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SPE 26642
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.
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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.
~
377
4 EFFICIENT MODELLING OF ASPHALTENE PRECIPITATION SPE 26642
378
SPE 26642 LONG NGHIEM, MOHAMED HASSAM, RAM NUTAKKI and ALBERT GEORGE 5
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%)
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)
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)
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
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
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
0.0
10.00 20.00 30.00 40.00 50.00
0.00
Dilution (ml/g)
384