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Society of Petroleum Engineers

SPE 26642

Efficient Modelling of Asphaltene Precipitation


L.X. Nghiem, * M.S. Hassam, and Ram Nutakki, * Computer Modelling Group, and
A.E.D. George, * CANMET/ERL
'SPE Members

Copyright 1993, Society of Petroleum Engineers, Inc.

This paper was prepared for presentation at the 68th Annual Technical Conference and Exhibition of the Society of Petroleum Engineers held in Houston, Texas, 3-6 October 1993.

This paper was selected for presentation by an SPE Program Committee following review of information contained in an abstract submitted by the author(s). Contents of the paper,
as presented, have not been reviewed by the Society of Petroleum Engineers and are SUbject to correction by the author(s). The material, as presented, does not necessarily reflect
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Abstract injection/production schemes such that asphaltene precipitation


can be avoided or minimized.
An efficient modelling technique based on the
representation of the precipitated asphaltene as a pure dense Asphaltenes are heavy hydrocarbon molecules that are in
phase is presented. The success of the approach is based on the colloidal suspension in the oil, stabilized by resins adsorbed on
division of the heaviest component in the oil into a non- their surface [5,6,7]. Changes in pressure, temperature and
precipitating and a precipitating component. The composition may cause asphaltene precipitation. The nature of
characterization of these components is discussed. This model the precipitated asphaltene is still under investigation. Two
was able to make quantitative predictions of experimental data scenarios are possible [2]: i) the asphaltene/resin micelles
from the literature as well as additional data from industry. precipitate essentially unaltered and ii) there is a dissociation
This was achieved with only a small number of adjustable of the asphaltene/resin micelles which cause the precipitation
parameters (two or three). The mechanistic aspect of the of the asphaltene.
model with regards to colloidal nature of asphaltene/resin
In field situations, asphaltenes will first flocculate and
micelles is also discussed. An algorithm for three-phase flash
depending on the flow dynamics mayor may not deposit. Only
calculations with asphaltene precipitation is described.
laboratory experiments are considered in this paper and all the
Introduction flocculated asphaltenes will be refemed to as precipitated
asphaltenes.
Asphaltene precipitation from reservoir fluids during oil
production is a serious problem because it can result in Modelling approaches
plugging of the formation, wellbores and production facilities.
Several approaches for modelling asphaltene precipitation
A description of asphaltene problems and remedial actions in
have been reported in the petroleum literature:
many areas throughout the world are given in [1,2,3,4].
Currently, mechanical and chemical cleaning methods of Solubility model
wellbores are being improviSed to maintain production, but The first important approach in modelling asphaltene
these methods are time-consuming and expensive. Asphaltene precipitation in petroleum engineering is due to Hirschberg et
precipitation also occurs frequently during enhanced-oil- al [5]. Vapor-liquid equilibrium calculations with a cubic
recovery by gas injection which impedes seriously the recovery. equation of state were first applied to split the mixture into a
A model for correlating and predicting asphaltene precipitation vapor and a l~quid phase. The liquid was then divided into
is highly desirable because it would allow the design of three components: asphaltene, resin and a component for the
remaining oil and solvent. The fugacities for these

References and illustrations at end of paper. 375


2 EFFICIENT MODELLING OF ASPHALTENE PRECIPITATION SPE 26642

components were calculated with Flory-Huggins polymer Proposed approach


solution theory [8]. The performance of the model depends on
This paper proposes a model for asphaltene precipitation
the molar volumes and solubility parameters of the oil, resins
which satisfies the following requirements:
and asphaltenes. Burke et al [9], Novosad and Costain [10]
and Kokal et al [11] used this approach to match their Ability to make quantitative predictions.
experimental data with a limited degree of success. These Compatibility with flash calculations with an equation of
authors reported that this model reproduces the asphaltene state.
behavior qualitatively, but further improvements are required
Small number of adjustable parameters.
for quantitative predictions. Kanakawa et al [12] extended this
approach by considering asphaltenes to be heterogeneous Computationally efficient for potential inclusion in a
polymers instead of homogeneous polymers as in [5]. compositional model.

Solid model The precipitated asphaltene is modelled in this paper as a


pure dense phase. This phase is referred to as the asphalt
The simplest model for the precipitated asphaltene is the
phase and can either be a liquid or solid. A novel approach for
single-component solid model that was tried by Gupta [13] and characterizing the asphaltene component is proposed which
Thomas et al [14]. The precipitated asphaltene is represented
resolves most of the modelling deficiencies associated with the
as a pure solid while the oil and gas phases are modelled with a
solid model reported in the literature [13,14]. A robust flash
cubic equation of state. Thomas et al reported that the solid
calculation procedure for vapor/liquid/asphalt systems is
model may require the introduction of a large number of
described. The model was tested using data from the literature
empirical parameters and excessive tuning in order to match
and the industry. The mechanistic aspect of the model with
experimental data: e.g. compositional dependence for
regards to the colloidal nature of the asphaltene/resin micelles
interaction coefficients and solid fugacity. These modifications
is also discussed.
made the model highly empirical and difficult to use. Thomas
et al [14] also investigated the representation of the Modelling the Precipitated Asphaltene
precipitated asphaltene as a multicomponent solid phase. They Thermodynamic model
used a liquid-solid model due to Won [15]. This model has
also a large number of parameters. Thomas et al observed that The precipitated asphaltene is represented as a pure dense
this model did not exhibit the correct behavior with increasing phase. This phase is referred to as the asphalt phase. The
solvent concentration and suggested some modifications to this fugacity of asphaltene in the asphalt phase is:
model.
lnf =lnt + va (p-p )

Thermodynamic-Colloidal model (1)
a a RT
The previous approaches are based on molecular
thermodynamics and are suitable for modelling situations where fa and f: are respectively the fugacities of pure
where the asphaltene/resin micelles precipitate essentially asphaltene at pressures p and p*, va is the molar volume of
unaltered. Leontaritis and Mansoori [7] proposed a different pure asphaltene, R is the universal gas constant and T is the
approach for asphaltene flocculation based on a temperature. As Equation (1) is valid for both pure liquid or
thermodynamic-colloidal model. Their approach is more pure solid, the asphalt phase can be either considered as a
applicable to situations where there is a dissociation of the liquid or solid.
asphaltene/resin micelles. As in [5], vapor-liquid equilibrium
Characterization of the asphaltene component
calculations were first performed with an equation of state to
establish the liquid phase from which asphaltenes may In a mixture of n c components, let the asphaltene
flocculate. Based on experimental measurements of the onset component be the nc-th component. When the vapor, liquid
of precipitation, a critical chemical potential for resins is and asphalt phases coexist, the following thermodynamic
estimated using Flory-Huggins polymer solution theory. This equilibrium equations are satisfied:
critical chemical potential is subsequently used to predict the
onset of precipitations at other conditions.
In f jv = In f il i=I,...,nc (2)

(3)

376
SPE 26642 LONG NGHIEM, MOHAMED HASSAM, RAM NUTAKKI and ALBERT GEORGE 3

The fugacities fiv and fn are calculated from a cubic gn c, +1 ;: In K nc:a + In cIIn ca - In cIIn c1 = 0 (5)
equation of state. In this work. the Peng-Robinson equation of
state [16] is used. where cIIij is the fugacity coefficient of Component i in Phase j.
The crucial step in modelling asphaltene precipitation is ~y the vapor-liquid K-values. and K n a the asphalt-liquid K-
~

the characterization of the asphaltene component both in value for the asphaltene component
solution and in the asphalt phase. One of the important
In conjunction with the above equations. the following
contributions of this paper is the approach for characterizing
material balance equations can be derived:
the asphaltene component. Previous approaches with the solid
model assumed that asphaltene was the heaviest component in
the oil. This assumption is flawed as it contradicts
I. (K iy -1)zi = 0
i=II+Fv (K iv -1)+Fa (Kia -1) (6)
observations reported in the literature of other heavy
components (e.g. resins and paraffins) that may not precipitate.
Accordingly. in this work. the heaviest component is split into (7)
two components: a non-precipitating component and a
precipitating component. These two components have where Fy and Fa are respectively the phase mole fraction of
identical critical properties and acentric factors. but their vapor and asphalt phases. and zi the feed composition. Note
interaction coefficients with the light components are different. that Kia=O for i=I •...•nc-1.
The precipitating component has larger interaction coefficients
The phase compositions are given by:
with the light components. Larger interaction coefficients
correspond to greater "incompatibility" between components Yil = zi
and favor the formation of the asphalt phase. I+Fy (K iy -1)+Fa (Kia -1) i=I •...•nc (8)
Mechanistic aspect of the model
Yiy = K iy Yil i=I •...•nc (9)
The non-precipitating component can be related to resins.
asphaltene/resin micelles that will not dissociate. and heavy
(10)
paraffins. The precipitating component corresponds to both
the asphaltenes that could dissociate and precipitate and to the Algorithm
asphaltene/resin micelles that precipitate unaltered. Because of
The multiphase flash calculation algorithm of Nghiem
identical critical properties and acentric factors. the non-
and Li [17] was modified to solve Equations (4) - (6).
precipitating and precipitating components behave as a single
Equations (4) and (5) are converged using the Quasi-Newton
component in solution. The larger interaction coefficients
Successive Substitution (QNSS) technique [17]. After each
between the precipitating component and the solvent
QNSS iteration. Equations (6) and (7) are solved for F y and Fa
components causes the precipitation of the former when
using Newton's method.
solvent is added.
Stability test
Estimation of model parameters
The above calculations are complicated by the fact that
The use of the model in Equation (l) requires the
knowledge of f:· and va at p. and T. f:is estimated from
the number of phases in equilibrium is not known a priori.
This was resolved by using a procedure where the number of
experimental solubility data as elaborated later. The molar phases is increased or decreased according to a phase stability
volume va can be estimated from solubility data at different analysis based on the Gibbs energy surface [17]. The flow
pressures. chart for the three-phase calculation procedure is shown in
Figure 1. The testing of the existence of another fluid phase
Three-Phase Vapor/Liquid/Asphah Flash Calculations
requires the solution of a set of nonlinear equations as
Equations described in [17]. The testing of the existence of the asphalt
phase requires the following simple check:
The equilibrium equations (2) and (3) can be rewritten in
terms of equilibrium ratios (K-values) as: If In f n 1 ~ In fa. the asphalt phase exists.
~

i=I .....nc (4)


If In f n 1 < In fa. the asphalt phase does not exist.
~

377
4 EFFICIENT MODELLING OF ASPHALTENE PRECIPITATION SPE 26642

Validation With Experimental Data


(11)
Outline
In this section, the proposed model was validated using
data from Hirschberg et al [5], Burke et al [9], and from an oil where the exponent e is a regression parameter used for
matching the saturation pressures. The interaction coefficients
company.
between C3IB+ and the hydrocarbon components of the solvent
Burke, Hobbs and Kasbou (1990) data were assumed to have the same value ~ which was used to
Table 1 reports the compositions of an oil and solvent match the amount of precipitate. Both the parameters e and ~
(Oil 2 and HCG 2) from Burke et al [9]. Table 2 shows the influence the saturation pressures and the amounts of
precipitation and saturation pressure data for different precipitate and had to be regressed simultaneously. However,
concentrations of solvent. The last column of Table 2 shows it was found that the coupling between e and ~ was weak and
the existence of material balance errors in the measurements of they could be obtained by regressing alternately on the
the amounts of asphaltene. In particular, the measurement at saturation pressures and amounts of precipitate. Two iterations
70 mole % of solvent deviated substantially from the other were required to obtain the desired match.
values. Ignoring this value gives an average value of total Matching both the saturation pressures and the amount of
precipitate of 7.80 weight %. precipitate yield e = 0.5761 and ~ = 0.120. The interaction
Based on the oil C7+ fraction specific gravity and coefficients for C3IA+ and C3IB+ are shown in Figure 2. The
molecular weight, application of the characterization method component C3IB+ has higher interaction coefficients with
of Li et al [18] and Nutakki et al [19] gave 10 pseudo respect to the solvent components than the component C3IA+.
components shown in Table 3. Note that the heaviest Figures 3 and 4 show the comparison between calculated
component of the solvent is not part of the oil. The heaviest amount of precipitate and saturation pressures and the
component of the oil, C 31 +, is split into two components: corresponding experimental values. If the precipitation data at
C3IA+ (non-precipitating component) and C3IB+ (precipitating 70 mole % solvent was discounted as discussed above, the
component). The mole fraction of C31B+ is calculated based on match data was excellent up to 78 mole % solvent. Note that
a total 7.80 weight % of precipitate: the precipitate measurements were performed over a wide
range of pressure (3014.7 psia [20786 kPa] to 5014.7 psia
Zc 31B+ =wc31B+ xM 01'[ +M c 31B+ [34575 kPa]) which validates the pressure dependence term in
Equation (1).
zC31B+ = 0.0780 x 202.4 + 617.6 = 0.0256 For solvent concentration above 78 mole %, the
To estimate f;, the precipitation data at 0 mole % measurements indicated a substantial drop in the precipitated
solvent and p* = 3014.7 psia [20786 kPa] and T* = 218 OF amount The model could not predict this behavior as the
[103.3 0c] was used. The amount of precipitate (0.14 weight predicted values were respectively 5.02 weight % and 5.11
weight % at 85 mole % and 90 mole % of solvent. Burke et al
% C3IB+) was removed from the feed. The fugacity of tc31B+
[9] and Chabak [20] attributed the decrease of precipitate at
in the remaining mixture was then calculated with the Peng- high solvent concentration to the switching of the mixture from
Robinson equation of state and equated to f;. A value for a bubble-point fluid to a dew-point fluid. The ability of the
volume va of 0.9 m3/kmol was found adequate for model to reproduce this behavior is under investigation.
extrapolating the asphaltene fugacity with respect to pressure Industry data
(the value of pure asphaltene given by the Peng-Robinson
Table 4 shows the composition of an oil and gas used to
equation of state is 0.776 m3/kmol). The above values of f; model asphaltene precipitation data provided by an oil
and va were used to calculate the fugacities of asphaltene at the company. The oil was modelled with 35 components. Figure
different test pressures in Table 2. 5 shows a good match between the predicted precipitation
The interaction coefficients between all hydrocarbons values and experimental data at 13000 kPa and 45 OC. The
components and CO2 are 0.15. The interaction coefficients values of the parameters used in the match are: e =1.4512 and
between hydrocarbons up to and including C3IA+ were ~ =0.126 for interaction coefficients between C30B+ and CO2 ,

calculated from: N2 , C I , C2 , and C3 . The total amount of precipitate in the oil


was not measured. This value was used as a matching

378
SPE 26642 LONG NGHIEM, MOHAMED HASSAM, RAM NUTAKKI and ALBERT GEORGE 5

parameter. It was found that choosing the amount of the Acknowledgments


precipitating component, C30B+, to be 65 mole % of C30+ gave
This research was supported by the Canada Centre for
good results. For this fluid, the calculations showed a decrease
Mineral and Energy Technology (CANME'I) and the Members
in the amount of precipitate at high solvent concentration as in
of the Computer Modelling Group (CMG). We thank
the experimental measurements. The calculated bubble-point
Professor R.A. Heidemann of the University of Calgary, and
pressure is 5564.6 kPa at 48°C compared to the experimental
Dr. Dennis A. Coombe of CMG for many enlightening
value 5509 kPa. The calculated GOR is 64.9 std m3/std m3 at
discussions.
89.63 kPa and 21.1 OC which is close to the experimental value
of 62 std m3/std m3. Nomenclature
Hirschberg, deJong, Schipper, and Meijer (1984) data interaction coefficient between Component i and k
exponent for interaction coefficient in Equation (11)
The liquid titration data with nCs and nC7 in the above
fugacity of precipitated asphaltene
reference was also matched with the proposed model. Table 5
shows the composition of the tank oil. Table 6 shows the split reference fugacity of precipitated asphaltene
of the C29+ component into a non-precipitating component fugacity of Component i in Phase j
(C29A+) and precipitating component (C29B+) based on the mole fraction of Phase j
experimental values of asphaltenes of 3.9 weight % and 1.9 function defined in Equations (4) and (5)
weight % for nCs and nG respectively. The respective K-values of Component i in Phase j
interaction coefficients are also reported. Figure 6 shows a molecular weight
good agreement between the calculated and experimental number of components
results. p pressure
P
. reference pressure
Conclusions
R universal gas constant
The following conclusions can be drawn from this research: T temperature
• An approach for modelling efficiently and quantitatively critical volume
asphaltene precipitation is proposed. weight fraction of Component i
global composition of Component i
• The division of the heaviest component of the oil into a value for interaction coefficients between the
non-precipitating and a precipitating component together precipitating component and the light components
with a proper characterization of these components is
'ij fugacity coefficient of Component i in Phase j
essential to a successful application of this model.
Subscripts
• From a mechanistic point of view, the precipitating
component can be related to asphaltenes that dissociate a asphalt
and to asphaltene/resin micelles that precipitate component
unaltered. The non-precipitating component corresponds j phase
to asphaltene/resin micelles that do not precipitate nor k component
dissociate, and to heavy paraffins. 1 liquid phase
v vapor phase
• The model was able to make quantitative predictions of
experimental data from the literature as well as additional References
data from the industry. 1. Leontaritis, K.J., and Mansoori, G.A.: "Asphaltene
• Two or three adjustable parameters were required to Deposition: A Survey of Field Experiences and Research
match experimental data. Approaches," J. Petrol. Sci. and Eng., Vol. I, 1988, pp.
229-239.
• As shown in one example, the model has the ability to
2. Leontaritis, K.J.: "Asphaltene Deposition: A
predict a decrease in asphaltene precipitation at high
Comprehensive Description of Problem Manifestation
solvent concentration. The general behavior of this
and Modelling Approaches," paper SPE 18892, presented
model as the solvent concentration increases is under at the 1989 SPE Production Operations Symposium,
investigation. Oklahoma City, Oklahoma, March 13-14.

379
6 EFFICIENT MODELLING OF ASPHALTENE PRECIPITATION SPE 26642

3. Leontaritis, K.J., Amaefule, J.O., and Charles, R.E.: "A 14. Thomas, F.B., Bennion, D.B., Bennion, D.W., and
Systematic Approach for the Prevention and Treatment of Hunter, B.E.: "Experimental and Theoretical Studies of
Formation Damage Caused by Asphaltene Deposition," Solids Precipitation From Reservoir Fluid," J. Can.
paper SPE 23810, presented at the 1992 SPE IntI. Petrol. Technol., Vol. 31, No.1, January 1992, pp. 22-31.
Symposium on Formation Damage Control, Lafayette,
15. Won, K.W.: "Thermodynamics for Solid-Liquid
Louisiana, February 26-27, 1992.
Equilibria: Wax Formation from Heavy Hydrocarbon
4. Thawer, R., Nicoll, D.C.A., and Dick, G.: "Asphaltene Mixtures," Fluid Phase Equilibria, Vol. 30, 1986, pp.
Deposition in Production Facilities," SPE Prod. Eng., 265-279.
Vol. 5, No.4, November 1990, pp. 475-480.
16. Peng, D.-Y., and Robinson, D.B.: "A New Two-Constant
5. Hirschberg, A., dejong, L.N.J., Schipper, B.A., and Equation of State," Ind. Eng. Chern. Fundam., Vol. 15,
Meijer, J.G.: "Influence of Temperature and Pressure on 1976, pp. 59-64.
Asphaltene Flocculation," Soc. Petrol. Eng., Vol. 24, June
17. Nghiem, LX., and Li, Y.-K.: "Computation of
1984, pp. 283-293.
Multiphase Equilibrium Phenomena With and Equation
6. Kawanaka, S., Leontaritis, K.J., Park, S.J., and Mansoori, of State," Fluid Phase Equilibria, Vol. 17, 1984, pp. 77-
G.A.: "Thermodynamic and Colloidal Models of 95.
Asphaltene Flocculation," ACS Symposium Series, 1989,
18 Li, Y.-K., Nghiem, LX., and Siu, A.: "Phase Behaviour
pp.443-458.
Computations for Reservoir Fluids: Effect of Pseudo-
7. Leontaritis, K.J., and Mansoori, G.A.: "Asphaltene Components on Phase Diagrams and Simulation Results,"
Flocculation During Oil Production and Processing: A J. Can. Petrol. Technol., Vol. 24, November-December
Thermodynamic-Colloidal Model," paper SPE 16258, 1985, pp. 29-36.
presented at the Proc. SPE Int. SYQ1p. on Oil Field
19. Nutakki, R., Nghiem, L., Li, Y.-K., and George, A.:
Chemistry, San Antonio, Texas, January 1987.
Optimal Representation of Heavy Fractions in the
8. Prausnitz, J.M., Lichtenthaler, R.N., de Azevedo, E.G.: Simulation of Multiple-Contact Processes," Paper No.
Molecular Thermodynamics of Fluid-Phase Equilibria, CIM/AOSTRA 91-57, presented at the Petroleum of
Second Edition, Prentice-Hall, Englewood Cliffs, New CIM/AOSTRA Technical Conference, Banff, Alberta,
Jersey, 1986, pp. 306-316. April 21-24, 1991.
9. Burke, N.E., Hobbs, R.E., and Kashou, S.F.: 20. Chaback, J.J.: "Discussion of Measurement and
"Measurement and Modeling of Asphaltene Modeling of Asphaltene Precipitation," J. Petrol.
Precipitation," J. Petrol. Technol., November 1990, pp. Technol., Vol. 43, No. 12, December 1991, pp. 1519-
1440-1456. 1520.
10. Novosad, Z., and Costain, T.G.: "Experimental and
Modeling Studies of Asphaltene Equilibria For a
Reservoir Under C02 Injection," paper SPE 20530,
presented at the 1990 SPE Annual Technical Conference
and Exhibition, New Orleans, Louisiana, September 23-
26,1990.
11. Kokal, S.L., Najman, J., Sayegh, S.G., and George, A.E.:
"Measurement and Correlation of Asphaltene
Precipitation From Heavy Oils by Gas Injection," J. Can.
Petrol. Technol., Vol. 31, No.4, April 1992, pp. 24-30.
12. Kawanaka, S., Park, S.J., and Mansoori, G.A.: "Organic
Deposition From Reservoir Fluids: A Thermodynamic
Predictive Technique," SPE Res. Eng., Vol. 6, No.2, May
1991, pp. 185-192.
13. Gupta, A.K.: A Model for Asphaltene Flocculation Using
an Equation of State, M.Sc. thesis, Department of
Chemical and Petroleum Engineering, University of
Calgary, June 1986.

380
TABLE 1
Oil and Solvent Composition
Burke et aI (1990) fluid

Composition (mol%)

Component Oil Solvent

1.42 17.76 TABLE 2


0.51 3.17 Asphaltene Precipitation Data
6.04 30.33 Burke et al (1990) fluid
7.00 26.92
6.86 13.09
0.83 1.26 Mixture Precipitates
Satutation Test Precipitates in Residual Total
3.35 4.66
Solvent Pressure Pressure From Live Stock-Tank Precipitates
0.70 0.17 (mol%) (psia) (psia) Oil Oil (wt%)
3.46 1.26 (wt%) (wt%)
3.16 0.78 0 600 3014.7 0.14 8.83 8.97
66.68 20 1050 3014.7 0.27 7.56 7.83
50 2310 3014.7 1.46 5.50 6.96
70 3750 4214.7 1.65 2.69 4.34
Oil C7+ molecular weight 281 78 4510 5014.7 3.21 4.63 7.84
Oil C7+ specific gravity 0.902 85 5000 5014.7 1.29 6.73 8.02
Oil molecular weight 202.4 90 4250 5014.7 1.10 6.01 7.17

TABLE 3
Modelled Oil and Solvent Composition for Burke et al (1990) Fluid TABLE 4
Modelled Oil and Solvent Composition for Industry Fluid

Composition (mol%)
Oil Solvent
Component Oil Solvent
Component mol% Component mol % Component mol%
C~ 1.42 17.76 0.009 CIS 2.153 0.060
N2+C I 6.55 33.50 0.751 C I6 1.872 0.000
14.377 CI7 1.735 29.140
~ 7.00 26.92
5.560 C I8 1.666 7.780
C3 6.86 13.09
6.649 CI9 1.605 31.760
C4G+ 0.00 8.73 1.762 ~o 1.221 6.780
C4-c; 24.66 4.637 ~I 1.132 14.280
C W C I6 22.41 2.433 ~2 0.981· 3.650
C n -C3o 19.62
2.976 ~3 0.919 3.290
3.933 ~ 0.782 1.950
C 3IA+ 8.92
6.055 ~ 0.713 1.020
C31B+ 2.56 6.858 ~6 0.658 0.240
5.706 ~7 0.617 0.050
4.581 ~8 0.576
3.449 ~9 0.501
2.894 C30A+ 1.471
3.326 C30B+ 2.732
2.709

TABLES TABLE 6
Modelled Composition for Hirschberg et al (1984) Tank Oil Non-precipitating and Precipitating Components for Different Solvents
Hirschberg et al (1984) Fluid
Component mol%
Interaction coefficient
CI 0.10
Composition (mol%) component-solvent
~ 0.48
Component nCs n~ nCs n~
C3 2.05
iC4 0.88 ~A+ 10.58 11.42 0.026 0.016
nC4 3.16 ~B+ 1.63 0.79 0.160 0.160
iCs 1.93
nCs 2.58
C6 4.32
~-CI6 47.45
Cn -C28 24.84
~A+&~B+ 12.21
381
2-PHASE FLASH 2-PHASE FLASH
(FLUID-ASPHALT) (FLUID-FLUID)

Figure 1 • Flow Chart


Three-Phase VaporlLiquidiAsphalt Flash Calculation

0.20 I I I

DC;",...
• C31 B+

+'
l::
CI>
0.15
• -
'0
ECI>
0
• • • •
0
l::
0.10 -
0
+'
0
e
CI>
+' 0
E 0.05 ~ -
0
0
0
0

0.00 I
g I:J:I

0 1 2 3 4 5 6 7 8 9 10
Component i (i=1 •...• 10)

Figure 2 - Interaction Coefficients for C31A+ (i=9) and C31B+ (i=10)

382
4.00 I

experimental
0 3014.7 psia
0 4214.7 psia X
J1
........ 3.00 J1 5014.7 psia
~
X calculated
.....
..c:
Ol
X
'ii)
~
'-"

.....c
Q)
2.00 -
..... X 0
'0. 0
'0
J1
~
a.. 1.00 J1

I
0.00 L.--...L..---L..----'-_--l.._--'_ _L-_...L..-_....L_---'-_--l
0.00 0.20 0.40 0.60 0.80 1.00
Mole fraction of solvent

Figure 3, Weight % Precipitate from Live Oil


Burke et al (1990) Fluid

6000
0 experimental
calculated
5000
........
c
'iii
a.
'-"
4000
Q)
L..
::J
Ul
Ul
~ 3000
a.
c
0
:;:;
cL.. 2000
.....::JC
(/)

1000

0
0.00 0.20 0.40 0.60 0.80 1.00
Mole fraction of solvent

Figure 4 - Saturation Pressures of Oil/Solvent Mixtures


Burke et al (1990) Fluid

383
30.00
0 experimental
calculated

0 25.00
'0
Q)
"'0
::J
.... 20.00

-'-
0

0>
15.00
'-J

Q)
.....
c
..... 10.00
'0.
'0
Q)
....
0- 5.00

0.00
0.00 2.00 4.00 6.00 8.00 10.00
Solvent-Oil ratio (1/1)
Figure 5 • ASphaltene Precipitation from Industry Crude Oil

4.0

,-.... 3.0 o experimental


~ o experimental
.....
.J::
calculated
0> calculated
'm
3=
.........
2.0
.....C
Q)
--~-----~------------------
~
.e-
0
Q)
L...
0... 1.0

0.0
10.00 20.00 30.00 40.00 50.00
0.00
Dilution (ml/g)

Figure 6 • Asphaltene Precipitation from Tank Oil


Hirschberg et al (1984) Fluid

384