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Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties

1
Upstream Process
Engineering Course
1. Physical Properties
Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
2
Liquid Density
Examples of Liquid and solid
Densities









Compound Density @ 15
o
C
(kg/m
3
)
Water 1000
Ethyl alcohol 785
Butane 563.2
Octane 706.7
Heavy Crude 903
Medium Crude 859
Light Gas Condensate 734
Steel Approx. 7800
Concrete Approx. 2300
Calculation of mixture density

One of the simplest methods is the API corresponding states method which uses a correlation to obtain a correction
factor that adjusts the density at standard conditions to the actual conditions.
Below are the equations used:

2 C
1 C
.
M x M

x M
dard tan s actual
i i m
i
i i
m
|
.
|

\
|
=
=

= v

Where: v - Molar Volume (m


3
/kmol) - density (kg/m
3
)
M - Molecular weight (kg/kmol) x - Mole fraction
C1 & C2 - Correlation factors for density correction
subscripts: m - mixed compound i - component i
Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
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Liquid Density - Example Calculation
. conditions actual the density to standard adjust the to factors n correlatio the find Now
Conditions @Standard kg/m 6 . 412
0864 . 0
69 . 38 M
kg/kmol 68 . 35 ) 1 . 0 124 . 58 ( ) 2 . 0 097 . 44 ( ) 8 . 0 07 . 30 ( M
kmol / m 0865 . 0
7 . 563
1 . 0 124 . 58
3 . 508
2 . 0 097 . 44
1 . 358
7 . 0 07 . 30
equation mixing volume Using

58.124 M , kg/m 7 . 563 0.5637 C
44.097 M , kg/m 3 . 508 0.5083 C
30.07 M , kg/m 1 . 358 0.3581 C
water. to relative given is data here , conditions standard at components of density Obtain the
3
m
m
standard m
m
3
m
3
4
3
3
3
2
= =
v
=
= + + =
=

= v

= = =
= = =
= = =
Example:

Calculate the liquid density of a saturated mixture of 70% ethane, 20% propane and 10 %butane at 100 bara and 25
o
C

Working:
and conditions standard at ) ( density Relative
databooks general in found be can (M) weight molecular

Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
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Liquid Density - Example continued
Chart: API correlation chart for liquid density
3
dard tan s actual
actual r actual r
standard r standard r
ci i cm
ci i cm
kg/m 11 . 423
745 . 0
764 . 0
6 . 412
1 C
2 C
So
0.764 C2 Chart n Correlatio From
907 . 0
6 . 328
298
T 16 . 2
31 . 46
100
P
barg) 100 & C (25 Conditions Actual @
0.745 C1 chart n Correlatio From
876 . 0
6 . 328
288
T Liquid Saturated P
bara) 1 & C 15 ( Conditions Standard @
K 6 . 328 ) 13 . 408 1 . 0 ( ) 82 . 369 2 . 0 ( ) 43 . 305 7 . 0 ( T x T
bara 31 . 46 ) 49 . 36 1 . 0 ( ) 49 . 42 2 . 0 ( ) 8 . 48 7 . 0 ( P x P
databooks standard from Properties Critical Taking
= |
.
|

\
|
= |
.
|

\
|
=
=
= = = =
=
= = =
= + + = =
= + + = =

Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
5
Liquid Density - HYSYS Equations
The computer simulation HYSYS uses an Equation of State by Hawkinson, Brombst & Thomson usually referred to
as COSTALD because it uses Corresponding Standard Liquid Tables.

0 . 1 T 0.25 ) 00001 . 1 T /( ] hT gT fT e [ V
95 . 0 T 0.25 ) T 1 ( d ) T 1 ( c ) T 1 ( b ) T 1 ( a 1 V
] V 1 [ V
V
V
r r
3
r
2
r r R
r
3 4
r r
3 2
r
3 1
r
0
R
R SRK
0
R
*
s
< < + + + =
< < + + + + =
e =
o
o
Where:
a = -1.52816 b = 1.43907
c = -0.81446 d = 0.190454
e = -0.296123 f = 0.386914
g = -0.0427258 h = -0.0480645


tables COSTALD in Found
factor Acentric
Volume Molar V
e Temperatur Reduced T
Tr of Functions V , V
Volume Liquid Saturated V
SRK
*
r
R
0
R
s
)
`

o
Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
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Liquid Density - Mixing Rules
The mixing rules for the variables in the previous equations are as follows:


( )( ) | |
( )
( )
*
m
cm SRK
cm
SRK i SRK
2 1
cj
*
j ci
*
i cij
*
ij
3 1 *
i i
3 2 *
i i
*
i i
*
m
*
m
n
1 i
n
1 j
cij
*
ij j i
cm
V
RT 80 . 0 291 . 0
P
sensitive) (shape Factor Acentric x
T V T V T V
V x V x 3 V x
4
1
V
V
T V x x
T
m
i m
e
=
e = e
=
+ =
=

= =
This is a much more complicated method and is not suitable for hand calculations.

Running the liquid density calculation in HYSYS returns a density of 456.5
.
kg/m
3
.

Using the API method we obtained a value of 423.11 kg/m
3
.

Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
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Vapour Density
ZRT P M calculated is Density and
M y M calculated then is mass molecular Mean The
Z. ility, compressib obtain the chart to ility compressib a with properties reduced the Use
T
T
T ,
P
P
P
Tr) (Pr, properties reduced Find
component vapour of fraction mole is y where T y T , P y P
: ables databook t and rule s Kay' using calculated are properties critical Mixed
m m
i i m
cm
rm
cm
rm
i ci i cm ci i cm
=
=
= =
= =


The main parameter in calculating vapour density is the compressibility. This can be calculated by either the appropriate equation of
state or activity model, or by generalised compressibility charts.
Compound Vapour Density
(kg/m
3
)
Air 1.21
Oxygen 1.335
Carbon dioxide 1.873
Methane 0.6784
Propane 1.865
Example Gas Densities:
@15
o
C, 1 bara
Calculation using compressibility charts is as follows:
Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
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Vapour Density - Example Calculation
Calculate the density of vapour using the same composition as the previous example except with 15 bara pressure
and 25 C temperature. At these conditions the mixture is single phase gas.
Component Yi Tci (K) YTci Pci (MPa) YPci Zci Yzci M Myi
C2 0.7 305 213.5 4.88 3.416 0.28 0.196 30.07 21.049
C3 0.2 370 74 4.25 0.85 0.274 0.0548 44.097 8.8194
C4 0.1 408 40.8 3.65 0.365 0.277 0.0277 58.124 5.8124
Sum 328.3 4.631 0.2785 35.681
907 . 0 6 . 328 / 15 . 298 T
324 . 0 3 . 46 / 15 P
T
T
T

P
P
P
properties reduced the
calculate next , properties critical mixtures the have We
r
r
c
r
c
r
= =
= =
=
=
Compressibility Chart
Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
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Vapour Density - Example
HYSYS uses the Equation of State selected by the user to calculate the compressibility factor.
This is an iterative process and is more accurate.

HYSYS result:
Density mixture = 26.58 kg/m
3

( )
3
m m
kg/m 25.7
298.15 8.314 0.84 1500/ 35.68
ZRT / P . M
0.84 Z charts ility compressib d generalise From
=
=
=
=
Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
10
Viscosity
Gas Compounds Viscosity
(cP)
Liquid Compounds Viscosity
(cP)
Air @ 5
o
C .017 Octane @ 5
o
C 0.75
Methane @ 5
o
C 0.01 Water @ 5
o
C 1.4
Steam @ 100
o
C 0.012 Heavy crude @ 15
o
C 24
Medium crude @ 15
o
C 5
Light gas condensate @ 15
o
C 1
System Vapour Phase Liquid Phase
Light Hydrocarbons
NBP < 155
o
F
Modified Ely & Hanley Modified Ely & Hanley
Heavy Hydrocarbons
NBP > 155
o
F
Modified Ely & Hanley Twu
Non Hydrocarbon
Systems
Modified Ely & Hanley Modified Letsou-stiel
Accurate prediction of viscosity is very difficult due to the number and type of variables.

Nearly all methods rely on critical data developed from the equation of state and accuracy is greatly
affected by the equations chosen.

HYSYS uses the following methods for viscosity calculation.
Example Viscosities:
Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
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Viscosity
Component viscosities can be found by using viscosity charts.
These can be found in data books along with co-ordinates which relate
to different compounds. There are separate charts for gases and liquids.
( ) | |
viscosity component
fraction mole component x , ity cos vis mixture where
x
used be can rule following the mixtures liquid of estimation ity For viscos
i
i m
3
3 1
i i m


=

Example:
Estimate the viscosity of a mixture of 30% Pentane and 70% Octane
at 25
o
C and 1 bar.

Working:
Find the co-ordinates for Pentane and Octane to be used with the chart.
Pentane - X=14.9, Y=5.2 Octane - X=13.7, Y=10
from the chart (mPas)= 0.23 for pentane
= 0.54 for octane note: cP = mPas
| |
) (cP 0.428
5700 . 0 1838 . 0
) 54 . 0 ( * 7 . 0 ) 23 . 0 ( * 3 . 0
3
3
3
1
3
1
m
=
+ =
(

|
.
|

\
|
+ |
.
|

\
|
=
HYSYS returns a liquid viscosity of 0.416 (cP)
Component X Y
Water 10.2 13
Pentane 14.9 5.2
Hexane 14.7 7
Heptane 14.1 8.4
Octane 13.7 10
Viscosity of Liquid
Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
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Viscosity
weight molecular Component - M component of fraction Mole - y
viscosity Component - , viscosity Mixture - where
M y
M y

used be can rule following the gases of estimation ity For viscos
i i
i m
i i
i i i
m

Viscosities are found from viscosity charts. The charts give the viscosity at 1
atmosphere and the required temperature. Correction for pressure and
temperature can be made by using a viscosity correction chart. This requires the
reduced P & T from Kays rule.

Example:
Estimate the viscosity of a gas with composition 40% methane & 60% propane
at 25
o
C and 5 bara pressure.

Working:
Calculated the viscosity of the gas at 1 atmosphere and the required temperature
Using co-ordinates: methane - X= 9.9, Y= 15.5 propane - X= 9.7, Y= 12.9
from chart (mPas) = 0.011 for methane
= 0.0084 for propane
Viscosity of Gases
Component X Y
Air 11 20
Carbon Dioxide 9.5 18.7
Methane 9.9 15.5
Ethane 9.1 14.5
Propane 9.7 12.9
Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
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Viscosity



The viscosity at the required Pressure and
Temperature can then be calculated by multiplying by
the viscosity ratio (found from viscosity correction
chart).

In this case the correction factor is very small.

From Kays Method:
Pr = P / Pc = (5 / 44) = 0.114
Tr = T / Tc = (298 /298) =1

Reading From chart /
1
will be very close to 1

therefore = 1 x 0.00915
= 0.00915 cP

HYSYS returns a viscosity of 0.0097 cP
Chart: Viscosity Correction
(cP) 00915 . 0
984 . 3 602 . 1
0335 . 0 0176 . 0
097 . 44 * 6 . 0 043 . 16 * 4 . 0
097 . 44 * 6 . 0 * 0084 . 0 043 . 16 * 4 . 0 * 011 . 0
m
=
+
+
=
+
+
=
Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
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Specific Heat Capacity
Gas / solid Compound Isobaric Heat Capacity,
Cp (J/kgK)
Liquid Compound Isobaric Heat Capacity,
Cp (kJ/kgK)
Air 0.996 Water 4.187
Propane 2.467 Octane 2.177
Decane 1.758
Steel 0.502 Heavy Crude 1.718
Medium Crude 1.750
Gas Condensate 2.077
Example Heat Capacity values:
term. correction a minus capacity heat ideal the is which
R
C C
w
R
C C
value. ideal adjust the to
found is term correction a ns calculatio other in the As liquids. and gases both to applied be can method AIChE The
p
0
p
0
p p
|
|
.
|

\
|
=
-
Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
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Specific Heat Capacity
factor Acentric
) P , f(T tables. from found term Correction
R
C C
) P , f(T tables. from found term fluid Simple
R
C C



R
C C
R
C C
R
C C
fraction mass w
Capacity Heat Ideal C
Capacity Heat Actual C
: where
r r
) 1 (
p
0
p
r r
) 0 (
p
0
p
) 1 (
p
0
p
) 0 (
p
0
p p
0
p
0
p
p
e

|
|
.
|

\
|

|
|
.
|

\
|
|
|
.
|

\
|
e +
|
|
.
|

\
|
=
|
|
.
|

\
|

Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
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Specific Heat Capacity - Mixing Rules
factor Acentric - x
Pressure Critical - P x P
e Temperatur Critical - T x T
capacity heat Ideal - C w C
i i m
ci i cm
ci i cm
o
pi i
o
pm

e = e
=
=
=
HYSYS Results from ethane, propane and butane mixture.

Gas Heat Capacity - 2 (kJ/kgC)
Liquid Heat Capacity - 2.971 (kJ/kgC)
The following mixing rules can be applied to the previous Heat Capacity Equations.
Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
17
Thermal Conductivity
HYSYS uses the general guidelines of Reid, Prausnitz & Poling to determine which model best suits each class of
component.
Hydrocarbon systems use the corresponding states method of Ely & Hanley
Glycols & Acids are calculated by Sato-Reidel method
Esters, alcohols and light hydrocarbons by Latini
Others use the Missenard & Reidel method
Vapour Phase is covered by Misic & Thodos and Chung covers the higher pressure range.







Gas / solid
Compound
Thermal Conductivity
(W/m
2
K)
Liquid Compound Thermal Conductivity
(W/m
2
K)
Methane 0.0286 Water 0.569
Propane 0.1181 Octane 0.144
Heavy crude 0.164
Carbon steel 51.9 Medium crude 0.146
Stainless steel 16.3 Gas condensate 0.132
Example Conductivities
HYSYS results from ethane, propane and butane mixture.

Gas Conductivity - 0.0217 W/m
2
K
Liquid Conductivity - 0.0744 W/m
2
K
Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
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Thermal Conductivity


point Boiling T
weight Molecular M
j and i components of fraction mole y , y
viscosity
component pure of ty conductivi Thermal
mixture of ty conductivi Thermal : where
) T , M , ( f A
A y
y
b
j i
i
m
b ij
n
1 i
n
1 j
ij j
i i
m


q


q =

=
=
Mixing rules for low pressure gases:
me molar volu liquid component Pure - V
ty conductivi thermal component Pure -
ty conductivi thermal Mixture -
fractions mole component - x
components of number - n : where
) / 1 ( ) / 1 (
2
V x
V x
i
li
lm
j i,
lj li
li
j j
i i
i
n
1 i
n
1 j
lij j i lm

+
=
= |
| | =

= =
Mixing rules for liquids:
Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
19
Surface Tension
A modified form of the Brock, Bird equation is used by HYSYS to calculate surface tension. This expresses surface
tension as a function of the reduced & critical properties of the compound.
Examples:
Component Surface Tension
(dyne/cm)
Water 73.82
Octane 25.05
Heavy crude 30.27
Medium crude 27.32
Gas condensate 23.39
HYSYS results from ethane, propane and butane mixture.

Liquid case Surface Tension - 2.733 (dyne/cm)
Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
20
Surface Tension
shape. molecular on dependent class chemical
each for fitted Parameter - C C C C b
molecules. Polar for account to modified be can a and Q
class chemical each for fitted Parameter a
281 . 0 )] T 1 /( P ln T 1 [ 1207 . 0 Q
b . ) T 1 ( Q T P
3
3
2
2 1 0
BR c BR
a
R
3
1
c
3
2
c
e + e + e + =
)
`

=
+ =
= o
Mixing Rules

=
=
ci i cm
ci i cm
T x T
P x P
re temperatu boiling Reduced - T
value acentric -
tension Surface -
: where
BR
e
o

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