chromatographic curve, curve,
B would be
CtI ) would
10 be read
read from
from the midvolume point -
the curve at its mid-volume
rather than on the amount of
of specific peaks.
peaks. The
The area slice
area slice
i.e.,
i .e., atat lUi11% (8:t(8% ++ 14%14% divided
divided by by two). The engineer
engineer who mode provides
mode provides this basic
basic area distribution data.
data.
does not
does have aa background
not have background In in petroleum distillation might
consider working
consider working through
through the example data
the example given in
data given in Table 5. PA ninefoot
nine-foot by
by 1/8inch
1/8-inch stainless
stainless steel
steel colum
colum packed
packed with
with
10% SP2100
10% SP-2100 on
on 80/100
80/100 supelcoport was
was used
used to
to conduct tt,E'
comJuct the
it
If distillation
distillation is
is performed
performed to high carbonnumber
carbon-number present analysis.
present PA blank
blank test
test showed
showed that
that normal
normal C
C7U
2 eluted
0 eluted
groups
qroups such
such as 20 then
C
,
as C20, then the
the resulting
resulting residue (021+) will
residue (C21+) will prior to
prior to any
any significant bleeding
bleeding of
of the
the column
column material.
material.
be aa semisolid
be semi-solid at
at room
room temperature.
temperature. To
To avoid
avoid large
large This observation
This observation suggests
suggests that
that baseline
base-line shift
shift will
will riot
l'Ot tie
be
moses
losses the
the column
column should
should be
be rinsed
rinsed with
with a observed up
observed up to
to 020.
C20'
volatile
volatile solvent
solvent after
after Distillation
distillation is
is completed,
completed. The
The
nxtracteci
extracted residue
residue can
can be
be retrieved
retrieved by
by evaporating the
the IlA flame ionization
ionization detector
detector was
was applied
applied and
and normal
normal hexane
hexane
solvent.
sol vent. We
We have
have found
found that
that total distillation losses
total distillation losses can
can was used
was used as
as an
an internal
internal standard
standard (2.5
(2.5 weight
weight percent
percent of
of the
the
be minimized using this procedure.
be minimized using this procedure. injected
injected sample).
sample). Although
Pithough the FID
the FlO should
should give
give similar
similar
response on
response on aa' weight
weight basis
basis for
for various
various hydrocarbons,
hydrocarbons, we
we
Properties Of
Properties of the
the residue
residue are not readily
are not readily obtained
obtained by
by found it
found it gave
gave values
values systematically
systematically low.
low. By increasing
By increasing the
the
direct
direct measurement
measurement due
due to
to its semi-solid character
its semisolid at room
character at room response factor
response factor of
of the
the internal
internal standard
standard by
by 15.5%,
15.5%, we
we found
found
conditions.
conditions. It
It may
may be
be necessary
necessary to back-calculate residue
to backcalculate residue that simulated
that simulated results
results match
match true
true distillation
distillation data
data very
very
nrnperties
properties isina measured
7
C properties and mass/mole
using measured C7+ properties and mass/mole
well.
well. Also, reproducibility
Also, reproducibility was
was good.
good. Fig. 10
Fig. 10 shows
shows aa - 12-
-12-
comparison of
comparison of distillation
distillation curves
curves on
on aa weight
weight basis.
basis. -13-
CONVENTIONAL PVT
CONVENTIONAL PVT ANALYSIS
ANALYSIS -13-
It should
it should be
be noted
noted that
that the
the correction
correction toto response
response factor
factor
The conventional
The conventional experimental procedures performed
experimental procedures on gas
performed on gas
is probably dependent on the particular fluid.
is probably dependent on the particular fluid. If a fluid If a fluid
condensates include
condensates include
has not
has not been
been studied
studied previously,
previously, then
then aa TSP
TBP or
or carbonnumber
carbon-number
di stillation should
distillation should probably
probably be run to
be run to calibrate
calibrate the
the constant-volume depletion
constantvolume (CVD)
depletion (CVO)
internal-standard response
internalstandard response factor.
factor.
constantcomposition (-mass) expansion
constant-composition (mass) expansion (CCEI
(CCE)

separator flash
separator flash
PNA Analysis
PNA Analysis Using
Using Mass
Mass Spectometry
Spectometry
The first
The f i rst two
two experiments
experiments are conducted in
are conducted in aa highpressure
high-pressure
lJsing GC-based mass
Using CCbased mass spectometry,
spectometry, RRI
RRI has
has been
been able toto cell with
cell with some
some means
means of visually observing
of visually phase behavior
observing phase behavior
determine the paraffinnaphthenearomatic
paraffin-naphthene-aromatic (PNA)(PNA) content of
pressure changes.
during pressure changes. Mercury is
Mercury usually used
is usually as an
used as an
carbon-number oistillation
carbonnumber fractions Cj
distillation fractions C7 to
to ClQ.
10
C
. The basic
The the pressure. Reservoir
injection
injection medium for
for changing
changing the pressure. Reservoir
technique is to identify compounds showing
technigue showing responses
responses with temperature is
is maintained
maintained by
by aa circulating-air syctem
circulating-air sy~tem
mass-to-charge values, m/z,
massto-charge m/z, approximately equal
egual toto molecular enclosing the
enclosing the cell.
wei ghts of the compounds
weights compounds in aa given
given family for a a given
carbon number. These values are approximately 14n+a, 14.n+a, where Separator
Separator flash experiments
experiments are
are designed
designed with
with the
the
nn is the number of carbon atoms and a equals eguals +2 for intention of (1)
(l) checking the recombined
checking the fluid composition
recombined fluid composi tion
paraffins, 0 for naphthenes,
naphthenes, andand -6
6 for
for aromatics (for the and (2) analyzing the of separator
the effect of separator pressure arid
pressure and
CIO
10 fraction, values of -6
C 6 and -88 are used for aromatics). temperature on oil gravity and total surface gas-oil
total surface ratio.
gasoil ratio. ):t.
~
Having located all compounds with the specified m/z ratio, Using the Hoffman-Crump-Hocott It may
method it
HoffmanCrumpHocott method be possible
may be possible toto en
I
relative amounts are found by integrating
integrating the various peaks determine a low-pressure
lowpressure Kvalue
K-value correlation
correlation from
from -....J
in the total-ion-count,
totalioncount, TIC, chromatogram.
chromatogram. compositional data reported from separator tests.
flash tests.
separator flash

An
An example spectrogram is given in Fig. 11 11 for the Constant-composition expansion is
Constantcomposition expansion merely an
is merely an isothermal
Isothermal
naphthene family. Only those peaks found in the
the proper time pressure-volume experiment.
pressurevolume experiment. Starting at or above
Starting at or above initial Initial
interval are integrated,
integrated; others are ions which result from with number of moles
reservoir pressure with a known number of moles of resevoir
a known of resevoir
the breakdown of
of large
large compounds.
compounds. fluid, pressure is reduced and volume is is measured.
measured. At
At
undersaturated conditions (above the the dew
dew point), volume
point), volume
Presently the identification andand integration of TIC peaks factors
compressibility factors
measurements can be converted into compressibility
is
is done
done manually for each carbon
carbon number group.
group. A A program is
is (Z:pV/NRT)
(Z=pV/F1RT).. saturated conditions)
Below the dew point (at saturated conditions)
now being developed to to automate thethe calculations
calculations;I it is
it is
retrograde condensation can be be observed.
observed. The of
volume of
The volume
based onon aa procedure
procedure somewhat
somewhat different
different than presently
presently liguid condensate is reported as a percent
liquid condensate is reported as a percent of dew-point of dewpoint
performed manually.
perforn~d manually. Such
Such aa program
program should
should make PNA analysis volume.
volume. CCE data are
CCE data are not sufficient to
not sufficient calculate
to calculate
from
from mass
mass spectrometry
spectrometry more
more routine. compressibility vapor in
compressibility factors of saturated vapor in equilibrium
factors of saturated eguilibrium
with liquid
with liguid condensate of moles
number of
condensate;I number In the
moles in vapor phase
the vapor phase
Alternative
Alternative methods
methods for
for estimating
estimating PNA
PNA content
content
is
is not known, only its volume.
only its
have
have been proposed. These
been proposed. These methods
methods rely
rely on
on measured
measured physical
physical
properties
properties including
including refractive
refractive index,
index, viscosity
viscosity and
and
oensity
aensity..
Description
description of the constant-volume depletion procedure is -14- data, and to what extent material-balance-derived
materialbalancederived data are
are -15-
taken from
from Whitson and Torp:
used in final CVO
CVD reports.)"
reports.)

lOA
P CVO
Cvb experiment is conducted
conducted at reservoir temperature and
Whitson and Torp also show that reported CVO CVD data are
are
begins
bepins at saturation pressure. Cell volume, or the volume
sufficient to calculate other physical properties, including
contained by the saturated fluid,
flub, is used as a reference
liquid density, composition, and heptanes-plus
heptanesplus molecular
volume."
volume.
weight, vapor density (using two independent methods),
Mercury is withdrawn from the bottom of
"Mercury of the cell,
cell, thereby K-values
Kvalues at depletion pressures, and black-oil PVT
lowering the pressure as fluid expands. Ouring
During this properties used by numerical reservoir simulators.
process, a second phsase evolves - either retrograde liquid

Engineers working with gas-condensate


gascondensate phase behavior
(for
for gas
qas condensates) or solution gas (for volatile oils).-
oils).
should certainly become familiar with the CVO
CVD procedure and

"Mercury
Mercury withdrawal is ceased when a predetermined pressure data which are reported in conventional reports. There are
are
is reached. Some laboratories measure liquid volumes at numerous concepts such as two-phase Z-factors
twophase ifactors and
and

several
overal pressures before any vapor has been removed; these wellstream surface volumes which are not welldocumented
well-documented or
or
rcporteu relative to cell volume, represent CCE.
values, reported understood in the industry.
They
[ney closely approximate volumes that would have been
measured if the process had been CVO .....
CVD... CUBIC EQuPTIONS-CF-STPTE
EQUATIONS-Of-STATE APPLICATION
PPPLICPTION

"Mercury
Mercury is reinjected into the cell at constant pressurepressure What is aa cubic equation of
of state? It
It is an equation
eQuation
while simultaneously
simultaneously withdrawing an equivalent volume of
volume relating pressure, temperature, composition and volume.
volume. ::x:a
vapor. When initial cell volume is reached, mercury Slightly oversimplified, we write a general form
form of the
the en
I
injection is ceased.
ceased, Withdrawn vapor is analyzed using gas cubic equation
equation as ex>
co
chromatography to determine composi lions. Moles of vapor
compositions.
produced are calculated using the real gas law and are
reported as aa cumulative percent of initialInitial moles. Vl + a'V
aV2 +
+ b'V cO
bV + c = 0 ... (2)
(2l
Compressibility
Compressibility factor also is calculated noting produced
noting
vapor surface volume and equivalent cell volume (at
vapor (at pressure
and temperature).
temperature), From measured vapor gravity and Constants a, bbandand cc are defined by by pressure, temperature,
composition, heptanes-plus
heptanesplus molecular mass is composition and moles of the fluid.
composition Since the equation
Since equation is
bac<-calculated.
back-calculated. Liquid
Liciuid volume is measured visually and cubic in volume, there may be one,
cubic one, two or three
three volumes
reported
reported as aa percent of cell volume, which is actually a Itlich satisfy the
which satisfy the specific conditions. Which Which one CoCo you
you
type of hydrocarbon liquid saturation.-
hydrocarbon liQuid saturation. choose if
choose there are,
if there are, say,
say, three
three volumes?
volumes? In practice we
In practice we
merely define
merely define the
the largest
largest volume
volume as
as aa vapor
vapor and
and the
the smallest
smallest
The
"The experimental
experimental procedure is repeated several times until volume as
volume as aa liquid; ifif aa third volume exists
exists between
between these
ao low pressure
pressure is reaChed.
reached. The remaining liquid is removed,
removed, two then it
two it is
is merely
merely ignored.
ignored. If If only
only one
one volume
volume satisfies
satisfies
distilled, and
and analyzed using gas chromatography.
chromatography. Measured the equation
the equation defined
defined byby specified
specified conditions,
conditions, then
then there
there is
is
liquid
lipuid composition shouldsnould check
check with material-balance
with materialbalance
obviously no
obviously no problem
problem in
in choosing
choosing the
the correct
correct volume.
volume.
derived composition.
composition. (Some major laboratories
laboratories smooth and
measured vapor compositions
adjust measured compositions until
until the material
material Why do
Why do we
we choose
choose aa cubic
cubic form? The answer
The answer lies in the
lies in
balance checks. This
balance checks. This procedure
procedure is discouraged. It is good
discouraged. It behavior of
behavior real fluids.
of real fluids. Consider water
Consider water for
for aa moment. At
At
practice to
practice to ask
ask it
if aa laboratory reports measured
iaoorator reports measured or smoothed
or smoothed room conditions
rccm conditions water
water behaves
behaves as
as aa liquid
liquid and
and has
has aa density
density
of approximately 1 glee .
i g/cc. When we begin to heat water its
When its -16-
-16-
density
density decreases
slightly (mass
decreases (mass remains
remains constant
constant while
while TC.
Tc. Calculate AA and
Calculate and 88 using
using Eqs.
Eqs. 5,
5; actually
actually Peng and
Peng and -17
- 17 -
volume increases). However, once
volume 100 OC
once we reach 100 the water
C the
0 water Robinson
Robinson introduce
introduce aa correction
correction factor for
for the
the A-term,
Aterm,

becomes a a vapor (steam) and its


its density changes abruptly,
abruptly, on reduced
dependent on reduced temperature
temperature (T/Tc)
(TITc) and
and acentric
acentric factor
becoming several orders
orders of magnitude lower than
than at
at 99 0C.
99 C. (along the
(along the same
same line
line as
as suggested
suggested by by Soave).
Soave). Having
Having

At
Mt 100
100 0C
OC we can actually say that water has two densities
densities -
calculated AA and
calculated and 6,
8, constants e, f and gg are found.
found. The
The
the saturated vapor density (steam) and saturated liquid cubic equation
cubic equation (Eq. 3)
3) is
is solved
solved for 7.
Z. Analogous to our

density (heated water).


density water). To correctly predict this abrupt previous discussion
previous discussion of multiplevolume
multiple-volume roots, the largest
the

change in density (i.e., volume, assuming a constant mass), Z-factor


7factor is
is assumed to represent
assumed represent vapor
vapor and
and the
the smallest
smallest
the cubic equation merely chooses the larger volume solution 7factor is assumed
Z-factor is assumed to represent
represent liquid; no
no choice
choice is posed
posed
to describe steam, and the smaller volume solution to if only one
if one 7factor
Z-factor root
root exists.
exists. Z, volume is found
Given 7,
Given found
describe heated water.
water. ZNRT/p.
from ZPPT/p. Oensity is merely NM/v
Density is NM/Vor pM/ZRT, where NM is
or pM/ZRT, is
molecular weight.
molecular
Cubic equations are usually expressed in terms of the
compressibility factor, Z,
7, which is defined by the real gas The procedure for finding volume
volume and density is

law: Z7 =
= pV/tfH.
pV/tRT. The general form of any cubic equation essentially the same for mixtures. Given composi tion,
composition, the

then becomes, A and 8


terms A 8 are calculated using appropriate mixing
mixing rules.
rules.
If the mixture lies in the singlephase
single-phase region, this
simplified procedure can bebe applied directly to thethe mixture
Zl + eZ2 +
+ eZ
2 + fZ
fZ ++ g = 0
g = (3) composition. If If the mixture splits into two phases, then
the procedure is performed for each phase;
phase; this
this requires,
however, that the composition of each phase be be known.
known. .
)::a

0'1
where constants e, f and gg are defined by pressure, Vapor-liquid
vaporliquid equilibria (VLE) calculations necessary for
(vLE) calculations necessary for I
1.0
determining phase compositions are complicated and will will not
not
temperature, and composition.
te~erature, If we consider only pure
c~ounds
compounds for the moment, then we can express e, f and g for be discussed here.
one of the more popular cubic equations of state - the

in the
the
Three points deserve mention at this point in
Peng-Robinson
PengRobinson (PR) equation,
discussion. First, the PR EOS E0S is an example of a
two-constant
twoconstant equation. The two constants are A B, as
A and 13,
0.45724
defined by Eq. 5. Second, the numerical constants - 0.45724

ee=Bl
" El - 1 and 0.07780 (approximate) - result
result from
forcing two
from forcing rigid
two rigid
ff "= A 3822
A - 38
- 28 . .. .. .......................... (4)
(4) van der Waais. Third,
thermodynamic criteria proposed by van der Waals. Third, the the

g =
= 8l +
+ 8822 _
-
AS
AB critical properties (as well as acentricaoentrio factor and
molecular weight) required for each component in in a mixture
mixture
are not well-defined
welldefined properties for petroleum fractions. In In
where
fact they are very difficult to estimate, and one may find find
A =
A = 0.45724(pIT
)Po)
0.4572h(P/T
/
2 (Tc
2
)(Tc 2 /pc) different
. (5)
(5)
that different correlations give considerably different
8 = 0.07780(p/T)(T
B /p
0.07780(p/T)(T
)
0 c/Pc) estimates.

about two-constant
Another general observation about equations
twoconstant equations
is that constant A vapor density
A usually dictates VLE and vapor density
To calculate volume of a pure compound, first specify
temperature, T, and critical constants Pc
pressure, p, te~erature, predictions, whereas 8 usually dictates liquid oensity
Pc and
and
T.-. has
prediction. Consequently, Tc vLE and
hms more influence on VLE
vapor density
vapor density predictions This
This equation
predictions than
than Pc'
c. Also,
Also, aa second
second -18-
-18- state
state has
has been
been obtained.
obtained. equation can
can be
be used
used to
to --19-
19-
correction
correction factor
factor the
the so-called
socalled binary accurately predict vapor
accurately predict vapor pressures
pressures of
of pure
pure substances
substances and

binary interaction
interaction and
parameter - is
parameter is often
often used
used to
to correct
correct VLE equilibrium
equilibrium ratios
ratios of
of mixtures."
VLE deficiencies
deficiencies for
for mixtures.
mixtures of
mixtures of compounds
compounds with
with unlike
unlike properties. Binary
properties. Binary
coefficients are
coefficients are also
also applied
applied toto constant
constant A.
"While
While the new equation
equation offers
offers the
the same
same Simplicity
simplicity asas the
the
A.
SRK
SRK (Soave-Redlich-Kwong)
(SoaveRedlich_Kwong) equation
equation and
and although
although both
both
This short explanation of cubic equations equations predict vapor densities
equations densities andand enthalpy
enthalpy values
values with
This short explanation of cubic equations of of state
state has
has with
been given to help the reasonable accuracy, more
more accurate
accurate liguid
liquid densities
densities can
can be
been given to help the reader understand
understand methods presently
presently be
used for tuning or matching an obtained with the new new equation. In regions
regions where
used for tuning or matching an EOS to to measured PVT
PVT data.
data. equation. where
Adjustments made to
Adjustments made to anan EOS
EUS during the tuning process engineering calculations are are frequently
frequently requireo
required the
the new
process are
are new
sual1y localized
usually iocalizeo toto the components describing the equation gives better agreement
agreement between
between predictions
predictions and
the C7+
+
7
C and
fraction.
fraction. This is
This is logical when one one realizes that experimental PVT data."
that the
the data.
greatest uncertainty lies
greatest uncertainty lies in proper definition of
in proper of critical
critical
properties for components which are "Since
Since two-constant
twoconstant equations
equations have
have their
their inherent
inherent
properties for components which are actually mixtures
mixtures ofof
tens or hundreus of limitations, and the equation obtained
obtained in this study is
in this study is no
rio
tens or hundreds of pure compounds. In addition
addition toto
adjustment of of heavyfraction critical properties,
exception, the justification for the new equation
equation is
is the
the
adjustment heavy-fraction properties, the
the
interaction parameter
parameter between methane (or carbon compromise of simplicity and accuracy."
accuracy. (our emphasis)
interaction carbon dioxide)
dioxide)
and heavy fractions may
and heavy fractions may be adjusted to match saturation
saturation Similar efforts by numerous other researchers and and
pressure.
engineers has led
led to an enormous availability of cubiccubic
equations of state (mostly two-constant equations). The
twoconstant equations). The
:P
0'1
Peng-Robinson
PengRobinson equation is certainly one of the more more I
.1AT[H1NG AN
MATCHING AN EQUATION
EQUATION Of
OF STATE TO MEASURED
fEASURED PVT DATA well-accepted and widely used
wellaccepted used equations. o
None of the cubic equations
None of the cubic equations of state presently available
available Another approach which has gained considerable
considerable acceptance
acceptance
have been able
able to accurately predict VLE and volumetric
have been to accurately volumetric in the petroleum
In the petroleum industry was proposed
proposed byby Joffe,
Joffe, Schroeder
Schroeder
properties off petroleum reservoir
properties without some kind
petroleum reservoir fluids without kind and Zudkevich.
and Zudkevich. TheyThey suggested that
that aa second correction term
correction tern
of adjustment. This is
is really
of adjustment. This really not difficult to understand
understand be used for the
be the RedlichKwong
Redlich-Kwong EOS
EOS constant
constant B.B. According
According toto
when you consider our inability
when you consider our inability to define constituents
constituents found
found method, the
their method, the correction
correction terms
terms for
for AA and B are found
B are found
in petroleum fractions,
in petroleum fractions, as well as inherent limitations
limitations ofof simultaneously by
simultaneously by matching
matching vapor pressures and saturated
cubic equations. In
cubic equations. In fact,
fact, aa new field ofof research
research has
has liquid densities
liquid densities of of pure
pure components.
components. Unfortunately the
Unfortunately the
evolvea
evolved toto develop
develop more
more accurate
accurate methods of
of correcting
correcting EQS
EOS resulting corrections
resulting corrections can can not
not bebe readily
readily expressed
expressed in in
predictions.
preoictions. AA few
few of
of these
these efforts are summarized below.
sunmarized below. functional form. The net
The net result
result of of the
the method
method isis toto
(Joe method
method for improve liquiddensity
improve liquid-density predictions.
predictions. In general,
In general, thethe
One for improving
improving EQS
EOS predictions improve the
predictions is to improve the
equation improvement in
improvement in liquid
liquid density
density using
using this
this method
method is
is superior,
superior,
equation itself.
itself. This can
This can be done in
be in aa number
number of
of ways.
ways. What
What
e though certainly
though certainly more
more complicated,
complicated, than results
results given
given by
by
we might
might consider
consider asas the
the purest
purest modification
modification isis exemplified
exemplified
by the work of Peng and Robinson. Their conclusions Peng and
Peng and Robinson.
Robinson.
by the work of Peng and Robinson. Their conclusions give give aa
summary
summary ofof their
their goals
goals ano
and the
the limitations
limitations of
of the
the proposed
proposed The
The last
last approach we
approach we will
will consider
consider does
does not
not directly
directly
equat
equation:
ion:
change the
change the form
form of
of the
the equation
equation by
by using
using pure
pure component
component
By data.
data. Instead, aa set
Instead, set of
of measured
measured PVT
PVT data
data are
are chosen
chosen to
to
"By modifying
modifying the
the attraction
attraction pressure
pressure term
term of
of the
the
semi -0mw r (cal van Get xaais equation represent the
rmoresent true phase
the true phase behavior
behavior of
of the
the reservoir
reservoir fluid,
fluid.
semi-empirical van der Waals equation ea newnew eouatlon
equation of
of
Selected parameters
Selected parameters used
used by
by the
the EQS
EOS are
are chosen
chosen as
as rearessioc
regressi on
We
We started
started the
the present
present analysis
analysis using
using Coats
Coab rinal
'inal 21-
variables and
vartaules and can
can be
be altered
altered to
to match
match the
the measured
measured PVT
PVT data.
data. -20-
-20- -21-
threepseudocomponent
three-pseudocomponent +
7
C
C7+ characterization
characterization but
hut retain
retaIn
ConKnonly the critical
usiunly the critical properties
properties ofof CC7+ fractions

7 fractions are
are
considered
considered regression
regression variables.
variabies. Binary
Binary interaction
interaction methane as
methane as aa pure compoent. Equivalent
pure compoent. critical properties
Equivalent critical properties
parameters between
paraeeters between methane
methane (or
(or carbon
carbon dioxide)
dioxide) andand Cj+
C7+ calculated as
were calculated
were suggested by
as suggested by Whitson.
Whitson.
aJJow aa simple
fractions allow simple means
means of
of matching
matching saturation
saturation
The error
The error function
function used in this
used in study was
this study was t.he average ot
ho averape ul
pfe<;'>ure.
p ressu cc.
absolute
absolute deviation of
deviation dew-point pressure
of dewpoint anu runtrican--
prpssure aru root-IIlt'an-
square of
square of all
all other
other CVP
CVD data, The regression
data, Tie [uul inc
regression stint Hlf> :
h aH
in All alternative
alternative to to adjustment
adjustment of critical
critical properties
properties and
and
arentric factor
acentric tactor is,
is, as
as suggested
suggested by
by Coats,
Coats, toto adjust
adjust the
the two
two
simplex algorithm
simplex algorithm for
for minimization (NeIder anti
minimization INelder anrt Mel).
Mel ',J).

.. lInerlcal constants
numerical con!:>tants (e.g., 0.45724 and 0.07780
(e.g., 0.45724 and 0.d7780 for
for the
the tir:al tupraf nrc
Regression
Regression variables
variables included
incluo'd cri
c ritical telltp"fnlurt',
t.US) in tie
-ti cuS)
I-I{ Hie defining equations
equations for
for AA and
and B.
B. It should be
It should be
critical
critical pressure
pressure and acentric
and acentric factor
fact.or for
lor all
al I I.t,r,!" Fyi
ftru r 7+
sited that for isothermal processes
IIoted processes (e.g.,
le.g., CVO), only two
CVD), only two of
of Lot-ft
pseudocomponents.
pseudocomponents. Also,
Also, interaction
interact iOll cm,fI icitif
ici","1. I1,'-1lwtri
WI".:II
lill' turee
the three properties (T c , Pc,
(Tc, Pc, and
and as) are independent.
w) are independent. Thus fe
methane
methane and
and the
the heaviest
heaviest Cy
CT' fraction (FiTs.
traction (f-13i. dil
All Il'"
!lilly
inly two of themthem need
need (should be)
be) adjusted simultaneously.
adjusted simultaneously. adjusted eisnltaioourly luster-n
parameters
parameters werp.
were not
not ad.lust.ed !.imuILalleCJu!;ly. .
lnst."" ...
lile
use fJisaovantages
disadvantages of Coats approach are 1) 1) its unclear sade with wi tfi grenpe
repeated minisi
minimi zaUon
zat ion was malle ~lruliP'; rtl three
of tllTPr
ploy-;ical
ptysical implications, and
and 2)
2) the resulting EOS Table 6 shows 1I1f> tie sequence if parseotor
parameters. SClluenCI' 1,1 P(Jfatw\(,r
rOllstant
constants5 can not be used in other simulators
simulators based on the adjustment. For early runs the methaneFl? lirfeisetino
tI.f' ",pt.loanp-FI? inlt;rnd.iroll
PH
ed EOS.
Cub.
was adjus ted to pi vI' an t-xar:t tar
coefficients was adjusted to nive an ,aet noat ci
cit if "I

une
dne problem
proBlem with the matching procedure is that no
dew-point
dewpoint pressure. For
coefficients were included in
tire two
the two final final
optinializatiori
in the optinlali
runs
runs
routine as
zatioll fl,utint!
these
lhe~('
as .
~

0'1
lie complete I
assurance ~ancan be made that a global minimum of the error a fourth regression variable. Table 77 give~ giver tI,e c(llliplete
function can be found. This is illustrated by an example Pengdobinson Edt
fluid characterization used by the Peng-Robinson trr tt,e
EllS tr.f the
match of a North Sea gas condensate previously presented in "best"
best match. The choice of three-parameter QroLJps eoch
for each
ornops I[.r
the literature
literature (called
(called NS-l
Nbi by Whitson and Torp, and regression was made arbitrarily.
Condensate a by Coats).
Condensate 4 by Coats).
Total error reduction during tire enti
tile rr
eriti ['(-' ri-crr-ssiun
n'crps~iun

Coats
Coats introduced three
three pseudocomponents
pseudocomponents to describe
describe the sequence (manual and automatic) was morf' tI'fln :'1.4
was more than ./, \I., ,

C7+
t fraction; Whitson and Torp
7
C Torp originally give carbon-number
carbonnumber resulting in a final errOT slightly than ~.
greater than
error slight! y qreater 2.1%. TIre
{I:I.. Tile
groups up
up to C20,
20 plus a C21+
C
, 21 residue, as well as a proposed
C
+ proposed problems.
conivotnence prIJIJIp.III-; .
initial error was undefined because of convelgencp
fivepseudocomponent regrouping.
five-pseudocomponent The
The original
original Whitson-Torp
WhitsonTorp
This procedure does
This does not guarantee global minimum
guarantee a global will
minilsuli ... be
i I I IJe
match of
match of CVO
CVO data
data was excellent
excellent except
except for
for liquid
liquid dropout,
dropout,
found.
found. In fact
In fact this example an interesliflf,
shows an
example shows feature.
interest liii. It'atllre.
which was
was overestimated
overestimated by several
several volume-percent.
volumepercent. An
An
pressure and temperature 01
If only critical pressure of tt,t: easiest
tie I,<,avies!.
automatic regression
regression routine
routine was not
not used, and manual
C7+
C fraction are are used as regression
used as variables tt.en
regression variat..le~. tit
then tk
adjust"~nts
adjustments were
were made
made based
based on
on previous
previous experience
experience with
resulting error
error function is
function is found to have a valley of local
to have a vaJJf'y of local
matching
matching condensate
condensate fluid
fluid behavior.
behavior.
minima as
as shown
shown in Fig. The valley
12. The
Fig. 12. is actually
valley is hounded;
actually bounlled;

Coats
Coats improved
improved the
the liquid
liquid dropout
dropout match
match at
at the
the expense
expensm of
of the 10-'
lO% contour
contour encircles
encircles the only slightly
valley only
the valley outside
slightly outside

aa poorer
poorer C7++ description
7
C description (molecular
(irolecular weight
weight and
and mole
mole the
the Pc-Tc bounds in
pcTc bounds Fig. 12.
in Fig. Two test
12. Two runs s~ow
test runs approaches
show approaches
fraction).
traction I. The
The adjustment
adjustment of
of EOS
COb constants
constants for
for methane
methane is
is to
to local
local minima along the valley
along the (Al to A5
valley (AI and Bl
AS and to 86).
hi to 46).
probably responsible for better gas densities (Z-factors).
probably responsible for better gas densities (Zfactors). Although
Although local
local minima have numerical
minima have values nearly
numerical values identical
nearly identical
Unfortunately
dnfnrtunately they
they infer
infer aa substance
substance with
with properties
properties similar
similar (cm. 22 %),
(ca. %), the
the resulting liquid dropout
resulting liquid curve has
dropout curve has aa

Lo afllon;
arqnn tlli <; alteration
tlas alteration is
is not
not entirely
entirely satisfactory.
satisfactory.
iistlnntiy different character
Ilblinctly different character atat the
the upper
upper ana
ano lower
lower ends
ends -22-
-22-
the valley (see Fig. 12). Global minima
(,I the valley lsee Fig. 12). Global minima have
have been
been located
located
or other examples we have studied.
l "r other examples we have studied. CONCLUSIONS
CONCLUSIONS -23-
-23-

iq. 15 snows results ot predicted CVD data using Proper


Proper characterization
characterization of
of petroleum
petroleum reservoir fluillS,
fluids, and
r iq. 13 shows results of predicted CVO data using the
the PR
PP reservoir and
iN. iote that
that C7+
C molecular
molecular weights
weights are particularly
particularly gas condensates, can
gas condensates, can be
be divided
divided into
into tt,ree
1 (1', . Noll' are poorly
poorly predicted,
predicted, three
iiii Jar to Cuats results.
results. Vapor categories.
categories.
', illii lar to Cuats Vapor compressibil1 ty factor
compressibility factor is
is
xt predicted as well as by Coats, In general,
"lit prl'dir.teu as well as by Coats. In general, however,
however, the
the
rtreIh match is as goou or better than 1. Chemical
1. Chemical analysi s, based
analysis, based on
on chroma ton raptly
chromaturira phy,, Ilbl i 11 nt iion
listillat un
p rl' ~,t-'lIt IIlatclt is as gooo or better than matches
matches previously
previously
iltoinerl by Whitson and Tarp and Coats. and
and mass
mass spectrometry,
spectrometry, provides
provides the necessary data
the nece~~ary data to
to llf:tprmiroe
d& tereine
IlI,lilinerl uy Whitson and Torp and Coats.
composition
composition and
and properties
properties of
of pure
pure compounds
compounds ana and ppi
pet raolf'lJIII
roleijill
fractions
fractions making
making up
up reservoir fluidS.
reservoir fluids.

2.
2. PVT
PVT analysis
analysis provides
provides phase
phase IIf'havior
behavior fli:ll"
uatu (.1 t the
reservoir fluid
fluid asas aa whole.
whole. 1111.:51:
those (Jata,
data, ir.clUlliflY
iiclutunq
volumetric ana
and vapor-liqlJirl equilibria,, call
vaporliqiilu t-'quilitJria he USl'U
can tJe usrd lIin'!clly
:irectly
in
in engineering calculatioll~
calculations or
di ij
a. ', tile
the l'asb
basis lur
fur
matching an equation
equation of
of statp.
state.

3. Prediction of reservuir
reservoir fluiufluid belo<lviur
behavior al.
at cOlluitJUII$
cnuuitiuuo
other than those measured E:'xpl:rinrp.nlally is malic nu$ Lie tJy
those xeasured experimentally is made PlJ~_~;ilJle by )::0
thermodynamic
thermodynamic property
prnperty corrf'latiorrs.
correlations. One
One or at t.he
the mOfe
euro 0"1
I
powerful correlations isis the
the cubic
cubic equation
equation ofof state
state (H.6).
(Ebb).
N
Simulation of
of complex physical processes
complex physical processes such
such as
as development
develupxierit
of miscibll ty can
misciblity can be
be achieved
achieved by by anan E(JS
Ebb duedue tu i ls
to its
consistent behavior
consistent behavior in near-critical regions.
in near-critical regions.

Our purpose
Our purpose has
has been
been to
to review
review these
these three
three areas
areas otof fluid
I JlJllj
characterization.
characterization. Most of our observations are
Most of uur observations are based on La~ed on
experience we have gained by working wi th gas-conuensate
experience we have gained by working with qascundensate
fluids from
fluids from the
the North
North Sea.
Sea. Hopefully
Hopefully some
some at of ttie
ti,e measured
mE'asured
data we
data we present
present will
will be useful far
be useful for those
those working
working withwith North
North
Sea gas
Sea condensates.
gas condensates.

In closing,
In closing, we
we would
would like
like to
to thank
thank Mmerican
American Petrutina
Petrol ina
Exploration Company
Exploration Company of
of Norway
Norway and
and Phillips
Phillips Petroleum
Petroleum Company
Comparry
Norway for
Norway for support
support which
which has
has allowed
allowed us
us tu
to perform
perform "lUch ot
each oh
the analysis
the analysis presented
presented in
in this
this paper.
paper.
HfFERENCES
Rif ERENCES
-24-
I. Annual Book of RSTM Standards: LITERATURE
LITERATURE GUIDE
WIDE TO GAS CONDENSATE
CONDENSATE FLUIO
FLUID BEHAVIOR -25-
25
1. Annual Book of ASTM Standards I "Standard
Standard Method
Method for
for Distillation
Distillation of
of
Crude Petroleum
Crude Petroleum (IS-Theoretical
(15Theoretical Plate Column),
Column), ASTM
RSTM 0
D 2892
2892 (1979),
(1979),
Part 24, 802-839.
802839.
1.
1. Eaton, B.A. and Jacoby,
Jacoby, R.H.I
R.H.: A
A New Depletion
Depletion Performance
Performance Correlation
Correlation
C. Coats,
Coats, K.H.:
N.H.: "Simulation
for Gas-Condensate
Gas_Condensate Reservoir
Reservoir FluidS,"
Fluids, J.Pet.Tech.
J.Pet.Tech. (July, 1965)
1965) 852-856
852856
L. Simulation of Gas-Condensate
GasCondensate Reservoir
Reservoir Performance," Trans. RIME, 234
Paper SPE
SPE 10517
10512 presented
Performance, ~.~,~
Paper presented at the Sixth SPE
SPE Symposium
Symposium on
on Reservoir
Simula tion, New Orleans, Reservoir
Simulation, Orleans, Jan.
Jan. 31
31 - Feb.
Feb. 3, 1982.
3, 1982. 2. Eilerts,
Eilerts, C.K., et al.1
al.: Phase Relations
Relations of Gas-Condensate
Gas_Condensate Fluids,
Fluids,
Coats, K.H.
K.H. and
Monograph
Monograph 10,
10, USBM, Washington D.C. (1957).
.
3. Coats, and Smart,
Smart, G.T.I
G.T.: "Application
Application of
of aa Regression-Based
RegressionBased
EO5 PVT
EOS PVT Program
Program to
to Laboratory
Laboratory Data,"
Data, Paper SPE
SPE 11197
11197 presented
presented at
at 3. Jacoby,
Jacoby, R.H., Koeller,
Koeller, R.C., and Berry, V.J., Jr.: "Effect
Effect of Composition
Composition
the 57th Annual Fall Technical Confer
the 57th Annual Fall Technical Conference
ence and
and Exhibition,
Exhibition, New
New Orleans,
Orleans, and Temperature
Temperature on Phase Behavior
Behavior and Depletion
Depletion Performance
Performance of Rich
Sept. 27-29, 1982.
1982. Gas-Condensate
GasCondensate Systems," J.Pet.Tech.
Systems, jec )i (July, 1959) 58-63;
5863; Trans. AlMEr
RIME,
4. Hoffman,
Hoffman, A.E.,
216, 406-411.
406-411. -- --
4. R.E., Crump,
Crump, J.S.,
].S., and Hocott,
Hocott, C.R.I
C.B.s "Equilibrium
Equilibrium Constants
Constants
for aa Gas-Condensate
for System, ~.
GasCondensate System," Trans. ~ (1953) ~,
RIME (1953) 198, 1-10.
110. 4. Katz, D.L. and Kurata,
Kurata, F.I
F.: "Retrograde
Retrograde Condensation,"
Condensation, Ind.Eng.Chem.
Ind.Enq.Cheiw.
5. Joffe,
Jotfe, J.,
J., Schroeder,
(1940),
(1940), 32, 817-827.
817-827.
5. Schroeder, G.M., and Zudkevich,
Zudkevich, 0.1
0.; "Vapor-Liquid
VaporLiquid
Equilibria with
Equilibria with the
the Redlich-Kwong
RedlichKwong Equation
Equation of
of State,
State, AIChE
RIChE J.
J. O.L., et
5. Katz, D.L., al.:: Handbook
etal. Handbook of Natural
Natural Gas Engineering,
Eng1neeLiill, McGraw Hill
(May, 1970),]&,3,
(May, 19701,16,3, 496-498.
496498. Book Co., Inc., New York CIty
City (1959).
(1959).
6. Katz,
6. Katz, O.L.
D.C. and
and Firoozabadi,
Firoozabadi, A.: "Predicting
Predicting Phase
Phase Behavior
Behavior of
of 6. Reid, B.C., Prausnitz, J.M., and Sherwood, T.K.: Pro erties of Gases
Condensate/CrudeOil Systems
Condensate/Crude-Oil Systems using Methane
Methane Interaction
Interaction Coefficients,"
Coefficients, and LiquidS, 3rd Edition, McGraw Hill Co., Inc., New York City 1977),
J.Pet. 16491655; ~.
tech.
J.Pet.Tech. (Nov., 1978), 1649-1655;
1978), Trans. ~,
RIME, ~.
228.
7. Standing,
Standing, M.B.:
M.6.: Volumetric
Volumetric and Phase Behavior
Behavior of Oil
011 Field Hydrocarbon
Hydrocarbon ):0
7. NeIder,
7. Nelder, J.A.
l.A. and
and Mead, R.I
B.; "A
A Simplex
Simplex Method
Method for
for Function
Function Systems,
Systems, Society
Society of Petroleum
Petroleum Engineers,
Engineers, Oallas,
Dallas, 1977. en
Minimization, Comp.J.
Minimization," Comp.J. (1965),2,
(1965),7, 308-313.
308313. I

a. Norvik,
Norvik, H.:
8. Yarborough,
Yarborough, L.:
L.; "Application
Application of a Generalized
Generalized Equation
Equation of State to W
L)
8. H.: PVT
PVT Program,
Program, User's
Users Manual
Manual and
and Documentation,
Documentation, Petroleum
Petrole um Reservoir
Reservoir FluidS," Equations of State in Engineerino
Fluids, Equations and
Engifleerifl9AO4
Report Number
Report Number T4-83,
T483, Rogaland
Rogaland Research
Research Institute,
Institute, Stavanger,
Stavanger, Research,
Research, Advances
Advances in Chemistry
Chemistry Series No. 182, ACS, Washington,
Washington, D.C.
Norway.
Norway.
(1979), 385-439.
fl979), 385439.
9. Peng,
9. Peng, D.-Y.
D.Y. and
arid Robinson,
Robinson, O.B.I
0.8.: "A
A New Two-Constant
TwoConstant Equation
Equation of
of
State, Ind.
state," md. and
and Eng. Chem.
Chess. Fund. (1976),15,1,
(1976),15,1, 59-64.
5964.
10. Soave,
10. Soave, G.:
G.: "Equilibrium
Equilibrium Constants
Constants from aa Modified
Modified Redlich-Kwong
RedlichKwong
Equation of
Equation of State,
State, Chem.
Chess. Eng. Sci. (1972)
(1972) Z.,6,
27,6, 1197-1203
11971203
11. Standing,
11. Standing, M.B.I
M.B.; "A
A Set of Equations
Equations for Computing
Computing Equilibrium
Equilibrium
Ratios of
Ratios of aa Crude
Crude Oil/Natural
Oil/Natural Gas System at Pressures
Pressures Below
Below
1000 psia, J.Pet.Tech.
1000 pSia," J.Pet.Tech. (Sept. 1979)
1979) 1193-1195.
11931195.
12. Whitson,
12. Whitson, C.H.I
C.H.: "Characterizing
Characterizing Hydrocarbon
Hydrocarbon Plus
Plus Fractions,.
Fractions,
EUR 183,
EUR 183, presented
presented at
at the
the EUROPEC Conference,
Conference, London,
London, Oct.
Oct. 21-24,
2124,
1980.
1980.

13. Whitson,
13. Whitson, C.H.
C.H. and
and Torp,
Torp, S.B.:
S.8.: "Evaluating
Evaluating Constant
Constant Volume
Volurs Depletion
Depletion
Data, J.Pet.Tech.
Data," J.Pet.Tech. (March,
(March, 1983)
1983) 610-620.
610620.
Ia. Whitson,
14. hitson, C.H.:
C.H.: "Effect
Effect of Physical
Physical Properties
Properties Estimation
Estimation on
on
EquationofState predictions,
Equation-of-State Predictions, Paper SPE 11200 presented
presented at
at the
the
57th Annual
57th Annual Fall
Fall Technical
Technical Conference
Conference and Exhibition,
Exhibition, New
New Orleans,
Orleans,
Sept. 26-29,
2629, 1982.
1982.
TABLE
ABl E 1
1 - Example Analysl
Analysiss of a
a Separato r-Gas
SeparatorG as Sample.
Sample. TABLE 22 - Example Analysi
-

-
Analysiss of a
a Separat or-Oil
SeparatorO il Sample.
Sample.

ANALYSIS
YSIS OF NATURAL GAS
,--- ANALYSIS
YSIS OF PRES
PRESSSURED OIL
URED
Sriin
Sitl H flle 0 11l.'l'l.l Il J.04.
04 0177 Sample analysed 83.04 . 14
Sample alllved
arrived 83.04.07
83.04.07 4
a Sample analysed
mple analysed 83.04 .22
83.04. 22
FIiCki
~ I(l NSr.r. / ll1 ______ _ ~ampll
k/C/IB Samoing
-

dale
ngdare 83 0313
83.03. 13
IFIeld
Field
N~ g ~~~
Li
Wl!H No -
I!8 Sampllngh mee
Samplinglim 20:37:33
20:37:33 Iris
hrs
WeliNo
Well No.
NSGC/118
i Sampling
_. __L Samplln dale !13 . 03.13
83.03 .13

88 j Samphllgh me
Samolvig lIme 20 : 38:01
20:38: 01 to,.
iris

Samplingg conditio
Samplin conditions:
ns:
f--- Samplingg conditio
SamplIn conditions:
ns:
- -- - - I Speclhc
Specilic gravlly
gravily
Sep er OC dlu
Se lemper ,luie
lt:?' 140
130.. U
Ii OF 0.6814
0.68 14
(Opefalor
0peaI0i entel
enlei value)
I Sep,
Sep. lempera1U
Speclhc gravlly
Specitic gavIry
re'
temperature 157.6
15 7.6 OF
F 11000,.,o,~ e~I
l0peraior euler ~ I _ _ . __0~~~_
oalvei ____ ____
Sep pressure
prCkriri
1--=--- .. _.oM.7
6b___
1 ._._ PSIG
PSIG IOtillow
Oil)low 525.0
525.0 BOPD
BOPD ~Sep,
Sep. oressure
______ ______ ______
pressure 707.2
______ ______ PSI ~I~O~III~
____ Oil lowI~~___
--

525.0
525. 0 80PD
BOPD
Cooke
Cflorre Slle
s/r 164 Inches
incnes Gas How
Gasllow 13475
I
-

MSCFPD Choke
Cfloke sIze /64 indies
164 Inches Gasllow
Gas 110w 13475
FlowIng
Eov:irig 1erisil5
<lellsl'Y 2. 140
I 40 (BSlCUF
.... _ . LBS/CUFT I HG
H (Drager))
..S(Drager 10 ppm
ppm ~ Flowing
Flowing
___ densllv
density
_ _ _ _ _ _ 226.6
226.6
_ _ _ _ _ _ _LB/BBl
LBIBBL
_ _ _-t-I_w_a,er
Watei How
13475 MSCFPD
MSOF PD

low '" BBUD


BBLJD
Mass
klirSS How
lieu. 7115580
70S 580 ~.~~!DAY. COD
BSIDAY ...J COz(Drag 2.3 volume-%
er):rage2voh tm
Mass lIow
Mass 110w 232440 LBS/DAY
lBS/DAY
PR: I'>
IS:: 10 ,\p r i 1 14
11/ April 14,. 1983
983
PR: 13:31
13:31 April 22, 1983
Molecul
Molecularar
COlnl'onenL l Wrigh Molecular
Molecul ar ::t:o
ri11f W" '1!.htt-S
-% :'101t!-%
lo3e-S Weight
Wc i sht Comeone
Component
nt WeightS
WeiSht-% Mole-%
MoleS Weight
WeiSht
C'\
nnitrogi
i tro gln
n 00d2. 82 0.59 28.02 y. W. ' -
it H 1
y. A
1 M.
nitrogen
nitrogen 0.01 0.04
0.04 28.02
28.02 yy.. = w . -
ia
ccarbon
arbon Jdioxid
i nx i <.l"
c 44.57
. 57 2.09 44.01 1
m"tha n.
rsetllilrir 56.90
66 . 90
1 carbon
carbon dioxide
dioxide 0.27
0.27 0.63 44.01 1 1 H.
1
.r:=-
83.84 16.04 methane
methane
ethane
etharu 2.12 13.37 16.04
11.40
1.40 7.63 30.07 ethane
proprn
prop an. 1.36
1.36 4.56 30.07
6-r.61
. 61 33.01
. 01 44 . 09
44,09 where propane
propan e
ii sn-bulan
SOIiiiLdfli,' 1.99
1.99 4.57 44.09
44.09 where
1. 41
1 .41 11.49
0.49 58 2
58.12 iso-buta
isobutane
norma lI but ne 0.86 1.49
1.49 58.12
58.12
norma a ne
biriarir 22.73
. 73 0.95 58.. 12
58 12 y .
y moleS
mo1e-% normal
normal butane
iso-(wn
isupriltanet a ne I .28
.

1 2.39 44.16
. 16 58.12 yy.. .. mole-%
mole%
1. 28 00.36
. 36 72)5S
72.1 iso-pent
isopentaneane 1
nonna
norluall pent an, w. ..= weight-%
Wi weightS 1.82
I .82 2.55 72.15
prerltarli 1.44
1 0.40
13.40 72.15 normal pentane
normal pentane w.
Wi = weightS
weight-%
hexanc
hexanurss 2.24 7*
2.40
2.40 3.36 72.15 A

2. 24 0.52 86.. 17*


86 Hi molecular
N. molecul ar weight hexanes
hexanes
heptan"
lipt anrslrs-pills
. 8.78 10
10.30
. 30 86,17*
86.17* M. .. molecul
Hi molecular
ar weight
Iris 0.
/1.60 60 0.12
0. 12 100 20*
100.. 20* heptan
heptaneespl
H
N = average
average molecul
molecular
ar weight s-plus
us 78.00 54.97 143.4
143.4 . .
**
N = average
H

average molecul
molecular
ar weight
tota
totall \OO.on
1(13.1)11 100.00
00.00 20.1 1*
20.11** 100 I/ (tw
(Zw./M
. /H ..)) total 100.00
100.00 100.00
100.00 101.07 100 I/ (I
1 1 = 100 w ./H .)
(Sw/N .)
1 1
A SS UlRl~ d
Ansirinil ..= (tYiHi)
(y.-M) I 100
** Assumed 0: Yj .~li)
(Ey.M .) I/ 100
**
** Spr .. if
Sp. iiiil' I:i,ravil.
r a v i lVy 00.6942
.&942 (laar=1
a i r=l!) . . . Heptane
lieptanespl
s-plu&
us Specific
Specific Cravity
Gravity =0.780
" O. 7802 (waterl)
2 (water= l)

Analysis 01
AnaJysll Cl +:
of C7 Analylla
Analysis of
of non-pI8ls
non.pressunz ed oilsample:
urized oIlsamp1e:

Real spesl'lc
Real gravily 60/60F
spesillc gravity 0. 7747
0.7747 BS&W
BS&W' < 0.06
['""-~
Analysed Sy

Average mol
mop WI
..--
143
143.4
.4
Analysed by
Analysed by
wl% .
Wi."' Sail
SaIl <
< 0.00011
0.00011 wl%
WI' ID

'--
- --- I Sullur
Siillirr conlenl
conlent
0)
00.. 03 wt %
A.6-1S
A.6-15

ThBLE 33 - Results
TABLE Results of
of Recombination
Recombination and
and Consistency
Consistency Check
Check for
for Separator-Gas
SeparatorGas and
ano Oil
Oil Samples.

Samples.

Sample Oescription
Sample Description I Field
Field NSGC/ IB, Well
NSGC/18, Well 88 (83.03.13)
(83.03.13)
Separator Pressure
Separator Pressure (psia)
(psia) I 700.6
700.6
Separator Temperature
Separator Temperature (OF)
(F) 151.8
151.8
Separator Gas-Oil
Separator GasOil Ratio
Ratio (scf/STB)
(scf/ST8) : 25670
25670

Comoositions (mole-%)
Compositions (moleX)
Hoffman-Crump-Hocott
HoffmanCrurrpHocott Analysis
Pnalysis
Ccinponent
Component xx yy zz FF K Kp b Tb
(=y/x) (R) (R)

nitrogen
nitrogen 0.04
0.04 0.59
0.59 0.57
0.57 3.544
3.544 14.75
14.75 10330. 470.0 109.0
10330. 470.0 109.0
carbon dioxide
carbon dioxide 0.63
0.63 2.09
2.09 2.04
2.04 2.295
2.295 3.317
3.317 2324. 652.0 194.0
2324. 652.0 194.0
methane
methane 13.37
13.37 83.84
83.84 81.48
81.48 2.701 4394. 94.0
2.701 6.272
6.272 4394. 300.0
300.0 94.0
ethane
ethane 4.56
4.56 7.63
7.63 7.53 1.907 1145.0 303.0
7.53 1.907 1.673
1.673 1172.
1172. 1145.0 303.0
propane
propane 4.57
4.57 3.01
3.01 3.06
3.06 1.384
1.384 0.659
0.659 461.5 1799.0 416.0
461.5 1799.0 416.0
isobutane
iso-butane 1.49
1.49 0.49
0.49 0.52
0.52 0.995 0.329
0.329 230.4 2037.0 471.0
230.4 2037.0 471.0
normal butane
normal butane 4.16
4.16 0.95
0.95 1.06
1.06 0.866
0.866 0.228
0.228 160.0 2153.0 491.0
160.0 2153.0 491.0
isopentane
iso-pentane 2.55
2.55 0.36
0.36 0.43
0.43 0.498
0.498 0.141 98.91 2368.0 542.0
98.91 2368.0 542.0
normal pentane
normal pentane 3.36
3.36 0.40
0.40 0.50
0.50 0.399 0.119 83.41 2480.0 557.0
83.41 2480.0 557.0
hexanes
hexanes 10.30
10.30 0.52 0.85 0.013 0.050 35.37 2780.0 616.0
35.37 2780.0 616.0
heptanesplus
heptanes-plus 54.97
54 . 97
100.00
100.00
0.12
I'1iCi':'OO
100.00
1.96
1.96
IOo":"OO
100.00
0.00218 1.53
1.53 *
*

Sp.
7
C
Cr- Sp. Gravity
Gravity I: 0.7802
0.7802 -
00.7789
. n89
C7+
C']+ Mol.
Mol. Weight
Weight 143.4
143.4 100.2
100.2 142.0
142.0
C7+ Watson Kw
C']+ Watson Kw : 11.95
11.95 11.95
11.95
Tot. Mol. Weight 101.1
Tot. Mol. Weight I 101.1 20.11
20.11 22.84
22.84

Sumary
Summary of
of Results
Results From
From Same
Same Well
Well During
Ouring First
First Flow
Flow Test
Test (81.05.21)
(81.05.21)
Separator
Separator Pressure
Pressure (psia)
(psia) 1099.9
1099.9
Separator
Separator Temperature
Temperature (F)
(OF) 193.7
193.7
Separator GasOil Ratio
Separator Gas-Oil Ratio (scf/STB)
(scf/STB) ...
9929
9929
C
+
7
C']+ Sp.
Sp. Gravity
Gravity : 0.7911
0.7911 - 0.7898
0.7898
7
C
C']+ Mol.
Mol. Weight
Weight 162.7
162.7 100.2
100.2 161.1
161.1
+
7
C Watson
C']+ Watson Kw
Kw : 12.04
12.04 12.04
12.04
Tot.
Tot. Mol.
Mol. Weight
Weight :I 102,6
102.6 19.40
19.40 26.1
26.1

* and Tb
bband Tb are
are not
not readily
readily defined
defined for
for C
+
7C']+ fractio
fractions.
ns. Tb Tb can
can be
be approximated
approximated by by the
the relatio
relation,
n,
Tb (KWy)l, where
Tb == (Ky)
,
3 where yy isis the
the C
C']+ specifi

7 specific gravity of
c gravity of the
the wellstream
wellstream fluid.
fluid. The
The value
value of
of bb
can be backcalcul ated, where
7
F(C
can be baCk-calculated, where F(C7+) is read from
) is read from the
the log
log Kp
Kp vs
vs FF straigh
straight line, extrapolated
extrapolated
t line,
to
to the
the measured
measured Kp
Kp value.
value.
51 4, ianesPlus Gharaci.erzation Based on Molecular Weight
TABLE
T4BLE 4a
4a - continued
continued
IIlt-l I ~" - 1-1ail
f'\Jtanes-Plus Characterization Based on Molecular Weight Calculated
Specific Gravity Measurements: Field NSGC/14, Calculated
Molecular
an" Specific Gravity Measurements: Field NSGC/lA. Measured
Measured Molecular
Weight
Date
Date Molecular specific
Molecular Specific
Calculated
Calculated Well
Well No.
No. Tested
Tested Weight
Weight Gravity
Gravity Kw (K wWeight
=12.02)
Measurso Molecular IS, (K
I
5 2.02)
Measured Molecular
Datc Molecular Specific Weight
Date Molecular Specific Weight
5. Tested Weight Gravity 168.1
11. '1 J ~In, Tested Weight Gravity w
Kw (K=l2.02)
(K w=12.02) NSGC/IA-13
NSGC/l13 81.06.28
81.06.28 170.2
170.2 0.797U
0.797U
12.04
12.04 168.1
168.8
81.08.30
81.08.30 172.7
172.7 0.7976
0.7976 12.06
12.06 168.8
164.0
82.02.04
82.02.04 163.4
163.4 0.7935
0.7935 12.01
12.01
l:/1R-1 81.02.14 154.3 0.7872 11.99 156.9 164.0
1" 1 l~1 / 1/\-10 li1.U2.14 154.3 0.7872 11.99 156.9 82.06.17
62.06.17 164.3
164.3 0.7920
0.7920
12.04 162.3
81.81.24 161.8 0.7907 12.03 160.8 12.04 162.3
G1.07.24 161.8 0.7907 12.03 160.8 82.09.02
82.09.02 161.1
161.1 0.7908
0.7908 2.02 161.0
41.10.01 150.3 0.7810 12.02 150.2 2.02 161.0
hl.IO.01
82.01.09 lSO.3 0.7810 12.02 150.2
150.9 0.7830 12.00 152.3
152.3 0.7881 12.03 157.9
b2.G1.U9
82.02.un
150.9
155.9
0.7830 12.00 NSGC/lA-lO
NSGC/IRlO 81.07.14
81.07.14 159.0
159.0 0.7881 12.03 157.9
1:12.02.U4 155.9 0.7875
0.7875 12.00
12.00 157.2
157.2 152.6 0.7861 11.98 155.7
s2.05.08 148.5
81.08.30
81.08.30 152.6 0.7861 11.98 155.7
62.05.08 148.5 0.7815
U.7815 11.99
11.99 150.7
150.7 150.3 0.7904 11.98 160.5
82.06.19 151.2 0./809
81.11.11
81.11.11 150.3 0.7904 11.98 160.5
82.06.19 151.2 0.7809 12.03
12.03 150.0
150.0 81.12.04 153.7 0.7849 12.01 154.4
82.07.117 155.2 0.7843 12.04 81.12.04 153.7 0.7849 12.01 154.4
1-12.07.07 155.2 0.7843 12.04 153.7
153.7 82.06.16 151.9 0.7821 12.03 151.3
01.119 150.1 0.7798 12.04 82.06.16 151.9 0.7821 12.03 151.3
h <.01.IJ9 ISO. I 0.7798 12.04 148.9
148.9 82.09.03 149.8 0.7813 12.01 lSO.5
82.09.03 149.8 0.7813 12.01 150.5
P.1,1 82.12.03
82.12.03 148.4
148.4 0.7801
0.7801 12.01
12.01
149.2
i1.u2.13 164.9 0.7947 12.01 165.4 149.2
I''-:,Ij- / I II - -~ li1.W.13 164.9 0.7947 12.01 165.4
81.04.03
1:11.04
hi.16.28
81.06.28
8].u8.2b
1:11.08
. 03
. 2&
166.7
166.7
164.1
164.1
165.9
165.9
0.7958
0.7950
0.7928
0.7928
0.7942
0.7942
12.03
12.03
12.03
12.03
12.03
12.03
165.8
165.8
163.2
163.2
164.8
164.8
NSGC/IA-15
NSGC/IR15 81.06.30
81.06.30
82.03.04
82.03.04
82.05.10
163.0
163.0
155.0
155.0
150.9
0.7896
0.7896
0.7846
0.7846
0.7822
12.06
12.06
12.03
12.03
12.01
15~.6
159.6
154.0
154.0
151.4
.
O'l
P1.1Ii.L16 163.8 0.7936 82.05.10 150.9 [1.7822 12.01 151.4 CI
BI.1O.U6 163.tl 0.7936 12,02
12.02 164.2
164.2 82.06.17 154.2 0.7835 12.03 152.6
81.12.0/i 162.4 0./917 82.06.17 154.2 0.7835 12.03 152.8
til. 17.04 162.4 0.7917 12.02
12.02 162.0
162.0 82.09.02 153.6 0.7823 12.04 151.5 O'l
47.01.09 161.5 0.7935 82.09.02 153.6 0.7823 12.04 151.5 0,
1,2. 01 .09 161.5 0.7935 11.99
11.99 164.0
164.0
12.84.01 10.0 0.7905 12.01 160.6
to . 04.01
10 .u 160 .0 0.7905 12.01 160.6 NSGC/lA-l
NSGC/l4l 81.08.31
81.08.31 172.5
172.5 0.7999
0.7999 12.03
12.03
171.6
.15 /i .2 171.6
IIL.U6.15 161.2 00.. 7902
7902 12.03
12.03 160.3
160.3 81.11.10
81.11.10 167.8
167.8 0.7948
0.7948 12.04
12.04
165.5
165.5
I1\i 82.02.01
82.02.01 164.2
164.2 0.7939
0.7939 12.02
12.02
164.5
8i h1.5.I6 150.6 0.7909 12.00 161.1 164.5
tt ,I.1 ' I ;\- 1" tl l. 07.16 159.6 0.7909 12.00 161.1 82.05.02
82.05.02 158.8
158.8 0.7919
0.7919 11.98
11.98
162.2
11.ij4lJQ 160.9 0. 7907 12.02 160.8 162.2
170.7
Ii 1. 04. fJ9
81.07.22 160 .9 0.7907 12.02 160.8 83.02.21
83.02.21 171.6
171.6 0.7992
0.7992 12.03
12.03 170.7
162.9 0.7913 12.04 161.5
161.5
.':n .U7.22
81.1J1L31 162.9 0.7913 12.04
155,5 0.7879 11.99 157.7
157.7 165.3 0.7918 12.06 162.1
AI .U8. 31
81.119.511 155.5
159.9
0.7879 11.99 NSGC/lA-4
NSGC/IA 4 81.08.29
81.08.29 165.3 0.7918 12.06 162.1
BI.05.30 159.9 0.788
0.7876 12.05
12.05 157.6
157.6 81.11.06 164.4 0.7929 12.03 163.4
-0.17.00 154.4 0.1858 81.11.06 164.4 0.7929 12.03 163.4
HI.I / .US 1?4 .4 0.7858 12.01
12.01 155.4
155.4 82.05.04 158.3 0.7873 12.03 157.0
-.ii.11 lSe.8 0.7045 82.05.04 158.3 0.7873 12.03 157.0
bL .Ul.1U 1'>4.8 0. 7848 12.03
12.03 154.3
154.3 82.11.02 157.6 0.7869 12.03 156.6
15.J4.L18 I52. 0.7826 12.01 82.11.02 157.6 0.7869 12.03 156.6
iJ7.04.U8 152.4 0 . 7826 12.01 151.9
151.9
82.111.117 150.1 0.7813 12.02 150.5
150.5
07. 117.07
82.10.111.
150.1
ISU.6
0.7813 12.02
0. 7813 12.02
12.02 150.5
150.5
fi 2 .IO. rJ/ '
83.81.07 150.6
1119.0
0.7813
H3 .01.07 149. 0 0.7792
0.7792 12.03
12.03 148.2
148.2
141 l1I.814.O J6 .3 0./958
". 11\ - II 1I1.G4.09
-0.1.b.(Jl
ti2 . !.I'J.OJ
165.3
170.9
170 .9
U.7958
0. 7986
0.7986
12.00
12.00
12.03
12.03
166.7
166.7
170.0
170.0
0.sj.Us tO.5 0.7936 12.02 164.2
112 .(J&.Ob
82.i.U4
164
j3.13
.5 0.7936 12.02 164.2
1-II' .f12II. U4 163.0 0.7935
0.7935 12.01
12.01 166.0
164.0
1'3.r12.2121 169.9
10 0.7990
169.9 0.7990 12.01
12.01 170.5
170.5
T8r3LE 4b
T/ltlLt: 41 - Heptane s-Plus Charact
Heptanesplus erizatio n Based on Molecul
Characterization TABLE 4b - continu
continued
ed
-

ar Weight
Molecular

and Specifi
Specificc Gravity Measure mentsl Field NSGC/IB
Measurements: NSGC/1B,.
Calcula ted
Calculated
Measured
Measured Molecul
Molecularar
Calcula ted
Calculated Date Molecul ar
Molecular specifi
Specificc weight
Weight
Measure d
Measured Molecul
Molecular well
Well No. Tested Weight Gravity Kw
K (K w=12.02)
(K12.D2)
ar
Date Molecul
MaIijaj ar Specifi
Specificc weight
Weight
11
\\f' ] 1 No. Tested Weight Gravity
Gravit Kw
K (K w=12.02)
(Kw=12.02J
NSGC/1B-18
NSGC/IB-l8 81.04.01 174.2 0.7995 12.05 171.1
81.06.1
81.06.100 170.0
170.0 0.7976 1:1.03
12.03 168.8
168.8
t.', Crllt'-1 6
tLC/IHLb 81.03.11 172.3 0.7989 82.01.2
82.01.233 155.9 0.7873 12.01
12.01 157.0
12.04 170.4
1:11.05.1
81.05.122 166.8 0.7967 12.01 167.8 82.05.1 9
82.05.19 154.0
154.0 0. 7851
0.7851 12.01 154.6
82.02.14 151.0
151,0 0.7834 12.00 152.7 82.08.0
82.08.099 151.3 0.7821 12.02 151.3
151.3
82.07.1
82.07.13 3 149.2 0.7793 12.03 148.3 82.10.0
82.10.077 149.0 0.7804 12.01 149.5
62.09.14
82.09.14 148.9
148.9 0.7793 12.03
12.03 148.3
148.3 83.01.0 6
83.01.06 148.5
148.5 0.7785 12.03
12.03 147.5
147.5
82.11.0
82.11.04 4 146.4 0.7774 12.02 146.4
83.02.0
83.02.04 4 143.7 0.7765 12.00 145.4 NSGC/1B-8
NSGC/IB-8 81.06.14 162.4 0.7904 12.04
12.04 160.
160.5:-
81.10.0
81.10.088 158.3
158.3 0.7877 12.03
12.03 157.5
157.5
NSGC/18-?0
NSGC/j0-20 81.03.11
81.03,11 174.9 0.8001 12.05 82.01.2
82.01.233 1SO.8
150.8 0.7633
0.7833 12.00
12.00 152.6
171.8
81.05.11 172.2
172.2 0.7991 12.04 170.6 82.02.1
82.02.144 147.8 0.7804 12.00 149.5
149.5
61.10.0
81.10.077 166.7 0.7953 12.03 166.1 82.04.11 149.4
149.4 0.7804 12.02 149.5
149.5
82.02.0
82.02.04
82.05.21
82.07.1
82.07.16
4
6
161.2
159.5
159.7
0.7925
0.7903
0.7904
12.00
12.01
162.9
160.4
82.06.1
82.06.19
82.09.14
82.11.0
82.11.04
9
4
146.9
146.9
145.1
145.1
145.0
0.7780
0.7765
0.7755
12.02
12.02
12.03
12.03
147.0
145.4
144.4
.
l=-
C"I
82.12.0
82.12,099 155.6 0.7875
12.01
12.00
160.5
157.2
NSGC/1B
cc/l85 -5 81.08.3
81.08.300 164.0 0.7936 12.02 164.2
....
I
'-I
N~Gr ' /If:j-9
NSQ(/159
61.03.11
81.03.11 177.7 81.11.2
81.11.288 152.2
152.2 0.7836 12.01 153.2
0.8031 12.04 175.4
81.05.1
81.05.100 168.4 0.7955 12.04 166.4
166.4 82.04.0
82.04.099 150.4 0.7817 12.01
12.01 150.9
15C.9
62.04.1
82.04.100 151.5 0.7827 12.01 152.0 82.05.2
82.05.211 158.0
158.0 0.7898 12.00
12.00 159.8
159.8
82.05.1
82.05.166 151.5
151.5 0.7824 12.02 151.6 82.06.1
82.06.188 154.7
154.7 0.7864 12.0U
12.Ou 156.0
156.0
62.06.1
82.06.177 . 152.9 0.7826 12.03 151.9 82.08.0
82.08.077 154.0
154.0 0.7858 12.00 155.4
83.02.1
83.02,133 153.0 0.7855 12.00 155.0 82.10.0
82.10.055 156.0
156.0 0.7881 12.00
12.00 157.9
83.01.01 155.5 0.7878 12.00 157.6
157.6
NSIX/16
(,[/15o
-6 81.03.31 181.4 0.8040 12.07 176.5
IH.IO.0
81.10,088 166.6 0.7960 12.02 166.9
166.9
IH.11.2
51.11.299 163.2
163.2 0.7930 12.02 163.5
163.5
82.05.1
82.05,166 157.0 0.7873 12.02 157.0
82.07.1
82.07.133 154.7 0.7845 12.03
12.03 153.9
82.09.1
82.09,133 153.5 0.7839 12.02 153.3
82.11.0
82.11.033 150.1 0.7835 11.99 152.8
83.02.0
83.02.033 148.2
148.2 0.7813 11.99
11.99 150.5
NSGf/Hl -3
NSL1I/1H-3 81.04.01 181.6 0.8058 12.05 178.7
81.06.14
81.06,14 174.0
174.6 0.8000 12.04 171.7
82.01.2
82.01.233 164.3 0.7963 11.99 167.3
82.05.1
82.05.155 159.8
159.8 0.7898 12.02 159.8
159.8
82.08.1
62.08.122 165.3 0.7935 12.03 164.0
82.10.1
82.10.100 160.5 0.7900 12.03 160.0
160.0
82.12.0
82.12.099 158.3
158.3 0.7896 12.01 159.6
83.01.0
83.01,099 169.3 0.7975 12.03 168.7
.....a. ..a--

]1\t3L8 4('
lAtlLt 14c - Heptane
HertanesPl us Charact
s-Plus Characterizati TABLE
T4BLE 4d
-
erizatio
on Based on
n Based on Molecul
Molecular Weight
ar Weight 4d - Heptane
s-Plus
HeptanesPl us Charact erizatio
Characterizati n Based
on Based on
on Molecul ar Weight
Molecular
and Specifi
and Specific Gravity Measure Weight
c Gravity Measurement
ments: Field NSGC/2.
s: Field NSGc/2. and
and Specifi
Specificc Gravity
Gravity Measure ments:
Measurement s: Field NSBO/3B
NSBO/38..

Calcula ted
Calculated
Calculated
Calcula ted Measure
Measuredd Molecul ar
Molecular
Measured
Measure d Molecular
Molecul ar Oate
Date Molecul ar Specifi
Molecular Specificc
Date Weight
Weight
Date Molecular
Molecul Specific
ar Specifi c Weight
Weight Well
Well No. Tested Weight
Weight Gravity
Gravity
Wi]
Wr ll NJu. Tested Kw
K (K w=11.90)
(<w11 .90)
o. Tested Weight
Weight Gravity
Gravity K (K
Kw w=11.99
(Kw=l l.99))
NSBO/3B
rB0/3Bl
-l 81.10.2
81.10.255 217.7 0.8446 11.9lJ
11.90 217.4
NSOC/2-5)
N:,GCn- 81.04.
81 22
: 04.22 143.6
143.6 0.7774 11.99
11.99 143.9
143.9 81.12.1
81.12.177 229.8 0.8535
0.8535 11.89 230.5
81.09.24
81.09.2 4 142.2
142.2 0.7763
0.7763 11.98 82.04.1
82.04.199 228.9 0.8532
11.98 142.8
142.8 11.89
11.89 230.0
62.06..22
82.06 22 139.o
139.4 0.7720 12.00
12.00 138.5
138.5
83.02. 18
83.02.1 8 134.1
134 .1 0.7683 NSBO/3B
NSBO/38l
-144 81.02.1
81.02.133 245.5 0.8621
11.98 134.8 11.90
11.90 243.7
81.09.1
81.09.133 247.8 0.8646 11.90 247.7
NSGC
NSGC /2-9
I7 -~ ul.03.14
81.03.14 150.6
150.6 0.7840 11.99
11.99 150.9 81.10.0
81.10.088 245.7 - 0.8637 11.90 246.2
82.01.09
82.01.0 9 139.1 0.7719 82.03.2
82.03.244 245.9 0.8636
12.00 138.6
138.4 11.90 246.1
62.02..10
82.02 10 137.0 0.7730 11.96 82.10.0
82.10.044 244.3 0.8637
139.5 11.89 246.2
82.07.18
82.07.1 8 138.7
138.7 0.7718
0.7718 12.00 82.12.0
82.12.022 246.7 0.8634
12.00 138.3 11.91 245.8
245,8
82.12.23
82.12.2 3 134.1
134.1 0.7678 11.99 134,3
134.3
NSBO/3B
NSBO/38-19
-19 81.02.1
81.02.13 3 251.0 0.8669 11.90
NSGCn - 8 81.113,13
tl1.03.1
81.09.24
fl1.09.2
82.12. 23
62.12.2 3
3
4
148.3
141,6
141.6
134.4
0.7817
0.7760
0.7760
0.7685
11.99
11.98
11.98
148.4
142.5
82.02.0
82.02.09
82.06.1
82.06.
9
166
251.6
255.7
0.8672
0.6670
0.8670
11.90
11.93
251.4
251.9
251.5
251.5
.en
:l=>

134.4 0.7665 11.98


11.96 135.0 83.02.0
83.02.08 8 250.9 00.8658
. 8656 11.91 249.6 I
.-.
N~\;(, / 2-1 81.03.133
81.03.1 151.6 NSBO/3B-11
NSBO/3B ex>
151.6 0.7848 11.99 151.77
151. ll 61.06.1
81.06.144 228.0 0.8530 11.89
11.89 229.7
229.7
81.09.26
61.09.2 6 142.7
142.7 0.7756 12.00 81.12.0
81.12.088 222.2
222.2
12.00 142.1
142.1 0.8502
0.8502 11.87 225.6
42.03.21
82.03.21 138.6
138.6 0.7721 11.99 135.0 82.04.1
82.04.199 223.7 00.8506
. 6506
135.0 11.88
11,88 226.1
226.1
NS[;(/7 - 4 81.04.2
61.04 1
. 21 144.9
144 .9 0.7783
0.7783 11.99
11.99 144.9 NSBO/3B-lO
NSBO/3B 10 81.06.088 257.9
257.9 0.6711
144.9 0.8711 11.90
11.90 258.2
258.2
82.01.10
82.01.1 0 140.4
140.4 0.7740 11.99 82.08.077
11.99 140.5
140.5 256.6 0.8704
0.8704 11.90
11.90 257.1
257.1
62.02.122
62.02.1 139,1
139 .4 0.7740 11.98 83.02.055 252.8
11.98 140.5
140.5 252.8 0.8702
0.8702 11.87
11.87 256.8
256.8
82.05.1
62.05.1 66 139.6
139.6 0.7733
0.7733 11.99
11.99 139.8
139.8
82.07.1
82.07 6
. 18 138.7
136 .7 0.7718
0.7718 11.99 NSBO/3B-18
NS80/381 8 81.06.1
81.06.111
2.12.23 11.99 138.3
138.3 242.7 0.8607
0.8607 11.91
11.91 241.5
82.12.2 3 134.1
134 .1 0.7o?8
0.7676 11.99
11.99 134.3 82.03.166
82.03.1 241.3
241.3 0.8605
134.3 0.8605 11.90
11.90 241.2
241.2
82.06.122
82.06.1 240.5 0.8610
0.8610 11.&9
11.89 242.0
242.0
NSGC/L-3 81.04.2
81.04 .222 145.1
145.1 0.7771
0.7771 12.01 83.03.099
83.03.0 244.0
12.01 143.6
143.6 0.8618
0.8618 11.91
11.91 243.2
82,01,0
62.01.088 137,u
137.4 0.7722
0.7722 11.97
11.97 138.7
138.7
82,112 .11
62.02.11 137.3
137.3 0,7714
0.7714 11.98 NSBO/3B-6
NSBO/3B-.6 81.10.088
81.10.0 223.9
11.98 137.9
137.9 223.9 0.8490
0.8490 11.90
11.90 223.8
223.8
83.U2.
83.U2.1 177 133.5
133 . 5 0,7670
0 . 7670 11.99 82.02.122
82.02.1 219.6
11.99 133.5
133.5 219.6 0.8482
0.8482 11.88
11.88 222 . 6
222.6
82.06.144
82.06.1 223.7
223.7 0.8486
0.8486 11.90
11.90 223.2
223.2
82.08.088
82.08.0 219.6
219.6 0.8468
0.8468 11.89
11.89 220.6
220.6
82.10.044
82.10.0 219.7
219.7 0.8474
0.8474 11.89
11.89 221.4
221.4
82.10.044
82.10.0 219.0
219.0 0.8470
0.8470 11.88
11.88 220.9
220.9
NSBO/3B-9
NSBO/3B 9 82.03.188
82.03.1 241.6
241.6 0.8596
0.8596 11.91
11.91 239.6
239.8
82.08.088
82.08.0 242.2
242.2 0.8610
0.8610 11.90
11.90 242.0
242.0
NSBO/3B-7
NSBO/3B 7 82.04.222
82.04.2 244.1
244.1 0.8628
0.8628 11.69
11.89 244.8
2414.8
82.10.244
82.10.2 245.8
245.8 0.8654
0.8654 11.89
11.89 249.0
249.0
82.12.077
82.12.0 242.6
242.6 0.8613
0.8613 11.90
11.90 242.5
22.5
TUBLE 6 - Minimization
Procedure for Matching CVD Data with the
T~8LE 6 - Minimization
PengRobinsonProcedure for Matching CVO Data with the
Equation of State.
Peng-Robinson Equation of State. TABLE
TABLE 77 - Final
Final -best-fit"
bestfit Properties
Properties used
used in
in the
the Peng-RObinson
PengRobinSon EOS
E05 to Predict
to Predict
Constant-Volume
ConstantVolume Depletion
Depletion Data
Data from
from Field
Field NSGC/IB.
NSGC/18.

Rdjusted
Pun Adjusted
Parameter Initial
Run Parameter Initial Final
final Data
Data Error
Error w y
zz MM Tc
No.
No.
(Cj+ Fraction)
(C7+ Fraction) Value
Value Value
Value Matched Reduction
Matched Reduction
Component
Component (%)
(%) (g/mol)
(g/mol)
Tc
(OR)
R)
0
( (p~~a)
Pc
(psia)
(water=!)
(water=l)

5 (C
F3)
1 0.2 0.3368 undefined
6 (CI-F3J 0.2 0.3366 Pd
Pd undefined 11 - carbon
carbon dioxide
dioxide 2.37
2.37 44.010
44.010 547.57
547.57 1071.0
1071.0
0.2250
0.2250
2 (Fl) 976.1 22 - nitrogen
nitrogen 0.31
0.31 28.013
28.013 227.27
227.27 493.0
493.0
0.0400
0.0400
2 T (F
c
Tc 976.1 1018.0
1016.0 evo
CVD undefined
undefined

667.8 0.0104
1)
Ur2) 1168.0 1261.0 33 - methane
methane 73.19
73.19 16.043
16.043 343.04
343.04 667.8 0.0104
c lF2)
T
Tc 1166.0 1261.0

707.8 0.0986
(P3) 1408.0 1395.0 44 - ethane
ethane 7.60
7.80 30.070
30.070 549.76
5119.76 707.8 0.0986
r1
c

c (F3) 1406.0 1395.0 55 - propane


propane 3.55
3.55 44.097
44.097 665.68
665.68 616.3
6i6.3
0.1524
0.1524
3 6 (C
-F3)
1 66 - iso-butane
isobutane 0.71
0.71 58.124
58.124 734.65
734.65 529.1
529.1
0.1848
0.1848
0.3368 0.3380 0.6

0.2010
3 6 (CI-F3) 0.3366 0.3360 Pd
Pd 0.6 77 - normal
normal butane
butane 1.45
1.45 58.124
58.124 765.32
765.32 550.7
550.7 0.2D10
B
8 - iso-pentane 0.64 72.i51 828.77 490.4 0.2223
P () 419.8 429.0 CVD 0.6 isopentane 0.64 72.151 828.77 490.4 0.2223
4 Pc (F 1) 419.6 429.0 CVO 0.6 99 - normal
normal pentane 0.68 72.151 845.37 488.6 0.2539
Pc (F2) 268.9
266.9 260.2
260.2
pentane 0.68 72.151 845.37 488.6
483.0
0.2539
0.2500 0.690
Pc (F2)
Pc (F3) 148.5 10
10 - hexanes
hexanes 1.09
1.09 84.000
84.000 931.97
931.97 483.0 0.2500 0.690
151.7
151.7

429.ob 0.4887b 0.758


Pc (F3) 146.5 11
11 - fraction
fraction 11 4.04
4.04 125.3
125.3 101o.37b
1010.37b 429.Ob 0.4887b 0.758
5 5 1
(C
- F3) 12
12 - fraction
fraction 22 3.44
3.44 213.2
213.2 1261.27b
1261.27b 302.3b
302.3b
O.6804b
0.6804b
0.825
0.3380 0.3385 0.4
0.825
0.907
5 6 (CI-F3) 0.3360 0.3365 Pd
Pd -0.4 13 - fraction
fraction 33 0.73
0.73 370.1
370.1 1319.87b
1319.87b
151.7b
151.7b
0.8040b
0.8040b 0.907
6 w (Fl) 0.5844
6 a (Fl)
w (F2) 0.5644 0.6040
0.6040 CVD
CVO 0.1
0.1
0.6801 0.6800
w (F2)
j (P3)
0.6601
0.8042
0. 6600 C'\
0.8030
w (F3) 0.6042 0.6030 Binary
Binary Interaction Coefficientsaa
Interaction Coefficients I

7 6 1
(c
F3) 0.3385 0.3388 U)
7 6 (CI-D) 0.3365 0.3366 Pd 0,3
-0.3
Pd LO

8 (P3)
Tc (F3) 1395.0 1320.0 CVD 11 22 33 44 55 66 77 B
8 99 10
10 11
11 12
12
13
13
6 Tc
Pc (F?)
1395.0
260.2
1320.0
303.1
evo
and
1.8
1.6
Pc
w (F2)
(Fl) 260.2
0.6040
303.1 and 11 -.200 .100
.200 .100 .130
.130 .135
.135 .130
.130 .130
.130 .125
.125 .125
.125 .125
.125 .110
.110 .110
.110 .110
.110
0.4887
0.4667 Pd
w -(Fl)
6 (0
1F3) 0.6040
0.3388 0.3840 Pd
6 (CI-F3) 0.3366 0.3640 22 .036 .050
.036 .050 .080
.080 .095
.095 .090
.090 .095
.095 .100
.100 .100
.100 .100
.100 .100
.100 .100
.100
Tc (Fl) 1018.0 1010.0 CVD 0.2 b
9 Tc (F!) 1016.0 1010.0 CVO 0.2 33 .039 .049 3
.384
.039 .049
b 84
c (F2)
0 303.1
303.1 302.3
302.3 and
and
wPc (P3)
(F2) 0.8027 0.8040 Pd
-(F3)
6w (C
1F3) 0.6027
0.3840 0.6040
0.3860 Pd
6 (CI-F3) 0.3640 0.3640 a. Equal
a. Equal to
to zero
zero except
except where
where specifi
specified otherwise.
ed otherwise.
b. Adjusted
b. Adjusted during
during regress
regression.
ion.
Notes:
Notes I
6 (0
-F3)
1 binary interaction parameter between methane and
6 (CI-F3) = the
binary interaction
heavie parameter between methane and
st C
fraction, P3,
7
the heaviest C7+ fraction, F3.
Pd = dew-point pressure
Po = oew-point pressure
Undefined error reductions result from convergence problems with
Undefined error reductions result from convergence problems with
Runl.
Run 1.
Critical temperature, Tc, and critical pressure,
Critical
R temperature,
and psia, Tc , ;and
resepectively critical pressure, Pc, have units
Pc' have units
acentric factor, a, is dimensionless.
DR and psia, resepectively; acentric factor, w, is dimensionless.
The error function after Run 2 was 4.8 %. The final error
The errorafter
function function
Run 9after Run 2 was 4.6 %. The final error
was 2.2 %. The error function is the average
offunction after
the absolu te Run
deviation 2.2
9 was %. The error function is the average
in saturation pressure and the root mean
of the ofabsolute
square errors deviation in saturation pressure and the root mean
for CVD data.
square of f'rrors for CVO data.
A.6-20
A.620

Table 5
Table CarbonNumber Distillation (ASTM
(PSIM D0 2892-78)
289278) Kesults
5 - Carbon-Number

Distillation Results for


for aa Mixture
Mixture of
of Numerous
Numerous
HeptanesPlus
Heptanes-Plus Fractions Sampled
Fractions Sampled from
from North
North Sea
Sea Gas-Condensate
GasCondensate and
and Black-Dil
BlackOil Reservoirs.
Reservoirs.

Initial Weighed
Initial Weighed Amount
Rmount of
of C7+
+ Material
7
C Material 2073.1 gci
2D73.1
Reflux Ratio
Reflux Ratio . 55 to
to 11.
Reflux Cycle
Reflux Cycle : 18
18 seconds
seconos
Distillation at
Distillation at Atmospheric
Rtmospheric (Normal)
(Normal) Pressure
Pressure 94
94 to
to 175
175 0C
C
Distillation at
Distillation at 100
100 mmm Hg
Hg . 175 to 244
244 0C
C
0
Distillation at
Distillation at 10
io mm Hg
iii Hg 244 to 345 0c
C

Normal
Normal Normal
Normal
BoilingPoint Boiling
Boiling-Point Boiling Molecular Cunulative
Cumulative
Carbon
Carbon Range
Ran e Point
Point Weight
Weight Density weight
Weight Volume
ldoluITin Moles Volume weIght Moles
WeIght
No.
No. (C)
(OC 1 (C)
(OC) (g)
(g) (g/cc) (g/mol)
(g/rnol) (cc) (mol)
(mel) (X)
(%) (X)
(%)
Moles
(X)
(%)

77 69 -
69 98a
98a 90
90 90.2b
90.2b 0.7276
0.7276 96 124.1 0.940 4.83 4.35
4.35 8.05
8.05
88 98 -
98 126
126 113
113 214.6
214.6 0.7452
0.7452 11D
110 288.0
288.0 1.951
1.951 16.03
16.03 14.70
14.70 16.70
16.70
99 126-
126 151
151 139
139 225.3
225.3 0.7651 122
122 294.5 1.847
1.847 27.49
27.49 25.57
25.57 15.81
15.81
10
10 151 -
151 175
175 163
163 199.3
199.3 0.7704
0.7704 137
137 258.7 1.455
1.455 37.56
37.56 35.18 12.46
35.18 12.46
11
11 175 -
175 194
194 184
184 128.8
128.8 0.7823
0.7823 151
151 164.6
164.6 0.853 43.96
43.96 41.40 7.30

41.40 7.30
12
12 194
194 - 216
216 205
205 136.8
136.8 0.7902
0.7902 161
161 173.1
173.1 0.850
0.850 50.70
50.70 48.00 7.28
...
48.00 7.28
13
13 216
216 - 235
235 226
226 123.8
123.8 0.8040
0.8040 181
181 154.0
154.0 0.684
0.684 56.69
56.69 53.97 5.86
-
53.97 5.86
14
14 235
235 - 256
256 246
246 120.5
120.5 0.8214
0.8214 193
193 146.7
146.7 0.624
0.624 62.40
62.40 59.78 5.34

59.78 5.34
15
15 256
256 - 273
273 265
265 101.6
101.6 0.8229
0.8229 212
212 123.5
123,5 0.479
0.479 67.20
67.20 64.68 4.10

64.68 4.10
16
16 273
273 - 288
288 281
281 74.1
74.1 0.8271
0.8271 230
230 89.6
89.6 0.322
0.322 70.69
70.69 68.26 2.76

6&26 2.76
17
17 288
288 - 304
304 296
296 76.8
76.8 0.8283
0.8283 245
245 92.7
92,7 0.313
0.313 74.29
74.29 71.96 2.68

71.96 2.68
18
18 304
304 - 318
318 311
311 58.2
58.2 0.8370
0.8370 259
259 69.5
69.5 0.225
0.225 77.00
77.00 74.77
74.77 1.93

1.93
19
19 318
318 - 332
332 325
325 50.2
50.2 0.8458
0.8458 266
266 59.4
59.4 0.189
0.189 79.31
79.31 77.19
77.19 1.62

1.62
20
20 332
332 - 345
345 339
339 45.3
45.3 0.8528
0.8528 280
280 53.1
53.1 0.162
0.162 81.37
81.37 79.37
79.37 1.39

1.39
21
21+ 345
345 - 427.6
427.6 0.8933c
0.8933c 545c
545c 478.7
478.7 0.785
0.785 100.00
100.lIi 100.00
100.00 6.72
..
6.72

Total/Reerage
Total/Average 2073.1
2073.1 0.8066
0.8066 177
177 2570.2
2570,2 11.679
11.679 100.00
iOO.0O

a. Most
a. Most likely
likely some
some of
of the
the C
7
C7 cut
cut was
was lost
lost during
during distillation
distillation ofof CC5 to
5 to 06
C6 fractions
fractions
and
and the
the period
period of
of storage
storage during
during which
which samples
samples were
were analyzed
analyzed (ca.
(ca. 22 years).
years).
b.
b. Distillation
Distillation loss
1055 was
was 5.0
5.0 grams (0.3 %);
grams (0.3 %); this
this weight
weight was
was added
added toto the
the C
C7 cut.
7 cut.
c. Not
c. Not measured,
measured, but
but backcalcul .ateO from
back-calculated from measureo
measured CC7+ properties.
7 properties .
A.6-21
A.621

0
C I

i
w
a:
~
(I) iO/7O60 /50

/ )
/ /
(I)
w
a:
Q.

/
//////
TEMPE
TEM PERRATUR
ATUREE ~
RESERV
RES OIR
ERVOIR
"1"EM:.eR
TE?E TlfE
RATAURE

Fig
Fig.. 1 1 - Hyp
Hypo oth etical
-
thetic al pre ssuure-te
press re-temmpera ture
peratu phase
re pha diagra
se diag m sho
ram showin
wingg the
the
isot her mal
isothermal ret rograd
retrog rade
e reg
region
ion for
for aa as
gas con
conde
dennsate.
sate.
A.6-22
A.622

REFINING
REFINING
TRANSPORTATION
TRANSPORTATION

WELLSITE
WELLSITE SlFIFACE
SURFACE
---------------, -I
I
SEPARATION? I
SEPARATION!
PROCESSING
PROCESSING
SAMPUNG
~. P\.M'
PUMP CESIGN
DESIGl
I
I
GAS IN.ECTION
GAS IN.EC11ON t
(RECYClING)
(RECYCUN

- CHEMCAL ANALYSIS
CHEMCAL ANALYSiS
,.
"

ANALYSIS
- PVT ANALYSIS
-

M.I.:n-PHASE
VERTiCAL
VERTICAL FLOW
FLOW
- PHAS
- PHASEE BEHA
BEHAVIOR
VIOR
MODE UNG (EOS)
MODEUNG (EOS)

APPU CA11ON
APPLICATION

PISCIBLEJ
MSCIBLEI I?wtdNSCIB
MASCIBLE LE
DISPLAE?g
OISPLAceJENT
ENT

SAMPIJNG
i//
L
j

- 11JRA11ON .-- -

NEAR-WELLBORE
BLOCKA

Fig.
Fig. 22 - Schem
- atic illustra
Schematic illustrating processes
ting proces which are
ses which are highly
highly
depend ent on
dependent on proper
proper fluid
fluid charac
characterization of gas
terization of gas
conden sate fluids.
condensate fluids.
A.6 - 23
A.6-23

I
I
,--.
I
,.. .. BUTANES && LIGHTER
BUTANES LlGHlER
3-

-TCD
TCD

SEPARATOR
SEPARATO R
GAS SAMPLE[
GAS SAMPLE
RUN 11
RUN
J cc
GC
--.
RECOvEINE
RECotveINED
SEPARATO
D
SEPARATOA-GAS
RGAS
COMPOSfl1
COMPOSITION
ON

lam
RUN 22
RUN BACKFLUS
BACKFLUSHH

FID ,
\ ,,
--.' .... PENTAtES
PENTAN2S && HEAVIER
HEAVIER

BUTANES & UGHTER


,.-. BUTANES
I ,
I

-TCC

GC RECOMBIN
RECotJSJNED
ED
SEPARATO
SEPARATOR-Oll
R-OIL
BACKFLUSH
BACKFlUSH COFOSITION
C()M:)OSITION
SEPARATOR
SEPARATOR
Oil SAMPlE
OIL SAMPLE

"" ,,
,/, --. PENTANES & tA
'--.. HEAVIER
VIER
" MOLECULAR
MOLECULAR WEIGHT

~-+-. SPECIFiC
SPECIFIC GRAVWy
GRAVITY

SULFUR CONlENT
CONTENT
HEPTANES-PLUS
HEPTANEs-PlUS
ANAlYSIS
ANALYSIS

Fig. 33 - Schematic of separator-gas and separator-oil analyses using


-

programmed gas chromatography,


chromatography, low-temperature
low-temperature distillation,
and heptanes-plus
heptanes-plus characterization.
characterization.
SEPARATOR-GAS ANAL
SEPARATOR-GAS YSIS
ANALYSIS SEPA RATOR-oIL ANAL
SEPARATOROIL YSIS
ANALYSIS
(DISTILLA nON BATCHE
(DISTILLATION S 11 &
BATCHES & 2)
2)

~iC' C33
C ,

iC~
C
nC nC.,
nC,
l

~
iCs
nc
nC

THERMAL CONDUCllVITY DETECTOR (TCD)


DETECTOR
Tt-ERMA
THERMALL CONDUCllVITY DETECT
CONDUC1]vrry OR (TCD)
DETECTOR
C.. +
C,+
C+
CO 2
~=========-----Cz
~===--C2
CO z
2
C

C
CI1
Nz
C
--- --- --- --- --- --- --- --- --- --- --- --- -- Cl1
::t:>
en
--- --- --- --- --- --- --- --- --- --- --- - I
rz
~

]~l!~~~~~~~~~~~~~~~~~~~~~~~~~iC5
~
nC s

s
6
C
C6 's (includi
(including
ng 2,2-dim
2
?, ethylpentane)
-dimethylpentane) ~C~2~~~~C~J~~~i~C~~~~~~~~~::::::::::::~~:::::
4
IC

iC
5
nC.
4
nC
iCs
nC
5s
nC
6a 6b
6d
FLAME IONIZA
FLAME IONIZATION
110N DETECTOR (FlO)
DETECTOR (FID) ~-"... 7a 6
6e
7b 6e 6a 2 -2,2-dim
, ethylbutane
dimethylbutane
7b
C,+
C, + (includnc
( including benzene and cyclohex 7cC6f 6b 2-methy lpentane
-rnetnylpentane
2
ane)
cyclohexane) 6f 6c 3 -3-methy lpentane
methylpentane

I 6g
fig
nCC 7 6d n-hexan
n-hexane
6e : methyl-
e
cyclopentane
methyl-cyclopentane
6f cyclohexane
cyclohexane
6g : benzene
c7 + 7a 2,2-dim
,
2 ethylpentane
dimethylpentane
7b : 2-methy lhexane
?methylhexane
7c
lc -3-methy
3 lhexane
methylhexane
FLAtvE IONIZAl10N DETECT
FLAME IONIZATION OR (FID)
DETECTOR (FlO)

C7 +
fHg.
i g. 44 - Two
-
Two gas
gas chromatograph
chromatograph runs (lCD
(TCD and
and FID)
FlO) used to analyze
~ cparator gas
separator qas from Well
Well 8, Field NSGC/lB,
8, Field NSGC/1B , tested
tested 8303. Fig. 55 - Two
Fig. Two gas
aas chromat ograph runs (TCO
cbomatoqraoh (TCD and PlO)
FlO) used
~sed tc
83 .03.13.
to enalyze
analyze
distilla tion batches 1 and 22 (resoectivelyl
distillation (respec tively) from separat or
separator
oil from Well
Well 8,
S, Field
Field NS(C/l5
NSr,r./lR. tected
tp~tprl R1
R1 01
fl 11
11
NORTH
NORTHSEA
SEA GAS
GASCONDENSATE I FIElD
FIELD 22 (NSGC/2)

~ r-----~::~~~~~==~----r_------~------~:
CONDENSATE! (NSGC/2)
~~i
~o

i
~"'I
~~
~o
U,

WATSON CHARACTERlZAn<l FACTOR cj> ,7-'"


Ii ,.
NSGC/1B WEll.
WELL 88 ," . qfb"

~g,r--::::-:~~-,---]
'-'"'
NSGC/1B ~
o ~,','I."'" .'
1
~

~ f
(1?
I!!
INITIAL lEST ANAlYSIS (POOR) ~
o

.
Li LATER lEST ANAlYSIS

.,~
C

~
IC
~o18
!!f1, C

.!-
:r a

~~I-----=~---=~--~----~----~
~ 18
o~
I3o ma me 155
135 liD
40 liS
45
ISO 155
IIILEClI..AA
4cLECLLAR
lIE I GIfT
CEIQ-IT


0'1

'7'1
NORm
NORTH SEA
SEA BlACK OIL)I F1EI..D
BLACK OIL FiELD 3B3B (NSB0/3B)
(NS80138) I

~S['
iC 4 N
U"I
0]
r.'\. . nc 4
'b 'f'lC S
i~I
' '/

.'
iC nC s
nC 5
5 ~o

C6
<V
C6 0l.ESTJCNAa.E DATA CRl..ED Ii
o WATSON ;/f
/
,til,' .,/
"
..
A

g:.' ,. .
CHARACTERIZATION FACTOR
,~,<f""
o ____ ______ ______ ________________ ______ I ,I' ",
0 I~-- ~~ ~ ~ ~ ~

o """
0.0 , ,,
i~ 0.6
0.5 .O
t.O 1.6
f.5 2.0
2.0 2.6
2.6 6.0
1.0 ,, ,
,,;'
,.,
HOFMAN-CRUF-flOCOTT
H(FFHAN-CRIJI'I>-+iOCOTT FACTOR.
FACT[It. FF b(
b( I/ThI/T)
IIlb- lIT) .?~,.,'
.,~ ,, , ,
" ,"
rig
Fig. 66 - Illustration
Illustration of
of how
how the
the Hoffman-Cru mp-Hocott method
Hoffman-Crump-Hocott method can
can be
be used
used ,ik.,',/
,
-

to
to isolate
isolate possible errors in
possible errors in separator-flu id analysis
separator-fluid analysis due
due to
to , ,, , ,,
sample-conta iner leakage, inaccurate analysis
sample-container leakage, inaccurate analysis or lack of
or lack of ~., ,
,, ,,
,
equilibrium during sampling. , ,
,, ,,
0
equilibrium during sampling.
,I' ," b
51 ,','
"I ' ,
250 2iO 250 250
260
.,210
o2 0 220
220 220 240 250
HIl.EClI..AA lIE IGIfT
HLLECLLP2I WEIiT

Fig. 77
Fig. - Heptanesplus

Heptanes-plus characterizat
characterization based onon measured
ion based measured
molecular weight
molecular weight and
and specific
specific gravity
gravity using
using the
the
Watson characterizat
Watson characterization factor.
ion factor.
A.6-26
A.6-26

u~
C)

~----~~----~------~-------.-------.
0
~
Li
a
.: ~ CUT- OFF (N-PARAFFIN) BOIUNG POINT
!IO
~ + MID-VOLUME (-NORMALi BOILING POINT
0
~
z
.J o
iiia
M)

8
-

~ ~--
0o --~20
--~--~---
20 40 ---~--
60 ----~----~ ~ ~ ~
80 tOO
100
ClJ1lLLATIV
CLJIU AT I VE
E VOLU
VOLUfE DIST
0 I ST I LLED. PERC
ILL. PERC ell'
ENT

Fig. 88 - Carb
Fig. Carbo n-num
on-n umbber distiilla
er dist llatio
tion n (ASTM
(ASTM DD 289?
2892-78) boilin
78) boili ngg poin
pointt curv
curve
-

for aa blen e
blend of hept
d of heptan espl
anes - plus fractiions
us fract ons from
from gas-c
gas-c onden
onde sate
nsate and
and
black-oil
-oil reservoirs
voirs inin the
the Nort
North Sea.
h Sea.
t~~ II--r-------,-----.---,--
e ASTM
ASTM CARBON-NlJ.'BER
CARBON-NUER DISTILLATION
DISTiLLATiON -I
GC SIMULATED
SIMULATED DISTILLA110N
DIS11LLA11ON e
GC ++ GC
CHROMATOGRAM i
GC SIMULATED
SIMULATED DlSTlLLA TION
DISTiLLATION

CHROMATOGRAM
.. ..J ..,
L..a CD en...
JL)LL) IP"'II iii ..
U
c:
U UC UC
eCCe:
UC

......
C)
uC
c:
u
...
c:
...
~
e+
..
~
3
+
u
z
c:
.... e+
+ :t:>
uC-)
i m

..
F- C
c:
t;
C/) e+
+ I
N

..
-....J

I
z

..61
C)
C

g@I-e
.

-

- CHROMATOAPHIC BASE LItE


CHROMATOGRAPHC BASE Lt 611~____~____~____~____~____~
-------------------------- I
0o ~
20 ~
40 ~
60 ~
80 ~
100
ClJ1l.LATIVE WEIGHT
IlEIBHT DISTILLED. PERCSfT
DISTIu.ED. PERCENT
ELECTRONC BASE
ELECTROt1C BASE UNE
UtE CIJl.LATIVE

CAFON NUM8ER 9 Fig. 1010 - Comparison


Comparison ofof ASTM
ASTM carbonnumber
carbon-number and
and OC-simulated
GC-simulated boiling
boiling
CARBON NUMBER 9 Fig. -

point curves
point curves (on
(on weightpercent
weight-percent basis)
basis) for
for aa blend
blend of
of
heptanes-plus fractions
heptanes-plus fractions from
from gascondensate
gas-condensate and
and black-oil
black-oil
Fig. 99 - Simulated
Fig.
Simulated distillation
-

chromatogram for
gas chromatogram
distillation gas for aa reservoirs inin the
reservoirs the North
North Sea.
Sea.
blend of
blend of heptanes-plus
heptanes-plus fractions from gascondensate
fractions from gas-condensate
and black-oil reservoirs
and black-oil the North
reservoirs inin the North Sea.
Sea.
A.6-28

NAPHTHENES
NAPHThENES
MASS SPECTROGRAM
(TOTAL ION COUNT - TIC)
-

7
C 8
C 9 C
C 10

o
7
c 1

m/z
m/z=98
98

m/z=112
mlz=112

9
c m/z=126
mlz=126

C 10 - - -- t---f-AJ....JII,i-'"""'----t - - -
-

m/z14O
mlz=140

Fig.
Fig, 11 - Example of GC-based mass spectrography used
-

to isolate and quantify the content of aa


particular hydrocarbon family (naphthenes)
in carbon-number distillation fractions up
to C10;
10 analogous spectrograms can be made
C
;
for paraffin and aromatic hydrocarbon families.
____________
____

A.6-29
A.6-29

25

20
~
15

~
187.5 - 1.:
187.5

~ I 10
10 IASLfl
fOS

lrI

175.0
175.0
.

I 55

"BEST
BEST" ~1ATCH
MATCH

i l62.5
A2 A3
3AN\ I 00
25
28

I
182.5 S.
I!!
20

.
1500
150.0

I
\g 81
15
15

10
10 .~
EASL
- EOS
EOS PREIlCnON
1290 1300 82
1280 1300 1310
1310 1320 55
1320 1330
1330
FRACTlON-3 C1TJCAL TEP.cERATh
FRACT1Of+-3 CRIT1CAL TEt.f'ERA1\.fE, DE
!lEG. RR

00
00 1000 2000
1000 2000 3000
3000 4000
4000 5000 eooo
5000 8000 7000
7000
PAESSl&
Pc1ES S ,PA
PSIA

Fig. 12
Fig. 12 - Result
Results of Peng
s of Peng-R obinso
Robins onn EQS
EOS match
match for
for consta
constant-volu
nt-volume
-

data from
from Field depletion
me depleti on
data Field NSGC
NSGC/1
/1BB illus
illust ratingg two
tratin two retrogr
retrograde- conde
ade-co nsatio
ndensa tionn
dropout
dropou curves for
t curves for EQS
EOS predict
predi ction
ionss with
with the
the same
same overall
overa ll error
error
function
functio n (appro
(approximate
ximately
ly 22 percen
perce nt).
t).
A.6-30
A.6-30

1.3
1.3 -

T------r-----~----_T----~~----~----~
. MEASURED
MEASURED
- + - BEST-FTT PR EQS MATCH
N
N

0.8
0.8 '--____......____......_____ _ 1 ' - -_ _ _ _......_ _ _ __ ' __ _ _ _....._ _ _- - '

80

7a
7a-----~----......------I'------~----'----~---~ a
9.0 ~----_----_T----.....,r------..----
9.0 __----_----....,
I..
0

1.0 '--_ _......___......____.-.Ii-.____ ____ ____ _____ _


1.0
~
~
~
190
190

~ .------
.....
C)
(.)
I- .----- .---
I
G , .. .... .. ' "
~
LU

----_.-... ...-- .-." ..


.--4--

j
..J ~-- .......
o
0
~
110
110 L--!~!:::::::...._~
I. .-
__.- a-

0o 1000
1000 2000
2000 3000
3000 4000
4000 5000
5000 6000
6000 7000
7000

PRESSURE,
PRESSURE. PSIA
PSIA

Fig.
Fig. 13
13 - Results
Results of
of predicted
predicted CVD
CVD data
data using
using the
the Peng
Peng-
Robinson EQS
Robinson EOS arid
and the
the proposed
proposed minimization
minimization
routine (best
routine ("best" match
match corresponds
corresponds toto liquid
liquid
dropout curve
dropout curve inin Fig.
Fig. 12,
12, upper
upper inset).
inset).
A.7-1

SPE 10224 SPE


80cIetu oIl"etrdeI.m~
Societu of at "'ME
Petrolezn Enieers of AIME

Two-Phase Pressure Test Analysis

Skjaeveland*
Bcbe, Rogaland Research Institute; Svein M. Skjaeveland
by Arild B0e, *
and Curtis H. Whitson, Rogaland Regional Col/ege
College

*Members SPE-AIME
*Members

Copyrlght
1Copyright 1981.
1981, Society of Petroleum Engineers ofof AIME
AIME
Fall Technical Conference and exhibition
This paper was presented at the 56th Annual Fall Exhibition of Society of Petroleum
01 the Society Engineers of
Petroleum Engineers held In
of AIME, held in
San Antonio, Texas, October 5-7, 1981. is subject
1981. The material is subject to correction by Permission to copy Is
by the author. PermIssion is restricted to an abstract of
of
not more than 300 words. Central ElIpressway,
Write: 6200 N. Central
words. Wrlle: Dallas, Texas
Expressway, Dallas, Texas 75206.
75208.

ABSTRACT is uniquely dependent on pressure and can therefore be


used both for drawdown and buildup analyses.
A
A theoretical basis is given for well test ana
ana-
lysis of solution-gas
solutiongas and gas-condensate
gascondensate reservoirs Multiphase-flow effects can also, to aa certain
in the infinite-acting
infiniteacting period. The study is limited extent, be adapted to the liquid model solutions if
to radial flow with a fully penetrating well in the total mobility and compressibility are used
.
3

2
used 2 '3. The
center of the drainage area. Porosity and absolute interpretation of the test will yield the effective
permeability are constants and gravitational and permeability. For solution-gas reservoirs, this
capillary effects are neglected. The tests are con-
con method becomes less reliable with increasing gas satur
ducted at constant surface rate. ation 4 A
ation. A better adaption to the liquid analogy can
be achieved by introducing aa pseudopressure
pseudopressure function
An analytical expression for the pressure - multiphaseflow equations, as suggested by
into the multiphase-flow
-

saturation relationship is derived from the time-depen-


timedepen Fetkovich
,
5
Fetkovich 5
, in analogy to the single-phase
singlephase gas case.
dent gas- and oil-flow
oilflow equations. This relationship 66 who gave
This suggestion was persued by Raghavan
Raghavan
can be used at the wellbore
weilbore to generate pseudopressure practical methods for calculating the pseudopressure
functions for drawdown and buildup that allow test function for oil in solution-gas drive reservoirs,
interpretation using the liquid analogy. and showed that the standard, liquid analogy, semi log
semilog
plots could be used to calculate the absolute for for-
The pressure-saturation relation for buildup is aa mation permeability from computer-generated test data.
limiting case of that for drawdown. They can both be In order to evaluate the oil pseudopressure function,
used together with the Boltzman transform to generate the relation between oil saturation and pressure must
saturation profiles as functions of radius at any stage be known. Raghavan did not, however, present aa theo-
of the tests conducted during the infinite-acting
infiniteacting retically-based relation, but demonstrated, through
period. examples, that the instantaneous, measured, producing
GOR could be used for drawdown interpretation. He
Theoretical developments are examplified by simu-
simu also suggested that the producing GOR at shutin could
lated drawdown and buildup tests in aa solution-gas
solutiongas be used for buildup analysis.
drive reservoir.
The main objective of this paper is to present
theoretical relationships between pressure and satur-satur
INTRODUCTION ation that can be used to evaluate pseudopressure
functions in the infinite-acting
infiniteacting period. The suggest-
suggest
Many transient pressure tests can be interpreted ed method should be valid for any multiphase system
using solutions of the diffusivity equation based on provided the fluid flow can be described by diffusivi-
diffusivi
the liquid analogy of reservoir fluids. In the liquid ty equations based on "beta"-formulation,
beta-formulation, i.e. for-
for
model the reservoir fluids are represented by aa single- mation volume factors. The examples, based on com- com
phase liquid with small and constant compressibility puter-generated test data, are limited to solution-
putergenerated solution
and constant viscosity. The corresponding diffusivity gas drive reservoirs.
equation is linear and solutions for aa variety of
boundary conditions have been presented in the litera-
litera
ture. Single-phase
Singlephase gas test can be interpreted within THEORY
the liquid analogy by introducing an integral trans-
trans
form, the pseudopressure function, originally suggested For simplicity, consider only the oil and gas
1
by Al-Hussainy et al.
.
1
al. This pseudopressure function phases to be mobile and the irreducible water to be
incompressible. The flow equations are then

References and illustrations at end of paper.


A.7-2
A.7-2
22 TWOPHASE PRESSURE
TWO-PHASE PRESSURE TEST
TEST ANALYSIS
ANALYSIS 10??l.
10224

RRk
k kk RRS
S SS
Gas:
Gas: V.[(
'J.[( sOB ro
110 00
++ __ r!L)9p]
~
gg
)Vpl ==
kkf
a
3
~ ~t so o
(~+
B
DO0
+
Bg
g
i) .. (1)
(1) Actually several
Actually,
used:
used:
several pseudopressure
pseudopressure functions
functions can
can be
be

pp
Oil:
rr kk rg
7.[( sg r
Oil: 'V[(2!L..!:9. ++ ~)Vp] =
jB Bg
r SS
sg g kk ro)VFJI = t "t (~+
(l3.r s So
(2)
a) .. (2)
..
Oil: (p) = ff acx dp
Oil: mo(p):
0
m
Po
dp ......................... (6)
(6>
Ilggg
wB0
110000
kf
a ~B
g 0
pp
Gas: mg(P) = ff aa dp
Gas: mg(p): dp ......................... (7)
(7
iw =
whereS
where So0 ++SSgg ++5S.lW =1.
1- 0
p
Po
The term
The term Rso
50 denotes
R denotes gas
gas dissolved
dissolved inin the
the oil
oil p
phase and
phase and rsg denotes oil
rsg denotes oil dissolved
dissolved in
in the
the gas
gas phase.
phase. Total:
Total: mt(p):
m(p)=f f (a+a)
(a+cc) dp
dp ...... . ............. (8) (8)
This last
This last term
term is
is included
included to
to make
make the
the system
system of of Po
equations equally
equations equally applicable
applicable toto gas-condensate
gas-condensate reser-
reser
voirs. The
voirs. The formation
formation volume
volume factors,
factors, B,
0
B ,
0
R Also, any
Also, any linear combination
combination of of aa and
and aa can
can be
bc
o Sg so ' B
' r
rs ' R g , used
B,
used in
in the
,
the definition of of mt.
can, in
can, in this
this case,
case, be
be derived
derived from
from aa constant
constan volume
voume mt, for
for example
example normalizing
normalizinG
depletion experiment,
depletion experiment, asas proposed
proposed by
by Whitson,
Whitson, et et al.
.
7
al.7 Eqs.
Eqs. 4 and
and 55 before adding.

The following
The following simplifying
simplifying notation is introduced
introduced In practical use, the choice of
of definition
depends on the characteristics
characteristics of the reservoir
reservoir and
and
Ss -= Ss
00 the boundary conditions of the test. ForFor an
an oil
oil
reservoir with constant surface-oil
surfaceoil rate.
rate, Eq.
Eq. 6 would
would
RR kk
so ro
ro kk be used. With constant surface-gas rate during
during the
the
aa= so

+~
+ test, Eq. 77 would be used. Eq. 8 would require
test. require con-
con
-~
B
0
3d
~

9
11gB stant total rate of gas plus oil at surface conditions.
conditions
r sg k g k In order to evaluate the integrals.
a ro In integrals, Eqs. 6 - 8.8,
-

B p
B
0 (3) the relationship between Sand
S and pp must be known.
known. This
This
-

gg relationship must be consistent with the pressure


pressure and
and
S
5
R
00 s saturation profiles developed around thethe well
well during
during
b single-phas~ pseudo-
the test. In contrast to the singlephase pseudo
B +
pressure function, the inultiphase
o g multiphase pseudopressure
pseudopressure
functions are not uniquely dependent on on pressure. in
pressure, in
r s s
o
general, but also depend on the history of the test.
the test,
e.g. mo(p)
(p) for aa drawdown test is different from
0
m from mo(p)
(p)
0
m
B +
drawdown 6
for buildup following the drawdown
g .
6

In these
In expressions, Rso.
these expressions. Rso, rsg' , BBg , 11,
0
B
rsg. Bo. 1lQ. l.1
IlQ ,
only depend
only depend on
on pressure
pressure p, and kkrg. kkro only depend
ony depena onon Line source solution
saturation S.
S.
rg ro
saturation
For
For radial
radial flow, and
and with the Boltzman
Soltzman transform
transform
We also introduce
We also introduce the following notations
notations ~r2
2
Pr
y : 4Kf Eq.
Eq. 55 yields
yields
x (--) partial
partial derivative of
of xx with
with
*....................
=
respect
respect to
to 5,
S, pp constant,
constant,
(3x
~(ay
d
$>
dP)
= -y
= - y
d13
(9 )
(9)
xx': (~)
--) (lp SS
partial
partial derivative
respect
derivative of
respect to
of xx with
P. sS constant,
to p, constant,
with
From Eq.
From Eq. 66 we
we have
have a.a $ : dmo/dy , and
= dm
/
0dy , and

where xx EE {a,
where a, b,
{a, a, b, }.
13}. d adSOJ
.
dS +
+ 3 dy
Eqs.
Eqs. 11 and
and 22 may
may then
then be
be written
written as
as
dS dm
= + 13)a
Gas:
Gas: V(aVp)
9(aVp):= t 3b~~
k3t (4)
(4)
Substituted in
Substituted in Eq.
Eq . 99 this
this gives
gives
din c. dm
dd dmo elmo
Oil:
Oil: V.(ccVp)
9(a9p):= tp 313~~ .... ..................... .. (5)
(5 ) Y~y Cfjf)
J) =: -()-(X) Yy --CGI ................ (10)
(10)

Formally,
where
where
Formally, the
the nonlineari ties of
non-linearities of Eqs.
Eqs. 44 and
and 55
given
given by
by the
the coefficients
coefficients aa and
and oa can
can be
be eliminated
eliminated by
by
introducing ()* dS
introducing an
an integral
integral transform
transform of
of the
the pressure,
pressure, the
the (r):(S*+I3')a-
( + 1
)a
.
1
................. .. (11)
(1)
pseudopressure
pseudopressure function
function m,
m, defined
defined oy Fetkovich s
by Fetkovich
.
5
A.7-3
A.7-3

10224
10224 A. BOE,
A. BOE, S.M.
S.M. SKJAEVELAND
SKJAEVELANO AND
AND C.H.
C.H. WHITSUN
WHITSON 33

*
The term
The (cIA) * is
term (c/A) is aa generalized
generalized compressibility
compressibi1ity-
mobility ratio.
ratio. For single-phase
For single-phase flow itit corresponds
corresponds 011.
'. dd ( dp.c!Q) + dcL ~ _ _ d
dct dp_ dB
mobility
to the
the compressibil
compressibility-viscosity product, and to the
ity-viscosity product, and to the
il: a dy Yay + dY Yay - Y dy ............. (16-
-

to
total compressibil
total compressibility divided by
ity divided by the
the total
total mobility
mobility
two-phase flow in
for twophase in the
the approximation
approximation given
given byby
a ,~
da
da == a' dY
dS ++ a
Martin!, as
,
3
Martin as will
will be
be verified
verified below.
below. Here dY
Here an d similarly
ay and . '1 ar 1y for
Slml for the
the other
other terms
terms
*
If the
If (cIA) * term,
the (c/A) term, Eq.
Eq. 11,
11, can bebe considered
considered aa
constant, Eq. 10
constant, Eq. has the
10 has the standard
standard line
line source
source solution For convenience,
solution For convenience, introduce
introduce
in logarithmic
in logarithmic approximation
approximation

141. 2 q
141.? 0q
N=y
N= y and K= Y ~
and K=y
dS
-$
mow == ll1
mow moi - kh
kh 0 .U(ln

to ++ 0.80907)1
'[i(ln tD 0.80907)] (12)
(12) and
and the
the flow
flow equations
equations become
become

where q qo is
0 is the constant surface rate, and
and dimension
dimension- dN N + b I + K. N
where Gas: aa dy ++ N.[a.N.
Gas: N.[a'yy
+ b'] + K.[a y + Il] =0
[+] = 0
less time
less time tD
to is defined by

0
t
to = 0.0002637
= cpr~t~o.)* ................ (13)
0.0002637 r(c/A)* (13)
Field units are used consistently.
Oil: N.[a'~++ ]
Oil:a*++ N.[d K.[a~++
B'] ++ K.[& 6] = 00
=

(c/A) * can be shown to vary


*
Although (cIA) vary with
with
pressure, our simulation results, as well as as Eliminating dN/dy between
Eliminating the two
between the two equations and
and noting
, show that the psedopressu
Raghavan's6,
6
Raghavans psel'tjopressure functiol'l
re function KIN == dS/dp, we get the general satu-ation
that K/N satuation - press

plots as aa semi log straight li,,~


semilog lire during the entire ure relation
infinite-acting
infiniteacting period. This can be explained from
the boundary condition
dS = (aa'
(ca - ad)
aa')!!
+ (cLb
y + (ab' - aB')
a13)
-

dm 141.22 qo
141. q0 ap ....... (17)
lim
lim(y-)
y-+O
y-O
(y Tv)
y
=
=
2kh
.................. (14) (aa - aa)~
(a& a) +

y
+ ((aaa -cL6)
ctb )

used in deriving Eq. 12. That is, when the producing Estimation of !!
y
- term

time becomes sufficiently large, Eq. 14 can be solved


directly and yields logarithmic
iogarithmic time dependence, At radius r and time t, from Darcy's
Darcys law:
independent of (c/A)*.
(c/A)

Interpreted results from simulated tests corre- corre 27rrkhcz(y) apJrr) = qo(y)
21frkha(y) q 0 (y) where qo(y)
=
(y) is the
0
q
ar
late fairly well witnwith the liquid reference curve if the
initial value, (c/A)i, surface oil rate. Hence
~ence
(c/A), is used in Eq. 13. 13. To corre-
corre
late exactly with the liquid'
liquid reference curve, (c/A)i
(c/X)
has to be adjusted by a constant correction factor, = ~ (y)
0
q
dp _ qo(y)
=

.
N
N y 41fkhct(y) which
usually between 1.0 and 2.0. This is also necessary ay - 4irkhcc(y) WhlCh

in Ra~havan's6
6 example. The slight error
Rahavans error in using
(c/A)i
(c/X) can be seenseen as a skin,
skin, usually small and shows that N N is bounded for all values of y.
negligible.
negl igible.
At the wel1bore:
welibore:
When
When the well during
during a drawdown
drawdown test
test reaches
pseudosteady state,
pseudosteady state, the Boltzman transform is no long- long N
N
a.t
.t
0
a
'0

er valid and
and the
the boundary condition,
condition, Eq. 14, breaks
Eq. 14, y = 1fr~h<Pa
irrhpc
down.
down. In In this flow
flow period
period then,
then, the
the pressure
pressure depend-
depend
ence
ence of (c/A)* can
of (c/A)* can be
be expected
expected to cause
cause deviations
from
from the liquid
liquid reference
reference curve.
curve, or
or
Nl .!. t
Line source solutions y = 1.
!! ct tw ................................. .. (18)
(18)
solutions for
for other
other choices
choices of

2
pseudopressure functions, Eqs.
pseudopressure functions, 8, can be
Eqs. 77 - 8, be derived
derived cpr h
similarly using different
similarly using different expressions (c/A)*.
for (c/A)*.
expressions for where
where tw t = 13.44
13.44 ___w __ , Field Units.
Units.
W q
qo
Relationship
Relationship between
between saturation
saturation and
and pressure
pressure 18 has
Eq. 18 has to be solved iteratively
be solved iteratively together
together with
with Eq. 11
1
since ao depends
since depends onon both
both saturation
saturation and pressure. Note
and pressure. Note
From
From the
the oil
oil equation,
equation, Eq. 9, and
Eq. 9, and the
the correspond- that Eq.
correspond that Eq. 18 is independent
18 is independent of
of absolute
absolute permeability
permeability k.
ing
ing gas
gas equation
equation we
we get
get Therefore, m
Therefore, 0
m -va1ues
-values can
can be
be generated
generated without
without knowledge
knowledge
of
of k.
k, o
~ da ~
Gas:. d da db
dp dp db
Gas. dY
aa(y_) dy Yay = - y dY .......... . ((15)
(Yay) ++-y- =- 15)
A.7-4
A.7-4

44 TWO-PHASE
TWOPHASE PRESSURE
PRESSURE TEST
TEST ANALYSIS
ANALYSIS 10224
10224

Limiting cases.
Limiting cases. The consequences
The consequences of of this
this expression
expression can
can be
be seen
seen as
as
follows.
follows, The The producing
producing gas-oil
gas-oil ratio
ratio RR is
is given
given by
by
We will first examine
We will first examine the
the two
two limiting
limiting cases
cases ofof RR == a/n.
a/cL. The
The total
total derivative
derivative of
of RR wHh
with respect
respect to
in
short and
short and long
long producing
producing times
times for
for aa constant
constant surface- piessure is
surface pressure is then
then
oil rate drawdown test. In these
oil rate drawdown test. In these cases cases Eq.
Eq. 17
17 is
is
solved without
solved without estimation
estimation of
of the
the N/y-term.
N/y-term.
dRdS
dR = R dS + R'R
dp R+
dp

dp
~~ __ !~i~i~!_f!Q~J_~_!_~_t~_!_ql
Substituting
Substituting from
from Eq.
Eq. 21,
21 we
we find
find
bounded, ~ ~ 00 as
as yy ~ ~ and
,
Since N
Since N is
is bounded, and Eq.
Eq. 17
17
yy
- -

reverts to
reverts to dR
dS
nb' a3
cb - aa' -

(19 )
dp
dp = a~
a -cLb
ni> that is,
that is, the
the gas-oil
gasoil ratio
ratio is
is aa constant.
constant, independent
independent
of pressure
of pressure (and
(and time).
time). This
This is
is an
an important
important obser-
obser
In order
In order to
to compare
compare with
with the
the results
results of
of Martinl,
,
3
Martin vation. For
vation. For aa drawdown
drawdown test
test in
in the
the infinite-acting
infinite-acting
we set rsg == 0,
we set rsg 0, substitute
substitute the
the expressions
expressions from
from Eq.
Eq. 33 period, when
period, when Eq. 21 becomes valid, the the gas-oil
gasoil ratio
ratio
and get
and get will stabilize.
will stabilize. The level of stabilization
stabilization depends
depends
strongly on the
strongly the rate and
and may be
be higher or
or lower
lower than
than
At B 0
A the initial gas-oil ratio, as determined from
the from our
our
ab -al3 0
=o
--+---ct
(S) simulation runs. The stabilization and and the
the shift
shift
from Eq. 19
from 19 to Eq. 21 occurs after aa very
very short
short pro-
pro
ducing time, only a few minutes for for the
the presented
presented
At example.
a cb
og Eq. 21 can also easily be derived directly
directly from
from
Eqs. 15 and 16 by neglecting the expansion
expansion terms
terms on
on
where total
total mobility
mobility is the right hand side of the equations.
equations.
where

k k Saturation as function of radius.


At = A

+ A
g
=.r.
0 infinite-acting
In the infinite-actin period. when
g period, when the
the Soltzman
Boltzman
and
and is valid, saturation
transform is saturation and
and pressure
pressure profiles
profiles
can easily be generated if Sand
S and pp are known functions
are known functions
+ BgR
0
S - SgBj at the
of time at the wellbore.
wellbore.
- -

Ct 0
B 0
B Bg
For aa drawdown test, at radius r and
For and time t,
t, the
the
saturation will
saturation will be equal
equal to
to the saturation
saturation at
at the
the
wellbore at
welibore at aa time
is
is the
the total
total compressibility of
compressibility of the fluids.
fluids. r2
2
r
Hence ti _)L t
t' ==...!!.
Hence r2
2
r
dS
0
dS o S'
Bc A
0
A During buildup,
During buildup, the
the saturation change ~
saturation change from
tS from
dp = So B
= 0
S ko +r
+ 0
c
ct (20)
(20)
the
the shutin
shutin profile,
profile, atat radius
radius rrand shutin time
and shutin time t,6t,

will
will be
be equal
equal toto the
the saturation
saturation change
change at
at the
the weliborE
wellbore
o t
at aa shutin
at shutin time
time
as
as shown
shown by
by Martin
.
3
Martinl.
Eq.
Eq. 19
19 can
can be be derived
derived directly
directly fromfrom Eqs.
Eqs. 15
15 and
and 1616 by
by t =it
neglecting
neglecting the the second-order
second-order flow terms l . Substituting
flow terms
.
3 Substituting 2
r
Eq.
Eq. 20
20 into
into Eq.
Eq. 1111 we find (c/A)*
we find (c/A)* == ct/At.
Ct/At. Therefore,
Therefore,
in
in the
the limiting
limiting case
case when
when tt -~ 0, or, if
0, or, ,f the
the second-
second-
order
order flow
flow terms
terms can
can bebe neglected,
neglected~ the the standard
standard inter Integration paths
inter- Integration paths.
pretation
pretation procedure
procedure is is applicable
.
2applicable. Our Our simulation
simulation
runs
runs show,
show, however,
however, thatthat Eq.
Eq. 1919 is
is only
only valid
valid at
at the
the 6Raghavan 6 points
Raghavan pOints out
out that
that the
the pseudopressu
pseudopressure
re
wellbore for very short producing
wellbore for very short producing times, times, only
only aa few
few function should
function should reflect
reflect the
the pressure
pressure and
and saturation
saturation
minutes
minutes for for the
the presented
presented example.
example. profiles occurring
profiles occurring inin the
the drainage
drainage area
area during
during the
the
test. To
test. To achieve
achieve this,
this, the
the integral
integral
p.
p.
JJ 1 n dp
1
dp
In this case Eq. 17 reduces
In this case Eq. 17 reduces to to pw
pw
could, for
could, for aa given
given time,
time, be
be evaluated
evaluated by
by iritegratior
integration
dS
dS - La
aa' - acL
an'
over the
over the saturation
saturation and
and pressure
pressure profiles,
profiles, i.e.
i .e . over
over
(21 )
Op =aci au - aa -
radius r.r . This
radius This approach
approach isis consistent
consistent with
with the
the pseudo
pseudo-
A.7-5
A,7-5

10224 A. BE.
A. S.M. SKJAEVELND
BgE S.M. SKJAEVELAND AND
AND CH.
C.H WHTTSON
WHITSON 55
10224

pressure equations
pressure equations suggested
suggested forfor steady-state
steady-state and and Pseudosteady state
Pseudosteady state (PSS)
(PSS)
pseudosteady flow,
pseudosteady Fetkovich s When
flow, Fetkovich
.
5 When the
the Boltzman
Boltzman
transform is
transform is valid,
valid, however,
however, the
the integration
integration over over ~~-_Q!:!!~QQ~Q.
A. Drawdown.
radius for
radius for aa fixed
fixed timetime isis equivalent
equivalent to to integration
integration
over time
over time forfor aa fixed radius rr == rr. In
fixed radius . In the
the infinite
infinite When the
When the well
well reaches
reaches PSS,
PSS. the
the Boltzman
Boltzman transform
transform
acting period,
acting period, the the pseudopressu
pseudopressure 'unction can
re function can there
there- is is no
no longer
longer compatible
compatible with with the
the boundary
boundary conditions.
conditions.
fore be
fore be evaluated
evaluated simply simply by by using
using thethe correct
correct pressure
pressure If If the
the use
use of of Eq.
Eq. 1717 isis extended into this
extended into flow period,
this flow period,
saturation relationship
saturation relationship at at the
the wellbore.
wellbore. deviation from
deviation from the
the liquid
liquid analogy
analogy will occur. Even
will occur. Even
if the
if the correct
correct SS vs vs pp relation
relation at at the wellbore were
the wellbore were
used, from
used, from the observed RR == a/a,
the observed a/a, it it is not obvious
is not obvious
Interpretation procedures,
Interpretation procedures, infinite
infinite acting
acting period.
period. to us
to us that
that aa continued
continued integration
integration only only ofof weilbore
wellbore
data would
data would givegive aa pseudopressu
pseudopressure re function
function thatthat proper
proper-
~~--~!:!!~gQ~Q.
A. Drawdown. ly describe
ly describe1 the the conditions within the
conditions within drainage area.
the drainage area.
Also, (c/X)
Also, (c/A) in in the expression for
the expression for dimensionles
dimensionless s
Eqs. 17
Eqs. 17 and
and 18 18 are
are used
used to
to generate
generate aa table
table of of SS time,
time, Eq.Eq. 13,13, varies
varies with
with pressure
pressure and will give
and will give
vs wf
VS Pwf' The The pseudopressu
pseudopressure function m
re function mo is
0 is calculated
calculated departure
departure fromfrom thethe liquid
liquid reference curve. It
reference curve. It isis
from q.
from Eq. 6. 6. AA semilog
semilog plotplot of
of m0m vsvs producing
producing time
time t therefore not
therefore not presently
presently evident
evident howhow the liquid analogy
the liquid analogy
gives straight line
gives aa straight line and absolu~e permeability
and absolute permeability kk is is of multiphase
of multiphase flow can be
flow can be extended
extended into the PSS
into the PSS period
period
calculated from
calculated from thethe slope.
slope. TheThe dimensionles
dimensionlesss pseudo
pseudo- in in order
order to accurately determine
to accurately determine the drainage area.
the drainage area.
pressure function
pressure function fllwD ~D cancan then
then bebe calculated
calculated and and
compared with
compared with thethe liquid
llquid reference
reference curve,
curve, ~! __ ~!!ilg!!p_f!:Q~_e~~

It can
It can easily
easily be be shown, without the
shown, without the use
use ofof
141.2
mwD == 141.2 kh qo mw ..................... . (22) (22) Boltzman
Boltzman transform,
transform, the
that the pp vs
vs SS relationship
relationship at
at
0 mw
q the wellbore is
the is still
still given by by Eq.
Eq. 19. This is
19. This is veri
veri-
fied in
fied in the
the presented
presented example.
example. But,But. if the pseudo-
if the pseudo-
pressure
pressure function is evaluated only
only based
based on
on wellbore
wellbore
where
where g Homer
data ofof SSand p, the
and p. the correspondin
corresponding plot will
Horner plot will
Pi
1
p not be aa straight
straight line with the the correct slope, as
correct slope, as
= = J dp shown in the example. This indicates
indicates that for
for buildup
buildup
mw
mw = mo(Pi)
(
0
m p) -
- m o wf ) =
mo(pwf)
(p a dp
from PSS,PSS. aa pseudopressu
pseudopressure re function evaluated from from
Pwf
wf correct wellbore data will not properly describe the
correct the
This
This method
method is is similar to that suggested by Raghavan Raghavan 6
6 saturation and pressure profiles occurring in the
He R = reservoir during the test. It appears that Raghavan's6 6
Raghavans
He used
used the gas-oil
gasoil ratio equation, R = a/a,
a/cl, to
for buildup better covers this
relate
relate saturation to pressure based on measured R
R suggested
suggested procedure
procedure better covers this
values. case. This lack of a
a liquid analogy makes it difficult
to accurately determine the average reservoir pressure
from the test.
~! __ ~!!ilg!!p

The
The saturation-pressure
saturationpressure relation at the wellbore weilbore
during buildup differs from the drawdown case. After
during buildup
shutin, the pressure gradient at the wellbore
shutin weilbore is zero EXAMPLE
and N/y = O.
and N/y = 0. Hence Hence Eq. 19 is valid during the whole
Numerical model.
buildup period.
The test data were generated by a radial, one-
radial one- ,
To
To interpret
interpret aa buildup test, test, the saturation at
the
the wellbore
weilbore at shutin
shutin must be known.
known. This value can dimensional, three-phase simulator with variable
be
be found
found from the drawdown S S vs p p or directly from bubble-point pressure developed at Rogaland Research
the
the gas-oil
gasoil ratio equation
equation and the observed
observed constant Institute. The formulation is implicit finite
difference with simultaneous solution of
simultaneous and direct solution
level
level ofof R. A
A table
table ofof S
S vs Pws
PwS is is then
then generated
using Eq.
using Eq. 19.19. The
The pseudopressure
pseudopressu re function
function ~ is
is pressures and
and saturations.
m
calculated
calculated from
from simula
by simula-
The validity of the model was checked by
tion and
tion and interpretation
interpretation of of several singlephase
several single-phase
P~,s
pws were also to
made to
also made
liquid pressure tests.
liquid pressure tests. Trial
Trial runs were
m =m rnO(pWfS) =
- = JI aa dp dp eliminate time and
eliminate time and space
space discretization errors. All
discretization errors. All
Pwf,s
wf, the
the example
example runs
runs were
were finally made with
finally made 40block
with aa 40-block
numerical grid,
numerical grid, the
the block lengths increasing
block lengths logarith
increasing logarith-
AA Horner
Homer or or MOH
MDH plot
plot will
will give
give the
the absolute
absolute permeabili
permeabil mically
mically with radius, and
with radius, and with
with the
the time-step size
timestep size
ty kk and
ty and the
the dimensionless
dimensionless pseudopressure
pseudopressure function
function controlled by
controlled by aa maximum
maximum saturation
saturation change
change ofof 0.025
0,025 and
and
aa maximum
maximum pressure
pressure change
change ofof 43.5
43.5 psi
psi (3 bar).
(3 bar).
m - kh m (23)
(23)
wD -= 141.2
mWD q m
141.2 qo w
Reservoir
Reservoir and
and test characteristics.
test characteristics.

can
can be
be calculated.
calculated. The
The example
example tests
tests are
are limited
limited to well fully
to aa well fully
penetrating
penetrating the
the center
center ofof aa radial
radial oil
oil reservoir with
reservoir with
This procedure is
This procedure is different
different from
from the
the one
one solutiongas drive.
solution-gas drive. In In all
all calculations,
calculations, the the oil
oil
6
suggested
suggested by
by Raghavan
.
6
Raghavan He
He used
used the
the gas-oil
gas-oil ratio
ratio pseudopressure function,
pseudopressure function, Eq.
Eq. 6, is therefore
6, is used. All
therefore used. All
equation
equation with
with R
R constant,
constant, equal
equal toto the
the value
value at
at runs
runs were
were made
made with
with aa constant surfaceoil rate
constant surface-oil of
rate of
shutin,
shutin, to
to generate
generate the
the SS vsvs Pws relationship.
relationship. 125.8
125.8 STB/D
STB/D (20
(20 SM3/D)
SM3/D) and
and with incompressible water
with incompressible water
A.7-6
A .7-6
66 TWO-PHASE
TWOPHASE PRESSURE
PRESSURE TEST
TEST ANALYSIS
ANALYSIS 10224
10224

at aa irreducible
at irreducible saturation
saturation ofof 0.30.
0.30. All
All tests
tests Results.
Results.
started with
started with initial
initial reservoir
reservoir pressure
pressure equal
equal to
to the
the
bubblepoint pressure.
bubble-point pressure. TheThe absolute
absolute permeability
permeability and
and Case
Case 1.
1.
porosity were
porosity were constant
constant and
and gravitational
gravitational and
and capillary
capillary
effects excluded.
effects excluded. The
The common
common reservoir
reservoir properties.
properties, Fig.
Fig. 11 shows
shows aa semi log plot
semilog plot of
of pseudopressure
pseudopressure
fluid properties function Illwo'
function liquid
liquid reference
reference pressure
pressure PO and well-
fluid properties and
and relative
relative permeabilities
pernieabilities for
for the
the wD
bore pressure D and well-
tests are
tests are presented
presented in
in Tables
Tables 1.2
1, 2 and
and 3.
3, respectively.
respectively. bore pressure p O. The
D The Illwo-curve
mcurve is is aa straight
straight line
line
with the correc~
with the correc slope
slope inin the
the infinite
infinite acting
acting period,
period,
parallel
parallel toto the
the liquid
liquid reference
reference curve.
curve A A slight
slight
Dimensionless variables.
Dimensionless variables. shift
shift between
between the
the two
two curves*corresponds
curvescorrespands to to aa correc-
correc
tion
tion factor
factor of 1.62 on
of 1.62 (c/A)., or aa skinfactor
on (c/A)j' skinfactor equal
equal
All plots
All plots are presented in
are presented in dimensionless
dimensionless form
form to
to -0.48.
-0.48, which should
should have Deen
seen zero since
since nono fixed
fixed
with the
with the pseudopressure
pseudopressure functions.
functions, mwO.
mwD, for
for drawdown
drawdown skin zone
skin zone is
is used
used in
in the
the model andand the
the gas
gas blockage
blockage
and buildup
and buildup defined
defined by
by Eqs.
Eqs. 22
22 and
and 23.
23. Dimensionless
Dimensionless around the well
around well isis incorporated
incorporated in the mwo-function.
mDfunction.
time, tOi' based on wellbore radius
o wellbore The lllwo-p10t
The m.-plot willwill therefore
therefore give
give the
the correct absolute
time, tDi, based radius is
is defined
defined byby
perme5ility, but a slightly
Eq. 13,
Eq. 13, with
with (c/A)* evaluated at
(dx) evaluated at initial
initial pressure. perme~Dility, slightly erroneous
erroneous skinfactor
skinfactor if if
Dimensionless time
Oimensionless time based
based on
on drainage
drainage area,
area, tOAi'
tDAj, isis (ciA).
(c/A). is is used
used in the
the dimensionless
dimensionless time,time, tOi' The The
given by
given by PwO-values
pWDvlues do not plot as as aa straight
straight line
line ana
and cannot
cannot
be used to interpret the test.
r
2
w
DAi tDi 2
The results are
are replotted in Fig. 2 on on aa linear
linear
Tir
e tOAi-scale.
tDA-scale. The infinite-acting
infiniteacting S S vs p relation.
relation,
Eq. 17.
17, has been used to evaluate Illwo
rn also in in the
the PSS
PSS
Dimensionless wellbore
Oimensionless wellbore pressures, PwO' period (tDAi>01o). The slope of ~O-curve
period (tOAi>0.10). Fn.,vD-curve is
is close
close
wD for drawdown
1T to the correct value 2n,2ir, but the Shlft
buildup, respectively, are defined by
and buildup,
and shift between the the
PO- and Illwo-curves
mWD-curves makes determination of drainage area
kh uncertain. Further extension of the drawdown to to
wD = 141.2 q
0 - wf tOAi
tnAi = = 2.7 shows that the rowO-values do not plot as a
DvalueS a
straight line, as also notea
noted by Raghavan'.
. Neither
6
Raghavan Neither
and
and of the two suggested methods are therefore applicable
applicable
for aa liquid analogy interpretation in the PSS PSS period
period..
kh
wD = 141.2 q
0 ws - Fig. 33 shows the development of producing gas-oil
gasoil
ratio with time. The simulated and calculated
calculated RR
All definitions are given in field units.
All values from Eq. 17 agree closely. RR drops downdown from
from
267 SM3/SM3
267 SM3/SM3 within about 55 minutes
minutes ahd then
then stays
stays
It should
It should be
be noted that kroj
kroi is
is not included
included in constant throughout the
constant infinite-acting period. Curve
the infiniteacting Curve
the definition
the definition ofof PwO. Correct slope of a
PwD Correct a PwD
PwO vs tDi
tOi 33 has been generated by using Eq. 19 until
until dS/dp
dS/dp
semilog plot becomes equal to the value calculated from
from Eq. 21 and
Eq. 21 and
semilog plot should therefore be 1.151/k
1.151/k i per log
ro
cycle, while
cycle. while for
for the
the corresponding
corresponding mwO-Plots,
m-pos, the the then using
then using Eq.
Eq. 21. Only aa coarse
coarse estimate of the
the
slope should
slope should be 1.151 per log cycle.
be 1.151 constant RR level is
constant is achieved.
The liquidreference pressure
The dimensionless liquid-reference pressure is
is Fig. 44 plots
Fig. simulated and calculated values
plots simulated values of
of
denoted
denoted by Po on
by p
0 on the
the plots.
plots. the oil saturation
the oil saturation atat the
the wellbore,
wel1bore. There
There is
is aa close
close
agreement betven
agreement bebeen simulated
simulated values
values and
and those
those from
from
Eq. 17.
Eq. 17.
Test
Test cases.
cases.
1.
1. Drawdown
Orawdown to
to 100
100 hrs
hrs which
which corresponds
corresponds to
to aa tDAi
tOAi == Case 2.
Case 2.
0.17.
0.17. The
The test
test therefore
therefore extends
extends slightly
slightly Fig. 55 depicts
Fig. depicts the results from
the results from buildup
buildup following
following
into
into PSS
PSS (tDAi>0.10).
(t OAi >0.10). the
the 55 hrs
hrs drawdown
drawdown inin an
an MDH
MOH plot.
plot. The
The m,,
IllwO-values

0 va1ues
plot parallel
plot parallel toto the
the liquid
liquid reference
reference curve
curve PO' as as
2.
2. Buildup
Buildup following
following aa drawdown
drawdown ofof 55 hrs.
hrs. The
The entire
entire longlong as ~tt. and
as t<<t, and have
have been
been calculated
calculated using
using Eq.Eq. 19.
19.
test
test is
is performed
performed inin the
the infinite-acting
infinite-acting period.
period. The mWD_curve
The rowO-curve can b~ shifted
can b shifted toto the
the PD-curve
PO-curve by by correct
correct
ing the
ing tHe value (ciA) . Any
value (c/A).. Any constant
constant formation
formation skj,nfact.oi
skinfactor
3. Buildup
3. Buildup following
following the
the 100
100 hrs.
hrs. drawdown,
drawdown. This
This test
test can
can then
then be be calcu1aled
calcula!ed using
using the
the corrected
corrected (c/A)...
(c/A)j'
examplifies
examplifies buildup
buildup from
from PSS,
PSS. This procedure
This procedure cannot
cannot bebe used
used for
for aa drawdown
drawdown test
test since
since
aa parallel shift in
parallel shift in that
that case
case is
is equivalent
equivalent to to aa non
non-
We
We also
also ran
ran aa drawdown
drawdown to tOAi == 2.7
to tDAi 2.7 followed
followed byby aa zero skinfactor.
zero skinfactor. TheThe Homer
Horner plot
plot is
is given
given inin Fig,
Fig. 6.6.
buildup
buildup toto further
further check
check the
the conclusions
conclusions from
from the
the The mn
The Illwo values
values fall
fallonon aa straight
straight line
line with
with slope
slope 1.15
1.15
100
100 hrs
hrs drawdownbuildup.
drawdown-buildup. The The results
results are
are not
not pre
pre- while the
while PwO-data do
the pWD-data do not
not form
form aa straight
straight line.
line .
sented
sented here
here since
since the
the main
main objective
objective ofof the
the study
study isis
to demonstrate
to demonstrate thethe validity
validity ofof the
the pseudopressure
pseudopressure Fig. 77 shows
Fig. shows an
an excellent
excellent match
match between
between simulated
simulated
approach
approach inin the
the infiniteacting
infinite-acting period.
period. and calculated
and calculated values
values ofof oil
oil saturation,
saturation. Eq.Eq . 19,
19, at
at the
the
wellbore during
weilbore during the
the buildup.
buildup.
A.7-7
A.7-7

10224
10224 A. B0E,
A. SBE, S.M.
S.M. SKJAEVELAND
SKJAEVELAND AND
AND C.H.
C.H. WIIITSON
WHITSON 7
~-------------------------------------

Simulated and
Simulated and calculated
calculated saturation
saturation profiles
profiles asas NOMENCLATURE
NOMENCLATURE
functions of
functions of radius,
radius, at
at shutin
shutin and
and after
after 55 mm
min buildup,
buildup,
are given
are given in
in Fig.
Fig. 8. The calculated
8. The calculated saturations
saturations are
are a. a,
a, b, BB== defined
a, b, by Eq.
defined by Eq. 33
generated from
generated from wellbore
wellbore data
data and
and by
by the
the use
use of
of the
the BS formation volume
== formation volume factor
factor
Soltzman transform,
Boltzman transform, asas explained
explained inin the
the text.
text. The
The
excellent agreement
excellent agreement verifies
verifies the
the validity
validity ofof the
the cc == compressibility
compressibil ity
Soltzman transform
Boltzman transform inin the
the infiniteact
infinite-acting period.
ing period. (C)*
(T)* ==defined
defined by
by Eq.
Eq. 1111
x
hh formation height
= formation
= height
Case 3.
Case 3. KK
dS
-- ydS
=y cry
The results
The results from
from buildup
buildup following
following the
the 100
100 hrs
hrs kk = absolute permeability
= absolute permeability
drawdown are
drawdown are shown
shown inin Figs.
Figs. 99 and
and 10.
10. The
The m
-mwo-values
0 values
do not
do not plot
plot parallel
parallel toto the
the liquid
liquid reference
reference curve
curve kr
kr == relative permeability
relative permeability
and the
and the Homer
Horner line
line has
has aa slope
slope of
of 1.30,
1.30, aa 13%
13% devia
devia- mm == pseudopressu re function
pseudopressure function
tion from the
tion from
performed
become more
become
the correct
performed further
correct value
further out
more pronounced
value 1.15.
out in
in PSS,
pronounced and
and the
1.15. If
PSS, these
If the
the buildup
buildup is
these discrepancies
the Homer
discrepancies
Horner plot
plot ceases
ceases
is
NN
PP
==

=
yy*
dp

pressure
= pressure
to give
to straight line
give aa straight line for
for the
the pseudopressu
pseudopressure re
function. Fig.
function. Fig. 11
11 shows
shows that
that the
the match
match between
between simu-
simu- pp == base pressure
base evaluation of
in evaluation
pressure in of
lated and
lated and calculated
calculated oil
oil saturations,
saturations, from
from Eq.
Eq. 19,
19, o re function
pseudopressure
pseudopressu function
is still
is still excellent.
excellent. Although the the correct
correct relationship
relationship
between pressure
between pressure and saturation at the weilbore
wellbore is is Pwf
wf = flowing
= flowing well pressure
well pressure
used, the m
used, -mwo-function
0 generated from these
function generated these data
data de
de- wf,s
= flowing well
= flowing pressure at
well pressure at shutin
shutin
parts from tne liquid analogy. The reason
t~e liquid reason for this
this well pressure
= shutin well pressure
= shutin
is probably
is probably that
that weilbore
wellbore data alone
alone will
will not
not properly
properly
represent the
represent the saturation and pressure profiles
profiles occur-
occur- q surface rate
= surface
=

iog
ing in the reservoir during the buildup from PSS. PSS. r = radius
=

RR = producing
= gas-oil ratio
producing gasoil
CONCLUSIONS rsg = oil-gas ratio
= dissolved oilgas
= solution gas-oil ratio
=
Methods have been presented for interpretation of s = saturation or oil saturation
= saturation
multi phase drawdown and buildup tests in
multiphase in the infinite
infinite-
acting period through the pseudopressure
pseudopressure approach. Siw = irreducible water saturation
=

In this period the pseudopressure


pseudopressure functions are cal-
cal
t = time or producing time
=
culated based on wellbore data only, with theoretical-
theoretical
ly consistent relations between pressure and satur-
satur tD = dimensionless
= dimensionless producing time based
based
ation. The relation for buildup is a special case of on wellbore
welibore radius
the general drawdown relation. At =
0
~tD dimensionless shutin time based
= dimensionless on
based on
Results from an example solution-gas
solutiongas drive well bore radius
wellbore
reservoir ~orrelate
orrelate with the liquid reference curve 0 =
tDA
t dimensionless producing
= dimensionless producing time based on
time based on
with (ciA)
(c/A) close to the initial value.
value, drainage area
During the drawdown test the producing gas-oil
gasoil xx = dummy variable
=
ratio quickly stabilizes
stabilizes and remains constant
constant through-
through x =
= partial derivative of x with

out
out the infinite
infinite acting
acting period. The
The saturation
saturation pro- constant p
respect to S. constant
files
files during
during this
this period
period can,
can, both
both for
for drawdown
drawdown and
x'
x =
= partial derivative of x with
x with
buildup, be generated
generated based
based only
only on
on wellbore data.
data,
respect to p, s
p. constant S
_ q,r
22
cpr
The
The proposed
readily
proposed interpretation
readily extended
extended to
interpretation methods
to the
methods are
are not
pseudoteady state.
the pseudo~teady state.
yy -m
=
A
~ = difference
= difference (change in)
(change in)
vV = gradient
= gradient
V
V. = divergence
= divergence
q, = porosity
= porosity
AA = mobility
= mobility
~u == viscosity
viscosity

Subscripts
Subscripts
oo ==oil
oil
gg gas
==gas
ww == well
well oror water
water
i == initial
initial
tt == total
total
D
0 == dimensionless
dimensionless
A.7-8
A.7-8
88 TWO-PHASE
TWO-PHASE PRESSURE
PRESSURE TEST
TEST ANALYSIS
ANALYSIS 10224
10214

ACKNOWLEDGEMENTS
ACKNOWLEDGEMENTS
We appreciate
We appreciate the
the economic
economic support
support from
from the
the
Royal Norwegian
Royal Norwegian Council
Council for
for Industrial
Industrial and
and Scientific
Scientific
Research (Grant
Research (Grant No.
No. 1840.07425)
1840.07425) and
and from
from Statoil.
Statoil.

REFERENCES
REFERENCES
1.1. Al-Hussainy, R.,
Al-Hussainy, R., Ramey,
Ramey, H.J.,
H.J., Jr.,
Jr., and
and Crawford,
Crawford,
P.B.: "The
P.B.: The Flow
Flow of Real Gases
of Real Gases Through
Through Porous
Porous
Media, J.
Media," J. Pet.
Pet. Tech.
Tech. (May
(May 1966),
1966), 624-636;
624-636; Trans.,
Trans.,
AIME, VoL
AIME, Vol. 237.
237.

2.
2. Perrine,
Perrine, R.L. : "Analysis
R.L.: Analysis of
of Pressure
Pressure Buildup
Buildup
Curves,
Curves," Drill, and
Drill. Prod. Prac.,
and Prod. Prac., API
API (1956)
(1956) 482.
482.
3.
3. Martin, J.C.:
Martin, J.C. : "Simplified
Simplified Equations
Equations of
of Flow
Flow in
in
Gas Drive
Gas Drive Reservoirs
Reservoirs and
and the
the Theoretical
Theoretical Founda-
Founda
tion of
tion Multiphase Pressure
of Multiphase Pressure Buildup
Buildup Analyses,"
Analyses,
Trans., AIME
Trans., AIME (1959)
(1959) Vol.
Vol. 216,
216, 309-311.
309-311.

4,
4. Weller, W.
Weller, W.T.: Reservoir Performance
T.: "Reservoir Performance During Two-
Two-
Phase Flow,"
Phase Flow, J. Pet. Tech.
J. Pet. Tech, (Feb.
(Feb. 1966)
1966) 240-246;
240246;
Trans., AIME,
Trans., AIME, Vol. 237.
237.

5.
5. Fetkovich, M.J.:
Fetkovich, M.J. : "The
The Isochronal Testing
Testing of Oil
Wells,," paper
Wells paper SPE 4529 presented at the SPE-AHIE
SPE-AIME
48th Annual
48th Annual Fall
Fall Meeting,
Meeting, Las Vegas, Nev., Sept.
30 - Oct.
30 Oct. 3,
3, 1973.

6.
6. Raghavan, R.:
Raghavan, R. : "Well
Well Test Analysis: Wells Producin~
Produci
by Solution-Gas
by Solution-Gas Drive,"
Drive, Soc.Pet. Eng. J. (Aug.
1976) 196
1976) 196 - 208;
- 208; Trans.,
Trans., AIME,
AIME, Vol. 261.

7.
7. and Torp, S.B. :
Whitson, C.H. and
Evaluating Constant
"Evaluating Constant Volume
Volume Depletion Data."
Depletion Data,
Paper SPE
Paper 10067, presented
SPE 10067, presented at the 56th
56th Annual
Fall Meeting of
Fall Meeting of SPE
SPE of
of AIME,
AIME, in San
San Antonio,
Antonio,
Texas, October
Texas, October 5-7.
5-7, 1981
1981
A.7-9
TABLE 11 - RESERVOIR PROPERTIES
-

Porosity 0.30
Absolute permeability, md 10.0
10.0
Initial pressure, bar 393.3
Initial bubblepoint pressure, bar 393.3
Connate water saturation, incompressible 0.30
Initial gas saturation 0.0
bar--11
Initial system compressibility, bar 1.303 E-04
Well radius, mm 0.10
External radius, m
m 200.0
200 .0
Height, mm 4.74

*
2 - FLUID PROPERTIES *
TABLE 2 -

P 0
B
Bo P
0
llo 5
R 0
Rso Bg
Bg Pg
llg
3
(bar) (Res m
/Sm
m
)
3 ISm 3 ) 19?1
(cp) (Sm
/Sm
(Sm
)
3 3
ISm )3
(Sm
/
3
(Sm 3
Res IRes m
)
3
m3
) 19?1
(cp)

393.330 1.806 0.298 266.964 298.85 0.0298


388.390 1. 791
1.791 0.300 261.867 296.99 0.0295
358.780 1.702 0.317 232.513 285.12 0.0281
324.240 1.605 0.348 200.793 269.48 0.0263
289.690 1.516 0.391 171.590 251.30 0.0246
255.140 1.434 0.446 144.715 229.88 0.0228
220.600 1.360 0.515 119.997
119.997 204.59 0.0210
190.990 1.302 0.587 100.408 179.63 0.0195
161. 370
161.370 1.249 0.671 82.196 151. 96
151.96 0.0181
131. 760
131.760 1.202 0.768 65.275 122.42 0.0166
102.150 1.159 0.881 49.553 92.32 0.0152
72.540 1.121 1. 011
1.011 34.925 63.03 0.0138
42.930 1.088 1.164 21.218 35.63 0.0125
13.320 1.058 1.350 7.887 10.55 0.0113

*
*PVT a crude oil system with 35 0 API, spesific
PVT properties represent a
gas gravity 0.75, initial solution gas-oil
gasoil ratio 1500 SCF/STB, and
0
200 F.
reservoir temperature 200F.
A.7-10
A.7-1O

PERMEABILITIES*
*
TABLE
TABLE 33 - RELATIVE
-RELATIVE PERMEABILITIES

SS k
krg kk
..:9. rg ro
ro
0.0
0.0 0.0
0.0 0.700
0. 700
0.0102
0.0102 0.000004
0.000004 0.660
0.660
0.0204
0.0204 0.000034
0.000034 0.622
0.622
0.0306
0.0306 0.000115
0.0001 15 0.585
0.585
0.0408
0.0408 0.000269
0.000269 0.550
0.550
0.0510
0.0510 0.000522
0.000522 0.517
0.517
0.0612
0.0612 0.000896
0.000896 0.485
0.485
0.0714
0.0714 0.00141
0.00141 0.455
0.455
0.0816
0.0816 0.00209
0.00209 0.426
0.426
0.0918
0.0918 0.00295
0.00295 0.399
0.102 0.00402
0.00402 0.373
0.112
0.112 0.00531
0.00531 0.348
rJ. 1
0.122
IL 0.00684
0.00684 0.324
0.133
0.133 0.00863
0.00863 0.302
0.143 0.0107 0.281
0.153
0.153 0.0130 0.261
0.163
0.163 0.0157 0.242
0.173
0.173 0.0187 0.224
0. 184
0.184 0.0220
0.0220 0.207
0.194
0.194 0.0256
0.0256 o. 191
0.191
0.204
0.204 0.0296
0.0296 0.176
0.176

* *
Generated from kro =
* *
k = 0.7(1S 2
()
1(S )2)
rg 0 0
*
So S
/
0 (1_S), = 0.3
A.7-11
A.7-1 1
a 16
16
Il.

a:
00
a 14
.'
it l' I/
a
Il. II
a:
a:
I/
00
a I/
it
12
12
I/
E I/

PPwD
WD , "
I/
10
10
,I/
I/
I/
B
8 I/
I/
I/
I/
6 //

,4 F

,
/

2
F.

o0
10_i 10 101 102 i0 L
10
i
ti

1Dimensionless
Fig. 1- tunctions vs. dimensionless producing lime,
Dimensionless pressure funcllons t. Cas.
time, '01' Case 1.
1

a 16
16
a
Il.
a:
a:

-.-- -.-
o0

rl
a l14'
P ___ -_ - - -
-.-- -.--
a:
o0 -.-
WD
WD _ . -

12
~ 12
E
6

.'
10
~.

8
------
6

,
1

22

o
0
00
00 05
05 10
10 15
15 20
20

toAl

Fig. 2 - Dimensionless pressure


Fig. 2Dimensionless funcllons vs.
pressure functions vs. dimensionless
dimensionless time, 'oAI Case
lime. tom, Case 1.
I.
A.7-12
A. 712

M
E 270
270
~
VI
~ I:-RSOI 11 SIMULATED
SIMULATED
~ 22 FROM
FROM EO
VI EQ 1717
33 FROM
FROM EOS
EQS 1919 AND
AND 2121
"-
0:ix

9o 260
I
260 -
I-
<l4
0:ix
-J
-l
o0
U,th
<l4
C>(0
CD 250 t-
~ 250
C-)
u0
~
c(0
- --
0
oa:
0: ...
a.0
Ll
240
240

'.,
-'- .

230
230

o0.OE+0
OE.O 5 OE.S
S OE.5 i 0Ev6
10E.6 115En6
SE.6 20E+6
2 OE*6 2SE+6
2 SEv6
ttoi
Di
Fig. 33Producing
Flo. gas-oil ratio
- Producing gaso()l1 ratio VS.
vs dimensionless
dimensionless time. 5 . Case
time, tD!
t Case t.
1.

70
10
w
UJ
a:
0:
0
0
CJI
-J
-l
-l
iJJ
UJ
~
68
68
I
I-
4
<l
zZ
00
C
I-
4<l
a:
0: 66
0~
I
I-
4<l
in
VI " 3
''('-
-J
-l ,
0
0 ,
64
64 ,
"

,
62 1 SIMULATED
62
2 FROM EO 17
3 FROM EOS 19 AND 21

60
60
10 10 1010 I iO 101 i0
10' 1O 106 iO
Di
Fig,
Fig.4Oil
4 - 011saturation
saluraliontalweilbore
wellbor.vsvsdimensionless
dimensionlesstime,
time.t
0I", Case
Cas. t
A.7-13
A.7-13

0
12
Il.
ii

a:
0
0
0 . -'- - -
~
10
oIl. 10 ,
Pwo "
WD ....
a:
0
0
, , .-
0
~ F.-
6E /
88
, //

, /

I
6
,
, PD
.. ------
4 m WD

o
10 10 10'
10 102 10 10'
10 10 106 io
At ot

FIg.
Fig. 5Dimensionless functions vs.
pressure functions
5 - Dimensionless pressure vs. dimensionless
dimensionless shutin
shutln time,
time. 1
41 01 , Case
Mo
. Case 2.
2.

12
o 12
~
6
0
Il.
a:
1t
o0
o /
6 10
l'
S
/
F

8 ,/

/
/

6 ,"/
//
/
/F

./
/

,/1

4 //
,
/
m

,
/
, ,"
2

....
/ F

,.
., .. .,

o --
io- 5
b 10-'
i0- 103
10- 102 10 10
IINVERSE
NVERSE HORNER TIME - t.I
HORNER TIME At/It
/ ( I vAt)
t.I) -

Fig. 86Dimensionless
Fig. pressure functions
- Dimensionless pressure vs. Inverse
functions vs. nverse Horner time ~II(I
Homer time. stit +i 41,.
t). Case 2.
Case 2.
A.7-14
A.7-14

70
w 70 --,-,----
.....,,.
-

0:ct
0C
OJ
II)
..J-J
..J-J
W
~
I- 68

z
0
I-

0:
::;) 66
I-

II)

..J
0

64

/ULAT1ED
SIMULATED
22 FROM
FROM EQ
EQ 19
19
62
62

60
60 I

10_I 10 10'
10 10 i 10 10 106
51
At

Fig. 7
FIg. - Oil
7-. Dii saturation
saturstion at wellbore vs dimensionless
welibore VS. dimensionless shutln time, ~t",
shut-in time. .. Case 2.
.5t
,
0

70
70 ,,,..,,, I
z
z
0
I-

4
0:
D
:::>
I-

II)
68
..J
0

66

+
SIMULATE D
SIMULATEO
CALCULATED
CALCULAT ED
61
64

62
62 ...

1Q 10 10 '
10 10 2
102
RADIUS (Ml
RADIUS (M I
Fig.
Fig. 8SaIraI,o , proliles
8 - Saturation profilesns'IS.radiLs
radiusalatIhe endolof5 5his
theend hrsdrawdowr,
drawdownaria
andvile
afterS 5mm
minhumloup
buildup
Case
Case2 2.
A.7-1S
A.7-15

Q
16
16
0a.
a::
C0
., 1414
rt
0
PWD . ' - _.
a:: Po--.-.--
.- ."
0
C
., 12
12
~ .-
CE .-
.-
.-
10
10 /
"
/
"
"
/
88 "
// "
I

,I
/
/

66 /I
//
/

4
/

22

o
0
101 10 101 102 io 1o 10 106 io
otei

FIg. 9Dimensionless
Fig. 9- Dlmenslonles. presssre
pres.ure funclions
sections v&
s. dimensionless shulln time,
dlmenslonles. shot-in time, .1101
1t Case 3.
ij' Case 3.

Q
16
16
rt
0
3

a::
ix
0
C
., 14 -
~
C
E
S

12 ". '" -
/
10
10
/
/
/
8 /
/ "
".
/
/
66

/
// "
44
/ -
."/
/

22

00 --- I I

1011
10
10 ' 1 10-
1066 10
10-5 10
10-4 10 -] 10-2 10- 10
10
IINVERSE HORNER TIME
NVERSE HORNER st/Itt +eat)
TIME - 61/1 6tI -

Fig.
Fig 10 - Dlmensionl.ss
10 Dimensionless pressure lsnctions vs.
pressare functions inserse Horner
vs Inverse Homer time, stIlt +4. 61).
time .lUI! Case 3.
tI Case 3.
A.7-16
A. 716

.70
.70 I I 11111111
9
uJ
1111111
I 111111111 111111 11111119 I I
Il1i11 111111111 I 1
UJ
a:::0
ooJ
CD
-J
....J
-J
....J
UJw
~ --
~
I-
.68
.68

zz 1.
o0
F
I-

a:::
D 66
~
F .66
U)
I.J)

.64
.64

.62
.62 1:1: SIMUL
SIMULATED
ATED
... 2:2: FROM
FROM EQ.
Ea. 19
19

.60
.60 I I 1

10-1 100 101 102 10 iO 106 7


io
tDi

Fig.
Fig. 11
11 - Oil
Oil saturation

saturationatatweilbore
wellborevs.
vs.dimensionles
dimensionless shut-intime,
s shut-in time,tDj.
dt OI Case
Case3.3.
A.8-1
A.81

RESERVOIR WELL
RESERVOIR WELL PERFDRMPNCE
PERFORMANCE
AND
1NO

PREDICTING DELIVERI\BILITy
PREDICTING DELIVERABILITY

by
by

Curtis H. Whitson

Rogaland Regional College


Rogaland College
Ullandhaug
4000 Stavanger, Norway
4000 Norway
1
I A.8-2
A.8-2

INTRODUCTION
INTRODUCT ION

Numerous publi cation


publicati onss addre
addressss the subje ct of well
subject
performance
perform ance and stabi lized deli delivverab
erability. Only a few,
however, have receiv ed gener
received al accep
general accepttance
ance for solvin
solving g
tradi tional produ ctionn and reser voir engin
productio eering
engineer ing problems.
Simplicity plays a signi fican
significa ntt role since the relati relationon
between
betwee n rate and wellb
weilboore
re flowing press ure is often used by
produ
producction
tion teams only intere sted in appro
interested approx ximat
imatee answe
answerrss to
design problems.

Produ ctivit
Productiv ityy index
index,, PI,
P1, is define
definedd as the ratio of rate to
pressure drop in the resevoir (q/6p (ci/p). It plays
plays an impor
importtant
ant
role in descr ibing
describin g a well'
wellss inflow perfor mance
ance.. PI
perform P1 is nearly
nearly
const ant for oil wells with wellb
constant weilboore
re flowing pressure above
the bubbl e point
bubble point,, leadin g to the simpl
leading est of all inflow
simplest
performance
perform ance relati ons.. Muska
relations 1
Muskat t was one of the first to use
1
the PI
P1 conce
concep ptt to under
undersstand
tand the role of physi cal factors
physical
such as partial penet ration
penetratio n,, perforatio
ration
n densi ty and
density
two-p hase, gas-o
twophase, gasoil flow.

The conce
concep ptt of skin factor, usua usuallly
ly attributed to HurstHurst2 and
2
van Everd
Everding
3 ingen , 3 and its subse
en, subseqquent
uent expre ssion
expressio n as aa flow
effici ency,, EF, provi
efficiency des a simple
provides simple means to accou accounntt for
nonid
nonideeal
al fluid flow. The idea can actually be found in
Muskat's
Muska t s treatm
treatmenentt of perforatio rationn effects on well
produ
prod ctivit
uctiv y. The Hurst
ity. Hurst-van
van Everd
Everdiingen
ngen conce
concepptt of skin is a
stead
steadyy-sta
statete dime
dimennsio
s: onles
nlesss pressure drop occur occurin ing
g at the
wellb ore..
wellbore It has since been modifi modified
ed to accouaccoun ntt for
high- veloc
high velocitity-fl
yflooww (HVF)
(HVFJ or turbulence effects, blocka blockage
ge due
to the buildup of aa gas or oil saturation
in the
near-wellb
near wellboorere region, and otheotherr nonide
non ideal behav
al reservoir beha ior.
vior.
Application
pplic ation of skin factorr to pred prediictin
cting erabiility
g deliverab lity has
becomee as import
becom important conceptt of prod
ant as the concep produ ctivit
uctiv y index.
ity index.
An
In important
important case of oilw
case oilwe ll
ell performance
inflow perform is when
ance is when
ure in the reservoir
pressure voir sink
sinkss below
below the bubble
bubble poin
pointt.. Gas
A.8-3
A .8-3

evolves and
evolves and reduces
reduces oil
oil productivity.
productivity. Evinger
Evinger and
and Muskat
Muskat It

show that
show that PI
P1 decreases
decreases asas oil
oil rate
rate increases.
increases. They
They suggest
suggest
a method
a method toto estimate
estimate the
the reduction
reduction in
in oil
oil productivity
productivity based
based
on steady-state
on steadystate flow.
flow.

The method
The method presented
presented by Evinger
Evinger and
and Muskat has never
never been
been
widely used.
used. The first study
study on two-phase,
twophase, gas-oil
gasoil flow
flow to
to
gain acceptance
gain acceptance by engineers
engineers came
came in 1968. 55 presented
1968. Yoge1
vogel
simple relation between oil rate and wellbore
aa simple welibore flowing
pressure based on
pressure on numerical simulation of saturated-oil
saturatedoil
systems with varying rock and fluid properties. This
relation has
relation has been and probably still is the industry
standard for
standard for predicting oilwell performance.
performance.

The Yogel
The Vogel relation has been modified by several workers.
Standing proposes simple extensions when a well experiences
Standing proposes
a change in flow efficiency
66 (damage or stimulation) or
efficiency
average
average reservoir pressure drops below the bubble bubble point.
point. 7
7
Patton
Patton and and Goland
Goland 8 extend the Vogel
8 Yogel relation for for
undersaturate
undersaturated wells experiencing
d reservoirs with wells experiencing drawdown
drawdown
below
below the
the bubble
bubble point.
point. AA recent
recent work
work by
by Richardson
Richardson and
and
9
Shaw
Shaw 9 proposes
proposes aa generalizatio
generalization of the
n of the Vogel
Yogel relation
relation based
based
on
on mathematica
mathematicall intuition.
intuition. ItIt appears
appears from results
results in
in this
this
study
study that
that the
the generalizatio
generalization has aa physical
n has physical basis.
basis.

Fetkovich
Fetkovich 1 0 presents
presents an
an excellent
excellent correlation
correlation of
of oilwell
oilwell
performance
performance onon data
data collected
collected from
from over
over 40
40 multirate
multirate tests.
tests.
He
He shows
shows that
that HVF
HYF effects
effects are
are present
present in
in oil
oil wells
wells and
and that
that
absolute
absolute open
open flow
flow potential
potential (AOFP)
(AOFP) is
is overestimate
overestimated if such
d if such
effects
effects are
are not
not considered.
considered. He He also
also draws
draws the
the analogy
analogy
between gasand
between gas-and oliwell
oilwell performance
performance byby comparing
comparing pressure
pressure
functions
functions which
which dictate
dictate the
the respective
respective flow
flow equations.
equations. It
It
would
would appear
appear that
that Fetkovichs
Fetkovich's study
study answers
answers the
the request
request in
in
Vogels
Yogel's paper
paper for
for field
field verification;
verification; the
the Vogel
Yogel correlation
correlation
cannot be
cannot be used
used without
without first
first determining
determining that
that HVF
HYF effects
effects
A.8-4
A.8-4

are
are insig
insignific ant, and
and this can
can only
only be
be done
done by running a
running
multi rate test.
multirate test.

The
The prese
present study
study build s on the sugge stionn that gas-an
suggestio d
gasand
oilwe ll pe~fo
oilwell performan
rmanc e are simil
ce ar and can be studie
similar studiedd using
using a
singl e approach.. In parti cular , a dimen
single appr oach sionle
dimensio ss soluti
nless on of
solution
the radia l flow equat ion includ
equation ing HVF effec ts is presented
including
in terms
terms of the pseud opres
pseudopr sure
essu re funct ion.
function. A
P simpl e
simple
correlation
lation is given given to estimate if if HVF shoul d be
should
consi dered
considere d..

The oil pressure funct ion is define


function definedd for both saturated and
under satura
undersatu ted oils with wellb
rated ore flowin
welibore flowingg press ures above
above
and below
below the bubbl bubblee point
point.. The resul ting expre ssions
expressio ns for
dimen
dimensiosionle
nlessss pseud opres
pseudopr sure
essu re are simpl
simplee to use (simi lar to
(similar
Vogel
Vogels'S relatiion)
relat on) and readi
readilyly determ ined.
determine d. It is shown that
the Eving
Evingeer-Mu
rMuskatskat (EM) stead y-sta
steadys te method of estimating
tate
oil pseud
pseudopropressure
essu re is accur ate enou
accurate enough
gh to reprod uce Vog
reproduce vogel 's
els
results based
based on a nume ricall simul
numerica ator.. The EM method is
simulator
simpllified
simp i fied by the introd uctio
introduct ionn of a genegenerraliz
alized relatiive
ed relat ve
permeeabil
perm abilit
ityy relat
relatiion.
on. It also appea rs that the EM
appears
pseud
pseu opres
dopr sure
essu re can be used to analyze transient well test tests
s..
A.8-S
A.8-5

EQUATIONS
EQUI\TIONS AND
IND DEFINITIONS
DEFINITIONS

A
R general
general expression
expression for
for the
the rate-pressure
ratepressure relation
relation of
of
aa given
given phase
phase (oil,
(oil, gas,
gas, or
or water)
water) is
is

PR
PR
q = CC
= JI F(p)dp,
F(p)dp (1)
(1)
Pwf
Pwf

where q
where q is surface rate; C C is a constant composed of
formation rock
formation rock properties, drainage geometry, and nonideal
characteristics such as partial penetration; F(p) is a
characteristics
pressure function evaluated from wellbore
pressure welibore flowing pressure,
Pwf, to
to average reservoir
reservoir pressure, PR.
PRo

Using the pressure function suggested by IUHussain


Using the AI-Hussainy,
y, Ramey,
and 11
and Crawford
Crawford for real gas flow, Eq.
Eq. 11 can
can be
be written

~akhTsc
oJ PR (2p/iigZ)dp
1rakhTs PR
qg = _________
= .1 (2p/lJg Z)dp. (2)
(2)
Tpsc{ln(r e/rw)-3/4+S}
Tpsc{ln(re/rw )_3/4+5} Pwf
Pwf

Using
Using the
the pressure
pressure function
function suggested
suggested by
by Evinger
Evinger and
and Muskat
Muskat
for
for oil
oil flow,
flow, Eq.
Eq. 11 can
can be
be written
written

2~akh 2rrakhPR PR k ro
kro
qo
0
q =
=------- .J
.1 dp
dp (3)
{In (r /r )-3/4+S}
{ln(re/rw) e w 3/4+s} Pwf
Pwf B
0
p
lJoBo

The
The definition
definition of
of CC and
and F(p)
F(p) should
should be
be obvious
obvious for
for
Eqs. and 3.
Eqs. 22 and 3. kh is
kh is the
the permeability
permeability-thickness product;
thickness product;
r e/rw is
is the ratio
the ratio ofof externalto
external-to-wellbore radius,
wellbore radius,
suggesting
suggesting aa radial
radial drainage
drainage area;
area; 3/4
-3/4 results
results from
from the
the
A.8-6
A .8-6

assum ption
assumpti on of
of pseud ostea
pseudost dy-sta
eady te flow,
state flow, asas does
does the use of PR PR
instea
insteadd ofof initi al or
initial or exter
external bound ary press ure; T
boundary T is the
reser
reservoir
voir tempe
temperatu
rature
re in
in absol ute units
absolute units, while
while Tsc
Tsc and Psc
Psc
defin
define standard condi tions;
condition s; s is the stead y-sta
steadys te skin
tate
facto
factor reflec ting the comp
reflecting osite
composi te effec
effect of nonid eal
nonideal
condi
condition
tions;
s; ~g
Ug and ~o are gas and oil visco viscosities
sities;; Z
Z is the
gas comp ressib
compress ilityy facto r; a is a units conve
ibilit rsionn const
conversio ant
constant
given
given in Table
Table 1.I for field and SPE prefe rred SI units .

The cente red-wwell


centered ell,, radia l-drai
radiald nage
raina ge assum ption
assumpti on can be
corrected by a skin facto r (as sugge sted by M.J. Fetko
suggested vich
Fetkovic h
in a personal comm commun unicat
icatiion)
on) equal
equal to 0.51n (31.62
O.5ln(31 /CA),
.62/C A),
wheree CA is the ~ietz
wher Dietz shape
shape factor. Earlo
Earlougher
2 12
ugher givesgives
value
valuess of CA for numer
numerououss draina
drainage ge shape
shapes.s. By inspe ction
inspectio n it
is seen that the effect of nonra dial draina
nonradial drainagege bound ariess is
boundarie
usual
usually
ly small
small:: if CA=O.l (very nonra dial or off
nonradial off -cent ered)
cente red)
then s=2.9
s=2.9,, if CA=10
CA=lO (mode rately
(moderate ly nonra dial)) then s=0.6
nonradial sO.6.. The
same obser vation
observati on is made quali tative
qualitativ ly by Musk
ely Muskat.
1 at.l

Trans ient Oeliv


Transient erabi
Delivera lity
bility

The pseu
pseud ostea
dost dy-sta
eady statete (pss) assuassum ption
mpti on is only valid
if prod
if produ ction
uctio n time is long enoug enoughh that the outeouterr boun
bound ary
dary
has felt the effectt of produ
prod ction.
uction. For tight,,
For
low-pperm
low ermea bility
eabil formaation
ity form tionss or shor
shortt prod
produ ction
uctio n tests thethe
assum
pss assu ption
mpti on may need to be repla replac ed by aa transient
ced ient
(time
(tim -depe
ed epenndent
dent)) ormu
rormulation
latio n.. This
This is
is done byby replacing
cing PR
PR
with initiial
with init al reservoir
voir pressure ure and
and the
the term ln(re
In(re/rw)
/rw)- 3/4
3/4
with an
with an appr
appro priate
opria expre
te expr ssion
essio dimen
n for dime sionle
nsio ss pressure.
nless ure.
In most
In most situations
tions,, an
an expr
expre ssion
essio for the
n for the transient
ient form
form of
of
In(re/rw)
ln(re /rw)- 3/4 is is thethe logarrithm
loga ithmiicc appr
approximat
oxim ion to
ation to
dimen
dime sionless pressure,
nsio nless ure, pj,
PO, (t(to>1
>
0 lO) 0):
:
A.8-7
A.87

In(r
ln(re/rw)-3/4 PD Z ~{ln(to)+O.80907}
e/r w)-3/4 * PO {ln
)
0 +0.809(t 07} (4a)
(4a)
.

For
For stimulated
stimulated wells
wells with
with induced-vertical-fracture
inducedverticalfracture
halflength ,, xf,
half-length Xf, an
an early-time
earlytime expression
expression (to<O.I)
<0.lJ is
0
(t is the
the
uniform-flux
uniformflux approximations
approximation:

In(r e/r w)-3/4 * PO


ln(re/rw)_3/4 PD Z Into, . (4b)
(4b)

which may apply


apply for
for months or years in low-permeability
lowpermeability
reservoirs.

Dimensionless time, to, is given by


Dimensionless

atkk
at
to
tD = ___--:::- ..tt. ..............................
= (5a)
~lJiCtFw2

If
If the
the well
well is vertically
vertically fractured then xxf should replace
replace
rw in
r in Eq.
Eq. 5a;
Sa; also, if
if Eq.
Eq. 4a applies, then 0.80907
0.80907 should
should
be
be replaced
replaced by
by 2.80907.
2.80907. Other
Other PD
Po solutions
solutions can
can be
be used
used
instead
instead of
of Eqs.
Eqs. 4a
4a and
and 4b.
4b. Earlougher gives
Earlougher gives numerous
numerous PD
PO
solutions
solutions applying
applying to
to aa variety of
variety of wellbore
wellbore and
and
externalbo
external-boundary geometries for
undary geometries for large
large ranges
ranges of
of tj.
to'

Production
Production time
time required
required to
to use
use the
the simplified
simplified pss
pss
formulation
formulation is
is given
given by
by

~lJiCtiA
tp55
tpss =- - - tfJp
=
tOApss (5b)
(5b)
atk

For
For most
most applications,
applications, tOApss of
of 0.1
0.1 can
can be
be useo;
used; this
this also
also
applies
applies to vertically fractured
to vertically fractured wells.
wells. Values
Values of
of tDpss
tOApss for
for
A.S-S
A.8-8

nonra
nonradial
dial geometries
etries can be found in Ref. 12. In Eqs. 5a
and 5b, c is poros
and 5b, ity; Ui
porosity; i and Ctictj are visco sity and total
comp ressib
compress ility
ibilit y at initial pressure; A A is the draina ge area;
drainage
kk is the absol
absoluteute perme abilit
permeabil ityy and at
at is a units conve rsion
conversio n
factor gi vOn in Table 11 for field and SPE preferred SI
givUn
units. For partially deple ted reservoirs Ui
depleted pj and Cti
Ctj should
should
be evaluated at avera ge reservoir pressure.
average

For many reservoirs it may take from a few hours to seve severral
al
weeks to reach pss condi tions.
condition s. In these cases
cases the
stabilized deliverab
erabiility
lity curve can be determ ined
determine d from a
transient mult
multiirate
rate test and shoul
shouldd apply for long periods
of time
time.. The only chang
changee in deliv erabi lity results from
erability
changess in the pressure integral in Eq. 1.
change

Low-p ermeability
Lowpermea bility (k<lm
(k<lmdd)) forma tionss may requ
formation requiire
re year
yearss or
even decad
decadeess to reach stabilized lized flow
flow.. In such cases cases the
conceept
conc pt of stabilized deliverab erabiility
lity is no longe
longerr valid. The
const ant C
constant C in Eq. 11 change
changess contcontiinua
nuall
llyy and the
erabiility
deliverab lity relat
relatiion
on must be upda update d accor
ted dinglly.
according y. Both
Both
low- and moder
low mOderate-permea
atep ermeab bility
ility reservoirs may producproducee at aa
consttant
cons ant weli
wellb ore or
bore or surface ce pressure. Once again
Once again the
conceept
conc pt of stabilizedlized deliv erab
erabiility
lity isis not directly useful;
inflow
inflo perforrman
w perfo mance is aa ratet
ce is rate-t ime instea
ime inste d of
ad of aa rate
rate-ppress
ressuure
re
relatiion.
relat on.

High Velo
High Veloc ity Flow
city Flow (Tur
(Turb ulenc
bule e)
nce)

The effec
The effectt of
of turbulence or or high velo
veloc ity flow (HVF) is
city is
not inclu
not includ ed in
ded in Eqs.
Eqs. 11 toto 3.
3. It It is
is commo
commonly
nly acce
accep ted that
pted that
gas flow can
gas can be
be influ
influe nced
ence by HVF.
d by HVF. This
This effectt is is usua
usuallly
ly
expre
expr ssed as
essed as aa rated
rate-depend
ependeent skin,, Dqg.
nt skin Dqg' Fetk
Fetko vich
ovic givess
h give
concllusiv
conc usive evide
e evid nce that
ence that HVF
HVF also
also exist
existss in
in saturatea
ated and
and
underrsatu
unde satura ted oil
ratec oil syste
system s. iield
ms. f ield data
data sugg
sugge st that
est that HVF
HVF can
can
dominate
nomin ate the
the oil
oil-rrate
ate equa
equattion
ion and
and that
that rated
rate-depend
ependeent skin
nt skin
A.8-9
A.8-9

is
is equally
equally applicable.
applicable. Based
Based on
on these
these observations
observations the
the
following
following developments
developments were
were made
made to
to generalize
generalize the
the analysis
analysis
of
of multirate gas and
multirate gas- and oilwell
oilwell tests,
tests, including
including prediction
prediction of
of
stabilized
stabilized deliverability.
deliverability.

First, an
an . equation was developed toto estimate
estimate the
the minimum
minimum
rate,
rate, qHVF,
qHvF, atat which
which HVF
HVF effects
effects might
might be expected,
expected,

rhii
qHVF
qHvF- = aHVF , (6)
(6)
yY

where rwr is the wellbore radius; hp h is the perforated


producing thickness; ~i is gas or oil viscosity at the
producing
minimumexpected wellbore flowing pressure; y is specific
minimum-expected
gravity of
gravity of gas or oil at standard conditions, relative
relative to
air
air or
or water, respectively; aHVF aHVF is a units conversion
factor given
factor given in Table 1 1 for field and SPE preferred
preferred SI
S1
units.
units. Eq. Eq. 66 is derived by
by assuming aa Reynolds
Reynold's number
number of
of
one at
one at the
the onset
onset of
of HVF,
HVF, and
and an
an average grain
grain diameter of
of
O.5m.lh1)
O.5mm. 1 ,lU The
The assumptions were made intentionally to to give
give
aa pessimistic
pessimistic estimate of qHVF.
estimate of

For
For saturated-oil
saturatedo il reservoirs,
qHVF for
reservoirs,
qHvF- for gas
gas should
should be
be
compared
compared with
with gas
gas rate
rate calculated
calculated from
from q
(qo(R-R
0 RR) s ) where
where q
qo is
0 is
the
the maximum
maximum oil
oil rate
rate expected
expected during
during stabilized
stabilized production,
production,
RR is
is the
the producing
producing gasoil
gas-oil ratio
ratio (GOR) and
(GOR) and Rs
Rs is
is the
the
solution
solution GOR
GOR at
at the
the minimum-expected
minimume wellbore flowing
xpected wellbore flowing
pressure.
pressure. 1A multirate
multirate test
test should
should be
be run
run if
if either
either gas
gas or
or
oil qHVF is
oil qHVF is lower
lower than
than the
the maximum
maximum gas
gas or
or oil rate expected
oil rate expected
during
during stabilized
stabilized production.
production.
A.8-10
A.8-1Q

Rewr iting
Rewrit ing Eq. 1
1 and including rated
rate-depend ent
epende nt skin, Oq,
Dq, gives

In(r e/r w
ln(re/rw )-3/4++s
j3/4 S PR
PR
qq =
= C
C f
f F(p)d
F(p)dpp. (7)
ln(r/r)_3/
In(r e/r w)-3/4+
4+sis+0q
-Dq Pwf
Pwf

The following defin itions


definit ions are made to simpl
simpliify
fy the following
development:

p
P
m(p) = JI
= F(p)d
F(p)dpp, .... ...... .... ...... .... ..... (8a)
Pa

md
mj =
= 1
1 - m(pw
m(pwff)/m(P
R),
)/m(pR ) (8b)

Qmax
Qmax = C-m(P
Cm(pRR),
) . ... ..... . .. . (8e)
(8c)

qd
q =
= q/Qma
q/Qrnaxx, .... .. . .. .. (ad)
(8d)

0d = Qmax
Dd = Qmax O.
D (8e)
(8e )
In(r /r
ln (re/rw)
e w )-3/4+
3/4+ ss

The defin
definitition
ion of pseudpseudo opres sure
pressu funct ion,
re functio n, m(p), uses
atmos
atmosppheric
heric refere
referen nce
ce press
pressuure
re (the lower integ ration
integra tion limit))
accor
accordding
ing to the definition of OFP. AOFP. md
m is aa dimen
dimenssionle ss
ionless
form of the pseud
pseudoopressure
pressu re drop which equal
equalss q/Qmx
q/Qmax if 0=0.
if D0.
Qmax is a theo
max theorretic
eticaall (noH
(no-HVVF)
F) POFP,
AOFP, wherea
whereass the true AOFP,
AOFP,
qmax,
qmax, may only be a a small fracti on
fractio n of Qmax
max if HVF effects
are signi fican
significa t.
nt. The defin ition
definit ion of dimensionle
dimens ss
ionless
A.8-1 1
A.8-11

ratedependentskin term,
rate-dependent-skin term, 0d,
d results
0 results from
from the
the previous
previous
definitions.
definitions.

Solving
Solving Eq.
Eq. 77 in
in terms
terms of
of dimensionless
dimensionless parameters
parameters gives
gives

22 ++ qd
Dq
Dd-qd m
q - md 0
== 0, ..................... (9)
(9)

or
or
.5
11 ++ (1 ++ 4.0dmd)0.S
4Ddmd)
qd ; 00 0 .... (lOa)
Dj j 0, (lOa)
20d
2

qd = md
= mj ; Dd = 0................. (lOb)
= O

Fig. 1
Fig. 1 presents the solutions of Eq. 9 9 graphically for
several values
values of 0d. This log-log
loglog type curve has proven
useful for analyzing multirate test data and predicting
useful predicting
stabilized
stabilized deliverability
deliverability..

PRESSURE FUNCTION
PRESSURE FUNCTIONSS

The
The pressure
pressure function,
function, F(p),
F(p), in
in Eq.
Eq. 11 is
is defined
defined
differently
differently for
for gas
gas and
and oil
oil systems.
systems. The gas
The gas function
function only
only
considers
considers pressure effects caused
pressure effects caused by
by fluid
fluid properties;
properties; note
note
that p/llgZ is
that P/ugZ is directly
directly porportional
porportional to
to l/ugBg.
1/llgBg. The
The oil
oil
function
function includes
includes the
the pressure
pressure dependence
dependence of
of oil
oil relative
relative
permeability
permeability,, implying
implying twophase
two-phase gasoil
gas-oil flow.
flow. Gas
Gas
condensate
condensate reservoirs
reservoirs also
also exhibit
exhibit twophase
two-phase gasoil
gas-oil flow.
flow.
They
They are
are not
not considered
considered here
here because
because of
of insufficient
insufficient
understandin
understanding and estimation
g and estimation of
of their
their PVT
PVT properties.
properties.
A.8-12
A.8I?

Gas Reservoirs
Gas Reservoirs
Calculation of
Calculation of the
the pseudopressure
pseudopressure function
function cancan bebe
simpli fied by makin
simplified by making certain assumptions
g certain assumptions about
about the
the behavior
behavior
of the pressure function.
of the pressure 3 13
function. F(p) F(p) for
for gases
gases can
can be
be separated
separated
into three region s
into three regions as shown in Fig.
as shown in Fig. 2.2. The
The low-pressure
lowpressure
region (<10000 kPa
region 10000 kPa oror 1500
1500 psia)
psia) can
can be
be approximated
approximated by by aa
straight line
straight line with
with zero
zero intercept,
intercept, yielding:
yielding:

F(p)
F(p) .(..i..)
2 1
= 2(_)p*p,
= (lla)
(ha)
UgZ
JJgZ
and
and
md
md = 11 -
=
(Pwf/PR)2,
(Pwf/PR) (lIb)
2 (lib)

where p* is
where p* is any
any low pressure
pressure in the linear region.
region. Eqs.
Eqs. 11
11
can actuall y be
can actually be used
used in any pressure
pressu re region ifif the
the drawdown
drawdown
is small enough
is small enough and p*
and p* is taken as the averag average of PR
e of PR and
and
Pwf.
Pwf Unfort unately this
Unfortunately this latter
latter case
case is
is seldom
seldom found
found in
in
practic e and it
practice and it should
should not
not be
be used
used unless
unless the
the assum
assumptions on
ptions on
which
which it
it is
is based
based are
are fully
fully unders
understood.
tood.
A.8-13
A.813

At
It high
high pressures
pressures (>22500
(>22500 kPa
kPa or
or 3500
3500 psia)
psia) the
the
gas
gas F(p)
F(p) function
function is
is nearly
nearly constant
constant and
and the
the following
following
simplification
simplification results:
results:

F(p)
F(p) = 2.(~)
= * z constant,
constant . . . . . . . . . . . . . . . . . .. ((12a)
128 )
llgZ
1.IgZ p

and
m
md = 11 - (Pwf/PR),
- (Pwf/PR) .. (12b)
(12b)

p* is any pressure in the region where F(p)


where p* F(p) isis
constant,
constant, though the value at PR
PR is
1S often used. This case
corresponds to a constant productivity index. The problem
problem
wi th using
with using Eqs. 12 is that wellbore
welibore flowing and average
average
reservoir pressure must always remain in the high-pressure
highpressure
region where F(p) is constant.
region

Ps the
As the search for gas reservoirs goes deeper and to to
lowerperm
lower-permeability
eability formations, the the range PR PR to
to Pwf
Pwf often
often
stretches over
stretches over all
all three
three pressure
pressure regions,
regions, thus
thus making
making both
both
the low
the low- and
and highpressu
high-pressure assumptions invalid.
re assumptions invalid. In general
general
the intral
the integral form
form ofof m(p)
m(p) given
given inin Eq.
Eq. 22 should
should bebe solved
solved
numerically, graphically
numerically, graphically or or analytically.
analytically. The resulting
The resulting
m(p) function
m(p) function is
is valid
valid for
for both
both wellbore
wellbore flowing
flowing and
and average
average
reservoir pressures
reservoir pressures during
during the
the entire
entire production
production life
life of
of aa
gas well.
gas well. 11
A.8-14
A.8-14

Oil Reservoirs:
Oil Reservoirs: Simplified
Simplified Approach
1\pproach
Fetkovich suggests
Fetkovich suggests that
that F(p)
F(p) for
for oil
oil systems
systems can
can be
be
approximated by
approximated by two
two straight
straight lines
lines joined
joined atat the
the bubble
bubble
point. This
point. This is shown schematically
is shown schematically in in Figs.
Figs. 3.3. Above
above the
the
bubble point,
bubble point, F(p)
F(p) only
only reflects
reflects the
the pressure
pressure dependence
dependence ofof
oil viscos ity
oil viscosity and formation
and format ion volume
volume factor.
factor. Defining
Defining yy as
as the
the
ratio of
ratio of F(PR)
F(pR) to
to F(Pb),
F(pb), then
then

(IQBQ)pb
yy =
= . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ((13)
13 )
(oBo)pR

for
for PR~Pb.
PRPb

Defining x
Defining x as the ratio of F(Pa)
F(pa) (Le.,
(i.e., at atmospheric
atmospheric
pressu re) to
pressure) to F(Pb),
F(pb), then
then

(kro/lloBO)Pa
(kro/ioBo)pa
xx =
= . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. (14)
(14)
(kro/uo Bo Pb
(kro/lloBo)Pb

for PR~Pb.
for PRPb
For
For unders aturated
undersaturated reservoirs
reservo irs there
there are
are two
two cases
cases to
to
consid er, as
consider, as shown
shown in
in Figs.
Figs. 3a
3a and
and 3b.
3b. Case
Case II corresp
corresponds
onds
to a compl etely
to a completely unders
undersaturated reservoir
aturated reservo where PbPwf
ir where Pb~Pwf~PR.
PR.
Case
Case II
II corresp
corresponds
onds toto anan unders
undersaturated reservoir
aturated reservo with
ir with
wells
wells produc ing at
producing at flowin
flowing pressures
g pressu below the
res below the bubble
bubble point,
point,
or
or PwfPb PR. For
Pwf~Pb~PR. For both
both cases
cases the
the F(p)
F(p) functio
function is given
n is given by
by
A.8-1S
A.8-15

(ly)Fb
F(ppb) = Fb + (PPb) . . . . . . . . . . . . . .. ((15a)
.
15a)
(Pb PR)

and
and

(1-x)Fb
(lx)Fb
F(p~Pb)
F(ppb) = xFb
= xFb ++ .p. (15b)
(15b)
Pb
Pb

Fig.
Fig. 3c
3c shows
shows Case III
III for saturated oil reservoir at or
for a saturated
below its bubble point. Generalizing the definition of of xx as
the ratio
the ratio of
of F(Pa) F(pR) at PR~Pb,
F(pa) to F(PR) pRpb, and assuming it
remains constant at all stages of depletion, the general
form of the saturated-pressure
saturatedpressure function is

(l-x)FR
(lx)FR
F(PSPb)
F(ppb) = xFR
= xFR +
+ .p. (16)
(16)
PR
A.8-16
A.816

Using the linea r relati ons sugge


relations sted by Eqs. 15 and 16,
suggested
the follow ing
following three expre ssions
expressio ns for dimen sionle
dimensio ss
nless
pseud opres
pseudopr sure,
essu re, md,
md, resul t:

Pb~Pw
PbPwf~PR
fPR : Comp
Complletely
etely Unde rsatur
Undersat ated
urate d

mj = 2.vy.(p/p-pf/p)

+ v(l-y)
2
(PR/ PbPwf/Pb) (17)
(PR/pbi)

Pwf~P
PwfPb~PR
bPR : Unde rsatur
Undersat ated;
urate d; Satur ated Flowing Press
Saturated ure
Pressure

m = 1 2vx.(pWf/pb) 2
(1.x) (pwf/pb)
-
-
(18)

where
11 _ _ _
v = _____ ; ..... ..... ..... ..... .. (19)
(x+l)+(y+l)(
(X+1)+ (y+1)(PR/Pb
pR/pb--1)
1)

Pwf~P
PwfPR~Pb
RPb : Comp
Complletely
etely Satur ated
Saturated

mj = 1 v(pf/p) 2
(iVH pwf/pR)

-
(20)

where

2x
2x
vv = =
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. (21)
(21 )
lx+l)
(x+1)

It was found that the minim


It minimuum
m valu
valuee ofof yy for phys
physiicall
cally
y
realistic systems rang
range
ess from 1.0 to 0.885
1.0 to 0.885 for PR/Pb
PR/Pb of 1.01.0
to 2.0,
to 2.0, as
as shown in Fig. 4a.4a. The effectt of yy on on m
md (i.e.
(i.e.,,
qo!qomnax
qo/qor ax if
if D=0)
0=0) is negl
negliigibl
gible , as
e, as shown inin Fig.
Fig. 4c.
4c. if
If yy is
is
set to
set to one,
one, then
then appr
appro ximat
oxim atee ress
expreion
ssionss can
can be
be writt
writteenn for
Eqs. 17, 18 and 19,
19,
A.8-17
A.8-17

Pb~Pwf~PR
PbPwfPR :: Completely
Completely Undersaturated
Undersaturated

md == 2v(PR/Pb-Pwf/Pb),
v(pR/pb-pWf/pb) ....... (22)
2 (22)

Pwf~Pb~PR
PwfPbPR : Undersaturated;
Undersaturated; Saturated
Saturated Flowing
Flowing Pressure
Pressure

md = 1 - 2vx(pwf/pb) - 2
v(l-x)(pwf/pb ) (23)

where
where
1
v
v
==
; (24
(24))
(x+1)+2(PR/Pb-1)
(x+l )+2(pR/pbl)

The general
The general quadratic relation for saturated oils, Eqs. 20 20
and
and 21, can probably be used for both undersaturated
undersaturated and
and
saturated conditions. The resulting simplicity should
usually outweigh any loss in accuracy. The dashed curves in
usually
the lower half of Fig. 4c illustrate the potential error in
using
using Eqs.
Eqs. 20 and 21. Fig. Sa
5a shows the saturated-oil
saturatedoil
pressure
pressure function, relative to its value at average
reservoir pressure, correspondin
reservoir corresponding values of
g to various values of VV in
Eq.
Eq. 20.
20.

It
It cannot
cannot be
be overemphasized
overemphasi zed that if
if HVF
HVF effects
effects are
are
neglible
neglible (DtJ) then m=q/q.
(0=:0) then md=q/qmax' For example,
For example, the
the simplest
simplest
relation, as
relation, as suggested
suggested by
by Fetkovich,
Fetkovich, assumes
assumes the
the pressure
pressure
function
function has
has zero intercept (x=0;V=0),
zero intercept (x=O;V=O), resulting
resulting inin

q/qmax
q/qrnax = 11 - (Pwf/PR)
= (Pwf/PR)2,
2 . (25)
(25)

which
which can
can be
be compared
compared with
with Vogels
Vogel's relation
relation (x=l/9;V=0.2
(x=1/9;V=0.2),
),
A.8-18

q/qrnax 1 O.2(pwf/pR) 2
0.8(p wf/pR) . (26)

Actua lly, Eq. 20 is aa speci


Actually, special al case of Eq. 18 when pR/pb=PR/Pb=l.l.
The same quadr atic form is given by Richar
quadratic Richardson
dson and Shaw (see
Fig. 5b). They sugge
suggesstt the equat ion
equation as an intuitive
gener alizat
generaliz ion of Voge
ation Vogell'ss relati on (V=0.
relation (V=O.2, 0=0)
D=0) for
saturated reservoirs. vogel
Vogel's s results actually show a
variation in V V from 0.1 to 0.7. It appea appearrs
s that V V remai
remainnss
consttant
cons ant during most of of deple tion and increases after
depletion
recov eriess of 88 to 10% initi
recoverie initia all oil in place. voge l'ss avera
Vogel averaggee
value of V=0.2
V0.2 corres
correspponds
onds to early deple tion..
depletion

Physi cally
Physicall y,, VV of 0.2 for saturated reservoirs corres ponds
corresp onds to
a linear F(p) funct ion with interc
function ept equal to one-n
intercept onenineth
ineth
the value at avera gee reservoir pressure (see Fig. 5a). The
averag
value of F(PR)
F(pR) chang
changeess accor
accordding
ing to condi tionss dictated by
condition
the mater ial balance, as shown schem
material atical
schemati ly in Fig. 3c.
cally

For all field examples given by Fetko Fetkov vich


ich (exce pt Field A,
(except
which is a highly depl
depleeted,
ted, low-p ressurree reser voir), maximu
lowpressu maximumm
drawdown is 20% or less. It can be shown that indep indepeenden
ndentt
of the pressure funct ion used, backp
function ressur
backpress uree slope
slope nn appea
appearrs
s
the same at low drawdo drawdowns,
wns, though extrapola polatted
ed AOFP'
AOFPss
differ. Using delta-
deltapress
pressuure-s
resqquare
uaredd versu
versuss rate
corres
correspponds
onds to assum
assumiing
ng x x of zero (V=O)
(v=0),, which results in a
relati vely pessi
relatively misti
pessimis ticc AOFP
AOFP.. The error in AOFP and
stabalized deliv erab
erabiility
lity may vary
vary,, depen
depend ding
ing on the natur
naturee
of the true pressure funct ion. If HVF effects are riot
function. not
present (0=0) then the error caused by using the
delta-
deltapress ure-s
pressu quare
resq d plotti
uared ng technique can be expre
plotting expresssed
sed
as -100'x /(1+x) perce
100.x/(1+x nt.
percent.

Fig. 66 shows aa Fetko


Fetkov vich
ich example plotte d as oil rate versus
plotted
1-(Pw
1(pw
,
2 f/PR)2
f/pR), corresp
correspondi ng to xx of 0.0 or V
onding V of 0.0, and oil
A.8-19
A.8-19

rate versus
rate versus 1-0.4(Pwf/PR)-0.6(Pwf/PR)2,
l0.4(pf/p)0.6(pWf/p) corresponding
,
2 corresponding to to xx
of 0.25
of 0.25 or or VV ofof 0.4.
0.4. Backpressure
Backpressure slope,
slope, n,n, is
is the
the same
same for
for
both curves (~
both curves ( 0.62),
0.62), but
but AOFP's
0FPs are 795 and 890
are 795 and 890 Sm Sm 3
/d
/d (5000
3 (SOOO
and 5600 STB/D), respectively.
and 5600 STB/D), respectively. The
The insert
insert figure
figure shows
shows
pressure functions
pressure functions corresponding
corresponding to to the
the two
two definitions
definitions of of
md. Fetkovich
md. Fetkovich gives angives an analogous
analogous example
example (his(his Fig.
Fig. 22) 22)
showing that
showing that delta-pressure
deltapressure (V=l,(v=l, x=l)
x=l) versus
versus rate
rate yields
yields an an
1\OFP of
AOFP of 5406 Sm /d (34000
5406 /
3
Sm 3
d (34000 STB/D)
STB/D),, whereas
whereas usingusing
deltapressuresquared (V=O,x=O)
delta-pressure-squared (V=0,x0) versus
versus rate
rate yields
yields an an AOFP
P0FP
of 1526 /
3
Smd3
of 1526 Sm /d (9600 ST8/D); backpressure
(9600 STB/D); backpressure slopes
slopes of of both
both
plots
plots areare the
the same
same (n=0.81).
(n=0.81).
A.8-20
A.8-20

Oil Reservoirs:
Oil Reservoirs: Evinger-Muskat
EvingerMuskat Method
Method
Evinger
Evinger and
and Muskat
Muskat suggest
suggest aa method
method for
for calculating
calculating thethe
m(p) function
m(p) function from
from PVT
PVT and
and relative
relative permeability
permeability data.
data. It It
assumes that producing
assumes that producing GORGOR is
is constant
constant at
at all
all points
points inin the
the
reservoir.
reservoir. This
This method
method isis probably
probably the
the most
most rigorous
rigorous
availab le without
available without access
access toto aa simulator.
simulator. ItIt is
is shown
shown in
in this
this
study that
study that Vogel's
Vogels results,
results, based
based on
on aa numerical
numerical model,
model, can
can
be reproduced
be reproduced using the
using the steady-state
steadystate method
method ofof Evinger
Evinger and
and
Muskat (see
Muskat Fig. 7).
(see Fig. 7).

First, PVT
PVT properties
First, properties (R (Re, 0 , ~o'
s , 8B
,
0 1-o 8Bg and ~g)
g and Pg) are
are tabulated
tabulated
from initial
from initial toto atmospheric
atmospheric pressure
pressure (see
(see Table
Table 2).
2). The
The
producing GOR,
producing GaR, R, is specified.
R, is specifi ed. At Pt each tabulated
tabulated pressure
pressure
the gasoil relati
the gas-oil relativvee permeabili ty ratio, krglk
permeability ro ,, is
krg/kro IS
calculated from the relation
calculated relation

~g(p)8g(p)
g(p)Bg(p)
krg/kro(P) = {R-Rs(p)}
krg/kro(p) {RRs(p)} _ _ __ . . . . . (27)
(27)
~0(p)80(p)
(
0
( p)B
p)

If
If experimental
experimental relativ
relative data are
e permeability data are availab
available,
le,
krg/kro should be
krg/kro should be plotted directl
plotted directly versus ,
y versus kro
1
k 0, asas shown
shown
in
in Fig.
Fig. 8.
8. If
If experimental
experimental data
data are
are not
not availab
available, then one
le, then one
of
of the
the curves
curves in
in Fig.
Fig. 88 can
can be
be used.
used. Pore size
Pore size distrib
distribution
ution
factor
factor of
of one
one should
should be
be used
used for
for most reservo
most reservoirs;
irs; ten
ten
applies
applies to
to unconsolidat
unconsolidated sandstones and
ed sandstones and onehalf
one-half to
to highly
highly
consolidated
consolidated sandstones.
sandstones.

Having
Having calcula ted krg/kro
calculated krg/kro(P) from Eq.
(P) from Eq. 27,
27, kro(p)
kro(p) is
is found
found
from the
from the relativ
relative permeability relatio
e permeability relation. The pressu
n. The pressure
re
function kro/~080
function kro/oB is tabulat
o is tabulated and plotted
ed and plotted versus
versus pressu
pressure.
re.
The
The m(p)
m(p) function
function can
can be
be calcula
calculated numerically as
ted numerically as follows.
follows.
First,
First, F(p)p
F(p)6p isis calcula
calculated
ted atat Pk
Pk, where
where F(p)
F(p) is
is the
the
average
average of
of values
values evaluated
evaluated at
at pressu
pressures Pk and
res Pk and pj, and
and
6p=Pk-Pj' The
P=PkPj The m(p)
m(p) function
function is
is calcula
calculated by summing
ted by sunming the
the
A.8-21
A.8-21

FF(p)tp values, starting


(p). 6p values, starting at at atmospheric
atmospheric pressure.
pressure. The
The
calculation procedure
calculation procedure is
is shown
shown in
in Table
Table 2.
2.

Dimensionless pseudopressure,
Dimensionless pseudopressure, md, mj, can
can be
be calculated
calculated and
and
plotted versus
plotted versus P/PR
P/PR asas shown
shown inin Fig.
Fig. 7.
7. The
The best-fit
bestfit value
value
of V for Vogels
of V for Vogel's results is
results is 0.2.
0.2. TheThe Evinger-Muskat
EvingerMuskat methoa
methoc
usually reproduces
usually reproduces simulated
simulated results
results with
with good
good accuracy.
accuracy.

The EM
The EM method
method also
also can
can be
be applied
applied to
to analysis
analysis of
of transient
well
well tests. Although
Pdthough this application is not rigorous it it
appears to
appears to be accurate enough
enough for practical puposes.

Raghavan1~
Raghavan suggests separate drawdown and buildup
pseudopressure functions.
pseudopressure The calculation procedure for
each is
each is essentially
essentially the same as proposed by Evinger and
Muskat.
Muskat. At/t a given drawdown time and wellbore
welibore flowing
pressure, producing
pressure, producing GOR is used to calculate krg/kro krg/kro
(Eq. and therefrom
(Eq. 27), and kro , krol~oBo
therefrom kro, kro/poBo and m(pwf).
m(pwf). Producing
GOR
GOR at shutin is
at shut-in buildup
is assumed to apply throughout the buildup
period.
period.

Boe,
Boe, et al. 15 show
et 5
al. show that
that after
after very
very short
short times
times the
the producing
producing
OCR becomes
GDR becomes constant
constant during
during transient
transient testing
testing.. In
In practice
practice
this
this means
means that
that observed
observed GOR
GOR is
is constant
constant during
during aa drawdown
drawdown
test
test and
and can
can be
be used
used to
to calculate
calculate both
both drawdown
drawdown and
and buildup
buildup
m(p)
m(p) functions.
functions. This method
This method was
was used
used to
to analyze
analyze drawdown
drawdown
and
and buildup
buildup tests
tests given
given by
by Raghavan,
Raghavan, resulting
resulting in
in estimated
estimated
permeabilitie
permeabilitiess of
of 6.19 and 6.45
6.19 and 6.45 md,
md, respectively;
respectively; model
model
permeability
permeability of
of 6.16
6.16 md
md is
is reported
reported by
by Raghavan.
Raghavan. Producing
Producing
OCRs
GOR's used
used by
by the
the EM
EM method
method in
in each
each case
case were
were 69.10
69.10 3/Sm
SmSm3
/Sm 3
3
(388
(388 scf/STB)
scf/STB) and
and 333.2
333.2 /Sm
3
SmSm /Sm 3 (1871
(1871 scf/STB),
scf/STB),
respectively.
respectively.

Boe,
Boe, et
et al.s
al.'s drawdown
drawdown and
and buildup
buildup tests
tests were
were also
also analyzed
analyzed
using
using the
the EM
EM method
method with
with RR of
of 267.2 Sm 3 /Sm 3 (1500
267.2 Sm/Sm
3 (1500 scf/STB).
scf/STB).
Estimated
Estimated permeabilitie
permeabi1itiess were
were 11.8
11.8 (short DC),
(short DO), 12.3
12.3
A.8-22
A.8-22

(BU; short
(8U; short DO)
DD) and
and 10.6
10.6 (BU;
(BU; long
long DO).
DO). Model
Model permeability
permeability
reporte d
reported by by Boe,
Boe, et
et a1.
al. is
is 10
10 md.
md. Although
Although the
the estimated
estimated
permea bilities are
permeabilities are only approximate, they
only approx imate, they are
are aa considerable
considerable
improv ement
improvement overover using
using pressure
pressure only.
only.

One problem
One problem withwith using
using thethe EMEM method
method is
is when
when producing
producing GORCUR
is less than
is less than Rs at 5
R at aa given
given drawdown
drawdown or or buildup
buildup pressure.
pressure. Eq.Eq.
22 gives
22 gives negative
negative krg/k
krg/kro for
for this
this situation,
situatio which also
n, which also cancan
ro
arise using the
ar ise using the Raghavan
Ragha van buildup
buildup method;
method; Raghavan
Raghavan does
does not
not
address the
address the problem.
problem. Based
Based on on limited
limited results
results in
in this
this study
study
it appear s that
it appears that bubble-pointt GOR
bubble poin CUR can
can be
be used
used instead
instead of of
produc
producinging GORCUR ifif R<Rsb.
R<Rsb. In practice
practice this situation
situation only
only
arises at early
arises at early stages of depletion
stages of depletion before critical
critical gasgas
saturat
saturationion hashas been reached
reached throughout
throughout the drainage
drainage radius
radius
of the well.
of the well.

NILYZ ING 4JLTIR


ANALYZING MULTIRATE DATA
ITE TEST DT

AA genera
generall procedure
proced ure is
is suggested
sugges ted for analyzing
analyz ing
multirate
multirate test
test data
data for gas
gas and
and oil
oil reservoirs.
reservoirs. The
The
dimen sionless logl
dimensionless log-log type curve
og type curve is is used
used toto determ
determine HVF
ine HVF
effects
effects and
and predict
predict deliver
deli verability
ability. If only aa single
If only single-rate
rate
well
well test
test is
is availab
available, then the
le, then the same
same proced
procedure is follow
ure is followed
ed
withou t type curve
without type-curve matching; aa value
matchi ng; value of
of 0Dd is
is assume
assumed (e.g.
d (e.g.
d
zero) or
zero) or estima ted from
estimated from aa correla
correlation.
tion.

Proced ure
Procedure
1.
1. Organi ze and
Organize and tabulat
tabulate available
e availab rock and
le rock and fluid
fluid data
data for
for
the
the particu lar well.
particular well.
2.2. Determ ine the
Determine the pseudc
pseudopressure function.
pressure functio n.

For
For gas
gas reservo
reservoirs m(p) isis defined
irs m(p) defined byby PVT
PVT data
data -

namely
namely Ug and
and Z.Z. First
First plot
plot p/p.
Z
0p/J,JgZ versus
versus pressu
pressure, then
re, then
A.8-23
A.8-23

integrate using
integrate using atmospheric
atmospheric base
base pressure.
pressure. Numerical
Numerical
integration using
integration using thethe trapezoid
trapezoid rule
rule is
is often
often simple
simple and
and
accurate (Table
accurate (Table 33 gives
gives an
an example
example of
of the
the procedure).
procedure).

oil reservoirs the


For oil. the EM
EM method
method can
can be be used
used to
estimate m(p).
estima~e m(p). Assuming
Pssuming R=Rsb,
RRsb, krg/kro' ro ' kro/~oBo,
krg/kro, kkro, kro/j.oBo, and
and
m(p) are
m(p) are calculated. For undersaturated
undersaturated reservoirs the
process isis continued
continued at P>Pb
P>Pb holding kkro
ro at its initial
(gasfree) oil
(gas-free) oil value. For
For partially depleted
depleted reservoirs
R may be considerably greater than Rsb
R RSb and the EM procedure
can be repeated. The results can then be simpli fied by
simplified
plotting md versus P/PR
plotting P/PR and fitting the data to one of the
curves in Fig. 4. The best-fit
bestfit value of VV is then used with
the generalized md relation (Eq. 21).

straightline pressure function for saturated


Using the straight-line
oils,
oi m(p)
Is, m(p) need only be calculated at average reservoir
pressure. The necessary relations are:

m(p) (
( kro ) J p{x ++ (1-x)P}dp
kro) (!-x)p}dp . (28a)
(28a)
= p
=
~oBo PR
B
0 PR 0
0 PR

or
or

m(p)
m(p)
k
kro)
= ((~)
= {xp
.
(l-X).p2}.
{xp ++ (l_x).2} ............ (28b)
(28b)
~oBo PR
B
0
ji PR 2PR
P
2 R

If
If VV is
is assumed,
assumed, then
then xx equals
equals V/(2V).
V/(2-V). Based on
Based on Vogels
vogel's
results,
results, VV is
is 0.2
0.2 and
and xx is
is 1/9,
1/9, resulting
resulting in
in
A.8-24
A.8-24

m(p)
m(p) = ~.(
=1.( kro)
kro) .
p2)
(p ++ ~.pZ) . (29a)
.
9 ~oBo
o PR
8
i-o PR PR
PR

Assuming x=O and V=O, as sugge sted by Fetko


suggested vich,
Fetkovic h, resul ts
ts
in a simpl er relati
simpler on which is recommended for pract
relation ical
practical
appli catio
applicati ns,
ons,

m(p) = ~.
= L..(k2
kro
ro ) .p2
).
..... ..... ..... ..... .... (29b)
2PR
PR \.1oBo
Po PR

For under satura


undersatu ted oils, first calcu late m(Pb)
rated m(pb) using
using Eq. 28
or 29 and PR=Pb
PR=Pb. m(p) at under satura
undersatu ted pressures is
rated
calcu lated from

m(p) = m(pb) + .(l+y)(p_pb).(kro


) . . . . . . . . . . .. (30)
uoo Pb

3. Note m(pR).

4. Convert each weli


wellbore
bore flow
flowin g pressure to a dimen
ing sionle
dimensio ss
nless
pseud
pseu opres
dopr sure
essu md.
re mj.

5. Plot mdm versus rate on tracin


traci g
ng paperr,,
pape using
usin g the
grid of Fig. 1.

6. Match the data with one of the 0 Dd type curv


d curveess by
adjussting
adju ting the traci
tracinngg paper from left
left to right, making
making sure
axes are held para
that axes paralllel
lel to
to the type
type curv
curve
e.. Only one
degreeee of
degr of freedom is allowed ed in the matchi
matching proce
ng proc ss.
ess.
shoulldd ensu
This shou ensurree aa unique
unique match.
match.
7. Note
7. Note the
the match poin
pointt:: q,
qM, qdM
qdM and
and DC.
Dd.
A.8-2S
A.8-25

8.
8. Calculate
Calculate the
the theoretical
theoretical maximum
maximum AOFP,
0FP, Q max = qw'qdM.
max qwqdM.
True P0FP,
True AOFP, qmax,
qmx, is read from the
is read from the matched
matched type
type curve
curve at
at
mj of
md of 1.
1.

9.
9. Assuming
ssuming permeability
permeability is
is known,
known, calculate
calculate the
the term
term
In(re/rw)-3/4+S.
ln(re/rw)_3/4+s. For
For gas
gas wells,
wells,

{In 4+s} = lTakhm(PR) Tsc


(re/rw)-3/4+S}
{ln(re/rw)-3/ = lrakhm(pR). , .......... (31a)
(31a)
Qmax Tpsc
Tpsc

and for
and for oil wells,

2lTakhm(PR))
2iTakhm(pR
{In(re/r w)-3/4+s}
{ln(re/rw) 3/4+s} =
= ................. (31b)
(31b)
Qmax

10. Calculate
10. {In(re/rw)-3/4+s}Dd/~ax.
Calculate DD from {ln(re/rw) 3/4+s}Dd/Qmax.

11.
11. Determine
Determine if
if flow periods
periods are stabilized
stabilized i.e., if
- i.e.,
if psspss
has been reached.
has been reached. If If weilbore
wellbore flowing
flowing pressure
pressure versus
versus time
time
plots
plots as
as aa straight
straight line
line on
on cartesian
cartesian coordinates,
coordinates, then
then flow
flow
is
is probably
probably stabilized
stabilized during
during production.
production. When
When
pressuretim
pressure-time data are
e data are not
not available,
available, Eq.
Eq. 5b
Sb can
can be
be used
used to to
estimate
estimate ifif production
production time
time is
is greater
greater than
than tpss.

12a.
12a. If
If 5tpss
t is reached
5 is reached during
during flow
flow periods
periods then
then the
the ratemd
rate-md
curve traced
curve traced from
from the
the type
type curve
curve isis the
the stabilized
stabilized
deliverability curve.
deliverability curve. The term
The term ln(re/rw)3
In(re/rw)-3/4 should be
/4 should be
estimated from
estimated from drainage
drainage area,
area, though
though aa value
value near
near eight
eight
should
should usually suffice.
usually suffice.

12b. If
12b. If t
5tpss isis not
not reached
reached during
during flow
flow periods
per iods then
then the
the
term
term ln(re/rw)3
In(r e/r w)-3/4 should be
/4 should be estimated
estimated from
from aa PD
PD function,
function,
e.g., Eq.
e.g., Eq. 4a
4a or
or 4b.
4b.
A.8-26
A .8-26

13. Calculate
13. Calculate skin
skin by
by subtracting
subtracting In(r e/r w)3/4
ln(re/rw )-3/4 found
found in
in
Step 12, from
step 12, from In(re/rw-3/4+s,
ln(re/rw3/4+s, found in
found in step
Step 9.
9.

14. If
14. If aa change
change in in skin
skin is
is anticipated,
anticipated, say
say from
from aa
stimulation treatment,
stimulation treatment, thenthen the
the test
test deliverability
deliverability can
can
be shifted to reflect
be shifted to reflect the the change
change in
in skin.
skin. This
This is
is done
done by
by
calculating aa new
calculating new AOFP
POFP as
as

{In (r e/rw)-3/4+s}test
{ln(re/ rw)3/4+s}test
qmax,new
qmax,new = qmax,test
= qmax,test (32)
.... (32)
{In(r e/r
{ln(re/ w)-3/4+s}new
rw)-3/4 +s}new

The new
The new value
value is
is located on the tracing paper at at md
m ofof 1;
1;
this point is aligned
this point is aligned with the type curve found from
from the
the
testd ata match
test-data match and a new deliverability
deliverability curve is drawn.
drawn.

The
The same
same proced
procedure
ure is follow
followed
ed for low
low-permeability
permeability
reservo irs having
reservoirs having aa transie
transient solution.
nt rate solutio In(r e/r w
n. ln(re/rw )-3/4,,
)3/4
or
or more
more correct ly, PD
correctly, PO, can
can bebe calcula
calculated
ted at severa
severall times
times
(e.g.,
(e. g., 1,1, 2,
2, 5,
5, and
and 1010 years)
years) and
and deliver
deli verabili ty curves
ability curves
drawn
drawn for
for each
each time
time based
based onon correct
corrected qmax (Eq.
ed qmax (Eq. 32).
32).

Appendix AA discus
Appendix discusses the metho
ses the method suggested
d sugges ted byby Standi
Standing for
ng for
correcting
correcting the
the rate
rate equatio
equation in saturat
n in saturated-oil reservoirs
edoil reservo irs
which
which are
are damag ed (HVF
damaged (HVF effects
effects are
are neglec
neglected by Standi
ted by Standing).
ng).

15.
15. For
For saturatedoil reservo
saturated-oil reservoirs
irs aa similar
similar correct
correction must
ion must
be
be made
made becaus
becausee of
of depleti
depletion. Material
on. Materi balance
al balanc results can
e results can
be
be used
used to
to estima
estimate
te kro/l1oBo
kro/oB o at
at several
severa l points
points of
of
depleti on.
depletion. The
The proced
procedure is to
ure is to correct
correct the
the true
true PiOFP
AOFP and
and
shift
shift the
the deliver ability curve
deliverability curve using
using the
the follow
following relation:
ing relatio n:
A.8-27
A.827

(kro/iioBo) PR new
-max,new

Hmax,test PRnew. (33)


(kro/uoBo)PR PR,test
test

This simplified
This simplified correction
correction for for depletion
depletion isis the
the same
same as
as
proposed by
by Standing 7
proposed 7 using
Standing using the
the Vogel
Vogel pressure
pressure function.
function. It
It
is also suggested
is also suggested by Fetkovich.
by Fetkovich.

Pn alternative
An alternative method
method is
is to calculate
calculate the EM
EM m(p) function
function
at each
at each new
new producing
producing GOR.
GOR. The
The engineer must decide if the
the
extra
extra calculations are justified
justified for predicting future
deliverability.
deliverability.

EXI\MPLE 1: SIMULATED
EXAtoR.E SIMtJLTED GASWELL KlOIFIEO
MODIFIED ISOCHRONAL
ISOCHRONL TEST (MIT)

The first example considers a low-permeability


The lowpermeability gas
gas
reservoir with
reservoir with rock and fluid in Table
properties given in Table 3.
3.
A numerical
numerical model
model including turbulence effects was
was used
used to
to
simulate
simulate the
the test
test procedure given in Table 4. The model
model was
was
checked
checked against
against numerous
numerous published
published results
results..

Data
Data from
from the 24hour
the 24-hour buildup
buildup are
analyzed in
are
analyzed in Fig.
Fig. 9.9.
Calculated permeability
Calculated permeability (0.009
(0.009 md)
md) is
is about
about 10%
10% lower
lower than
than
model
model permeability
permeability.. Calculated skin
Calculated skin (0.87)
(0.87) isis about
about 33%
33%
lower
lower than
than calculated
calculated by
by subtracting
subtracting pD(tD)
PO( to) (Eq.
CEq. 4a)
4a) from
from
calculated
calculated 0
m
mO at
Pwf s.
at
Pwf,s. ,Deviations result
Deviations result from
from the
the
relatively
relati vely short
short production
production period
period (12
(12 hours);
hours); transient
transient
effets
effets do
do not
not reach
reach far
far into
into the
the reservoir,
reservoir, and
and turbulence
turbulence
dominates
dominates the
the small
small drainage
drainage region.
region. Since
Since similar
similar errors
errors
might
might bebe expected
expected inin actual
actual tests
tests ofof lowpermea
low-permeability
bility
reservoirs,
reservoirs, the
the calculated
calculated kk and
and ss are
are used
used to
to analyze
analyze MIT
MIT
results .
results.

MIT
MIT data
data given
given in
in Table
Table 44 are
are analysed
analysed using
using thethe previously
previously
proposed
proposed procedure.
procedure. Starting
Starting with
with step
step 3,3, results
results are
are as
as
follow:
follow:
A.8-28
A .8-28

m(p) is
3.3. m(PR) is equal
equal to to m(Pi)
) or
1
m(p or 2.973.10
2.973l0 7
kPa
kP
/
2
2
Pas/Pas.
a . For For
MIT, howev er, the
MIT, however, the correct m(PR)
correct m(pR) to to use
use for
for calculating
calculating md mj
(Step
(Step 4) is m(p) corresponding
4) is m(p) corresponding to to Pws
Pws immediately
immediately cefore
t,efore the
the
drawdo wn begins
drawdown begins. For rates 565.2, 1130.5,
. For rates 565.2, 1130.5, 1695.7,
1695.7, and
and 2261.0
226L0
/
3
5md,
3
Sm /d, m(PR) m(pR) are are 2.965.10 7
2.965l0, , 2.935.10
2.935l0, 7
, 2.889.10
2.889l0,
7
, and
and
2.834l0 kPa
2.834.10 7 kP
/
2 2
Pas /Pas,
a , respectively.
respectively.

4. Table
4. Table 44 gives
gives md
md for
for each
each wellbore
weilbore flowing
flowing pressure.
pressure.

5.
5. Fig. 10
Fig. 10 shows
shows the
the type-curve
typecurve match
match of
of qg-md
qg_md data
data using
using
Fig.
Fig. 1.
1.

6. The
6. The Od=2
0
2 type curve
d= type curve is
is chosen
chosen to
to give
give aa best-fit.
bestfit.

7. The
The match
match point
point is chosen 3
7. chosen as qgM=6218
qgj= Sm
8
l
62 /d
3
5m /d at
at qOM=1.
qj=l.

8. The
8. The theoretical
theoretical AOFP
\0FP is 6218 Sm/d.
3
5m 3
/d. True
True AOFP
P0FP of
of
3109 Sm
3109 /d
3
Sm 3 is read
/d is read from Fig. 10 at md
m of
of 1.

9. Using
9. Using calcula
calculated permeability
ted permea bility (0.009 md)
md) and
and Eq.
Eq. 29a,
29a,
In(re/r w
ln(re/rw )-3/4+S
)3/4 is 2.833.
+s is

10. D0 is
10. is 2.833x
2. 833x2/6218
2/6218 or 9.11.10-k4 1/Sm
or 9.1110 1/Sm
/
3 d.3
/d. Using
Using thethe
model value for
model value for HVF factor, ,
HVF factor, S, 00 is
is 1.061 3
1.06.10-0 1/5m1/Sm 3
/d, aa
/
3 d,
reason able check.
reasonable check. althou
Although skin resulti
gh skin resulting from HVF
ng from HVF effects
effects
at
at 3109
3109 3 Sm
/ 3
Smd /d is
is only
only 3,
3, it
it reduce
reduces AOFP to
s P0FP to half
half its
its
theoret ical
theoretical (noHVF)
(no-HVF) value.
value.

11.
11. Produc tion after
Production after 88 hours
hours is
is not
not stabiliz
stabilized,
ed, asas is
is
easily shown
easily shown by by calcula
calculating
ting t to of
0 of t
56.20.1O-
6.2(h0l0
5.t(hr), or
or tto
r), 0
(t=8hr ) of
(t=8hr) of 4.96
4.96.10- 4
10. To
To reach
reach pss
pss after
after only
only 88 hours
hours would
would
require
require aa drainag
drainage radius of
e radius of 6.71
6.71 m,
m, clearly
clearly smalle
smaller than
r than
the
the true
true drainag
drainagee area.
area.

12b.
12b. The
The term
term ln(re/rw
In(re/rw)-3/4 is replace
)3/4 is replaced by 0
d by PO(tO)
(
p
) given byby
t given
Eq.
Eq. 4a,
4a, and
and equals
equals 3.230.
3.230.

13.
13. Steady -state skin
Steady-state skin isis 2.833
2.833-3.230 or 0.4,
3.230 or -0.4, which
which should
should
be compa red with
be compared with zero
zero used
used inin the
the moe1.
model. Practic
Practically, the
ally, the
A.8-29
A.8-29

value
value of
of -0.4
0.4 would
would be
be interpreted
interpreted as
as zero
zero since
since no
no
stimulation
stimulation has
has been
been used.
used.

14. This gas


14. This gas well
well is
is an
an obvious
obvious candidate
candidate for
for acid-
acid or
or
hydraulic-fracture
hydraulicfracture treatment. Assuming
Assuming aa vertical
fracture of
fracture of 76.2
76.2 mm half-length
halflength can be created,
created, the following
following
analysis
analysis is performed.
performed.

After
After ~timulation,
stimulation, test deliverability will shift
shift to the
right in Fig. 10.
10. Using Eq. 32,
32, the true AOFP at 1,
1, 2,
2, 5,
10, and
10, and 25 years is calculated and given in Table 5. Fig. 10
10
shows the shifted deliverability curves; note that the
original
original test curve is
is reached after 25 years.

If the well produces at constant wellhead pressure, then aa


tubing performance curve can be imposed on Fig. 10. This
would
would yield rate as a function of time, the relation needed
for engineering design.

EXAMPLE 2: SATURATED
EXAFLE ISOCHRONAL
SPJURATED OILWELL ISOCHRON AL TEST

The basic
basic data for this example are taken from
from
Fetkovich's
Fetkovichs Well 5-C,
5C, Field D.
D. PVT and
and relative
relative
permeability
permeability data
data were
were estimated
estimated from correlations
correlations (Table
(Table
6).
6). Measured rates and pressures
Measured pressures at
at the end
end of
of each
each 4hour
4-hour
drawdown are
drawdown are given
given in
in Table
Table 7.
7. Six months separate
Six months separate the
the two
two
fourpoint
four-point tests
tests and
and average
average reservoir pressure
pressure has
has dropped
dropped
about
about 690
690 kPa.
kPa.

Pseudopressures
Pseudopressu are calculated
res are calculated using
using the
the EM
EM method
method assuming
assuming
RR equal
equal to
to the
the bubblepoi
bubble-point solution GOR.
nt solution GOR. m(pi)
m(Pi) equals
equals
19.63 kPa/Pa' s.
19.63 kPa/Pas. After depletion
After depletion of
of 690
690 kPa,
kPa, kro/jioBo
kro/J..loBo atat
average reservoir
average reservoir pressure
pressure of
of 24821
24821 kPa
kPa is
is 90%
90% its
its initial
initial
value.
value. Using the
Using the producing
producing GOR
GOR calculated
calculated by
by aa Tamer
Tarner
material
material balance
balance (Table
(Table 6) ,
6), pseudopressures
pseudopressu res are
are
..,

i A.8-30
A.8-30

recalculated. m(PR)
recalculated. m(pR) is
is 97%
97% m(Pi),
m(p), considerably
considerably less
less change
change
than experiences. This
kro/jioBo experiences.
than kro/~oBo This suggests
suggests aa potential
potential error
error
using the
using the correction
correction procedure
procedure given
given byby Eq.
Eq. 30.
30. The
The
follow ing analys
following analysis uses
is uses m(p)
m(p) calculated
calculated by
by the
the EM
EM method
method at
at
producing GOR.
producing GOR.

The test
The test data
data are
are analyzed
analyzed using
using the
the multirate
multirate procedure
procedure
presented earlier.
presented earlier. starting
Starting with
with step
Step 3,
3, results
results are
are as
as
follow
follow: :

3. m(pj) is
3. m(Pi) is 19.63
19.63 kPa/Pas.
kPa/Pas. At
Pt PR
PR of
of 24821
24821 kPa,
kPa, m(PR)
m(pR) is
is
19.07 kPa/Pas.
19.07 kPa/Pas.

4. Wellbore
4. Weilbore flowing pressures
pressures are
are converted to md
converted to m in
in
Table 7.
Table 7.

5. Fig.
5. Fig. 11
11 shows the type-curve
typecurve match of qo-md
m with
0
q with
Fig. 1.
Fig. 1.

6.
6. The Dd=20
The Dd=20 type
type curve
curve is chosen toto give
give aa best-fi
best-fit.
t.
Flows
Flows P3
A-3 and
and Bi
B-1 appear to
to deviate
deviate from the
the other
other data.
data.

7. 3
7. The
The match
match point
point is
is qoM
i of
0 of 7631
7631 3
Smd
5m
/ /d at
at qj
qDM of
of 1.
1.

8. 3
8. Theore tical PDFP
Theoretical AOFP isis 7631
7631 3Smd.
Sm
/ /d. True P0FP
True AOFP is
is 1526
1526
/
3
Sm3
Smd,/d, as
as read
read from
from Fig.
Fig. 1111 at
at mj
md of
of 1.1.

9.
9. Using
Using permea
permeability reported
bility reporte Fetkovich
by Fetkov
d by from buildu
ich from buildupp
analys is and
analysis and core
core data
data (2470
(2470 md),
md), ln(re/rw
In(r e/r)3/4
w)-3/4+s is 20.4
+s is 20.4
using
using Eq.
Eq. 31b.
31b. m(pR)
m(PR) ofof 28
28 kPa/Pa
kPa/Pa's is assumed.
s is assumed.

10.
10. D0 is
is 20.4x20/763
20.4x20/7631 or 0.0535
1 or 0.0535 3
1/Sm
l/Sm
/ d. 3
/d.

11.
11. Time
Time to
to pseudo
pseudosteady-state flow, t pss , based
steadystate flow, based on
on aa
drainag e area 2,59.10 6 6 2
drainage area of
of 2.59'10 m m (640
2 (640 acres)
acres) is
is approx
approximately
imately
six
six hours.
hours.
A.8-31
A.831

12a.
12a. The
The term In(r e/r w)-3/4 is replaced by PO(tO).
ln(re/rw)3/4 pD(tD). Using
Eq. 4a, its value is B.7.
8.7.

13.
13. Steady-state
Steadystate skin is 20.4-B.7
20.48.7 or 11.7.

If steady-state
14. If steadystate skin calculated in Step 13 13 is due to
damage (we 11 is fully penetrating), then an acid treatment
(well
should clean up the near-wellbore
nearweilbore region. Assuming skin can
be reduced to zero, the change in deliverability is
estimated by correcting the true AOFP and shifting the
deliverability curve. Also, In(r e/r w)-3/4 at stabilized
ln(re/rw)3/4
conditions should replace PO(t04hr).
pO(tD4hr). For 640-acre
640acre spacing,
the value of In(r e/r w)-3/4+s is B.35
ln(re/rw)3/4+s 8.35 with s=O.
s=0. Stabilized
3
1526x20.4/8.35 or 3729 Sm
AOFP is 1526x20.4/B.35 /d.
3
Sm /d. The deliverability
curve is shown in Fig. 11.

The above procedure was repeated using the


delta-pressure-squared
deltapressuresquared procedure suggested by Fetkovich.
Results are presented in Table 77 and Fig. 11 (dashed lines).

CONCLUSIONS

purpose of
The purpose of this paper has been
been to review wellknown
well-known
aspects of predicting
of reservoir well performance
predicting reservoir performance and
and to
to
present
present some
some new concepts
concepts which
which have
have been
been developed.
developed.
Perhaps the
Perhaps most important
the most important point
point to
to be
be made
made is
is that
that gas
gas- and
and
oilwell tests
oilwell tests should
should be
be conducted
conducted and
and analyzed
analyzed in
in the
the same
same
manner.
manner. The stucy
The stUdy gives
gives aa description
description of
of nonideal behavior
behavior
of gas
of gas and oil
and oil flow; in particular,
in particular, high
high velocity
velocity flow
(turbulence) and
(turbulence) and variation
variation in
in the
the pressure
pressure function
function have
have
been described.
been described. Several conclusions
Several conclusions are
are made
made based
based on
on the
the
results of
results of this
this study:
study:

1. AA dimensionless
1. dimensionless solution
solution of
of the
the radial
radial flow equation
equation
has been
has been developed.
developed. It accounts
It accounts for
for ratedependent
rate-dependent effects,
effects,
A.8-32
A.8-32

steadystate skin,
steady-state skin, and
and variation
variation in
in the
the pressure
pressure function.
function.
The solution
The solution is
is equally
equally applicable
applicable to
to gas
gas and
and oil
oil wells.
wells.

2. The
2. The Vogel
Vogel inflow
inflow performance
performance relation
relation has
has been
been gi ven
given
physical meaning.
physical meaning. It It represents
represents an an expression
expression of
of the
the radial
radial
flow equation
flow equation based
based on
on thethe following
following twotwo assumptions:
assumptions:
(a) no
(a) no high-velocity-flow
highvelocityflow effects
effects areare present (D=O), and
present (0=0), and
(b) the
(b) the saturated-oil
saturatedoil pressure function, kro/~080'
pressure function, kro/poBo, is is aa
linear function
linear function with with intercept
intercept at at atmospheric pressure
having one-nineth
having onenineth the value
value atat average
average reservoir pressure.
pressure.

3. General
3. General expressions for dimensionless
dimensionless pseudopressure
pseuaopressure of
of
oil wells
oil wells are developed based on the straight-line
straightline pressure
functions suggested
functions suggested by Fetkovich. These expressions, equalequal
to vogel's
to Vogels dimensionless
dimensionless rate, qo/qomax,
/qrnax, if rate-dependent
0
q ratedependent
effects are
effects are negligible,
negligible, are applicable to undersaturated-
undersaturated and
saturatedoil reservoirs producing at wellbore
saturated-oil weilbore flowing
pressures above and below the bubble point.
pressures above

4.
4. good approximation
A good approximation of dimensionles
dimensionlesss pseudopressu
pseudopressure
re for
for
oil
oil wells
wells producing
producing atat saturated
saturated or
or undersaturate
undersaturated reservoir
d reservoir
pressures
pressures isis the
the original
original Vogel
Vogel expression
expression for dimensionles
dimensionlesss
rate.
rate. The
The possible
possible error
error introduced by by using
using the Vogel
Vogel
relation
relation isis nono larger
larger than
than reported
reported byby Vogel
Vogel for
for saturated
saturated
systems
systems having
having different
different PVT
PVT and
and relativ
relative permeability
e permeability
relations
relations than
than the
the reservoir
reservoir used
used toto develop
develop his
his general
general
correlation.
correlation.

5.
5. The
The EvingerM
Evinger-Muskat
uskat method
for predicting
method
for predicting oilwell
oilwell
performance
performance at
at saturated
saturated conditions
conditions is
is reviewed.
reviewed. The
The method
method
is
is made
made easierto
easier-to-use by introducing
use by introducing generalized
generalized relativ
relative
e
permeability
permeability curves.
curves.

6.
6. It
It is
is shown
shown that
that the
the Evinger-Muskat
EvingerM uskat method
method for
for
calculating
calculating oil
oil pseudopressu
pseudopressure is applicable
re is applicable to
to transient
transient
well
well test
test analysis.
analysis. Saturated-oil
Saturatedo drawdown and
il drawdown and buildup
buildup
A.8-33

tests reported in the literature were used to check the


validity of the method.

7. A? general procedure is given for analyzing multi rate


multirate
tests performed on gas and oil wells. Two examples
illustrate the procedure.

Standings method for correcting the Vogel relation for


8. Standing's
damaged and stimulated wells is discussed. The assumptions
on which it is based are given, and improvements are
suggested. It appears that the original method is physically
unrealistic for wells with negative skin.
A.8-34

NOMENCLATUR
\UMENCLA E
TURE

aa = units
= units-conve rsion
conver sion const
constaant
nt in flow equatio
equation n
aHVF
aHvF = units-
= unitsconve rsion
conver sion constant
consta nt in high
high- veloc
velocitity-fl
yflo ow
w
equat
equatioionn
at =
at units- conve
= units converrsion
sion const
consta ant
nt in dimen sionlestim
dimensionles ss-time
equat
equatioions
ns
A == area, m 22 (ft
(ft2)
)
2
BB == forma
formattion
ion volume facto r, m m
3 3
/Sm /Sm 3 (ft (f
/
3 scf3
/scf
t or
RB/STB
RB/STB for gas or oil, respectively) ly)
cti == initia
Cti initi all (or avera
averag gee reservoir pressure) total
comp
compressressib ility,
ibilit kPa- 1 (psf
y, kPa (psi- 1))
CC == const
consta ant
nt in flow equatequatio ionn
Do == high-
highveloc
velocitity-fl
yflo ow
w term, l/Sm /d
3
l/Sm 3
/d (l/scf
(l/scf/d)/d)
Dd =
Dd = dimensionles
sionlesss high
high- veloc
velocitity-fl
yflo ow w term
EF = flow effici
= ency
efficiency
F(p) = = press
pressuurere functi
functio on
n (also F; Fb Fb == F(pb),
F(Pb), etc_)
etc.),,
kP
/
2 Pa2
kPa /Pa-sas or kPa/kPa/PPasa-s 2 (psia 2
(ps
/ cp /cp or psia/
ia psia/c p) for
cp)
gas or oil, respectively
hh == total forma formattion
ion thickness ness,, mm (ft)
hp = = perforated or produc producing ing thickness ness,, mm (ft)
kk = absol
absolu ute
te perm eabili ty, ~m2
eability, 2 (md ~ ~m2)
1.1m )
2
1m
krg =
krg = relative permea permeabilit
bilityy to gas
kro = relat
kro relatiive
ve permea
permeabilit y to oil
bility
mm = = semi-
semilog
log slope of Homer Horner plot, kPa 2/Pa-s
kP
/
2 Pa s/cy /cycl
clee
a
or kPa/P
kPa/Pas/ a-s/cy cle (psia
cycle (p
/
2 cp/c 2/cp/c
si ycle ycle
a or
pSia/cp/cy
psia/ cp/cycle)
cle) for gas or oil, respectively ly
m(p) == pseud pseudo opres
pressusure
re funct ion, 2
function, kPa
kP
/ Pa2 /Pa-sas or Kpa/Pa
Kpa/Pa-ss
(psia ia
(ps
/
2 cp 2/cp or psia/c
psia/cp) p) for gas or oil,
respectively
md == dimensdimensionle
ionlessss pseuco
pseudopres
pressusure function
re functio n
nn == reciproca rocall of slope of logl log-loogg ratep
rate-pseudoseudoppress ure
ressure
(backpress
(backp ure)) curve
ressure
pp = = absol
absolu ute
te pressure, kpa (psia))
p* =
4
p = speci fic pressu
specific pressure low- or high
re in low high- presspressu ure
re region
A.8-35
A.8-35

of gas
of gas reservoirs,
reservoirs, kPakPa (psia)
(psia)
Pa =
Pa atmospheric pressure,
= atmospheric pressure, kPakPa (psia)
(psia)
Pb =
Pb = bubble-point
bubblepoint pressure,
pressure, kPa kPa (psia)
(psia)
PD =
PO dimensionless pressure
= dimensionless pressure
PR =
PR = average reservoir
reservoir pressure, kPa (psia) (psia)
Psc = = pressure
pressure at standard conditions,
conditions, kPa (psia) (psia)
Pskjn =
Pskin average pressure in the skin
= average skin region, kPa (psia)
Pwf = = measured wellbore
weilbore flowing pressure, kPa (psia)
Pwf,s = welibore flowing pressure at shut-in,
= wellbore shutin, kPa (psia)
Ps =
~Ps = pressure drop due to skin in near-wellbore nearweilbore
region, kPa (psia)
qd = dimensionless rate =
= dimensionless = q/Qmax

qg = surface gas rate, Sm


= surface /d
3
Sm3
/d (scf/D)
PHVF =
qHVF = surface rate at the onset of high velocity flow

3
(turbulence), Sm Smd
/
3 /d (scf/D or sTaiD STB/D for gas or oil,
respectively)
qmax = = true maximum surface rate (AOFP), Sm
3
Smd
/
3 /d (scf/D or
sTaiD for gas or oil, respectively)
STB/D
Qmax == theoretical maximum surface rate (AOFP) if aa
max
3
well had no HFV effects, Sm Smd
/
3 /d (scf/D or STB/D
sTaiD
for gas or oil,oil, respectively)
re == externalboundary
re external-boundary drainage
drainage radius,
radius, mm (ft)
(ft)
rw == weilbore
rw wellbore radius,
radius, mm (ft)
Cft)
RR == producing
producing gasoil
gas-oil ratio,
ratio, 3 SmSm
/
5m 3
/Sm 3 (scf/stb)
(scf/stb)
Rs == solution
5
R solution gasoil
gas-oil ratio,
ratio, SmSmS&
/
3 3
/Sm 3 (scf/stb)
(scf/stb)
ss == steadystate
steady-state skin skin factor
factor
SS == saturation,
saturation, fraction
tt = time,
time, hours
hours unless
unless otherwise
otherwise specified
specified
to == dimensionles
tD dimensionless time
s time
5
ttpss == timetime to to reach
reach pseudosteady
pseudosteady state, state, hours
hours
tDApss == dimensionles
tDp5s dimensionless time to
s time to reach
reach pseudosteady
pseudosteady state
state
TT == absolute
absolute temperature,
temperature, KK (R)(oR)
Tsc == absolute
Tsc absolute temperature
temperature at at standard
standard conditions,
conditions,
(oR)
KK (R)
1

A.8-36
A. 8-36

vV == param eter in gener


parameter al quadr
general atic rate equat
quadratic ion
equation
xx == ratio of press ure functi
pressure on F(p) at atmos
function pheric
atmospheric
press ure to F(p) at avera
pressure ge reser
average voir press
reservoir ure
pressure
(satu rated -oil reser
(saturatedoil voirs ); ratio of press
reservoirs); ure
pressure
funct ion F(p) at atmos
function pheric press
atmospheric ure to F(p) at
pressure
bubbl e-poi nt press
bubblepoint ure (unde
pressure rsatu rated -oil
(undersaturated_oil
reser voirs )
reservoirs)
xF = = verti cal-f ractu re half-l
verticalfracture ength , m
halflength, m (ft)
yy == ratio of press ure functi
pressure on F(p) at avera
function ge
average
reser voir press
reservoir ure to F(p) at bubbl
pressure e-poi nt
bubblepoint
press ure for under
pressure satura ted reser
undersaturated voirs
reservoirs
Z
Z = = real-g
realgasas comp ressib ility facto
compressibility factorr

Greek Symbols
Symbols

~ =
= visco sity, Pas
viscosity, Pas (cp)
, =
= poros ity, fracti
porosity, on
fraction

Subsc ripts
Subscripts

gg =
= gas

new =
= evalu ated at new reservoir
evaluated reser voir condi tions
conditions
oa =
= oil
test = evaluated
= evalu ated at test condi tions
conditions

Super script s
Superscripts

EF=l
EF=l = value of property
= prope rty (q
(q or
or pwf)
Pwf) which would be
measured if stead
measured y-sta te skin was zero (flow
steadystate
effici ency equal
efficiency equal to one)

EFfl
EFl = rate which would
= would be
be measured
measured if
if steadystate
stead y-sta te
skin was nonzero
skin nonzero (flow efficiency
effici ency different
diffe rent than
than
one)
A.8-37

REFERENCES
REFERENC ES

1. Muskat, M.: Physi cal


Physic al princ iples
Princip les of Oil Produ
Producction,
tion,
Intern
Internaation al Human Resources Development Corporation
tional ration,,
Bosto
Bostonn(198 1).
( 1981).

2. Hurst
Hurst,, W. "Esta
Estabblishm
lishmeent
nt of the Skin Effec
Effectt and Its
Impediment to Fluid Flow Into a Wellb ore,"
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Pet.Enng.
g.
(Oct.,
(Oct.,11953)
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3. van Everd
Everdiingen
ngen,, A.F.: "The
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on the Produ
Producctive
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Evingeer,
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lation
Theo retica
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Producctivit
tivityy Facto
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, Trans
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146, 126-1 39.
126139.

5. Vogel
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Infloww Performance
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ance Relatio ips for
nships
Soluti
Solutioon-Ga
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J.Pet.
J.Pet.TTech.
ech. (Jan.
(Jan.,, 1968) 83-92
8392..
6. Stand
Standiing,
ng, M.B.: "Inflo w Perfor
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ance Relat ionsh
Relatio ips for
nships
Damaged Wells Produ
Produccing
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J.Pet.T Tech.
ech.
(Nov.
(Nov.,, 1970) 1399-
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7. Stand
Standiing,
ng, M.B.: "Conc erning the Calcu
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ech. (Sept
(Sept.,., 1971) 1141-
11411142.
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Patton n,, L.D. and Golan
Goland d,, M.: "Gen
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Predi
Prediccting
ting Well Behavior,ior," Pet.E ng.
Pet.En g. (Sept
(Sept.,., 1980) 92-10 2.
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9. Richa
Richarrdson
dson,, J.M. and Shaw, A.H.: "Two-TwoRate
Rate IPR Testing -
AA Pract ical

Practic al Produ
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J.Can..Pet.T
Pet.Teech.
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1982) 57-61
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10.
10. Fetko
Fetkovvich,
ich, M.J.: "The
The Isoch ronal
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paper SPE 4529 prese nted
presen ted at the SPE-Al ME 48th Annual Fall
SPEAIME
Meeting,
Meetin g, Las Vegas,
Vegas, Nev., Sept.
Sept.330-0c
0Oct.3,
t.3, 1973.
1973.
11. AI-Hu ssainy, R., Ramey, H.J., Jr., and Crawf
AlHussainy Crawfoord,
rd, P.B.:
P.6.:
"The
The Flow of Real Gases Throu
Throug ghh Porou
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ech.
(May, 1966)
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624636;
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12. Earlo
Earlouugher
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is,
SPE Monograph Serie s, Vol. 5, Dalla
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A.8-38
A.8-38

13. Theory
13. Theory and
and Practice
Practice of
of the
the Testing
Testing of
of Gas
Gas Wells,
Wells, Energy
Energy
Resources Conservation
Resources Conservation Board,
Board, Calgary,
Calgary, Alberta,
Alberta, Canada,
Canada,
Chapter 4.
Chapter 4.

14. Raghavan,
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Wells Producing by
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Solution Gas Drive,"
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(Aug., 1976)
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15. Boe, A.,


15. Boe, A.., Skjaeveland,
Skjaeveland, S.M.,
S.M., and
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paper SPE
SPE 10224
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the
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Golan, M.:
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A.8-39
A.8-39

APPENDIX A
A - DISCUSSION OF STANDING'S
STANDINGS METHOD FOR CORRECTING
DAMAGED/STIMULATED WELLS
INFLOW PERFORMANCE OF DAMAGED/STIMULATED

Standing suggests a method for using the Vogel relation


to average results of multirate tests and to correct for
damage or stimulation in the near-well bore region.
nearweilbore The
averaging procedure should probably not be used since
valuable data showiRg
showing rate-dependent
ratedependent skin effects might be
lost.

To ease the comparison with Standing's


Standings work it is assumed
that HVF effects are neglible (0=0)
(D=O) and that dimensionless
pseudopressure, md,
mj, equals the Vogel rate-ratio,
rateratio, qo/qomax.
q/qrnx.
This assumption, as shown by Fetkovich, may result in
erroneous interpretation of test data.

Instead of limiting the discussion to Vogel's


Vogels relation,
equations are developed in terms of the general quadratic
form (Eq. 20). Following Standing's
Standings arguments, the ratio of
rate to AOFP with EF
EF =
= 1
1 (no-skin)
(noskin) is

EF=i EF=i
qo/qomax 1 V(pwf /PR) (lV)(pwf /PR)
,
2 ... (A1)

EF=l
EF=1
The noskin
no-skin wellbore
welibore flowing pressure, Pwf
Pwf ,is
, is given by

EF=l
Pwf
Pwf =
= Pwf
Pwf +
+ ~Ps.
Ps (A-2)
(A2)

where Pwf
Pwf is the measured well bore flowing pressure, and ~Ps
welibore 5
Ap
is pressure arop
crop due to skin - positive for positive skin

and negative for negative skin.


A.8-40

Using the defin ition of


of flow effici ency,,
efficiency

EF = PR
=
- Pwf - 6ps
. . . . . . . . . . . . . . . . . . . . . . . . . .. (A-3)
PR - Pwf
- Pwf

the no-sk
noskin wellb
weilboore
re flowing pressure is given by

EF=l
=1
Pwf
Pwf = PwfEF
PwrEF ++ (l-EF)
(lEFPR
)pR (A-4)

stand
Standiing
ng sugge sts that EF
suggests EF be estimated by

In(r e/rw)
in (re/r w)-3/4
EF Z .
In(re
_3/4
in (re/r/rw)-3/4+S
w) 3/4+s
.......................... (A(P5)
-5)

To e at this expre
arrive ssion
expressio n the oil pressure funct ion,
function,
F(p),
F(p), must be appro
approxximat ely
imatel y the same at avera
averaggee pressure and
in the skin zone. It also assumes that pressure
drop in the
reservoir is given by

2irakh kro
0
q (PR-PJ ... ...... . (A-6)
(/-6)
in(re/rw)3/4 i.i
B
0

If kro/Uo Bo is evaluated at the average of PR


kro/poBo EF=l
PR and Pwf,
p, then
Eq. A-6
A6 is consi stentt with the Vogel
consisten Vogel relat
relatiion.
on. The pressure
funct ion in the near-
function nearwellb ore
welibo re region
region is proba
probab bly
ly less than
tzis valu
valuee.. A
A more correct expre ssion
expressio n for EF is given by
A.8-41
A.841

= ln(re/rw)3/4
.. (A-7)
.(p7)
ln(re/rw)3/4 + SF(Pavg)/F(Pskin)

The ratio F(Pav


F(Pavgg)!F(P skin)
)/F(Psk in) can be shown to equal

F(Pav
F(pavgg)) = 2x
2x +
+ (l-x){
(lx){
2 2+EF
2+EF((Pwf/ PR-l)
pwf/pR }/2 ,,
l)}/
...
(A-B)
(8)
F(Psk
F(Pskjin)
n) 2x +
+ (l-x){
(l_X){l-EF+
l_EF+(l+EF )Pwf/
(l+EF) PR}/2
pwf/pR }/2

which can be simpl


simpliified
fied by evalu
evaluaating press ure
ting the pressu re functi
functioon
n
in the near-w ellborree region at the measured welibo
nearwelibo wellbore
re flowing
press ure,
pressu Pwf,
re, Pwf,

_) ~ 2x ++ (l-X)(
F(Pav
F(Pavgg) 2x (lx)(l+Pw f/PR)
l+pwf/ /2.
pR)/2
(A-9)
(/9)
F(Psk
F(pskjin)
n) 2x ++ (l-x)P
2x (lx)pwf/PR
wf/pR

Fig. A-l
Pl shows the influe
influennce
ce of the press
pressuure-fu
refunctio n ratio
nction
on flow effici
efficie ency
ncy for sever
severaall values
values of positiv
posit ive
e skin;
In(r /r
ln(re/rw
e w )-3/4 equal to 77 and vogel
)3/4 Vogel's press ure
s pressu re functi on
functio n
(x=l/9
(x=l/9)) are used. The influe influennce is great
ce estt at large
greates
drawdowns (low Pwf/PR values)) and skin less than 10. The
Pwf/PR values
appro
approxximat ion
imatio n given by Eq. J\9A-9 is good at Pwf/PR
Pwf/PR above 0.5
but is relat
relatiively
vely large for large drawdowns with skin values values
of 33 to 5. The corre ction
correct ion shoul
should d not be applie
appliedd to wells
with negat ivee skin factors.
negativ

Using the Stand


Standiing
ng proce dure
proced ure for stimu
stimullated
ated wells can lead
to nonph
nonphyysical
sical results. Fig. P2 A-2 shows the case of a well
with EF of 1.5 (high ly stimu
(highly stimullated
ated).). The no-sk
noskin welibo
wellbore
re
flowing press
pressure
ue is negativ
negativee at measured welibowell bore
re flowing
pressures
pressu res less than PR(EF -l)!EFF;j onet
pR(EF1)/E one-t hird PR for EF of
hird PR
1.5. Also, at measured wellb
weliboore press ures
re flowing pressu res less than
11..8-42
A.8-42

PR.{(EF-I-x/(I-x)/EF}
PR{(EF1/(1)/EF} the the rate
rate decreases
decreases with
with increasing
increasing
drawdown;
drawdown; at
at one-fourth
onefourth PR
PR for
for EF
EF of
of 1.5
1.5 using
using Vogel's
Vogeis
relation.
relation.

Assuming
Pssuming an
an estimate
estimate of
of EF
EF can
can be
be made,
maoe, the
the general
general
rate-pressure
ratepressure relation
relation using
using Standing's
Standings arguments
arguments is
is

EF=I
EF=l
qo/qornax = I1 - V{(Pwf/PR)EF
qo/qomax V{(pwf/pR)EF ++ (I-EF)}
(l_Ef)}

- (I-V){(Pwf/PR)EF
- + (I-Ef)}2,
(l-VJ{(pwf/pR)EF + (1EF)} (A-IO)
(-1O)

or
or
EF=I
EF=1
EFII
EF1 qo/qomax
qo/qornax
qo/qomax = - - - - - - - - - - - (A-II)
qo/qomax (11)
I1 - V(I-EF)
VElEF) - (I-V)(I-EF)2
(1V)(1EF)
2

The
The denominator
denominator in Eq. A-ll
Ali represents the ratio of of AOFP
with skin to AOFP without skin. A-10 reproduces
Eq. AiD
Standing's
Standings Fig. 22 for VV of 0.2 (x of
of 1/9); an
an equivalent
16
expression is given by Couto and Golan
Golan for V
6 of 0.2.
V of 0.2.
A.8-43
A8-43

TABLE 11 - UNITS CONVERSION FACTORS

Field SPE Preferred SI


Quantit:!
Cuantity Gas Oil Gas Oil
a 0.006328 0.001127 8.527.lO_8
8.527.10- 8

at 0.0002637 3.553.10-
3.553lO
9

3.0611O 6
3.061.10 9.326.108
9.326.10 8 1.085.106
1.085.10 6
aHVF
aHvF 634.5

kk md md (~llm2)
)
2
(pm
hh ft m
m
r ft m
m
pp psia kPa
c l/psi
1/psi l/kPa
1/kPa
p
II cp Pas
Pas
-yy air=l
air=1 water=l
water=1 air=l
air=1 water=l
water1
TPLL 22 - ROCK
TABLE ROCK AND
PND FLUID
FLUID PROPE
PROPERTIE
-

RTIESS FOR
FR VOGEL
VOCEL DATA
DT

Read From
Read From vogel
Voqels
's Fig.
Fiq. 9a
9a Eving er-Mu
Evinqer Musskat
kat Method Using
Method Usinq R
R of
of 102.4
102.4 Sm 3
Sm/S
3 /Smm3
Pp 5
R
Rs 0
B
Bo 3 83 .1003
Bg1 103
IJo 10 9 11g1
3
IJg. 0 krg/k
krg/kro kkro F(p)
F(p) ~ml0 -3 m(p). 10- 3
ro Am10
3 m(p)10
3 md
(kPa)
(kP~ (S
/
3
) Sm
(Sm 3 m
/Sm 3 ) 3 3 md
(m /Sm
/5m
(m
)
3 (Pa
(PaSs)) (m
/Sm
(m
)
3 3
/Sm 3 )
) (Pas
(Pas) (Eg.2 2)
(Eg.22) 12.el ow)
(belo w) (l/Pa s)
(l/Pas) (kP/P as))
(kP/Pas
14686
14686 102.4
102.4 1.30
1.30 1.03
1.03 6.67
6.67 0.019
0.01955 0.0 0.444
0.444 331.6
331.6 276.8
1379
137900 98.85
98.85 1,29
1.29 1.04 276.8 aa 2553.
2553.11 0.000
0.000
1.04 7.13 0.018
0.01888 0.0003
0.00035656 0.384
0.384 286.1
286.1 469.8
12066
12066 93.51
93.51 1.28
1.28 1.12
1.12 8.08
469.8 2276.
2276.33 0.108
0.108
1034 0.017
0.01788 0.0008
0.00089393 0.371
0.371 259.1
259.1 419.8
419.8 1806. 5
103422 85.49
85.49 1.27 1.22
1.22 9.46 0.016
0.01699 0.0017
1806.5 0.292
0.292
8618
8618 75.70
0.00174 4 0.353
0.353 228.0
228.0 361.8
361.8 1386.
1386.77 0.457
75.70 1.26
1.26 1.38
1.38 11.4 0.015
0.01599 0.0027
0.00278 8 0.457
6895
6895 66.79
66.79 0.334
0.334 191.8
191.8 306.0
306.0 HJ24.9
1024.9 0.598
0.598
1.25 1.60
1.60 14.1 0.015
0.01522 0.0038
0.00382 2 0.326
0.326
5171
5171 56.99
56.99 163.3
163.3 257.6
257.6 718.9
718.9 0.718
0.718
1.23 1.93
1.93 19.4 0.014
0.01422 0.0052
0.00527 7 0.322
0.322 135.6
3447
3447 44.53
44.53 1.18 2.47
135.6 210.2
210.2 461.3
461.3 0.819
0.819
27.7 0.013
0.01344 0.007 37
0.00737 0.316
0.316 108.3
108.3 161.4
1724
1724 30.28
30.28 1.14
1.14 3.30 58.8
161.4 251.1
251.1 0.9U2
0.902
101 0.012
0.01244 0.014
0.01400 0.297
0.297 79.1J
79.0 88.2 89.7 0.965
101 0.00
0.00 1.02 4.23 1000.0 0.965
1000. 0 0.011
0.01144 0.270
0.270 0.128
0.128 29.7 1.5 1.5 0.999
0.999 .co
l=-
03
I
a. 276.8
a. 276.810
.10 3 = (1468
= (14686-1 3790
6-137 )(331
90)(3 31.6+
.6+2
286.1
86.l))/2.
/2. m(p) =
= ~m
m starti ng at atmos
starting pheric
atmosphe ric pressure (101 kPa)
kPa)..
~
~

Reac
Reaa From
From Vog els
vogel 's Fig.
Fig. lOa
iDa

S
So kk
0 krg
ro krg
0.80
0.8066 0.44
0.4444 0.0
0.0
0.78
0.7811 0.39
0.3900 0.00
0.0000
0039
39
0.75
0.7566 0.32
0.3299 0.00
0.0011
0.70
0.7066 0.23
0.2388 0.01
0.01
0.65
0.6566 . 159
0.159 0.02
0.0233
O0.606
.606 0.09
0.0966 .047
O0.047
0.55 6
0.556 0.05
0.0522 0.07 8
0.078
0.50
0.5066 0.02
0.0266 0.11
0.1155
A.8-45
A.8-45

TABLE 33 - RESERVOIR
TABLE RESERVOIR ROCK
-
ROCK Ai"D
ND FLUID
FLUID PROPGRTIES
PROPORTIES FOR
FOR GAS
01\S WELL
WELL IN
IN EXAMPLE
EXPMPLE 11

Numerical Model:
Numerical Model:

1Dimensional, Radial,
1-Dimensional, Radial, Fully-Explicit
FullyExplicit (Fully-Implicit
(FullyImplicit Check)
Check)
40 Blocks
40 Blocks with
with Radii
Radii at
at Pressure
Pressure Points
Points rj=1.252rj_l
r=l.252r_ (r1=0.1006
1 =O.1006 m).
1
(r m).
Minimum:M aximum Time
Minimum:Maximum Time Step
Step (days)
(days) == 10- 11
lO:O. :0.1l with
with Multiplication
Multiplication
Factor 1.
Factor 1.5.
5.

General Properties:
General Properties:

rw =
rw 0.1006 m
= 0.1006 m Pi
P1 =
= 20684 kPa
re =
re 642.1 m
= 642.1 m (320 acre) T
T = 79.44 0c
1D
0
hh = 30.48 m
= 30.48 m Yg =
= 0.75 (air=l)
(air=1)
kk = 0.01 md (~~m2)
= (iim
)
2 S
Sg =
= 1.0
1.0
$ 0.1
= 0.1
= cgj
cgi =
= 4.1047
4.104710- kPa- 1
.108a kPa
S13 = 3.9361
= 15 m
3.936.10O m- 1 Bgj = 4.924010-~
4.9240 m3/Sm~
Bgi = 10 m/
3Sm

PP ~g.103
3
iig10 p/~gZ1O-6
6
P/pgZl 0 6m.l0- 12
2
iml0 2m(p)10- 12
m(p)lO
(kPa)
(kPa) (Pas)
(Pas) ZZ (kPa/Pas)
(kPa/P as) (kPa
2
(kP
/ Pas2/Pas)
a)
22408
22408 0.0228 0
0.02280 0.8347
0.8347 1177
1177 2.015 aa
2.015 33.756
33.756
20684
20684 0.0216 7
0.02167 0.8229
0.8229 1160
1160 1.977
1.977 29.726
29.726
18961
18961 0.0205 4
0.02054 0.8149
0.8149 1134
1134 1.922
1.922 25.772
25.772
17237
17237 0.0194 2
0.01942 0.8091
0.8091 1097
1097 1.847
1.847 21.928
21.928
15513
15513 0.0183 4
0.01834 0.8084
0.8084 1046
1046 1.747
1.747 18.234
18.234
13790
13790 0.0173
0.01730
0 0.8127
0.8127 981
981 1.620
1.620 14.740
14.740
12066
12066 0.0163 0
0.01630 0.8222
0.8222 899
899 1.463
1.463 11.500
11.500
10342
10342 0.0154 6
0.01546 0.8370
0.8370 799
799 1.279
1.279 8.574
8.574
8618
8618 0.0146 9
0.01469 0.8566
0.8566 685
685 1.071
1.071 6.016
6.016
6895
6895 0.0140 3
0.01403 0.8805
0.8805 558
558 0.845
0.845 3.874
3.874
5171
5171 0.0134 8
0.01348 0.9075
0.9075 423
423 0.608
0.608 2.184
2.184
3447
3447 0.U13O4
0.01304 0.9369
0.9369 282
282 0.364
0.364 0.968
0.968
1724
1724 0.0127 1
0.01271 0.9679
0.9679 140
140 0.120
0.120 0.240
0.240
101
101 0.0125 2
0.01252 0.9981
0.9981 88 0.000
0.000 0.000
0.000

a. 2.015.1
a. 01212 == (22408
2.015.10 (22408-20684)(1177+1160).106/2
_20684)(1177+1160).lOb/2
A.8-46

TABLE
TABLE 4 - TEST PROGRAM AND RESuL
PROGRAM TS FOR
RESULTS FR GAS WELL IN EXAMPLE 11
EXAMPLE

tt t.t qa Pw m ( Pw ) 10
rn(p
2 10- 1 2 m
md
(hr) (hr)
Chr) (Sm
Sm
/
3 d)3
/d) (kPa)
(kPa) (kPa
(k
/
2 Pa 2
/Pa's
Pa s))
-
-
-
20684 29.73
29.73
0-
0 12 12 1413 16058
16056 22.78
22.78
12-
12 36 24 0 20484 29.27
29.27
36-18
361800 144 0 20652 29.65
29.65
180-18
1801888 8 565 19257 26.45
26.45 0.108
0.108
188-1 96
188196 8 0 20517 29.35
29.35

196-2
196204
04 8 1130 17322 22.12
22.12 0.246
0.246
204-2
204-2112
2 8 0 20320 28.89
28.89

212-2
212220
20 8 1696 14715 16.62
16.62 0.425
0.425
220-2228
220 28 8 0 20080 28.34
28.34

228-2 36
228236 88 2261 10928 9.57 0.662
0.662
236-2242
236 42 8 0 19797 27.70
27.70

242-2
242-2550
0 8 2826 2082 0.39 0.986 aa
0.986
,
250-2
250274
74 24 00 20322 28.90
28.90
a. High
Higheest
st rate not used to analyze data.

TABLE
TABLE 5
5 - AOFP CORR
-
CORRECTION
ECTIO N FOR GAS WELL IN EXAM
EXAMPPLE
LE 1I

t New AOFP
New AOFP
(yr) to
tD Po aa
PD (Sm 3 /d)b
(5m3/d )b
test 0.000
0.00 50
050 3.23 3109
3109

11 0.542
0.54 2 1.16
1.16 7593
22 1.08
1.08 1.50
1.50 5872
5872
55 2.71
2.71 1.90
1.90 4635
4635
IC
10 5.40
5.40 2.22
2.22 3967
3967
25 13.6
13.6 2.80
2.80 3145
3145

Unifor9tl
a. Unifcr rm-fluuxx solu
soluttion
ion exce
excep
ptt for test poin
pointt..
topss for xe/x
5
tj xe/xff of
of 1515 is
is grea
greatter
er than
than 100.
i0(J.

AOFP new
b. w
6
AOF Pn = 0 =
(3.23-O
(3.23
; 0.4)x3 109/P
.4)x3 1O9O; -0.4 is
/p 0.4 is steady
stead y-
state skin
state skin estin
estimatec
ated from test.
test.
A.8-47
A.8-47

TABLE 66 - ROCK
TABLE ROCK AND
ND FLUID
FLUID PROPERTIES
PROPERTIES FuR
FOR OIL WELL TESTS
OILWELL TESTS IN
IN EXAMPLE
EXPiPLE 22

General Properties:
General Properties:

rw 0.1006 m
== 0.1006 rn Pi
Pi == 25476
25476 kPa
kPa (bubble
(bubble point)
point)
re
re 1284.2 m
== 1284.2 in (assumed)
(assumeo) TT == 93.33
93.33 0c
C
hh ==6.096m
6.096 m YAPI= 43.7 0
Y?pI 43.7
kk == 2470 md ('::'~m.2)
2470 md )
2
(jm Siw == 0.32
0.32

~ 0.21
== 0.21 Cti
Cti = 3.626lO6 kPa-
= 3.626.10- kPa1

Relative Permeability:
Relative Permeability:

Corey Relation
Corey Relation (Fig. 8) with A
A of 1.

5
c* 5
{1
*
.
2
*
0
} {l_
.
}SS
rro
krg = 0
S = S
/
0 (1S)

PVT Properties:
PVT Properties:

PP Rs
<s Bo ~0103
iilO 8g 10 3
BglO
3 ~g.103
ug10
3 m(p)1O- 6 a
m(p)l0
a
6 RR bb F PR
Pb ?
FFfPRV /
(kPa) )
3 3
(Sm/Sm
(5m /5m 3) (m
)
3 3
(m/Sm/Sm 3) (Pas)
(Pas) 3
(mSm
/
(m
)
3 3
/Sm ) (Pas) (kPa/Pas) (Sm
(Pas) (kPa/Pas) 3
/Sm
(Sm
)
3 /Sm 3)
31026
31026 249.3
249.3 1. 7116
1.7116 0.2646
0.2646 3.79
3.79 0.0313
0.0313 32.271
32.271 249.3
249.3 0.942
0.942
29303
29303 249.3
249.3 1. 7186
1.7186 0.2583
0.2583 3.91
3.91 0.0301
0.0301 28.427
28.427 249.3
249.3 0.961
0.961
27579
27579 249.3
249.3 1.7265
1.7265 0.2524
0.2524 4.05
4.05 0.0288
0.0288 24.508
24.508 249.3
249.3 0.979
0.979
25476
25476 249.3
249.3 1.7377
1.7377 0.2456
0.2456 4.27
4.27 0.0273
0.0273 19.631
19.631 249.3
249.3 1.0GO
1.000
24821
24821 241.7
241.7 1. 7175
1.7175 0.2493
0.2493 4.34
4.34 0.0268
0.0268 18.354
18.354 241.8
241.8 0.933
0.933
24132
24132 233.9
233.9 1.6962
1.6962 0.2533
0.2533 4.43
4.43 0.0263
0.0263 17.335
17.335 234.6
234.6 0.838
0.838
23442
23442 225.8
225.8 1.6751
1.6751 0.2575
0.2575 4.52
4.52 0.0257
0.0257 16.405
16.405 229.0
229.0 0.747
0.747
22408
22408 214.1
214.1 1.6436
1.6436 0.2641
0.2641 4.67
4.67 0.0249
0.0249 15.113
15.113 227.4
227.4 0.624
0.624
20684
20684 194.7
194.7 1. 5918
1.5918 0.2762
0.2762 4.98
4.98 0.0236
0.0236 13.144
13.144 264.3
264.3 0.450
0.450
17237
17237 156.7
156.7 1.4906
1.4906 0.3054
0.3054 5.84
5.84 0.0208
0.0208 9.685
9.685 661.0
661.0 0.241
O.2LL1
13790
13790 120.4
120.4 1.3931
1.3931 0.3442
0.3442 7.32
7.32 0.0182
0.0162 6.722
6.722 1719.0
1719.0 0.139
0.135
10342
10342 85.5
85.5 1.3C01
1.3001 0.3993
0.3993 10.1
10.1 0.0160
0.0160 4.210
4.210 3526.0
3526.0 0.083
0.083
6895
6895 52.9
52.9 1.2129
1.2129 0.4849
0.4849 16.1
16.1 0.0143
0.0143 2.182
2.182
5171
5171 37.6
37.6 1.1720
1.1720 0.5L92
0.5A92 22.3
22.3 0.0136
0.0136 1.367
1.367

3447
3447 23.2
23.2 1.1337
1.1337 0.6401
0.6401 34.7
34.7 0.0131
0.0131 0.706
0.706
1724
1724 10.2
10.2 1.0989
1.0989 0.7778
0.7778 71.9
71.9 0.0128
0.0128 0.222
0.222
101
101 0.4
0.4 1.0727
1.0727 0.9699
0.9699 124.0
124.0 0.0125
0.0125 0.002
C.O02

a. m(p)
a.
~
m(p) calculatco
calculated usinc
using the Evinger-~uskat
the Evinoeri. method with
uskat nethcc with RR of
of 249.3
249.3 3
Sm
Sm
/
3/Sm 3
Srn.
ann F(pp) from
t. R ana F(PR) from Tamer
Tarner material
material balance.
balance.
_____
____

A.8-48

TABLE
TRBLE 7 - 4-HOUR ISOCHR
4HOUR ONAL TEST RESUL
ISOCHRONL TS FOR OIL WELL
RESULTS iELL IN EXAMPLE 2.

EXAMPLE

m(p~)
m(p)
6 'IG-6
lO in kPa/F a's
kPa/Fas
PR=25
pp=25476 kPa 19.631 29.84
29.8477
(Evin
(Evinaaer-M
erMuskat)
uskat) (Fetk ovich
ovich))
qo Pwf m(pwf
m(p)f).l0
6 '10- 6 md m(pwf '10- 6
m(p)f).l0
6 md
Flow 10
ID (Sm
[Sm
/
3 d)3
/d) (kPa) (kPa/ Pa's))
(kPa/Pas (kPa/ Pa's))
(kPa/Pas
A-I
Pl '366.9
366.9 24401 17.73
17.7333 0.096
0.09677 27.38
27.3800 0.082
A-2
P-2 0.08277
230.8
230. 8 24950 18.60
18.6066 0.052
0.05222 28.62
28.6288 0.040
0.04099
A-3
1\3 120.4
120.4 25325 19.33
19.3366 0.015
0.01500 29.49
29.4944 0.011
A-4
P-4 66.6
0.01188
25376 19.43
19.4366 0.0099 29.61
29.6144 0.007
0.00788
6
m(PR
m(pR)'10-
6 ).10 in kPa/P a's
kPa/Pas
PR=24
24821
PR 821 kPa 19.07
19.0700 27.076
(Evin
(Evingger-M
erMuskat)
uskat) (F etkov
(Fetk ichh))
ovic
B-1
8-1 106.4 24676 18.80
18.8055 0.013
0.01399 26.76
26.7611 0.016
8-2
52 0.01600
164.6 24475 18.43
18.4355 0.033
0.03333 26.236 0.027
0.02777
B-3
8-3 224.6 24327 18.16
18.1655 0.047
0.04755 26.00
26.0099 0.039
B-4
5-4 366.1
0.03944
23757 17.25
17.2566 0.0952
0.0952 24.803 0.083
0.08399

a. Test A run 71/12 /23 and Test 8B run 72/0


71/12/23 72/06 /10..
6/10
A.8-49

D
1

-o
'C
E
E
Ui
LLI
..
cr
a:
::)
D
0 0.1-
0.1
0
Ui
LLI
If
0
0
Q
D
::)
Ui
LLI
If
0Cl)
0

z~
OD1E
0.01
0
en
z
LLI
-
:E
Q

0.001 . I I I I 11.1 I I I I I .1.1

0.001 0.01
0101 o.
0.11 1
DIMESIONLESS RATE, qd

Fig. 11 - Log-log plot of dimensionless rate-pseudopressure solution


-

including high-velocity-flow effects.


A.8-50

66
x10
x10
3200 80

.
(1)
tI)

co
0. ~
U,
"-
co
CD
0.
I-- HIGrPRESSlR:
REGION ,,- "-
:.
CD

2400
24O0 60
60
.
," :.
~
.
" ...
N
" -4
Q,
,,/ '0
C'i
,
0
....
Z ," " >C
01600
1600 4O
40
~
C-)
zZ
","
"
I en
:::J
D
//-- U)

!
LL.
U.
W
cc 800
j800 "
" 20
20
:::J
en "" w
LU
en
Cl) "
w
LU
cc "
"" if
0
0. "
, ..." "
...'

0 ... -............ 0
0 10000 20000 30000
PRESSURE, kPa

Fig. 22 - Real gas pressure and pseudopressure funct


- i ons for reservoir
functions
fluid in Example 1.
A.B'-51
A.8-51

--- DEPLETION
- -
DEPLETION
Cc)
(c)
Fb

FR

0
xFb
xF
r
1
P

(b)

yFb

xF,'
b
4
r

$1
Fb
yFb

xF

PRESSURE
PRESSURE

Fig.
Fig. 33 - Schematic
- Schematic of
of simplified
simplified oil
oil pressure
pressure
function for conditions of flow.
function for three conditions of
three flow.
2.5
2.5 IA

22 k.-~~~~~~~~--~~--~~
~~ ~.885 }
-, Q..Q
22 :::: x =1/9 (VOGEL)

-~
Q.a:
1.5
1.5

- >-
11 1.5
1.5
I'
,'",.
,~

,Q..Q
0.5
0.5 Q.~ -
(b)
6
0
00 i=
c(
11 1.5 2 11 4
a:
,Q.a:
zz
11 MAXIMUM
-------------------------- Q.~ - W
UI
a:
= .co
)::0

oI-
0
;:::: LL
LL.Q 00
.. CI)
U)
CI)
U)
W
LU
00
I
<.1l
01
N
0, i=
I. a:
Z LLa:
Z LL 4
c( a.
Q.

~"
.>-
a: 0.5
UI
W
6
0;:::: 0.9
(j)1 0.9
w
UI
a:
=
D
t
{Yx =0.885
= 1/9 (VOGEL)
(0
0
Cl)
Cl)c( 0
Cl)
UJ
~a: UI
W
a:
0
Q. 0-
0

11 1.5
(8)
Le)
1.5 22 0
0 0.2
0.2 0.4
0.4 0.6
0.6 0.8
0.8 11
PRE SSURE RAT
PRESSURE IO, p /p
RATIO,
RR bb DIM ENSIONLESS PSE
DIMENSIONLESS PSEUDOPRESSURE, md
UDOPRESSURE, m

Fig. 4 Various pressure functions illustrating the effect


Fig. 4 - drive
Various pressure functions illustrating the effect of
-

of unde
undersaturated oil flow
rsaturated oil flow on
on trad
traditional solution-gas
itional solu tion-gas
drive (satu rated) inflo
(saturated) w oefo
inflow performance.
-mance.

L
A.8-53
A.8-53

11
- _. .
,a.a.a: 0.8
0.8
00
.
t= 0.6
0.6

-

a:
w

LU
a:D 0.4
0.4 rr
I

ia:w
U)
Co
LU
0.2
0.2
:r :--

0 1.4
Q. :*VOGEL:V0.2
T
1
i iT
0
OSliilOii 2
.i&iii.ili;i~"""""~--""""'''''''''''''''''''iIiia
o0 0.2
0.2 0.4
0.4 0.6 0.8 11
DIMEN
DIME SIONLES
NSIO NLESS
S PSEU
PSEUD
DOPR
OPRE
ESSU RE,, md
SSIJRE md
(DIMENSiON.ES
<DM:NS IONLESSS RATE
PATE Ifif 0=0)
D 0)

U.. vv

x
U
.. 0.9
0.9
0
< 0.8
0.8

Z 0.7
0.7
0
0.6
0.6
C-)
0.5
0.5
0.4
0.4
LU 03 SATURATED OIL: (P Ip <1)
0.3
0.2 R b
D 0.2
(0 (a)
01
0.1
CO
LU
0.2 0.4 0.6 0.8 1
0
PRES
PRE SURE
SSU TIO, , /P
RATIO
RE RA p/PR

Fig . 5 5 - Sat
Fig. uraated
Satur ted oil
oil pre
-

press
ssuure and pse
re and pseud
udoopres
pressusure
re
fun ctio
funct ions.
ns.
11
E e V
Tl

uf ' Eq. 21, V= 0.4


LU
!5Cl)D
~
Cl)
Eq. 21, V=O If
II
~~
~~
LU
IY ~~
It CI)~ FR 1 .k----~----~----r_--~----_,
8D
0
~~
w
:J ~.,
,o.~ 0.8
LU ~
C)
~ 25o
C O.0.11 0. lR a.
0.
o ' ..
tn
C,) Pa ~
tn
C) PRESSURE 00
1= 0.6
~z ~
o0 w
m
C,)
z
LU
~ co
ffi
LU
~ ~
Cl)
C)
I
U1
U,
~

Q w
LU
fC- .- EVINGER-tvI..ISKAT METHOD
USING VOGEL PVT & RP. DATA

0.01 0'
0 , e e

o0
.,
10 100 1000 0.2 0.4 0.6
11 0.8
OIL RATE
RATE,, Sm
/d
3
Sm 3
/d DIMENSIONLES
DIMENSION S PSEU
LESS DOPRESSURE,
PSEUDOPR ESSURE, md

Fig
Fig.. 6
6 - Multi
Multirrate
ate oilwe
oilwell
ll test analy
analyssed
ed usin~
using two Fig. 7 - Best-fi
Best- fitt of pseudo
-

pseudopres
pseudo sure
pressu re funct ions
functio ns (Fetko 1
7 -
pseudopres sure
pressu function
re functio n
(Fetko

1 vich
vich Well 3-C, (dime
(dimennsion lesss Vogel rate) using the
sionles
Field C). Evinger-Muskat
Evinger-Mus method and Voge
kat method Vogel l's base-
s base-
reser voir
case reservo ir rock and fluid data.
-.4
10-6 10-5 10

0
0
1

e
OJ)j

0
~ 0.8 0.9

o
AJrIvavgu3d 3ALLV13i 110

I ns
CD
0

0.8

d
co
PORE SIZE
:E DISmlBUTION

~ 10 1 0.5 )::0

A.8-55
00
I
0

!
0.4 01
01

0.2
~

o PfWl100
4

1
0

0.1 1 10

0
0.0001 0.001
krg Ikro =(R-RS)UcP/uOBO (81 tria)
I)-

.-

Fig. 8 - Generalized relative permeability relation for use with the Evinger-
-4-)


00

(4
ci) -

V)
w:D

( 4-

4..)

-
Lr3

MCI)
CI) -4-

5-

r 4-
ci)

>r

4-) cJ

-4-)

LU
ci)

ci)
S-ctl
S 4-
clj

>,

(
ci) -4-

Ou
S-a)
z

vo
ci) 0..
ci)

ci)

>

a)
Muskat method of calculating saturated oil pseudopressure.
0


Cf)

-
S

0
0

C..)

C-)

5-

ci)

S.
ci)
z
A.8-56
A.8-56

30
30----------~~--~----~--------~
LL
D
Cl) 29

28
g
X t-1[r
U)
27
0.
ZC 26

Cl)
25

24
24~--------~~--~----~~------~
0.01 0.1 1
INVERSE HOiER
HORNER DE, ~tI(t+~
TIME, t/(t+t)

Fig.
Fig. 99 - Homer
Horner analysis of simulated

simulated buildup well
well test
test in
in
Example 1.
1.

1----------~----------~---,~~~
1
-e- TEST
TEST DATA
-- DATA
E ASSUMtJG
ASSUMN3 VER11CAL
VERTICAL FRACTURE
FRACTURE
WITH 76.2 m
WITH 76.2 m HALF-LENGTh
HALF-lENGTH

CI)
zCl)
01.11
0.1
zo

a.
LI
25 10 5 2 1 YEARS
0.01
0.0 1 L..- - - -......."""1...
0 0 " " - - -...
1000.w.--------0000'"
10
10 100 1000 1
10000
3
GAS
GAS RATE, /
3Sm
RATE, Sm d /d

Fig.
Fig. 1010 - Log-log
Log-log type-curve
-
type-curve match
match of
of gaswell
gaswell modified
modified isochronal
isochronal
test
test inin Example
Example 1.1.
A.8-57
A.8-57

'0 11
E
E
--'EVINGER-MUSKAT m(p)
W
UI --A-FETKOVICH m(p)
a:
D (pressure-squared)
~
Cl)
Cl)
til
LII
W
a:
0
Q.
TEST A (71/12/23)
0o 0.1 TEST B (72/06/10)
Q
:J
Iii
W
Cl)
til
0
Q.
Cl)
til
Cl)
til
UI
~
-J
z
Z GIl /
o 0.002
-
0
Cl)
t il
z
001
0.01 ,,
,
....-
GIl
0..
..... /
/
/

Z
w
UI , ,," ....a. /
/

,,
I

-
:E
Q ,,
, , 0.001 U. /

,,
"
,
,, " 10000 20000 30000
PRESSURE. kPa
,
0.001
0.001
10
10
" 100
100 1000
1000 10000
10000
3
OIL
OIL RATE,
RATE, 3
Sm
Sm
/ d /d

Fig. 1111
Fig. -- Log-log
Log-log type-curve
type-curve match
match of
of oilwell
oilwell isochronal
isochronal test
test
in Example
in Example 22 (Fetkovich
(Fetkovich Well
Well 5-C,
5-C, Field D). insert
Field D); insert
illustrates saturated
illustrates saturated oil
oil pressure
pressure functions
functions
corresponding
correspondin g toto the two methods
the two methods of
of calculating
calculating
pseudopressures
pseudopressu (Evinger-Muskat
res (Evinger-Mu vs. Fetkovich).
skat vs. Fetkovich).
w
LU.....

~
0
coz
0Z
rS
wo
Q.()
o
-Jz
..J~ S~N
-D
C5&L
CLI- 11 ~~~~--~---T--~---r--~--~
--~~

-0.6 -----------=:J~ 0.5


.....---;i"".---
0.8
0.8
2
LJ
LL
UJ
LU
. 3

o>z0 0.6
0
q
qo >-
:---I.+r8IIJI+~ = ~'1
4
E F
1.5
EF =1.5
q EFt1
qo,max
omax z
LU
UJ
:
----: I I8l = Eqo 0
q
(j 6
~----- 1m +~
0.8 0
qo,~ax
--="""-1
q EF=l it
0.6 o,max u..
Li. CP

~
LU
0.4
UJ 0.4 L 10
U,
OD

~
0.2 o0
..I
-J
-0.6
-0.6 0.4
-0.4 -0.2
-0.2 00 0.2
u..
U. 0.2
0.2 0.4
0.4 0.6 0.8 11
0.6 0.8 1.
NO-SKIN PRESSURE
NO-SKIN PRESSURE RATIO,
RATIO, wf p!r
EFl,
IPR
R
0.2
.__ __..............--......
rPWIEF
IPwiEF +(1EF)PR]/P R
+(1-E F )PR]/PR .I 30
- EXACT
0o
0.2
0.2 0.4
0.4 0.6 0.8 11 --- APPROXIMA 1 E
0.6 0.8
MEASURED
MEASURED PRESSURE RATIO, pP
PRESSURE RATIO, /p 0o ' ,
wt Ip.
wf RR o
0 0.2
0.2 0.4
0.4 0.6
0.6 0.8
0.8 1
MEASURED PRESSURE
MEASURED PRESSURE RATIO,
RATIO, pp /p
Ip
Fig. wf
wf RR
Fig. A-i
A-1 - Physical
Physical description
-
descr iption of
of why
why the
the
Standing
Standing method
method for
for correcting
corre cting the
the
Vogel
Vogel relation
relati on for
for stimulated
stimulated wells Fig. A2
Fig. Effect of
A-2 - Effect of two-phase,
two-phase, gas-oil
gas-o il flow
flow onon the
the relation
relati on
wells

between flow
flow efficiency
effici ency and
can
can lead
lead to
to nonphysical
nonphysical rate-pressure
rate-p ressu re between and positive
posit ive skin
skin factor;
facto r;
behavior.
behavior . In(r /r )-3/4 = 77 and
ln(re/rw)_3/4 and Vogels
Vogel IS saturated
satura ted oil
oil
presseurew function
ressurQ f ' n are
unctl0 assume d .
are assumed.
I
A.9-1
A.9-1

DISCUSSION
DISCUSSIO OF CONSTANT
N OF CONSTANT-PRESSURE
-PRESSURE
RATE DECLINE
RATE DECLINE DURING
DURING DEPLETION
DEPLETION
by
by

Curtis H.
Curtis H. Whitson
Whitson
1983
1983

In 1956,
In 1956, Tsarevich
Tsarevich and Kuranov 1 made
and Kuranov made the
the observation
observation that
that
aa well
well producing
producing at
at constant
constant weilbore
wellbore flowing
flowing pressure
pressure will,
will,
after sufficient
after sufficient time,
time, produce
produce atat aa rate
rate which
which decreases
decreases
exponentially..
exponentially They show
They show that
that the
the exact
exact rate
rate solution
solution is
is an
an
infinite sum
infinite sum of
of exponential
exponential terms.
terms. Retaining only
Retaining only the
the first
first
term gives
term gives aa surprisingly
surprisingly good
good estimate,
estimate, usually
usually within
within 11 or
or
percent of
22 percent of the
the exact
exact solution.
solution. The exponential
The exponential rate
rate
expression given
expression given by
by Tsarevich and
and Kuranov is,
is,

qo
qD =2
=clexp{-(bl/rOe)2tO},
t D}
clexp{(bl/ rDe) (1)

where q
qo
0 is dimensionless pf),
q( t )J,J8/kh (Pi -Pwf
dimensionless rate, q(t)1B/kh(p ), tD
to is
is
dimensionless
dimensionless time, kt/lhICtrw2,
kt/4pcr and rOe
,
2 dimensionless
rDe is dimensionless
external radius, re/rw.
re/rw. Constant bl1 is the first and
b
smallest
smallest root of
of the equation

0 bn/rDe
Y1(bn
( )
)J Jl(bn)Yo(bn/rDe) 0 (2)

which results from the exact solution to the


constant-pressure
constantpressure problem originally solved
solved by 22
Hurst.
by HUrst.
Constant
Constant ci
1 is
c is given
given by

(b
2
1
2Y
)
1
c
= Ylz(bl/rDe) Yiz(bi)
-

where
where JO,
3j, Jb
.J, YO,
, and
0
Y and Yb
, are
1
Y are regular
regular Bessel
Bessel functions
functions of of
order
order zero
zero and
and one.
one. Tsarevich
Tsarevich and
and Kuranov
Kuranov give
give values
values of
of bi
1
b
and
and cl1 for
c for dimensionless
dimensionless radii
radii from
from 2020 to 106.
to 10 6
Table
Table II
reports
reports these
these values,
values, asas well
well asas those
those calculated
calculated by by this
this
author
author for
for rOe
rDe from
from 1.5
1.5 to
to 18.
18. Dimensionless
Dimensionless times
times for
for
which
which Eq.
Eq. I1 isis within
within one
one percent
percent accuracy
accuracy are
are noted
noted by
by an
an
asterisk.
asterisk.
A.9-2
A .9-2
FETKOVICH APPROACH
FETKOVICH APPROACH

3
Fetkovich 3
Fetkovich gives
gives an
an empirical
empirical method
method for
for defining
defining Eq.
Eq. 11 in
in
terms of
terms of reservoir variables
reservoir variables for
for rOe
rDe ~ 10,
10,

2
exp{_2t0/[(rDe2_1)(ln(rQe
exp{-2to/[(roe - 1)(ln(roe )-1/2)]}
)_1/2)l }
qo
qD = , .... (3)
In(ro e )-1/2
ln(rDe)1/2

or,
or, as
as expressed
expressed by
by Fetkovich,
Fetkovich,

-tOd
tDd

qOd
q=e = e , (4)
(4)

where
where

qOd
qDd = (lnrOe-l/2)qo
(lnr_1/2)q (Sa)
(5a)

tDd = 2t0/[(rQe2_1)(lnrDe_1/2)] ............... (5b)


Fetkovich notes that tOd
Fetkovich tDd of
of 0.3 marks the approximate start
start
of depletion
of depletion - at which time Eq. 33 becomes useful
useful as
as an
an
approximation to the analytical exponential q
approximation qo solution
0 solution
(Eq. 1).
(Eq. 1).

It
It should
should be
be mentioned
mentioned that
that Fetkovich
Fetkovich does
does not
not use
use the
the exact
exact
analytical
analytical qQ(t)
qo(tO) expression
expression to
to derive
derive Eq.
Eq. 3.
3. Instead,
Instead, he
he
bases
bases his
his definition
definition on
on an
an empirical
empirical form of
of the
the exponential
exponential
decline
decline equation
equation (Arps~)
(Arps) using
using common
common expressions
expressions for
for
initial
initial oil
oil in
in place
place and
and maximum
maximum initial
initial rate.
rate. His
His purpose
purpose
is
is to
to show
show how
how the
the q(t)
qo(tO) depletions
depletion-stems collapse to
tems collapse to form
form aa
single
single exponential
exponential curve.
curve. Within
Within the
the accuracy
accuracy of
of type
type curve
curve
matching
matching field
field data,
data, for
for which
which the
the constant-pressure
constantpr essure
solution
solution is
is suggested,
suggested, the
the expression
expression given
given by
by Fetkovich
Fetkovich is
is
useful
useful and
and accurate.
accurate.
AA.9-3
.9-3
URAIET!RAGHAVAN
URAIET/RP AND EHLIG-ECO
CHAVAN AND EHLIG-ECOMOMlDES!RAMEY APPROACH
MOMIDES/RAMEY APPROACH

Almost simultaneous
Almost simultaneously in 1980
ly in 1980 and
and 1981,
1981, Uraiet
Uraiet and Raghavan 5
and Raghavan
5
and EhligEcon
and Ehlig-Economides
omides andand Ramey
Ramey' presented
6 presented very
very similar
similar
results about
results about the
the application
application of
of constantpr
constant-pressure transient
essure transient
rate solutions
rate solutions to
to drawdown
drawdown and
and buildup
buildup testing.
testing. Both
Both sets
sets
of authors
of authors suggest
suggest the
the following
following expression
expression for
for qD
qo during
during
depletion,
depletion,

exp{-2to/[roe2(lnroe-3/4)]
exp{_2tD/[rD e2(lnroe_3/4)] }}
qo = -----=~-~ro:------'.
=
1 InrOe-3/4
nre3/4
.............. (6)
(6)

Uraiet and Raghavan


Uraiet and Raghavan claim
claim that
that the
"the times
times at
at which
which the
the
closed outer
closed outer boundary
boundary influences
influences the
the wellbore
wellbore flow rate are
are
given (empirically)
given (empirically) by
by"

tolroe
tcj/roe
2
2 = 0.318
= 0.318 +
+ 0.040log(rOel00O)
0.O40log(r/ /lOOO). .......... (7)
(7)

The range of rOe


roe for which Eq. 77 is applicable
applicable is not
specified; from other results in their study, it appears
that 500~rOe~10~.
that Eq. 88 only can be used for 5OOroe1O
.
4

Ehlig-Economides
EhligEconomides and Ramey state that Eq. 66 is an "exact"
exact
/rk>o.l and rOe~lO~.
solution for torw2/A>0.1
2
torw rDelO. It is probably more
accurate to call Eq. 6 an approximate asymptotic solution.

Uraiet and Raghavan misleadingly attribute Eq. 6 to


Fetkovich; clearly, Eqs. 4 and 6 are not equivalent. On the
other hand, Ehlig-Economides
EhligEconomides and Ramey claim that that
Fetkovich's
Fetkovichs use of 1/21/2 in Eq. 4 is in error. This
suggestion deserves some comment.

First, there areare two differences


differences between Eqs. 44 and and 6: (1)
(1)
Eq.
Eq. 4 uses InrOe-1/2
lnrDel/2 while
while Eq.
Eq. 66 uses
uses InrOe-3/4,
lnrQe3/4, and
and (2)
(2) Eq.
Eq.
44 uses
uses rOe2-1.
l while
2
rDe while Eq.Eq. 66 uses rOe .
2
rDe2 Based
Based on on
Ehlig-Economides
EhligEconomides and Ramey's
Rameys arguements,
arguements, Eq. 66 cancan bebe used
for rOe>10~
for 4 and
rDe>10 and toRO.l.
tDA>O.l. At
At such
such large
large values
values of of
dimensionless
dimensionless radii
radii the
the difference
difference between
between Eqs.
Eqs. 44 and
and 66 is
is
quite
quite small.
small.

Second, it
Second, is not
it is not obvious
obvious which
which of
of the
the equations,
equations, 44 or
or 6,
6, is
is
more
more accurate
accurate at
at values
values of
of rOe
rDe less than 1O~.
less than l0. From
From aa
A.9-4
A .9-4
practical point of of view, constant-pressure
constantpressure production will
usually occur in stimulated, low-permeability
lowpermeability wells. For
such cases, the true welibore
wellbore radius, rrw,
w, used to define rOe
rOe
should be replaced by rwe- s
re,, where skin, s, 5, is negative for

stimulated wells. ConSidering


Considering a relatively large drainage
area of
of 900 m (~ 640 acres) and a relatively small welibore
m (z wellbore
radius of 0.09m, rDe rOe is 10000, 3700, 1350, 500, 190, and 70,
for skins of of 0, -1,
1, -2,
2, -3,
3, -4,
4, and -5,
5, respectively.
Clear ly the value of
Clearly of rOe
rDe for most practical cases will be
less than 10",
10k, and it may often approach values less than
100.

PAPATZACOS APPROACH

In aa personal communication, Paul Papatzacos suggested the


following approximation to the depletion q(tQ)
qO(tO) solution,

exp{_2tD/[rDe+(lnrQe)/(rDe2_1)_(3rDe2_1)/4l}
qD= . (8)
[rDe(1nrDe)/(rDe2_1)_(3rDe2_1)/4j /(rQe
1)
2

This expression was derived using approximations to Bessel


functions found in the constant-rate
constantrate pressure solution,
which was then inverted using Laplace transformation. The
di fference between Eq. 88 and Eq. 66 arises from a more
difference
general development to better account for "small"
small values of
dimensionless radius.
A.9-5
A.9-5

GENERAL COMMENTS
GENERAL COMMENTS

Fig. 11 was
Fig. was prepared
prepared to
to compare
compare the
the various
various approximatio
approximations to
ns to
the constantpressure
the constant-pressure q
qo solution
0 solution during
during depletion.
depletion. Absolute
Absolute
deviation
deviation was
was calculated
calculated by
by integrating
integrating the
the absolute
absolute
deviation in q
deviation in qo given
0 given by
by Eqs.
Eqs. 4,
4, 6,
6, and 88 from the
the tD
to value
value
given in
given in Table
Table 11 to
to tD
to at
at which
which qqo from Eq.
0 Eq. 11 becomes
becomes 0.001.
0.001.
The basis
The basis of
of comparison
comparison was
was qD
qo given
given by
by Eq.
Eq. 1.
1.

that Eq. 88 gives


It appears that gives the best
best overall
overall approximatio
approximation,
n,
as compared with Eqs. 44 and
and 6. Although Eq. 44 is
is inferior to
Eqs. 66 and
and 8,
8, it
it still
still provides
provides aa good
good approximation
approximation for
engineering/type-curve
engineering/typecurve matching of If high
of field data. If high
accuracy is required for q(tjJ)
qOCtO) values, either Eq. 11 or a
series solution should
partial expansion of the infinite series should be
be
used. Otherwise, the simplest and most accurate expression
is Eq. 6. For decline typecurve
type-curve matching, the exponential
solution given by any of
of Eqs. 4, 6, or 8 can be used. Field
data which are affected by rock and fluid heterogenities
heterogenities can
hardly be expected to fit exactly the idealized model used
to generate the constant-pressure
constantpressure rate solution.
A.9-6

REFERENCES
1. Tsarevich, K.A. and Kuranov, LF.:
I.F.: "Calculation
Calculation of the
Flow Rates for the Center Well in a Circular Reservoir
Under Elastic Conditions,
Conditions,.. Problems of Reservoir
Hydrodynamics, Leningrad (1956) Part I, 9-34.
934.

2. Hurst, W.: "Unsteady


Unsteady Flow of Fluids in Oil Reservoirs,"
Reservoirs,
Physics (Jan. 1934)1,
1934)5, 20-30.
203D.

Decline Curve Inalysis


3. Fetkovich, M.J.: "Decline Analysis Using Type
Curves,"
Curves, J.Pet.Tech. (June 1980) 1067-1077;
10671077; Trans. PJME,
AIME,
269.
4. Arps, J.J.: "Analysis
1\nalysis of
of Decline Curves,"
Curves, Trans. AIME,
fUME,
160, 228-247.
228247.

5. Uraiet, A.A. and Raghavan, R.: "Unsteady


Unsteady Flow to a Well
Producing at a Constant Pressure
Pressure" and "Pressure
Pressure Buildup
Analysis for a Well Produced at Constant Bottomhole
1\nalysis
Pressure," J.Pet.Tech. (Oct. 1980) 1803-1824;
Pressure, 18031824; Trans.
AIME, 269.
fUME,

6. Ehlig-Economides,
EhligEconomides, C.A.
C.P. and Ramey, H.J.: "Transient
Transient Rate
Decline nalysis
Analysis for Wells Produced at Constant
Pressure" and "Pressure
Pressure Pressure Buildup for Wells Produced at
a Constant Pressure,
Pressure," Soc.Pet.Eng.J. (Feb. 1981) 98-114;
98114;
Trans. AIME,
fUME, 271.
A.9-7
A.9-7

TABLE 11
TABLE - First
First Roots
Roots of
of Eq.
Eq. 22 used
used toto Define
Define Consta nts in
Constants Eq. 11
in Eq.
For Estima
For Estimating the Consta
ting the re Dimen
Constant Wellbore Pressure Dimensionless
nt Weilbo re Pressu sionless
Rate Solutio
Rate Solution During Deplet
n During Depletion. Also the Dimensionless
ion. Also the Dimen sionles s
Time at
Time at which
which Eq.
Eq. 11 deviate the Exact
deviates by 1 % from the Exact Solution.
s by 1 % from Solutio n.

rOe 1
b
bl cl *
0
t
tD*
rDe

1.5
1.5 4.33482
4.3348 2 4.41653
4.41653 5.706E02
5.706E-02
2.0
2.0 2.72155
2.7215 5 2.41705
2.4170 5 2.243E01
2. 243E-0l
2.5
2.5 2.16515
2.1651 5 1.74659
1.7465 9 4.972E01
4.972E-0l
3.0
3.0 1.87679
1.8767 9 1.40979
1.4097 9 8.729E0l
8.729E-0l
3.5
3.5 1.69753
1.6975 3 1.20489
1.2048 9 l.349E +00
1. 349E+00
4.0
4.0 1.57382
1.5738 2 1.06666
1.0666 6 1.925E+00
1.925E+00
5.0
5.0 1.41180
1.4118 0 88
0.890488
0.8904 3.371E+00
3. 37lE+00
6.0
6.0 1.30843
1.3084 3 0.781811
0.781811 5.201E+00
5.201E+00
7.0
7.0 1.23557
1.2355 7 0.7072 93
0.707293 7.416E+00
7. 416E+OO
8.0
8.0 1.18078
1.1807 8 82
0.652582
0.6525 1.OO1E+01
1.oo1E+0l
10.0
10.0 1.10269
1.1026 9 11
0.576811
0.5768 1.631E+01
1. 631E+01
12.0 1.04869
1.04869 0.526121
0.526121 2.410E+Ol
2.410E+0l
14.0 1.00848
1.00848 0.489355
0.489355 3.335E+01
3.335E+0l
16.0 0.977006
0.977006 0.461214
0.461214 4.407E+01
4.407E+Ol
18.0 0.951463
0.951463 0.438822
0.438822 5.622E+01
5. 622E+0l
20.0 0.930177
0.930177 0.420469
0.420469 6.982E+O1
6.982E+01
25.0 0.889299
0.889299 0.386060
0.386060 1.1O1E+01
1.101E+0l
30.0 0.859514
0.859514 0.361715
0.361715 1.592E+02
1.592E+02
40.0
40.0 0.817934
0.817934 0.328786
0.328786 2.837E+02
2.837E+02
SO.O
50.0 0.789445
0.789445 91
0.306991
0.3069 4.428E+02
4.428E+02
100.0
100.0 0.716692
0.716692 0.254234
0.254234 1.749E+03
1.749E+03
200.0
200.0 0.660753
0.660753 0.216711
0.216711 6.844E+03
6. 844E+03
SOO.O
500.0 0.603471
0.603471 0.181181
0.181181 4.130E+04
4. 130E+04
1000.0
1000.0 0.568803
0.568803 0.161125
0.161125 1.605E+05
1.605E+05
2000.0
2000.0 0.539461
0.539461 0.145044
0.145044 6 .237E+05
6. 237E+05
4000.0
4000.0 0.514223
0.514223 0.131865
0.131865 2.424E+06
2. 424E+06
10000.0
10000.0 0.485704
0.485704 0.117711
0.117711 l.458E
1. +07
458E+07
25000.0
25000.0 0.461458
0.461458 0.106288
0.106288 8.780E+07
8. 780E+07
100000.0
100000.0 0.430803
0.430803 0.0926732
0.0926732 1.330E+08
1.330E+08
250000.0
250000.0 0.413591
0.413591 0.0854380
0.0854380 8.024E+09
8.024E+09
1000000.0
1000000.0 0.391084
0.391084 0.0764036
0.0764036 1.219E+11
1. 219E+11
oC
MN

z EQ. 8
~
0
I
~
>
>
w
w
0
C

.-::::>WDIw4LD
.....

-J
~
0
U)
~ID

o0
.....

1.0
I
co
c!o

U)
LD

0
o

100
10 10
10 f02 108
fO 101 fO&
106
DIME
DIM NSION
ENS LESS
IONLES S EXTER
EXTE NAL RAD
RNAL RADIU
IUSS
Fig.
Fi~. 11 - Erro
Errorrss in
-
in appr
approoxim
ximat
atee solu
soluti ons to
tions to the
the cons
const ant-p
tant- ressu
press re rate
ure rate solu
soluti on durin
tion during deple
g depl tion..
etion
B.1-1
8.1-1

FLUID
FLUID : HOFF
HOFFMAN/CRUMP /H~
NAN/CFUMP/HO(x RESERVOIR
Yrr RESER On.
VOIR OIL

EXPERIMENTAL
EXPE DISTILLATICN
RtNTAL DISTI DATA
LLATICT DNPA

M:>LECl.JLAR
M:>LE t4DLE
t4DLE SPOCIFIC
QJL2R SPECI FtC 3)ILIN G POINT
roILING POINT EIGHT
\"EIGHT
FRACI'I~1
<DMP FPAC \"EIGHT
tEIGH T GRAVI'IY
GRVI (om. R)
IY (D. R) (om.
(D1x. K)
K) cric t
FRACl'ICN
cDMP IIE

Cl
ci 0.5200
0.5200
2C2 0.0381
0.0381
C3
C3 0.0237
0.0237
IC4
1C4 0.0076
0.0076
NC4
NC4 0.0096
0.0096
ICS
1C5 0.0069
0.0069
NCS
NC5 0.0051
0.0051
C6S
C6S 0.0206
0.0206
C7
C7 0.0263
0.0263 99.0
99.0 0.7490
0.7490 668.86
668.86 371.59
371.59 0.0356
0.0356
CB
3 0.0234
0.0234 110.0
110.0 0.7580
0.7580 717.89
717.89 398.83
398.83 0.0352
0.0352
C9 0.0235
0.0235 121.0
121.0 0.7790
0.7790 763.12
763.12 423.96
423.96 0.0388
0.0388
C9
ClO 0.02240
0.0224 0 132.0
132.0 0.7860
0.7860 805.11
805.11 447.28
447.28 0.0404
0.0404
CiO
Cl1
Cli 0.02412
0.02412 145.0
145.0 0.7980
0.7980 844.27
844.27 469.04
469.04 0.0478
0.0478
Cl2
(22 0.02457
0.0245 7 158.0
158.0 0.8120
0.8120 880.99
880.99 489.44
489.44 0.0530
0.0530
Cl3
(23 0.02657
0.0265 7 172.0
172.0 0.8260
0.8260 915.54
915.54 508.63
508.63 0.0624
0.0624
Cl4
L4 0.03262
0.0326 2 186.0
186.0 0.8460
0.8460 948.15
948.15 526.75
526.75 0.0829
0.0829
Cl5 0.03631
0.0363 1 203.0
203.0 0.8510
0.8510 979.09
979.09 543.94
543.94 0.1007
0.1007
(25
Cl6
16 0.02294
0.0229 4 222.0 0.8520
0.8520 1008.38
1008.38 560.21
560.21 0.0696
0.0696
Cl7
17 0.01714
0.01714 238.0 0.8380 1036.30
1036.30 575.72
575.72 0.0557
0.0557
Cl8
18 0.01427
0.01427 252.0 0.8460 1062.97
1062.97 590.54 0.0491
0.0491
Cl9
19 0.01303
0.01303 266.0 0.8510 1088.48
1088.48 604.71 0.0473
0.0473
C20
20 0.01078
0.01078 279.0 0.8710 1112.91
1112.91 618.28 0.0411
0.0411
C21
21 0.00871
0.00871 290.0 0.8780 1136.30
1136.30 631.28 0.0345
0.0345
C22
2 0.00715
0.00715 301.0 0.8840 1158.80
1158.80 643.78 0.0294
0.0294
C23
23 0.00575
0.00575 315.0
315.0 0.8890
0.8890 1171.92
1171.92 651.07 0.0247
0.0247
C24
4 0.00481
0.00481 329.0
329.0 0.8930
0.8930 1192.15
1192.15 662.31
662.31 0.0216
0.0216
C25
5 0.00394
0.00394 343.0
343.0 0.8970
0.8970 1211.87
1211.87 673.26
673.26 0.0185
0.0185
C26
26 0.00335
0.00335 357.0
357.0 0.9000
0.9000 1231.12
1231.12 683.96
683.96 0.0163
0.0163
C27
27 0.00280
0.00280 371.0
371.0 0.9030
0.9030 1249.89
1249.89 694.38
694.38 0.0142
0.0142
C28
8 0.00250
0.00250 385.0
385.0 0.9060
0.9060 1268.16
1268.16 704.53
704.53 0.0131
0.0131
C29
29 0.00232
0.00232 399.0
399.0 0.9000
0.9080 1285.88
1285.88 714.38
714.38 0.0126
0.0126
C30
co 0.00195
0.00195 413.0
413.0 0.9100
0.9100 1303.01
1303.01 723.89
723.89 0.0110
0.0110
C31
c31 0.00170
0.00170 427.0
427.0 0.9120
0.9120 1319.47
1319.47 733.04
733.04 0.0099
0.0099
C32
32 0.00156
0.00156 441.0
441.0 0.9140
0.9140 1335.22
1335.22 741.79
741.79 0.0094
0.0094
C33
33 0.00143
0.00143 455.0
455.0 0.9160
0.9160 1350.19
1350.19 750.11
750.11 0.0089
0.0089
C34
c4 0.00130
0.00130 469.0
469.0 0.9170
0.9170 1364.33
1364.33 757.96
757.96 0.0083
0.0083
C35
c35 0.00118
0.00118 483.0
483.0 0.9180
0.9180 1377.62
1377.62 765.34
765.34 0.0078
0.0078
1.00000
1.00000 87.32
87.32

C7+ 0.36840
C7+ 0.36840 198.7
198.7 0.8409
0.8409 1.0000
1.0000
B.1-2
B.12

FLUID : HOFFMAN/CRI.JMP/~
FLUID HOE N/CIUMP/HOOYI9: RESERVOIR
RESE1JOIR OIL
OIL

PENG/ROBINSaJ EOUATICN
PENG/ROBINSC:N OF STATE
HOUiTIC OF STATE

CRtTICAL
CRITICAL

PRESSURE
PRESSURE TEME>ERA'1URE
TEMPER1IURE
JLE
IDLE ACENl'RIC
ENTPIC
coii FRACTIQl
CDMP FRAI0N (PSIA)
(PsIA) (KPA)
(KPA) (IlEl3.
(DHO. R)R) (IlEl3.
(DHO. K)K) E7\Cr0R
FACIOR

cr7
(2 0.02630 453.4 3126.0 995.2 552.9 0.3024
c
C8 0.02340 426.9 2943.0 1048.4 582.4 0.3583
C9
C9 0.02350 412.2 2842.0 1099.4 610.8 0.4070
ClO
cio 0.02240 392.0 2703.0 1143.5 635.3 0.4570
cii
Cl1 0.02412 371.5 2561.0 1183.1 657.3 0.5060
(22
Cl2 0.02457 355.2 2449.0 1220.6 678.1 0.5513
13
Cl3 0.02657 339.1 2338.0 1255.0 697.2 0.5954
Cl4
14 0.03262 328.0 2262.0 1288.8 716.0 0.6351
15
Cl5 0.03631 307.2 2118.0 1315.8 731.0 0.6805
L6
Cl6 0.02294 285.2 1966.0 1339.4 744.1
744,1 0.7267
17
Cl7 0.01714 265.0 1827.0 1361.4 756.3 0.7718
(28
Cl8 0.01427 256.8 1771.0 1387.8 771.0 0.8064
19
Cl9 0.01303 248.4 1713.0 1412.6 784.8 0.8404
(20
C20 0.01078 246.4 1699.0 1439.6 799.8 0.8676
(21
C21 0.00871 242.5 1672.0
1672.0 1464.2 813.4 0.8957
(22
C22 0.00715 238.5 1644.0 1487.6 826.5 0.9231
(23
C23 0.00575 230.5 1589.0
1589.0 1497.8
1497.8 832.1
832.1 0.9448
(24
C24 0.00481 224.1 1545.0
1545.0 1516.9
1516.9 842.7 0.9727
0.9727
(25
C25 0.00394 218.3
218.3 1505.0
1505.0 1535.6
1535.6 853.1 0.9998
(26
C26 0.00335 212.6
212.6 1466.0 1553.8
1553.8 863.2
863.2 1.0265
1.0265
(27
C27 0.00280
0.00280 207.3
207.3 1430.0
1430.0 1571.5
1571.5 873.1
873.1 1.0524
1.0524
(28
C28 0.00250
0.00250 202.4
202.4 1396.0
1396.0 1588.8
1588.8 882.7
882.7 1.0776
1.0776
(29
C29 0.00232
0.00232 197.6
197.6 1362.0
1362.0 1605.4
1605.4 891.9
891.9 1.1024
1.1024
0
C30 0.00195
0.00195 193.0
193.0 1331.0
1331.0 1621.5
1621.5 900.8
900.8 1.1265
1.1265
1
C31 0.00170
0.00170 188.7
188.7 1301.0
1301.0 1636.8
1636.8 909.4
909.4 1.1497
1.1497
(22
C32 0.00156
0.00156 184.6
184.6 1272.0
1272.0 1651.5
1651.5 917.5
917.5 1.1720
1.1720
(23
C33 0.00143
0.00143 180.6
180.6 1245.0
1245.0 1665.3
1665.3 925.1
925.1 1.1935
1.1935
(24
C34 0.00130
0.00130 176.6
176.6 1218.0
1218.0 1678.0
1678.0 932.2
932.2 1.2143
1.2143
(25
C35 0.00118
0.00118 172.8
172.8 1191.0
1191.0 1689.8
1689.8 938.8
938.8 1.2342
1.2342
B.1-3
B.1-3

FLUID: HOFEN1N/C
FLUID HOFFMAN/CRUMP/HOCOTl' RESERVOIR OIL
RUMP/H0CtYII RESERVOIR OIL

SOAVE/REDLICE/K~1G
SAVE/REDL Ic/KwjNG EXUITIt OF STME
EOUATICN OF STATE

QUTI( L
CRITICAL

PRESSURE
PRESSURE TEMPERMU RE
TEMPERMURE
IDLE
4DLE -
E2SiTRIC
ACfNl'RIC
mMP FRACrION
aDMP FRACl'ICt7 (PSIA)
(PSIA) (KPA)
(KPA) (DID. R)
(DEx3. R) (DEn. K)
(rx3. K) FACIOR
FAC'IDR

c:7
c7 0.02630
0.02630 514.4
514.4 3547.0
3547.0 1006.5
1006.5 559.2
559.2 0.3024
0.3024
CE
c 0.02340
0.02340 483.9
483.9 3336.0
3336.0 1059.9
1059.9 588.9
588.9 0.3583
0.3583
C9
c 0.02350
0.02350 466.7
466.7 3218.0
3218.0 1111.1
1111.1 617.3
617.3 0.4070
0.4070
ClO
cio 0.02240
0.02240 443.5
443.5 3058.0
3058.0 1155.2
1155.2 641.8
641.8 0.4570
0.4570
Cl1
cal 0.02412
0.02412 419.8
419.8 2895.0
2895.0 1194.6
1194.6 663.7
663.7 0.5060
0.5060
Cl2
(22 0.02457
0.02457 401.1
401.1 2765.0
2765.0 1232.0
1232.0 684.5
684.5 0.5513
0.5513
Cl3
ca 0.02657
0.02657 382.6
382.6 2638.0
2638.0 1266.2
1266.2 703.5
703.5 0.5954
0.5954
Cl4
(24 0.03262
0.03262 369.8
369.8 2550.0
2550.0 1299.8
1299.8 722.1
722.1 0.6351
0.6351
Cl5
(25 0.03631
0.03631 346.2
346.2 2387.0
2387.0 1326.4
1326.4 736.9
736.9 0.6805
0.6805
Cl6
(26 0.02294
0.02294 321.1
321.1 2214.0
2214.0 1349.7
1349.7 749.8
749.8 0.7267
0.7267
Cl7
(27 0.01714
0.01714 298.2
298.2 2056.0
2056.0 1371.4
1371.4 761.9
761.9 0.7718
0.7718
Cl8
(28 0.01427
0.01427 288.8
288.8 1991.0
1991.0 1397.5
1397.5 776.4
776.4 0.8064
0.8064
Cl9
19 0.01303
0.01303 279.2
279.2 1925.0
1925.0 1421.9
1421.9 790.0
790.0 0.8404
0.8404
C20
(20 0.01078
0.01078 276.8
276.8 1908.0
1908.0 1448.6
1448.6 804.8
804.8 0.8676
0.8676
C21
21 0.00871
0.00871 272.3
272.3 1877.0
1877.0 1472.9
1472.9 818.3
818.3 0.8957
0.8957
C22
(22 0.00715 267.7 1845.0
1845.0 1496.1
1496.1 831.1
831.1 0.9231
0.9231
C23
(23 0.00575 258.6 1783.0 1506.0
1506.0 836.7
836.7 0.9448
0.9448
C24
(24 0.00481
0.00481 251.4 1733.0
1733.0 1524.8 847.1
847.1 0.9727
0.9727
C25
(25 0.00394 244.7 1687.0 1543.2 857.4 0.9998
0.9998
C26
(26 0.00335
0.00335 238.3 1643.0 1561.1 867.3 1.0265
1.0265
C27
(27 0.00280
0.00280 232.3 1601.0 1578.5 877.0 1.0524
1.0524
C28
(28 0.00250
0.00250 226.7 1563.0 1595.5 886.4 1.0776
1.0776
C29
(29 0.00232 221.2 1525.0 1611.9
1611.9 895.5 1.1024
1.1024
C30
SO 0.00195
0.00195 216.0 1489.0
1489.0 1627.6 904.2 1.1265
1.1265
C31
31 0.00170
0.00170 211.1 1455.0
1455.0 1642.7
1642.7 912.6 1.1497
1.1497
C32
32 0.00156
0.00156 206.4 1423.0
1423.0 1657.0
1657.0 920.6
920.6 1.1720
1.1720
C33
33 0.00143
0.00143 202.0
202.0 1392.0
1392.0 1670.5
1670.5 928.1
928.1 1.1935
1.1935
C34
c34 0.00130
0.00130 197.4
197.4 1361.0
1361.0 1683.0
1683.0 935.0
935.0 1.2143
1.2143
C35
5 0.00118
0.00118 193.1
193.1 1331.0
1331.0 1694.6
1694.6 941.4
941.4 1.2342
1.2342
B.1-4
B.1-4

HOF'El1AN E9
FIlJID :: HOFFWN
FLUID ET AL. RESERVOIR GAS
AI... RESEIWOIR GM:)

EXPERIMENTAL DISTnLATICJil DPTA


EXPERIMENTAL DISTILL1TIC DATA

?DLE
M)LE 4DLEJLAR
M)LEClJIAR SPECIFEC
SPECIFIC roILING POINT
BDILING POrnI' IEIGHT
\'EIGHT
cDMP
roMP FPACrION
FRACrICN EIGHT
\'EIGHT GRAVITY
GRVIf (DEG. R)
(DB3. R) (DEX.
(DEG. K)
K) icrictsi
FRACrICJil

Cl
ci 0.91350
0.91350
C2
2 0.04030
0.04030
C3
3 0.01530
0.01530
IC4
1C4 0.00390
0.00390
NC4 0.00430
0.00430
ics
ICS 0.00150
0.00150
NCS
NC5 0.00190
0.00190
C6S
C6S 0.00390
0.00390
c7
(2 0.36100
0.36100 100.00
100.00 0.7450
0.7450 668.86
668.86 371.59
371.59 0.1660
0.1660
c
C8 0.28500
0.28500 114.00
114.00 0.7530 717.89 398.83
398.83 0.1494
0.1494
C9
9 0.22200 128.00
128.00 0.7730 763.12 423.96 0.1306
0.1306
ClO
CLO 0.15800 142.00 0.7790
0.7790 805.11 447.28
447.28 0.1031
cai
Cl1 0.12100 156.00
156.00 0.7930 844.27 469.04 0.0868
Cl2
C12 0.09700
0.09700 170.00
170.00 0.8040
0.8040 880.99
880.99 489.44
489.44 0.0758
0.0758
Cl3
13 0.08300
0.08300 184.00
184.00 0.8160
0.8160 915.54
915.54 508.63
508.63 0.0702
0.0702
Cl4
CL4 0.06900
0.06900 198.00
198.00 0.8360
0.8360 948.15 526.75
526.75 0.0628
0.0628
cis
Cl5 0.05000
0.05000 212.00
212.00 0.8400
0.8400 979.09
979.09 543.94
543.94 0.0487
0.0487
Cl6
16 0.03400 226.00
226.00 0.8390
0.8390 1008.38
1008.38 560.21 0.0353
ca
Cl7 0.02300 240.00
240.00 0.8350
0.8350 1036.30
1036.30 575.72
575.72 0.0254
Cl8
18 0.01500
0.01500 254.00 0.8500
0.8500 1062.97
1062.97 590.54
590.54 0.0175
Cl9
19 0.01000 268.00 0.8650
0.8650 1088.48
1088.48 604.71 0.0123
C20
20 0.00600 282.00 0.8730
0.8730 1112.91
1112.91 618.28 0.0078
C21
2i 0.00400 296.00 0.8760
0.8760 1136.30
1136.30 631.28 0.0054
C22
22 0.00200 310.00 0.8780 1158.80
1158.80 643.78 0.0029

1.00000
1.00000

(2+
C7+ 1.54000 141.25 0.7867 1.0000
1.0000
l

B.1-5
B.1-5

FLUID :: HOFFMAN
FLUID m' AL.
HOFFMAN ET RESERVOIR GAS
AL. RESERVOIR GAS

PENG/ROBINSCN
PENG/POBI EOUATICN OF
NSa EX2UATION OF STATE
STATE

CRtTICAL
CRITICAL

PRESSURE
PRESSURE TEMPERMU PE
TEMPERA'IURE
M)LE
1DLE - AcEflPIC
ACENTRIC
roMP criou
vip FRACl'ICN (PSIA)
(PsIA) (KPA)
(IPA) (om. R)
(DEXL R) (rm. K)
(DFX. K) FACIOR
FACrOR

c:l
C7 0.00361
0.00361 445.4
445.4 3071.0
3071.0 992.7
992.7 551.5
551.5 0.3062
0.~062
CB
c 0.00285
0.00285 406.7
406.7 2004.0
2804.0 1041.4
1041.4 578.6
578.6 0.3687
0.3687
C9
C9 0.00222
0.00222 383.2
383.2 2642.0
2642.0 1088.9
1088.9 604.9
604.9 0.4226
0.4226
do
ClO 0.00158
0.00158 357.2
357.2 2463.0
2463.0 1130.1
1130.1 627.9
627.9 0.4770
0.4770
Cl1
dii 0.00121
0.00121 339.5
339.5 2341.0
2341.0 1170.2
1170.2 650.1
650.1 0.5254
0.5254
Cl2
(22 0.00097
0.00097 323.4
323.4 2230.0
2230.0 1207.2
1207.2 670.7
670.7 0.5717
0.5717
Cl3
13 0.00083
0.00083 310.0
310.0 2138.0
2138.0 1242.2
1242.2 690.1
690.1 0.6150
0.6150
Cl4
(24 0.00069
0.00069 301.8
301.8 2000.0
2080.0 1276.9
1276.9 709.4
709.4 0.6534
0.6534
Cl5
(25 0.00050
0.00050 288.5
288.5 1989.0
1989.0 1306.8
1306.8 726.0
726.0 0.6945
0.6945
Cl6
(26 0.00034
0.00034 274.8
274.8 1895.0
1895.0 1334.1
1334.1 741.2
741.2 0.7351
Cl7
c17 0.00023
0.00023 261.5
261.5 1803.0
1803.0 1359.5
1359.5 755.3
755.3 0.7749
0.7749
Cl8
(28 0.00015 255.9
255.9 1764.0
1764.0 1387.3
1387.3 770.7
770.7 0.8073
0.8073
Cl9
ca 0.00010 250.8 1729.0
1729.0 1414.0
1414.0 785.5 0.8382
C20
(20 0.00006
0.00006 244.1
244.1 1683.0
1683.0 1438.2
1438.2 799.0
799.0 0.8698
0.8698
C21
(21 0.00004
0.00004 236.5 1630.0
1630.0 1460.6 811.4
811.4 0.9016
0.9016
C22
(22 0.00002 229.1 1580.0 1481.9
1481.9 823.3 0.9325

EUATIW OF STATE
S0AVE/REDLIaI/KWNG EOUATICN
SOAVE/REDLI<ll/KW>NG

CRITIL
CRITICAL

PRESSURE TEMPERA!IURE
TEMPERA'IURE
IDLE
MDLE - AENTRIC
ACENTRIC
DMP
(l)MI? FRACl'ICN
FpAcrIaJ (PSIA)
(PsIA) (KPA) (rm.
(DEx. R) (DID.
(DEx. K) FAC1tR
FACrOR

c:l
C7 0.00361 505.4 3484.0 1003.9 557.7 0.3062
CB
8 0.00285 461.0 3178.0 1052.9 585.0 0.3687
C9
c 0.00222 433.9 2992.0 1100.5 611.4 0.4226
ClO
(20 0.00158 404.1 2786.0 1141.7
1141.7 634.3 0.4770
cii
Cl1 0.00121 383.8 2646.0 1181.7
1181.7 656.5 0.5254
Cl2
(22 0.00097 365.2 2518.0 1218.5
1218.5 676.9 0.5717
Cl3
13 0.00083
0.00083 349.8 2412.0 1253.3
1253.3 696.3
696.3 0.6150
0.6150
Cl4
(24 0.00069 340.2 2346.0 1287.7 715.4 0.6534
Cl5
15 0.00050 325.0
325.0 2241.0 1317.3
1317.3 731.9
731.9 0.6945
0.6945
Cl6
(26 0.00034
0.00034 309.4 2133.0 1344.4
1344.4 746.9
746.9 0.7351
0.7351
Cl7
(27 0.00023
0.00023 294.3
294.3 2029.0 1369.5
1369.5 760.8
760.8 0.7749
0.7749
Cl8
(28 0.00015
0.00015 287.7
287.7 1984.0
1984.0 1397.0
1397.0 776.1 0.8073
0.8073
Cl9
(29 0.00010
0.00010 281.9
281.9 1944.0
1944.0 1423.3
1423.3 790.7
790.7 0.8382
0.8382
C20
(20 0.00006
0.00006 274.2
274.2 1891.0
1891.0 1447.3
1447.3 804.1
804.1 0.8698
0.8698
C21
(21 0.00004
0.00004 265.5
265.5 1830.0
1830.0 1469.3
1469.3 816.3
816.3 0.9016
0.9016
C22
(22 0.00002
0.00002 257.1
257.1 1773.0
1773.0 1490.3
1490.3 827.9
827.9 0.9325
0.9325
B.2-1
B.21

FLUID :: STINDING/KTZ
FLUID STANDING/KATZ MDCIURES
MIX'lURE'S

REVIEW OF
REVIEW OF SURFACE
SURFACE MIXIURES
MIX'lURES USED
USED 10 REXDMBINE
'ro RECOMBINE

GrSOLINE
NA'1URAL~
NAIUPAL
S'IOO<-'mNI( OIL
SI0CX-T?NK OIL (C7+)
(c::7+) CRUDE
"CRJDE" aosiacis
COMPOSITICNS (MDL)
(MJL)
GAS
G1S NO.1
NO.1 NO. 2
NO.2
COMP
ari (IDL)
(1oL) (M:>L)
(tioL) (M:>L)
(MOL) (VOL)
(voL) (M:>L)
(MDL) (MJL)
(M0L) AlB
A/B C/F/Gil-I
C/F/G/H DD EE

N2
N2 0.0043
0.0043
CO2
c02 0.0051
0.0051
Cl
ci 0.9320
0.9320
C2
2 0.0425
0.0425
3
C3 0.0161
IC4
1C4
NC4
NC4 0.0813 0.1134 0.0547
0.0547 0.0764
0.0764 0.0700
0.0700 0.0331
0.0331
ICS
KS 0.1285 0.1353 0.0865
0.0865 0.0912 0.1106
0.1106 0.0523
0.0523
NC5 0.2695 0.2448 0.1815 0.1650
0.1650 0.2320
0.2320 0.1098
0.1098
~ 0.2807
0.2807 0.2443 0.1890
0.1890 0.1647
0.1647 0.2417 0.1143
0.1143
Fl 0.1455 0.1589 0.1250
0.1250 0.0936
0.0936 0.2464 0.1785 0.1874
0.1874 0.1595 0.2054
0.2054
F2 0.0945 0.1033 0.1250
0.1250 0.0763 0.2007 0.1292
0.1292 0.1351 0.1093 0.1574
0.1574
F.3
P3 0.1250 0.0580 0.1526 0.0498 0.0497 0.0212 0.0904
0.0904
F4 0.1250 0.0473 0.1244
0.1244 0.0406
0.0406 0.0406 0.0173 0.0737
FS
PS 0.1250
0.1250 0.0400 0.1052 0.0344 0.0343 0.0146
0.0146 0.0624
0.0624
F6 0.1250 0.0308 0.0810 0.0265 0.0264 0.0113 0.0480
0.0480
F7
P7 0.2500 0.0341 0.0897 0.0293 0.0292 0.0125 0.0532
0.0532
1.0000 1.0000 1.0000 1.0000 0.3801
0.3001 1.0000 1.0000
1.0000 1.0000
1.0000 1.0000 1.0000 1.0000

MIOT
Ml'OT 17.28 83.40 83.07 228.5 130.7 130.5 103.5 169.4
S:;'IOT
3iYr 0.5960 0.6536 0.6528 0.8685 0.7680 0.7681 0.7171 0.8184
API 85.00 85.20 31.40 52.75 52.72 65.82 41.39

M:7+ 107.40 106.80 228.5 188.3 185.7 155.9 211.3


SPGC7+ 0.690 0.690 0.8685 0.8398 0.8376 0.8084 0.8572
0.8572
M>W+
MDLC7+ 0.2400 0.2622 1.0000 0.4883 0.5027 0.3457 0.6905

RATIO OF VOWME
VQUJME NA'lURAL
NA1URAL GAS 'ro
10 S'IOO<-TANK
S1G(17K OIL 50/50
50/SO 50/50 75/25 25/75
M>LE
MOLE FRACrIctl
FRACflCtJ NA'IURAL
NMURAL GAS IN "CRUDE
CRUDEII MIX'lURE
MIX1URE 0.6734 0.6740 0.8609 0.4073
B.2-2
B.22

FLUID STANDING/KATZ
FLUID : STANDING MIX'lURES (SIoQ-17\
/KPiTZ MI)CIURES (SIOO<-TJ\NKNK OIL
On.. a)MPOSiTIa [)
CDMPOS1TICN)

EXPERIt-lENTAL
EXPERIMEN TAL DISTILLPTI ON DATl
D1S'l'ILLATICN DATA

IDLE MDLEQJLI
DLE SPEcrFIC
R SPECIFIC
M)I...EaJLAR WILING POINT
)ILING POINT EIGHT
\'E1GHI'
CDMP FRACl'1ON
cDMP FRACIION ~1GHT
EIGHT GRAVI'lY
GRAVIIY (Dm.
(DEX. R)
R) (om.
(DEX. K)
K) FRACIcN
FRACT1CN

Fl
El 0.24640
0.24640 94.00
94.00 0.7035
0.7035 631.00
631.00 350.56
350.56 0.1014
0.1014
F2
F2 0.20070
0.20070 127.00
127.00 0.7753
0.7753 780.00
780.00 433.33
433.33 0.1116
0.1116
F3
E3 0.15260
0.15260 176.00
176.00 0.8173
0.8173 908.00
908.00 504.44
504.44 0.1175
0.1175
F4
F4 0.12440
0.12440 225.00
225.00 0.8500
0.8500 1028.00
1028.00 571.11
571.11 0.1225
0.1225
0.10520
1'5 0.10520
F5 277.00
277.00 0.8865
0.8865 1128.00
1128.00 626.67
626.67 0.1275
0.1275
0.08100
F6 0.08100
F6 375.00
375.00 0.9232
0.9232 1220.00
1220.00 677.78
677.78 0.1329
0.1329
0.08970
F7 0.08970
F7 730.00
730.00 0.9950
0.9950 1901.39
1901.39 1056.33
1056.33 0.2866
0.2866

1.00000
1.00000 228.49
228.49 0.8682
0.8682 1.0000
1.0000

FLUID :: STANDING
FLUID STANDnlG/KATZ MIX'lURES
/KATZ MIXIURES

REVIEW OF
REVIEW OF RECOMBIN
RECDMBINED MIX'lURE COMPOSIT
ED M]XIURE ITS (M0L)
CDMPOS1TICNS (MJL)

COMP A
A BB CC D
D E
E F G
G H
H

N2
N2 0.0039
0.0039 0.0039
0.0039 0.0035
0.0035 0.0038
0.0038 0.0040
0.0040 0.0035
0.0035 0.0036
0.0036 0.0035
0.0035
CO2
D2 0.0046
0.0046 0.0046
0.0046 0.0042 0.0045 0.0047 0.0042 0.0042 0.0042
0.0042
Cl.
Cl 0.8396
0.8396 0.8440
0.8440 0.7648 0.8274 0.8563 0.7688 0.7694
0.7694 0.7686
0.7686
C2
2 0.0383
0.0383 0.0385 0.0349
0.0349 0.0377 0.0391 0.0351 0.0351 0.0350
0.0350
cr
C3 0.0145 0.0146 0.0132 0.0143 0.0148 0.0133 0.0133
0.0133 0.0133
0.0133
1~4
Nc4 0.0054
0.0054 0.0052 0.0137 0.0079 0.0134 0.0134 0.0133
0.0133 0.0134
0.0134
ics
1CS 0.0086
0.0086 0.0082 0.0164 0.0124 0.0042 0.0160 0.0159
0.0159 0.0160
0.0160
NC5
N5 0.0180
0.0180 0.0171 0.0296 0.0260 0.0089 0.0289 0.0288
0.0288 0.0289
0.0289
a:;
c 0.0188
0.0188 0.0178 0.0295 0.0272 0.0093 0.0288 0.0287
0.0287 0.0289
0.0289
Fl
Fl 0.0177
0.0177 0.0169 0.0337 0.0179 0.0166 0.0328 0.0326
0.0326 0.0330
0.0330
F2
P2 0.0128
0.0128 0.0122 0.0242 0.0123 0.0128 0.0237 0.0236
0.0236 0.0237
0.0237
F3
P3 0.0049
0.0049 0.0047
0.0047 0.0089
0.0089 0.0024
0.0024 0.0073 0.0087
0.0087 0.0087
0.0087 0.0087
0.0087
F4
F4 0.0040
0.0040 0.0038
0.0038 0.0073
0.0073 0.0019
0.0019 0.0060
0.0060 0.0071
0.0071 0.0071
0.0071 0.0071
0.0071
1'5
PS 0.0034
0.0034 0.0032
0.0032 0.0062
0.0062 0.0016
0.0016 0.0051
0.0051 0.0060
0.0060 0.0060
0.0060 0.0060
0.0060
F6
F6 0.0026
0.0026 0.0025
0.0025 0.0047
0.0047 0.0013
0.0013 0.0039
0.0039 0.0046
0.0046 0.0046
0.0046 0.0046
0.0046
F7
P7 0.0029
0.0029 0.0028
0.0028 0.0052
0.0052 0.0014
0.0014 0.0043
0.0043 0.0051
0.0051 0.0051
0.0051 0.0051
0.0051
1.0000
1.0000 1.0000
1.0000 1.0000
1.0000 1.0000
1.0000 1.0000 1.0000 1.0000
1.0000 1.0000 1.0000
1.0000 1.0000
GAS
GAS
M:>L
M0L 0.9009
0.9009 0.9056
0.9056 0.8206
0.8206 0.8878
0.8878 0.9189 0.8249 0.8256
0.9189 0.8249 0.8247
0.8256 0.8247
FRAC.
FRAC.
B.2-3
B.23

ruJID
FLUID : STANDING-KATZ MIXIURES
STANDINGKATZ MIX'IURES

PENG/ROBINSCN UZTIcti OF STATE


PFNG/RORLNScN mtJATICN STPTE

CRITICAL

PRESSURE TEMPEEThEIURE
TEMPERA'IURE
AENTRIC
ACENTRIC
CDMP (PSIA)
(PsIA) (KPA) (DID.
(DEx. R) (rm.
(D1x. K) FACIOR
FACl'OR

Fl.
Fl 431.6 2976.0 939.5 521.9 0.2815
F2 394.1 2717.0 1113.6 618.7 0.4322
F3 324.4 2237.0 1239.8 688.8 0.5975
F4 284.7 1963.0 1362.0 756.7 0.7471
FS
ES 256.2 1766.0 1462.5 812.5 0.8743
F
F6 205.5 1417.0 1536.2 853.5 1.0231
F7
E7 163.8 1129.0 2270.2 1261.2 1.8258

FLUID : STANDING-KATZ
STPNDINGK1TZ MIX
I
t UPES
MIX'IURES

so/rIIa1/Kw mtJATICN
SOAVE/REDLI<ll/KIDNG EUATIW OF STATE

CRITICAL

PRESSURE TEMPER1!IURE
TEMPERA'IURE
PcENTRIC
ACENTRIC
cxt
CDMP (PSIA)
(Psm) (KPA) (DID.
(DEY3. R) (rm.
(Dx. K) FACl'OR
FACIOR

Fl.
FL 490.1 3379.0 950.4 528.0 0.2815
F2 446.1 3076.0 1125.3 625.2 0.4322
F3 366.1 2524.0 1250.9 695.0 0.5975
F4 320.4 2209.0 1372.1 762.3 0.7471
FS
ES 287.7 1984.0 1471.4 817.5 0.8743
F6 230.3 1588.0 1543.7 857.6 1.0231
F7
P7 181.5 1252.0 2260.7 1256.0 1.8258
B.3-1

FIlJID
FLUID : EILERIS tDC9URES
EILERl'S MIX'lURES

EXPERIMENTAL DISTILLATICN
EXPERIMEISJTAL DIILLTIC! DATA

PRERrIES FOR ALL


A'VERPJ3E POCPERrIES
AVERE
MIX'lURES S'lUDIED
MIXIUPES IUDIED Ir{ EILERl'S
t
S EIIERIS
!DLE
MJLE FR1II
FRACl'ICN
)ILING POINT
IDILING -

DL.
MJL. SPEC.
SPOC. oo-L/
CD-L/ aT-p/
CH-P/
CDMP
(DMP tEIGHT
~IGHT GR. (R) (K) S44
544 843

N2 0.00414 0.01375
CD2
cD2 0.00468 0.00794
Cl
Ci 0.90162 0.76432
C2 0.04067 0.07923
C3 0.01616 0.04301
1G4
I04 0.00464 0.01198
NC4
N04 0.00390 0.01862
I5
ICS 0.00274 0.00937
NCS 0.00123 0.00781
C6-1
61 86.17 0.6600 589.10 327.28 0.00175 0.00744
C6-2
2 86.17 0.6640 615.40 341.89 0.00243 0.00661
C7-1
C71 100.20 0.6850 640.80 356.00 0.00097 0.00290
C7-2
C72 100.20 0.6940 662.90 368.28 0.00068 0.00295
CB
G3 114.22 0.7068 717.90 398.83 0.00291 0.01040
c
C9 128.25 0.7217 763.10 423.94 0.00207 0.00613
ClO
cia 142.28
142.28 0.7341 805.10 447.28 0.00167 0.00338
cii
Cl1 156.30 0.7441 844.30 469.06 0.00122 0.00176
Cl2
i2 170.33 0.7526 881.00 489.44 0.00092 0.00153
Cl3
13 184.35 0.7603 915.50 508.61 0.00096 0.00087
Cl4
14 198.38 0.7667 948.20 526.78 0.00113
Cl5
15 212.41 0.7724 979.00 543.89 0.00093
Cl6
L6 226.43 0.7773 1008.40 560.22 0.00096
Cl7
L7 240.46 0.7818 1036.30 575.72 0.00029
Cl8
L8 254.48 0.7858 1063.00 590.56 0.00029
Cl9
IL9 268.51 0.7893 1088.50 604.72 0.00021
C20
20 282.54 0.7925 1112.90 618.28 0.00018
C21
21 296.56 0.7955 1137.00 631.67 0.00021
C22
22 310.59 0.7981 1161.00 645.00 0.00018
C23
23 324.61 0.8006 1184.00 657.78 0.00017
C24
24 338.64 0.8029 1207.00 670.56 0.00009
1.00000 1.00000
HFX.Z\NESPLUS 1DLE FRACIT
HEXJ\NES-PWS MJLE FRACl'ICN 0.02022 0.04397
~DLECl.JI.AR EIGFfl
HFXZ\NESPIIJS ?IDLEOJLAR
HEXJ\NES-PWS ~IGHl'
1 147.33 112.53
HEXNIESPLUS GRVIIY
SPECIfiC GRAVI'lY
HEXJ\NES-PWS SPOCIFIC 0.7365 0.7037
B.3-2
B.32

FllJID : : FLUID
FLUID En.ERl'S (GENERAL)
FllJID EILERS (GENERAL)

PENG/ROBINSCN
PENG/R0EIN EXlUATICN OF
SaJ BU1TIctT OF STA
STATE

CRITICAL
CRITI(L CRITIC.L
CRITICAL
PRESSURE
PRESSURE TEMPERMU RE
TEMPERMURE
IENTRIC
~C
CDMP
wrip (PSIA)
(PsIA) (KPA)
(IcPA) (DID. R)
(ix. R) (IE3. K)
(D]x. K) FACIOR
FAC'roR

~-1
ci 425.7
425.7 2935.0
2935.0 882.7
882.7 490.4
490.4 0.2521
0.2521
~-2 439.6
439.6 3031.0
3031.0 921.8
921.8 512.1
512.1 0.2649
0.2649
C7-1
C71 392.6
392.6 2707.0
2707.0 938.8
938.8 521.5
521.5 0.3109
0.3109
C7-2
C72 407.2
407.2 2008.0
2808.0 972.2
972.2 540.1
540.1 0.3207
0.3207
CB 377.4
377.4 2602.0
2602.0 1030.8
1030.8 572.7
572.7 0.3851
0.3851
C9 353.5
353.5 2438.0
2438.0 1077.4
1077.4 598.6
598.6 0.4403
0.4403
Cl.0
8i0 333.2
333.2 2297.0
2297.0 1120.3
1120.3 622.4
622.4 0.4925
0.4925
Cl.1
aLl 315.3
315.3 2174.0
2174.0 1159.7
1159.7 644.3
644.3 0.5421
0.5421
Cl.2
L2 299.5
299.5 2065.0
2065.0 1196.4
1196.4 664.7
664.7 0.5890
0.5890
Cl.3
l3 285.7
285.7 1970.0
1970.0 1230.6
1230.6 683.7
683.7 0.6335
0.6335
Cl.4 273.3
273.3 1884.0
1884.0 1262.9
1262.9 701.6
701.6 0.6761
0.6761
Cl.5 262.0
262.0 1807.0
1807.0 1293.1
1293.1 718.4
718.4 0.7166
0.7166
Cl.6
16 251.8
251.8 1736.0
1736.0 1321.8
1321.8 734.3
734.3 0.7555
0.7555
Cl.7
17 242.5
242.5 1672.0
1672.0 1348.9
1348.9 749.4
749.4 0.7927
0.7927
Cl.8
c28 234.0 1613.0
1613.0 1374.7
1374.7 763.7
763.7 0.8284
0.8284
Cl.9
19 226.1
226.1 1559.0
1559.0 1399.3
1399.3 777.4
777.4 0.8628
C20
(20 218.8 1509.0 1422.7 790.4 0.8959
0.8959
C21
(21 212.2 1463.0 1446.0 803.4 0.9284
C22
(22 206.1 1421.0 1469.4 816.3 0.9605
C23
(23 200.4 1382.0 1491.7 828.7 0.9915
C24
(24 195.2 1346.0 1514.2 841.2 1.0221
B.3-3
B.3-3

FLUID : EILERS
FLUID En.ERI'S (GENERAL)
(GENERAL)

PENG/ROBINSCN
PENG/ROBI EDUATICN OF
NSctJ BUTIaS OF STA
STATE

QITICL
CRITICAL RITIa.L
CRITICAL
PRESSURE
PRESSURE TEMPERMU RE
TEMPERA'lURE

P.ENTRIC
ACENTRIC
roMP
coi (PSIA)
(PsIA) (KPA)
(KPA) (rm. R)
(rE3. R) (om. K)
(DEx. K) FACIOR
FACroR

Cl5-1
cr5i 425.7
425.7 2935.0
2935.0 882.7
882.7 490.4
490.4 0.2521
0.2521
Cl5-2
c62 439.6
439.6 3031.0
3031.0 921.8
921.8 512.1
512.1 0.2649
0.2649
C7-1
C71 392.6
392.6 2707.0
2707.0 938.8
938.8 521.5
521.5 0.3109
0.3109
C7-2
C72 407.2
407.2 2808.0
2808.0 972.2
972.2 540.1
540.1 0.3207
0.3207
03 377.4
377.4 2602.0
2602.0 1030.8
1030.8 572.7
572.7 0.3851
0.3851
C3
c9 353.5
353.5 2438.0
2438.0 1077.4
1077.4 598.6
598.6 0.4403
0.4403
ClO
GO 333.2
333.2 2297.0
2297.0 1120.3
1120.3 622.4
622.4 0.4925
0.4925
Cl1
cii 315.3
315.3 2174.0
2174.0 1159.7
1159.7 644.3
644.3 0.5421
0.5421
Cl2
12 299.5
299.5 2065.0 1196.4
1196.4 664.7
664.7 0.5890
0.5890
Cl3 285.7
285.7 1970.0
1970.0 1230.6
1230.6 683.7
683.7 0.6335
0.6335
Cl4
14 273.3
273.3 1884.0
1884.0 1262.9
1262.9 701.6
701.6 0.6761
0.6761
Cl5
15 262.0
262.0 1807.0
1807.0 1293.1
1293.1 718.4
718.4 0.7166
0.7166
Cl6
G6 251.8
251.8 1736.0
1736.0 1321.8
1321.8 734.3
734.3 0.7555
0.7555
Cl7
17 242.5 1672.0 1348.9 749.4 0.7927
0.7927
Cl8
G8 234.0 1613.0
1613.0 1374.7 763.7 0.8284
0.8284
Cl9
19 226.1 1559.0
1559.0 1399.3
1399.3 777.4 0.8628
0.8628
C20
2O 218.8 1509.0 1422.7 790.4 0.8959
0.8959
C21
(21 212.2 1463.0 1446.0 803.4 0.9284
0.9284
C22
(22 206.1 1421.0 1469.4 816.3 0.9605
C23
(23 200.4 1382.0 1491.7 828.7 0.9915
0.9915
C24
(24 195.2 1346.0 1514.2 841.2 1.0221
B.3-4
B.34

FLUID : EILERl'S
FllJID EILERIS (GENERAL)

9)AVE/REDLICll/KW>NG UATIW
S0l\.VE/REDLIaIJKWJNG STA
EXlUATICN OF STATE

CRLTICL
CRITICAL CRITICAL
PRESSURE
PRESSJRE TEMPERMURE
?ENTRIC
ACENTRIC
ai
CDMP (PSIA)
(PsIA) (KPA)
(IPA) (DEX3.
(Dx. R) (DEX3.
(DEX. K) FACIOR
FACI'OR

0)-1
1 483.8
483 .8 3335.0 893.2 496.2 0.2521
0)-2
C62 499.4 3443.0
3443 .0 932.6 518.1 0.2649
C7-1
C71 445.8 3074.0 949.8 527.7 0.3109
C7-2
C72 462.2 3186.0 983.4 546.4 0.3207
ca 427.8 2950.0 1042.2 579.0 0.3851
c9
C9 400.3 2760.0 1089.0 605.0 0.4403
ClO
cio 376.9 2599.0 1131.7 628.7 0.4925
Cl1
l_1 356.3 2457.0 1171.1 650.6 0.5421
Cl2
12 338.2 2332.0 1207.6 670.9 0.5890
Cl3
L3 322.4 2223.0 1241.6 689.8 0.6335
Cl4
c14 308.1 2124.0 1273.6 707.6 0.6761
Cl5
15 295.2 2035.0 1303.5 724.2
724,2 0.7166
Cl6
16 283.5 1955.0 1331.9 740.0 0.7555
Cl7
c17 272.9 1881.0 1358.8 754.9 0.7927
Cl8
18 263.1 1814.0 1384.3 769.1 0.8284
Cl9
L9 254.1 1752.0 1408.6 782.5 0.8628
C20
(20 245.8 1695.0 1431.7 795.4 0.8959
C21
(21 238.2 1643.0 1454.7 808.2 0.9284
C22
(22
C23
(23
231.3
224.8
- 1595.0
1550.0
1477.7
1499.7
820.9
833.1
0.9605
0.9915
C24
(24 218.9 1509.0 1521.8 845.4 1.0221
B.4-1
B.4-1

FLUID :: JNX)Bf
FLUID SYN'IHEn'IC MDCIURES
JAroFN SYNflIETIC MIX'lURES

REOJMBINED MDCIURE
PEODMBINED CDMPOSITICNS (L)
MIX'lURE XDMPOSITISIS (M:>L)

co
<DMI? si
S-1 S-2
52 S-3
5-3 s4
5-4 5-~
5-5 S-6
5-6

N2
N2 0.0128
0.0128 0.0153
0.0153 0.0158
0.0158 0.0166
0.0166 0.0177
0.0177 0.0191
0.0191
<D2
JD2 0.0139
0.0139 0.0156
0.0156 0.0159
0.0159 0.0165
0.0165 0.0172
0.0172 0.0182
0.0182
ci
Cl 0.5634
0.5634 0.6526
0.6526 0.6715
0.6715 0.6995
0.6995 0.7401
0.7401 0.7906
0.7906
C2 0.0709
0.0709 0.0701
0.0701 0.0699
0.0699 0.0697
0.0697 0.0693
0.0693 0.0689
0.0689
C3
3 0.0509
0.0509 0.0427
0.0427 0.0410
0.0410 0.0384
0.0384 0.0347
0.0347 0.0301
0.0301
104
104 0.0164
0.0164 0.0123
0.0123 0.0113
0.0113 0.0101
0.0101 0.0082
0.0082 0.0058
0.0058
N04
NC4 0.0376
0.0376 0.0285
0.0285 0.0266
0.0266 0.0238
0.0238 0.0197
0.0197 0.0145
0.0145
IC5
1(5 0.0208
0.0208 0.0149
0.0149 0.0137
0.0137 0.0118
0.0118 0.0092
0.0092 0.0058
0.0058
NC5
Nc5 0.0249
0.0249 0.0177
0.0177 0.0162
0.0162 0.0139
0.0139 0.0107
0.0107 0.0066
0.0066
cs
(])S 0.0365
0.0365 0.0255
0.0255 0.0232
0.0232 0.0197
0.0197 0.0147
0.0147 0.0085
0.0085
Fl
Fl 0.0282
0.0282 0.0195
0.0195 0.0177
0.0177 0.0150
0.0150 0.0110
0.0110 0.0061
0.0061
F2
F2 0.0174
0.0174 0.0121
0.0121 0.0109
0.0109 0.0092
0.0092 0.0068
0.0068 0.0037
0.0037
ro
E3 0.0120
0.0120 0.0083
0.0083 0.0075
0.0075 0.0063
0.0063 0.0046
0.0046 0.0025
0.0025
Fl4-
F4 0.0201
0.0201 0.0139
0.0139 0.0125
0.0125 0.0106
0.0106 0.0077
0.0077 0.0042
0.0042
ES
ES 0.0201
0.0201 0.0138
0.0138 0.0125
0.0125 0.0105
0.0105 0.0077
0.0077 0.0042
0.0042
~
F 0.0323 0.0223
0.0223 0.0202
0.0202 0.0270
0.0270 0.0124
0.0124 0.0067
0.0067
F7
E7 0.0216 0.0149 0.0135
0.0135 0.0114
0.0114 0.0083
0.0083 0.0045

1.0000 1.0000
1.0000 1.0000 1.0000
1.0000 1.0000 1.0000
1.0000

FLUID : JNJJFN
JAODBY SYN'IHm'IC
fflErIC MIX'lURES
1
SYN (SPjazroR OIL CDMPOSITICN)
MIxIupEs (SEPARA'IDR WMPOSITIaSJ)

DISTILLATICN DATA
EXPERIMENTAL DISTILUTICN

mLE
DLE mLEClJLAR
MDLEQJLAR SPECIFIC
SP:EcrFIC )ILING
IDILING POINT EIGHT
VEIGHI'
<DMI?
ODMP FRACl'ICN
FRACTION VEIGHI'
?EIGHT GPAVIW
GRAVI'lY (JJEX:;.
(Da. R) (lm.
(rir. K) FRACKt
FRACrICN

Fl
FL 0.19145 89.00 0.6799 610.00 338.89 0.1286
F2
E2 0.14954 98.00 0.7181 660.00 366.67 0.1106
ro
E3 0.09275 110.00 0.7403 710.00 394.44 0.0770
0.0770
0.06424
Fl4-
F4 121.00 0.7542 760.00 422.22 0.0587
ES 0.10721 131.00 0.7628 810.00 450.00 0.1060
~
F6 0.10700 144.00 0.7749 860.00 477.78 0.1163
F7 0.17252 165.00 0.7859 910.00 505.56 0.2148
Fa
ES 0.11529 216.00 0.8140 850.00
850.00 472.22 0.1880

1.00000
1.00000 132.49 0.7585 1.0000
1.0000
B.4-2
B.4-2

FllJID :: JACYJBf
FTJJID SYN'IHETIC MIXIUPES
JAro'iN SYNThETIC MIX'lURES

EDUATICN OF
PENG/ROBINSCN EUATICtI
PEG/RO&NSC OF STATE
STATE

RITIQL
CRITICAL

PRESSURE
PRESSURE TEMPER?URE
TEMPERA'IURE
- AENTRIC
.ACENTRIC
CDMP
a1P (PSIA)
(PsiA) (KPA)
(IcPA) (rm. R)
(Dix. (rm. K)
(DEx. FACIOR
FACl'OR

El
Fl 433.0 2985.0 912.6
912.6 507.0
507.0 0.2641
F2
F2 433.3 2987.0
2987.0 977.4 543.0
543.0 0.3046
F3
F3 412.4 2843.0
2843.0 1033.5
1033.5 574.2
574.2 0.3587
1M-
F4 396.1 2731.0 1089.8
1089.8 605.5 0.4126
0.4126
F5
ES 383.9
383.9 2647.0
2647.0 1146.4
1146.4 636.9
636.9 0.4661
F6
E6 367.3
367.3 2532.0
2532.0 1200.3
1200.3 666.9
666.9 0.5237
0.5237
In
F7 334.4 2305.0 1246.5
1246.5 692.5 0.5929
Fa
F8 243.3 1678.0 1130.8
1130.8 628.2 0.6098

FLUID : JA(DEf
FllJID SYNTHETIC MIXtURES
JAro'iN SYNIHETIC MIX'IURES

saA.vE/REDLIa/IcwJNG E)DU?TICT OF STATE


SOAVE/REDLICli/KIDNG EDUATICN

RITIc.L
CRITICAL

PRESSURE TEMERtURE
TEMPERA'IURE
AENTRIC
~C
ar
CDMP (PSIA)
(PsIA) (KPA) (1m.
(DEX. R) (DE73.
(D. K) FACIOR
FACl'OR

Fl 491.9 3392.0 923.3 513.0 0.2641


E2
F2 491.7 3390.0 988.6 549.2 0.3046
F3
f3 467.5 3223.0 1045.0 500.6
580.6 0.3587
F4
1M- 448.5 3093.0 1101.4 611.9 0.4126
F5
ES 434.3 2994.0 1158.1 643.4 0.4661
F6 414.9 2861.0 1211.8 673.2 0.5237
In
F7 377.3 2602.0 1257.7 698.7 0.5929
FS
Fa 274.9 1896.0 1141.8 634.3 0.6098
B.5-1
B.51

FLUID
FLUID : 0LDS/SNE/1
OWS/SN3E/r..;..c:zx (1945: GENERAL)
ACEY (1945; GENERAL)

EXPERIMENTAL
EXPERIMEN DISTILLATICN
TAL DISTILLPiT DATA
IaSI DZTA

roILING
BDILING
POINr
POINT RECDMBINED
PE(DMBINE CDMPOOITICN
D CDMPOSIT AT GIVEN
IW AT GOR (scF/sTB)
GIVEN GOR (ea' /STB)
IDL. SPEC.
MDL. SPEC.
W!:IGm'
CDMP W.IGHT
(X)MP GR.
GR. (R)
(R) (K)
(K) 552
552 940
940 2205
2205 5361
5361 7393
7393 14440
14440

CD2
032 0.0020
0.0020 0.0037
0.0037 0.0060 0.0076
0.0060 0.0076 0.0081
0.0081 0.0086
0.0086
Cl.
at 0.2630
0.2630 0.3902
0.3902 0.5797 0.7148
0.5797 0.7148 0.7470
0.7470 0.7922
0.7922
C2
(2 0.0516
0.0516 0.0604
0.0604 0.0733 0.0826
0.0733 0.0826 0.0847
0.0847 0.0878
0.0878
C3 0.0782
0.0782 0.0710
0.0710 0.0602 0.0526
0.0602 0.0526 0.0507
0.0507 0.0482
0.0482
lCA
1C4 0.0255
0.0255 0.0214
0.0214 0.0153 0.0110
0.0153 0.0110 0.0099
0.0099 0.0085
0.0085
NC4
NC4 0.0614
0.0614 0.0504
0.0504 0.0339 0.0222
0.0339 0.0222 0.0194
0.0194 0.0155
0.0155
1<5
I5 0.0283
0.0283 0.0225
0.0225 0.0142 0.0081
0.0142 0.0081 0.0067
0.0067 0.0047
0.0047
NCS 0.0343
0.0343 0.0304
0.0304 0.0162 0.0085
0.0162 0.0085 0.0067
0.0067 0.0041
0.0041
Fl
El 93.0
93.0 0.7212
0.7212 621
621 345.0
345.0 0.0842
0.0842 0.0652
0.0652 0.0368 0.0166
0.0368 0.0166 0.0117
0.0117 0.0050
0.0050
F2
F2 100.0
100.0 0.7451
0.7451 671
671 372.8
372.8 0.0817
0.0817 0.0641
0.0641 0.0379 0.0191
0.0379 0.0191 0.0147
0.0147 0.0084
0.0084
F3
E3 109.0
109.0 0.7665
0.7665 714
714 396.7
396.7 0.0764
0.0764 0.0591
0.0591 0.0334 0.0150
0.0334 0.0150 0.0106
0.0106 0.0045
0.0045
F4
F4 128.0
128.0 0.7892 772
772 428.9 0.0669
0.0669 0.0518
0.0518 0.0293 0.0132
0.0293 0.0132 0.0093
0.0093 0.0039
0.0039
F5
ES 155.0
155.0 0.8170 852
852 473.3 0.0572 0.0443 0.0250 0.0112
0.0250 0.0112 O.ooeo
0.0080 0.0034
0.0034
F6
F 204.0
204.0 0.8433 951 528.3 0.0449
0.0449 0.0347
0.0347 0.0196 0.0088
0.0196 0.0088 0.0063
0.0063 0.0026
0.0026
F7 274.0
274.0 0.8822 1130 627.8 0.0444
0.0444 0.0342 0.0192 0.0088
0.0192 0.0088 0.0062
0.0062 0.0026
0.0026
1.0000
1.0000 1.0000
1.0000 1.0000 1.0000 1.0000 1.0000
1.0000 1.0000

MIX'lURE
XIURE IDLEaJI.J\R
MDLEOJLAR W!:IGHT
EIGHT 81.29 67.50 46.97 32.30 28.82 28.82 23.91
23.91
\'EIGHT
EIGHT FRACl'ICN
FRACICT TRAP GAS 0.0571 0.1213 0.2867 0.5335 0.6292 0.8111 0.8111
IDLE
DLE FRACI'ICN
FRACI( TRAP GAS 0.2285 0.4030 0.6628 0.8482 0.8936 0.9546
0.8936 0.9546
HE){}lNES-PllJS
HEX1ESPLJJS IDLE
4DLE FRACl'ICN
criar 0.4557 0.3534 0.2012 0.0927 0.0668 0.0304 0.0304
HEXPNES-
HFXNES-PUPllJS
JS IDLEaJI.J\R
MDLEJLAR \'EIGHT
VEIGHT 138.43 PRDPERrIES SAME
C+ PRPERl'IES
05+
HE){}lNES-PllJS
HEX1ES-PLUS SPECIFIC
SPECIEW GRAVI'IY
GRAVIIY 0.7981 ItDCIUPES
FOR ALL f.IIX'lURES
8.5-2
B.5-2

FLUID :: OLDs/SAGE/LACEY
FLUID OIDS/SH3E/'J..ll.CFX (1945;
(1945: GENERAL)
GENERAL)

PENG/ROBINSCE E)DUMICT
PENG/ROBINSON EDUATICN OF
OF STME
STATE
CRITICAL
ClUTICAL

PRESSURE TEMPERMURE
TEMPERA!IURE
?ENTRtC
ACENTRIC
CDMP (PSIA)
(Psm) (}cpA)
(KPA) (om. R)
(na. (om. K)
(tm. FACl'OR
FACIOR

Fl
FL 445.3
445.3 3070.0
3070.0 930.9
930.9 517.2
517.2 0.2665
0.2665
F2
F2 446.4
446.4 3078.0
3078.0 995.7 553.2
553.2 0.3076
0.3076
F3
F3 435.3 3001.0
3001.0 1046.4
1046.4 581.3
581.3 0.3507
0.3507
F14
F4 395.6
395.6 2728.0
2728.0 1104.4
1104.4 613.5
613.5 0.4239
F5
ES 356.2
356.2 2456.0
2456.0 1186.3
1186.3 659.1
659.1 0.5224
0.5224
~
FE 295.4
295.4 2037.0
2037.0 1277.2
1277.2 709.5
709.5 0.6610
0.6610
Tn
F7 258.3 1781.0
1781.0 1466.0
1466.0 814.4 0.8746

FLUID :: OLDS/S1GE/LCEY
OIDS/SH3E/'J..ll.CFX (1945;
(1945: GENERAL)
OOAVE/REDLIaI/KIDNG
SOAVE/REDLIaI/KVDNG EDUATICN
FDUTIS OF srATE
STATE

CRITICRL
ClUTICAL

PRESSURE
PRESSURE TEMPERMURE
TEZ4PERAIURE
AENTRtC
ACENrRIC
corip
CDMP (PSIA)
(PsIA) (KPA)
(xPA) (rm.
(D1x. R) (tm.
(ox. K) FACl'OR
FACIOR

Fl 505.7 3487.0 941.8 523.2 0.2665


F2 506.5 3492.0 1007.0 559.4 0.3076
F3 493.4 3402.0 1057.9 587.7 0.3507
F14
F4 447.9 3088.0 1116.0 620.0 0.4239
F5
ES 402.5 2775.0 1197.8 665.5 0.5224
~
F6 333.0 2296.0 1288.0 715.6 0.6610
Tn
F7 290.1 2000.0 1474.9 819.4 0.8746
B.5-3

FLUID : OWS/SPGE/I.J>Cf:t:
0LDS/SNE/L1CEY (1949; GEfSIERAL)
GENERAL)

EXPERIMENTAL DISTn..LATICN
IMENTAL DISTIL DATA
L1TIS DITA

ro:n.:rm
B)ILING RECDHBINED
RE)MBINED CDMPOOITICN
(0MPCSITICtI
POINT AT GIVEN GOR (SCF/STB)
(scF/sTB)
IDL.
MDL. SPEC.
COMP
WMP \'EIGHI'
EIGHT GR. (R) (K) 274 460 620 811 2580

CO2
c.02 0.0004 0.0009 0.0011 0.0014 0.0022
ci
Cl. 0.1996 0.3151 0.3858 0.4485 0.6665
C2 0.0445 0.0494 0.0523 0.0549 0.0641
(:3
C3 0.0764 0.0728 0.0706 0.0686 0.0619
104
IC4 0.0205 0.0178 0.0161 0.0147 0.0096
N04
NG4 0.0641 0.0554 0.0500 0.0452 0.0287
ICS
KS 0.0256 0.0215 0.0191 0.0169 0.0092
NCS 0.0271 0.0228 0.0201 0.0178 0.0096
a5S
cs 0.0564 0.0466 0.0405 0.0352 0.0166
Fl 104.0 0.7451 685.0 380.6 0.0988 0.0818 0.0712 0.0617 0.0288
F2 117.0 0.7699 735.0 408.3 0.0907 0.0742 0.0642 0.0552 0.0242
F3 141.0 0.8035 814.0 452.2 0.0786 0.0643 0.0556 0.0478 0.0209
F4 194.0 0.8333
E14 958.0 532.2 0.0592 0.0485 0.0419 0.0360 0.0158
F5 490.0 0.9365 1332.4 740.2 0.1581
FS 0.1289 0.1115 0.0961 0.0419

1.0000 1.0000 1.0000 1.0000 1.0000

MIX'lURE
MIXIURE IDLEClJI.M
MDLEQJLAR \'EIGHT
EIGF1T 142.5 120.4 106.8 94.7 52.9
\'EIGHI'
EIGHT FRACl'ICN
FRACIION TRAP GAS 0.02066 0.05082 0.07539 0.10311 0.29778
IDLE
MDLE FRACI'ICN
FRACICT TRAP GAS 0.14432 0.29994 0.39469 0.47865 0.77218
HEPTANES-PIlJS
HEPTANESPLUS IDLE
MDLE FRACl'ICN
FRACTION 0.4854 0.3977 0.3444 0.2968 0.1316
HEPTANE&-PIlJS
HEPTANESPLUS IDLECl.JLAR
MDLEQJLAR \'EIGHT
EIGHT 248.27 (2+ PIOPE}flES SAME
C7+ PIDPERl'IES SANE AIDUT
ABDUT
HEPTANES-PIlJS
HEPTANES-PLUS SPECIFIC GRAVI'lY
GRAVtY 0.8767 'lEE SAME
IHE SANE FOR ALL NDCIURES
MlX'IURES
8.5-4
B.5-4

FLUID OUJS/SN3E/~
FWID : : OLDS/SAGE (1949: GE7JER2L)
/IACEY (1949; GENERAL)

PEl'G/ROmNSCN
PENG/R0BI OF STATE
EXlUATICN OF
NSCtI EUATIT STATE

CRITICAL
cITICAL RITIL
CRITICAL
PRESSURE
PRESSURE TEMPERMU RE
'I'EMPERA'lURE
-
AEI?rRIC
ACENl'RIC
<DMP
cxi (PSIA)
(PsIA) (KPA)
(KPA) (m::;. R)
(DEX. R) (IE3. K)
(Ix. K) FACIOR
FAC'roR

Fl
Fl 432.5
432.5 2982.0
2982.0 1008.9
1008.9 560.5
560.5 0.3264
0.3264
F2
F2 411.6
411.6 2838.0
2838.0 1064.4
1064.4 591.4
591.4 0.3815
0.3815
F3 376.0
376.0 2592.0
2592.0 1148.3
1148.3 637.9
637.9 0.4743
0.4743
Fl4
F4 310.2
310.2 2139.0
2139.0 1292.4
1292.4 718.0
718.0 0.6572
0.6572
~
ES 168.6
168.6 1162.0
1162.0 1635.2
1635.2 908.5
908.5 1.1923
1.1923

SOAVE/REDLIOi/KIDNG
S0AVE/RED EDUATICN OF
LIGI/KVNG EUzTIc OF STATE
STATE

CRITICAL
CRITICAL CRITICAL
CRITICAL
PRESSURE
PRESSURE TEMPERNL URE
'I'EMPERA'lURE
-
ACENTRIC
ACENTRIC
CDMP
aip (PSIA)
(PsIA) (KPA)
(KPA) (m::;. R)
(DEX. R) (IE. K)
(Dix. K) FAIOR
FACroR

Fl
Fl 490.6
490.6 3383.0
3383.0 1020.3
1020.3 566.8
566.8 0.3264
0.3264
F2
F2 466.3
466.3 3215.0
3215.0 1076.0
1076.0 597.8
597.8 0.3815
F3
F3 425.3
425.3 2932.0 1159.9
1159.9 644.4
644.4 0.4743
Fl4
F4 349.7 2411.0 1303.2
1303.2 724.0 0.6572
0.6572
~
ES 188.5 1300.0 1640.9 911.6 1.1923

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