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OIL ASSOCIATION
SPE/PS-CIM/CHOA 97763
PS2005-343
Heavy-Oil Dilution
J.-F. Argillier, I. Hnaut, P. Gateau, and J.-P. Hraud, Inst. Franais du Ptrole, and P. Glnat, Total S.A.
Copyright 2005, SPE/PS-CIM/CHOA International Thermal Operations and Heavy Oil Symposium
Introduction
This paper was prepared for presentation at the 2005 SPE International Thermal Operations
and Heavy Oil Symposium held in Calgary, Alberta, Canada, 13 November 2005.
The increasing oil demand and advances in heavy oil
This paper was selected for presentation by an SPE/PS-CIM/CHOA Program Committee
following review of information contained in a proposal submitted by the author(s). Contents of
production technologies is leading to the increased production
the paper, as presented, have not been reviewed by the Society of Petroleum Engineers, of this type of hydrocarbon. The reserves in Alberta, Canada
Petroleum SocietyCanadian Institute of Mining, Metallurgy & Petroleum, or the Canadian
Heavy Oil Association and are subject to correction by the author(s). The material, as represent a potential resource of 1.7 billion barrels of oil and a
presented, does not necessarily reflect any position of the SPE/PS-CIM/CHOA, its officers, or
members. Papers presented at SPE and PS-CIM/CHOA meetings are subject to publication
further 1.3 billion are considered to exist in the orinico belt
review by Editorial Committees of the SPE and PS-CIM/CHOA. Electronic reproduction, fields, Venezuela. The API gravity of these oils is extremely
distribution, or storage of any part of this paper for commercial purposes without the written
consent of the SPE or PS-CIM/CHOA is prohibited. Permission to reproduce in print is low Athabascan heavy oil has an API gravity of between 8-
restricted to a proposal of not more than 300 words; illustrations may not be copied. The
proposal must contain conspicuous acknowledgment of where and by whom the paper was
10 API and Orinico Belt heavy oil has an API gravity of 10-
presented. Write Librarian, SPE, P.O. Box 833836, Richardson, TX 75083-3836, U.S.A., fax 12. These high densities lead to correspondingly high
01-972-952-9435.
viscosities in the Athabascan case over 1,000,000 centiPoise
and between 1,500 and 3,000 for Venezuelan heavy oils at
Abstract reservoir temperatures. These physical properties make heavy
oil difficult to produce, separate and then transport. Most
Heavy or extra heavy crude oils cannot be transported by pipeline systems require the dehydrated crude to have an API
pipeline without a prior reduction of their viscosity. This is gravity specification of 19API (400 cP viscosity).
commonly obtained by blending the oil with light
hydrocarbons. In that case, the resulting viscosity of the Although potential alternatives exist (Partial Upgrading on
mixture depends only on the dilution rate, and on the site, Oil in water emulsion, Core Annular Flow) this
respective viscosities and densities of the oil and of the specification is in most cases obtained by dilution with a
diluent. Classical diluent are light crudes, condensates, lighter hydrocarbon additive. Condensates have been used
naphtha. Availability of the diluent and its possible recycling until the end of the 80's to transport almost the whole
needs of course to be taken in account. In this work we have production of the Canadian crude [1, 2]. Another choice to
studied the influence of composition of the diluent on the dilute heavy oils is to use of a light crude, with an API gravity
viscosity reduction efficiency. In particular we show that the range from 35 to 42 [2, 3]. Light oils are less efficient in
addition of a polar solvent to a solution of asphaltenes in reducing the viscosity of heavy oils than condensates and they
toluene acts on the colloidal structure of the asphaltenes. The are subjected to the same limitations of availability and of
relative viscosity of the solution decreases, as well as the size compatibility with asphaltenes. Naphtha seems to be an
of the aggregates of asphaltenes. In the same way, by mixing interesting alternative to the use of condensates [1]. Because
hydrocarbons and solvents owning polar functional groups in its high API gravity, it is very efficient in diluting heavy oils.
their molecule, it is shown that the efficiency of the dilution of Naphthas show a good compatibility with asphaltenes and are
heavy crude oils is enhanced. Hansen's theory can be used to easily recycled. Dilution with naphtha associated with solvent
screen the solvent efficiency. At constant dilution rate, the recycling has been used in Canada and in Venezuela.
higher the polarity parameter or the hydrogen bonding
parameter of the solvent, the greater the relative viscosity This study aims at showing that the polarity of the thinner
reduction of the diluted crude oil. Nevertheless, solvent has some influence of the viscosity reduction of the solution.
owning high hydrogen bonding are generally more viscous Some of the results presented here have been described
than hydrocarbons. The influence of their interactions with the elsewhere [4].
asphaltenes is hidden when the results are expressed in
absolute viscosity. Polar solvents giving few hydrogen
bonding give a significant reduction of the viscosity of the
diluted crude oil. From an economical point of view, any
improvement of the efficiency of the thinner could be a benefit
for the process, by reducing the amount of solvent needed to
get an acceptable viscosity, and therefore allowing a greater
quantity of crude to be transported.
2 SPE/PS-CIM/CHOA 97763
Experimental part 25
Dilute regime Concentrated
regime
Heavy oil sample and naphtha characteristics 20
Relative viscosity
The heavy crude used in this study is Venezuelan extra C*
heavy oil, 8.5 API degree. SARA analysis is shown in Table 1. 15
10
SARA SARA (% weight) on C20+
(% weight) pentane heptane heptane SARA fractions 5
original heavy crude
C20+ C H N O S
0
Asphaltenes 17 14.1 83.8 7.5 1.3 1.7 4.8 0 5 10 15 20 25 30
% weight asphaltenes
Resins 33 37.3 82.8 8.9 1.5 2.0 4.3
Aromatics 37 37.2 84.3 10 <0.3 1.1 4.0 Figure 1: Concentration regimes: influence of asphaltene
content on heavy oil viscosity.
Saturates 12 11.4 86.6 13 <0.3 <0.2 <0.1
For asphaltene studies, asphaltenes have been precipitated Evolution of the viscosity of the mixture of the Venezuelan
with pentane using the norm ASTM 863-69 and then grinded. heavy oil and naphtha is shown on Figure 2 for different
Remixing of asphaltenes in maltenes is carried out at 80C for concentrations of naphtha. As expected the viscosity decreases
an hour. strongly with the diluent weight fraction.
The naphtha used as diluent has been analysed by gas
chromatography: it is composed of 24.9 weight % of Lederer [7] proposed a modified version of the classic
n-paraffin, 29.4% of iso-paraffin, 30.9% of cyclic paraffin and Arrhenius expression to represent the mixture viscosity:
14.8% of aromatic.
VO VO
log = log O + 1 log S
Viscosity measurements VO + VS VO + VS
Samples have been mixed under gentle steering for 24
hours before viscosity measurements are performed using a a where VO, O, VS, S are respectively the volume fraction and
controlled stress rheometer AR2000 from TA Instruments. the viscosity for the oil (O) and the solvent (S) and where is
The geometry used is cone-plate ( 6 cm, angle 2). Double an empirical constant varying between 0 and 1. The fitting of
cylinder Couette geometry was used to measure viscosity of the parameter to the values presented in Figure 2 using a
different diluent mixtures. least-square method leads to the value of 0.418 for .
100
Schematically, heavy crude oils can be divided into a non
colloidal liquid, the maltenes and a dark brown powder, the 10
Viscosity (Pa.s)
17.04( O S ) O3.2745 S1.6316 parameters are close from those of ASTM Fuel B for which
0.5237
According to the theory of Hildebrand, the parameter t is Table 2: Hansen parameters of naphtha (approximation)
a measure of molecular interactions. The solubility parameter and polar co-solvents.
is defined by:
1
E 2
Efficiency of polar solvent as diluent
= LV
VM The solvents have been mixed with naphtha at 10 and 50%
with ELV as cohesion energy and VM as molar volume. v/v. This allows getting synthetic solvents with polarity
In order to be able to distinguish between dispersion parameter varying from 0 to 6.4. The Venezuelan heavy oil
forces, polar interactions and hydrogen bonding, Hansen [see has been diluted with 15% by weight with the synthetic
ref. 9] divided this solubility parameter in three parts, i.e. the solvents. Viscosity measurements have been performed at
dispersion part d, the polar part p and the hydrogen bonding 20C. To compare dilution efficiency of solvents, results are
part h, called cohesion energy parameters: presented using relative viscosity defined as:
2t = d2 + 2p + 2h rel(c,T) = (c,T) diluent (T) with:
The cohesion energy parameters of solvent mixtures can - (c, T ) , the viscosity of the diluted crude at a concentration
be calculated from the parameters of each solvent using the c and temperature T (Pa.s).
following equation: - diluent (T ) , the viscosity of the thinner at the temperature T
i =n
= i Vi (Pa.s).
i =1
This representation allows taking no account of the simple
where is the Hansen parameter of the mixture (dispersion, dilution effect and on the contrary to emphasis the eventual
contribution from organisation and structural modifications.
polar or hydrogen bonding part), i is the Hansen parameter of
the pure solvent i and Vi is the volume fraction of the solvent i
in the mixture. 3500
The dispersion component of the Hildebrand parameter
quantifies the London dispersion forces (or induced dipole- 3000
der Waals interactions and we can think they will not have any 2500
We can see on Figure 3 that increasing the polarity of the hexanol, the dissociation phenomenon is maximal and
solvent leads to a decrease of the relative viscosity of the linkages between the elementary particles are broken. An
diluted oil. When the polar parameter becomes high, the increase of the hexanol fraction from 10 to 50% in toluene
efficiency with naphtha tends to a plateau. Note that if we use leads to an increase of both the radius of gyration and the
nonane instead of naphtha, the relation between the polar relative viscosity. Hhexanol, like heptane, is a non-solvent of
parameter p of the solvent and the relative viscosity is almost the asphaltenes. Then, when all the possible sites able to
linear [4]. One can think that the maximum in efficiency is establish associations between the alcohol functions and the
reached when all the polar sites, even the weakest, are asphaltenes are saturated, hexanol acts as a flocculant,
associated with solvent molecules. An optimum of viscosity inducing an increase of the gyration radius and of the relative
reduction is reached in naphtha with methylethylketone, and viscosity.
using an even more polar solvent like butyronitrile does not
seem to improve significantly the efficiency of viscosity Influence of hydrogen bonding
reduction.
We have studied the influence of the hydrogen bonding
Role of polar components on asphaltenes properties parameter following the same approach as for polarity. The
selected products and their Hansen parameters are listed in
In order to better understand the influence of polar solvent, Table 3.
we dissolved asphaltenes precipitated with pentane in solvent
mixtures containing increasing amounts of hexanol, up to d p h
toluene/hexanol (50/50 v/v). Optical microscopic observations Solvent
1/2 1/2
show that no flocculation occurs even at 50%. Viscosity (Mpa ) (Mpa ) (Mpa1/2)
measurements have been performed at low temperature (3C) Octanoic acid 15.1 3.3 8.2
in order to emphasis the difference of viscosity between the
solutions and the solvent. Results are given in terms of relative Butyric acid 14.9 4.1 10.6
viscosity defined as rel (c, T ) = (c, T) diluent (T ) . In parallel,
1-Octanol 17.0 3.3 11.9
small angle X-ray scattering (SAXS) measurements have been
performed to get an estimation of the radius of gyration of 1-Butanol 16.0 5.7 15.8
asphaltenes. Hexanol 15.0 8.5 13.7
75 1.25
Contrary to the polar solvents, it has not been possible to
use mixtures of hydrogen bonding solvents with naphtha and
Radius of gyration ()
70 1.2
Relative viscosity
3500
oil by naphtha is about 27 vol% which represent 22.5 wt% of
dilution. As shown in Figure 7, the addition of 30 wt% of
3000 MEK as the diluent decreases the crude oil dilution rate of 2
points.
Relative Viscosity
2500
2000
25
1500 24 Correlation
23 Experimental
1000
topping's outlet, three products are found: the first one is economic viability evaluation. Later on, the MEK losses will
naphtha (C180-) which can contain MEK, the second one is vary between 0 wt% to 10 wt%.
diesel (C180- - C380-) and the last one is atmospheric residue. To
maximise the conversion, this last one is divided in a vacuum For the basic economic study, hypothesis on products
distillation in two streams: vacuum gasoil and vacuum residue, prices are:
which is also upgraded in a coking unit. To obtain synthetic - heavy crude oil: 8 $/bbl,
crude oil properties, naphtha and diesel from topping and - methylethylketone : 900 $/t,
coker must be hydrotreated and the vacuum gasoil - SCO: 27 $/bbl (for a Brent price at 30 $/bbl),
hydrocracked in mild conditions. The final product, SCO, is - coke: 11 $/t.
the result of these different products blend.
To compare the different cases and the influence of MEK
EXTRACTION PIPELINE UPGRADING
M EK M ake-Up
losses, the net realization is defined by the difference between
Diluent Naphtha and
finished products prices (receipts) and raw materials costs
MEK
(expenses). We do not consider an additional cost for
RECOVERY
UNIT investment and operating cost.
HYDROTREATER
Diesel
Synthetic
Crude
Oil
Figure 9 shows the evolution of the net realization with the
T
O
P
P
MEK losses. As we can see it decreases when the MEK losses
Diluted Crude
I
N
G
Vacuum Gasoil MILD
HYDROCRAKER
increase.
D
I
V
S
T
490
A I 0% MEK in diluent
C L
Atmospheric Residue
U
U
L
A
480 10% MEK in diluent
460
Vacuum Residue CONVERSION DES
COKER
FRACTIONS LOURDES
Crude Oil
450
Coke
440
Figure 8: Upgrading process flowsheet.
430
420
On the basis of this process, we make an approximate mass
410
balance in five different cases to determinate the quality and
0 2 4 6 8 10
quantity of SCO product. The first one is the basic case with MEK losses (wt %)
only naphtha used as diluent. In cases 2 to 5, the MEK fraction
in the diluent is increased from 10 wt% to 50 wt%. For these Figure 9: Evolution of the net realization with the MEK
cases the following hypotheses considered are: losses.
- the inlet topping flowrate is 140 kBPSD,
- diluent can be a mixture naphtha / MEK, The reference, calculated on the basic case is about
- the viscosity of the diluted crude is 400 cP, 447 $/year (dotted line). For all other cases, the net realization
- no revamping of separation, conversion and is better if the MEK losses are less than 5 wt%.
hydrotreatment units,
- SCO properties are similar (density: 29.5 API, As a consequence, for a process application of MEK as co-
sulfur: 0.17 wt%). diluent, a process must be developed with a high MEK
recovery rate. In the last part, we will study a process solution
Case number 1 2 3 4 5 to recycle the maximum MEK flowrate.
MEK
Diluent allow recycling, the boiling point of the co-solvent must fall in
the boiling range of the hydrocarbon cut of the mixture.
F
References
Figure 10: Flowsheet of the MEK recovery unit.
1. Urquhart, R.D., (1986), Heavy Oil Transportation:
After the topping, the mixture naphtha / MEK is flashed in Present and Future. J. Can. Pet. Technol., 25, 2, 68
flash drums. The aim of the flash is to recover the naphtha 71
flowrate used as diluent. It can be possible with an adjustment 2. Todd, C.M., (1988), Downstream Planning and
of operating conditions like temperature and pressure. With Innovation for Heavy Oil Development A
this naphtha, an important amount ok MEK is recycled in the Producer's Perspective. J. Can. Pet. Technol., 27, 1,
diluent stream. 79 86
3. Guevara, E., Gonzalez, J., Nuez, G., (1998), Highly
The second part of the recovery unit is composed of two Viscous Oil Transportation Methods in the
distillation columns. These units must reduce the MEK Venezuela Industry, Proc. 15th World Pet. Congress,
content in the naphtha. Since the MEK boiling point is about 495 502
80C, in the first distillation, the heavy naphtha (C80+) is 4. Gateau, P., Hnaut, I, Barr, L., Argillier, J-F., Heavy
recovered at the bottom of the column and the light naphtha Oil Dilution, Oil & Gas Science and Techology
cut with MEK at the top. The aim of the second distillation Rev. IFP., Vol 59 (2004), N5 , 503-506
column is to recover the MEK at the bottom and light ends of 5. Hnaut I., Barr L., Argillier J-F., Brucy F.,
naphtha at the top. Bouchard R., (2001), Rheological and Structural
Properties of Heavy Crude Oils in Relation With
Based on the process simulation of flash and distillation, Their Asphaltenes Content, SPE 65020.
the recovery rate of MEK in naphtha is above 99 wt%. 6. Argillier J-F, Barr L., Brucy F., Dournaux J-L.,
Hnaut I., Bouchard R., (2001), Influence of
This basic study shows that MEK can present an economic Asphaltenes Content and Dilution on Heavy Oil
advantage if losses are below 5 wt%. From a technical point of Rheology, SPE 69711.
view, MEK can be easily recovered with flash and distillation 7. Lederer E.L., (1933), Proc. World Pet. Cong. (Lond.)
units. 2, 526-528
8. Shu W.R., (1984), A Viscosity Correlation for
However, other aspects of the global process (crude oil Mixtures of Heavy Oil, Bitumen, and Petroleum
production process and upgrading units) must be also be Fractions, SPE 11280
considered. Both technical and economical detailed studies are 9. Barton Allan (1992), Handbook of solubility
curently being performed to check the economy of the global parameters and other cohesion parameters, 2nd Ed.
process. CRC Press.
Conclusions