Energy Fuels 2010, 24, 2956–2963 : DOI:10.

1021/ef9014263
Published on Web 04/05/2010

Cubic-Plus-Association Equation of State for Asphaltene Precipitation in Live Oils

Zhidong Li and Abbas Firoozabadi*
Reservoir Engineering Research Institute (RERI), 385 Sherman Avenue, Suite 5, Palo Alto, California 94306

Received November 22, 2009. Revised Manuscript Received March 8, 2010

We apply a cubic-plus-association equation of state (CPA-EOS) to study the asphaltene precipitation in

live oils from temperature, pressure, and composition effects. The live oils are characterized by considering
the pure components, the pseudo-hydrocarbon components, and the hydrocarbon residue. The hydro-
carbon residue is further divided into the “heavy” component and asphaltenes. The asphaltene precipita-
tion is modeled as liquid-liquid equilibrium between the upper onset and bubble point pressures and as
gas-liquid-liquid equilibrium between the bubble point and lower onset pressures. In our work, the self-
association between asphaltene molecules and the cross-association between asphaltene and “heavy”
molecules are taken into account. The EOS parameters are either directly available, from our recent work,
or from fitting the bubble point pressure. The cross-association energy between asphaltene and “heavy”
molecules depends upon the temperature but is independent of the pressure. We reproduce the experiments
of the amount and onset pressures of asphaltene precipitation in several live oils over a broad range of
composition, temperature, and pressure conditions.

1. Introduction The lyophilic model includes the solubility theory,2-13 cubic

Asphaltenes are operationally defined as a group of crude
components insoluble in normal alkanes but soluble in aro-
matics. They represent the heaviest and most polar portion of
a petroleum fluid. Asphaltene precipitation from the change
of pressure, temperature, and composition may lead to serious
plugging problems during the oil production, transportation,
storage, and refining. Our knowledge on asphaltenes is limi-
ted, and the mechanisms of aggregation and deposition are
not completely understood.1
The prevailing theoretical approaches for asphaltene pre-
cipitation can be classified into two main categories, lyophilic
and lyophobic, corresponding to two different hypotheses on
the mechanisms of asphaltene precipitation and stabilization.2
*To whom correspondence should be addressed. Telephone: 650-326-
9259. Fax: 650-326-9277. E-mail: af@rerinst.org.
(1) Vargas, F. M.; Gonzalez, D. L.; Creek, J. L.; Wang, J. X.; Buckley,
J.; Hirasaki, G. J.; Chapman, W. G. Energy Fuels 2009, 23, 1147.
(2) Correra, S.; Merino-Garcia, D. Energy Fuels 2007, 21, 1243.
(3) Hirschberg, A.; Dejong, L. N. J.; Schipper, B. A.; Meijer, J. G.
SPE J. 1984, 24, 283.
(4) Wang, J. X.; Buckley, J. S. Energy Fuels 2001, 15, 1004.
(5) Jamshidnezhad, M. J. Jpn. Pet. Inst. 2008, 51, 217.
(6) Kraiwattanawong, K.; Fogler, H. S.; Gharfeh, S. G.; Singh, P.;
Thomason, W. H.; Chavadej, S. Energy Fuels 2007, 21, 1248.
(7) Akbarzadeh, K.; Alboudwarej, H.; Svrcek, W. Y.; Yarranton,
H. W. Fluid Phase Equilib. 2005, 232, 159.
(8) Akbarzadeh, K.; Dhillon, A.; Svrcek, W. Y.; Yarranton, H. W.
Energy Fuels 2004, 18, 1434.
(9) Mofidi, A. M.; Edalat, M. Fuel 2006, 85, 2616.
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L. Fuel 2008, 87, 85.
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Yarranton, H. W. AIChE J. 2003, 49, 2948.
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Teclemariam, A. Energy Fuels 2005, 19, 1261.
(13) Correra, S. Pet. Sci. Technol. 2004, 22, 943.
(14) Gupta, A. K. MS Thesis, University of Calgary, Calgary, Alberta,
Canada, 1986.
(15) James, N. E.; Mehrotra, A. K. Can. J. Chem. Eng. 1988, 66, 870.
(16) Godbole, S. P.; Thele, K. J. Society of Petroleum Engineers (SPE)
Annual Technical Conference and Exhibition, Washington, D.C., Oct
4-7, 1992; SPE 24936.
equations of state (EOS),14-23 and perturbed-chain statistical
associating fluid theory (PC-SAFT).1,24-28 In this model,
asphaltenes and oil constitute a true solution. The molecular
size and dispersion attractions dominate asphaltene phase
behavior in crude oils. Asphaltene precipitation is due to the
reduction of the solvent power of the hydrocarbon fluids. The
separation of asphaltenes is described as a traditional liquid-
liquid or solid-liquid phase equilibrium. The lyophobic
model includes the colloidal theory,29 micellization theory,30-33
and McMillan-Mayer-SAFT.34-36 In this model, asphaltenes
are insoluble in the crude oil but can be stabilized by resins
(17) Kohse, B. F.; Nghiem, L. X.; Maeda, H.; Ohno, K. Society of
Petroleum Engineers (SPE) Asia Pacific Oil and Gas Conference and
Exhibition, Brisbane, Queensland, Australia, Oct 16-18, 2000; SPE
64465.
(18) Du, J. L.; Zhang, D. Pet. Sci. Technol. 2004, 22, 1023.
(19) Vafaie-Sefti, M.; Mousavi-Dehghani, S. A.; Mohammad-Zadeh,
M. Fluid Phase Equilib. 2003, 206, 1.
(20) Sabbagh, O.; Akbarzadeh, K.; Badamchi-Zadeh, A.; Svrcek,
W. Y.; Yarranton, H. W. Energy Fuels 2006, 20, 625.
(21) Behar, E.; Mougin, P.; Pina, A. Oil Gas Sci. Technol. 2003, 58,
637.
(22) Szewczyk, V.; Thomas, M.; Behar, E. Rev. Inst. Fr. Pet. 1998,
53, 51.
(23) Szewczyk, V.; Behar, E. Fluid Phase Equilib. 1999, 158, 459.
(24) Gonzalez, D. L.; Ting, P. D.; Hirasaki, G. J.; Chapman, W. G.
Energy Fuels 2005, 19, 1230.
(25) Gonzalez, D. L.; Hirasaki, G. J.; Creek, J.; Chapman, W. G.
Energy Fuels 2007, 21, 1231.
(26) Gonzalez, D. L.; Vargas, F. M.; Hirasaki, G. J.; Chapman, W. G.
Energy Fuels 2008, 22, 757.
(27) Ting, P. D.; Hirasaki, G. J.; Chapman, W. G. Pet. Sci. Technol.
2003, 21, 647.
(28) Vargas, F. M.; Gonzalez, D. L.; Hirasaki, G. J.; Chapman, W. G.
Energy Fuels 2009, 23, 1140.
(29) Leontaritis, K. J.; Mansoori, G. A. Society of Petroleum En-
gineers (SPE) International Symposium on Oilfield Chemistry, San
Antonio, TX, Feb 4-6, 1987; SPE 16258.
(30) Pan, H. Q.; Firoozabadi, A. SPE Prod. Facil. 1998, 13, 118.
(31) Pan, H. Q.; Firoozabadi, A. SPE Prod. Facil. 2000, 15, 58.
(32) Pan, H. Q.; Firoozabadi, A. AIChE J. 2000, 46, 416.
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1188.

r 2010 American Chemical Society 2956 pubs.acs.org/EF

Energy Fuels 2010, 24, 2956–2963 : DOI:10.1021/ef9014263
peptized on their surface. Resins are considered to be the
compounds chemically intermediate between all of the other
species in the oil and asphaltenes. Asphaltene precipitation is
due to the resin desorption from the surface of asphaltene
particles.
These two types of models have been used in correlating and
predicting the onsets and amount of asphaltene precipitation
in various petroleum fluids, with some limitations that may
restrict their applications in the petroleum industry. First, in
some of the theories, the reservoir fluid is represented by either
asphaltene þ resin or asphaltene þ solvent. The two-compo-
nent model is an oversimplification, and it may not be of value
for use in compositional reservoir simulators. Second, most of
models cannot describe the gas, oil, and asphaltene phases
within a unified framework; i.e., they cannot work indepen-
dently. Third, some of the methods contain many complex
equations and/or adjustable parameters, which may compli-
cate the implementation in the simulation modeling. Finally,
some approaches do not account for the polar-polar and
polar-induced polar interactions pertinent to asphaltenes and
other components (e.g., resins and aromatics), which could
also be important for the proper description of the asphaltene
phase behavior.
In a recent paper, we have proposed a cubic-plus-asso-
ciation equation of state (CPA-EOS) to study asphaltene
precipitation in model and real heavy oils from the addition
of n-alkanes.37 We have examined the effects of tempera-
ture, pressure, and n-alkanes on asphaltene precipitation
and demonstrated that our model can reproduce the experi-
ments. This is the first time that CPA-EOS is applied to
study the asphaltene problem. Our approach is, in princi-
ple, a lyophilic model; i.e., the asphaltene-containing fluid
is regarded as a true solution. Differently, besides the
molecular size and dispersion attractions, the polar-polar
interactions relevant to asphaltenes and other components
are taken into consideration. However, different from the
lyophobic model, we do not specifically require the species
that are polar (e.g., resins) and easy to be polarized (e.g.,
aromatics) to stabilize asphaltenes in petroleum fluids.
They may either inhibit or promote asphaltene precipita-
tion depending upon the composition of the petroleum
fluid. Our approach includes the possible intermolecular
interactions relevant to asphaltene problems and can par-
tially and in some cases completely overcome the current
limitations.
In this work, we apply our CPA-EOS to investigate asphal-
tene precipitation in several live oils from a pressure decrease
and mixing with CO2 at high temperature and pressure.
Within a unified theoretical framework, we successfully
capture the bubble point pressure, asphaltene precipitation
amount and onset pressures, and gas-oil-asphaltene three-
phase coexistence. More importantly, our model can be read-
ily implemented in compositional reservoir simulators. The
remainder of this paper is organized as follows: Section 2
describes the modeling and the formulation of our CPA-EOS
for asphaltene systems in live oils. Section 3 compares calcula-
tions to experiments for asphaltene precipitation in seven live
oils induced by a pressure decrease and CO2 mixing. In section
4, the main results and conclusions are summarized.
(35) Wu, J. Z.; Prausnitz, J. M.; Firoozabadi, A. AIChE J. 2000, 46,
197.
(36) Buenrostro-Gonzalez, E.; Lira-Galeana, C.; Gil-Villegas, A.;
Wu, J. Z. AIChE J. 2004, 50, 2552.
(37) Li, Z. D.; Firoozabadi, A. Energy Fuels 2010, 24, 1106.
2957
Li and Firoozabadi
2. Modeling and Theory
In this work, asphaltene precipitation in live oils is modeled as
the traditional liquid-liquid or gas-liquid-liquid phase separa-
tion. The live oils are complex fluid mixtures of thousands of
components. We characterize them by considering the pure
components (N2, CO2, H2S, C1, C2, C3, iC4, nC4, iC5, and nC5),
the pseudo-hydrocarbon components (C6, C7, C8, etc.), and the
hydrocarbon residue (Cnþ). The pseudo-hydrocarbon compo-
nents are defined by lumping a number of hydrocarbon compo-
nents within a certain normal boiling point range.38 For instance,
C6 includes all of the components with the normal boiling point
between those of nC5 and nC6. Full characterization can avoid the
extra parameter adjustment because the required EOS para-
meters are either standard for the pure components or correlated
for the pseudo-hydrocarbon components. Thus, our model
requires not only the asphaltene precipitation information but
also the complete fluid analysis. The hydrocarbon residue is
further divided into the “heavy” component and asphaltene.
The “heavy” component contains the heavy alkanes, heavy
aromatics, and all resins. Here, the heavy alkanes and heavy
aromatics are those not included in pure components and pseudo-
hydrocarbon components. The “heavy” component represents
the secondary most polar component in petroleum fluids. The
higher the molecular weight, the higher the aromatic content
and the higher the polarity. Although we coarse-grain the
heavy alkanes, heavy aromatics, and resins as only one pseudo-
component, the necessary physical features are essentially pre-
sented and well-described in our work. The advantages of our
method have been demonstrated in detail in our recent work.37
Specifically, for the asphaltene precipitation in live oils, the
additional advantage of our model is that it is based on the
existing fluid characterization, which can be readily implemented
in the compositional reservoir simulators.
In the framework of CPA-EOS, the excess Helmholtz free
energy Aex consists of the physical part, which describes the non-
associating molecular interactions, such as short-range repulsions
and dispersion attractions, and the association part, which
describes the polar-polar interactions (self-association and
cross-association) of asphaltene and “heavy” molecules.
The physical contribution is represented by the Peng-Robinson
(PR)-EOS39
pffiffiffi !
Aex
ph a 1 þ ð1 þ 2ÞbF
¼ - lnð1 - bFÞ - pffiffiffi ln pffiffiffi ð1Þ
nRT 2 2bRT 1 þ ð1 - 2ÞbF
where R is the universal gas constant, T is the absolute tempera-
ture, n is the total number of moles, and F is the molar density of
the mixture. a and b are the energy and volume parameters of the
mixture. They can Pbe estimatedP by applying the van der Waals
mixing rules: a = i,jxixjaij, b = ixibi, and aij = (aiaj)1/2(1 - kij),
where xi, ai, and bi stand for the mole fraction, energy para-
meter, and volume parameter of component i, respectively,
and kij is the binary interaction coefficient (BIC) between
components i and j (kij = 0 if i = j). ai and bi can be determined
from the critical properties and acentric factor of an individual
component
R2 Tci2  pffiffiffiffiffiffi 2 RTci
ai ¼ 0:45724 1þci ð1 - Tri Þ , bi ¼ 0:0778 ð2Þ
Pci Pci

with ci ¼ 0:37464 þ 1:54226ωi - 0:26992ωi 2 , ωi < 0:5 ,
0:3796 þ 1:485ωi - 0:1644ωi 2 þ 0:01667ωi 3 , ωi > 0:5
where Tri, Tci, Pci, and ωi denote the reduced temperature, critical
temperature, critical pressure, and acentric factor of component i,
respectively.
(38) Firoozabadi, A. Thermodynamics of Hydrocarbon Reservoirs;
McGraw-Hill: New York, 1999.
(39) Peng, D. Y.; Robinson, D. B. Ind. Eng. Chem. Fundam. 1976,
15, 59.
Energy Fuels 2010, 24, 2956–2963 : DOI:10.1021/ef9014263 Li and Firoozabadi

Table 1. Properties of the Seven Live Oils22,23,36,49-51

fluid A fluid C1 fluid Y3 fluid X1 fluid X2 fluid X3 Weyburn oil

Concentration (mol %) of Pure Components and Pseudo-hydrocarbon Components

N2 0.49 0.91 0.47 0.09 0.27 0.38 0.96
CO2 11.37 1.57 1.59 1.02 4.07 4.02 0.58
H2S 3.22 5.39 1.44 0.05 0.3
C1 27.36 24.02 32.22 42.41 30.53 46.07 4.49
C2 9.41 10.09 12.42 10.78 7.13 7.72 2.99
C3 6.70 9.58 10.29 6.92 5.92 5.62 4.75
iC4 0.81 1.83 2.03 1.55 2.43 1.14 0.81
nC4 3.17 4.83 4.87 2.92 1.11 2.35 1.92
iC5 1.22 2.27 2.22 1.47 0.82 0.75 1.27
nC5 1.98 2.74 2.71 1.82 0.79 0.67 2.19
C6 2.49 4.77 4.12 2.86 1.36 0.82
C7 2.87 2.67 1.03
C8 3.14 3.82 1.58
C9 2.74 4.17 1.91
C10 2.32 4.07 0.79
C11 1.90
Concentration (mol %), MW, and SG of Hydrocarbon Residue
C12þ C7þ C7þ C7þ C11þ C11þ C6þ
mol % = 18.82 mol % = 32.00 mol % = 25.62 mol % = 28.11 mol % = 30.83 mol % = 25.15 mol % = 79.74
MW = 337.94 MW = 334.66 MW = 284.36 MW = 209.50 MW = 302.09 MW = 330.77 MW = 230.00
SG = 0.906 SG = 0.882 SG = 0.805 SG = 0.852 SG = 0.872 SG = 0.881 SG = 0.870
Concentration (wt %) of Asphaltenes in STO
1.40 3.80 3.25 0.5 or 0.4 4.35 3.40 4.90

The contribution to the excess Helmholtz energy because of
association is derived from the thermodynamic perturbation
theory.40-43 It is the same as that used in the SAFT.44-47 We
assume that each asphaltene molecule has NA identical associa-
tion sites and each “heavy” molecule has NR identical association
sites
   
Aex 1 - χA 1 - χR
ass
¼ NA xA ln χA þ þ NR xR ln χR þ
nRT 2 2
The subscripts “A” and “R” represent asphaltenes and the
“heavy” component, respectively. χA and χR are the mole frac-
tions of asphaltene and “heavy” molecules not bonded at one of
the association sites, respectively. Association bonding occurs
between two sites, with one on asphaltene molecule and the other
on either asphaltene or a “heavy” molecule. “Heavy” molecules
are assumed not to associate with themselves. As a result, χA and
χR are given by
1 X2,22 and X3,23 precipitation is from the pressure decrease.
χA ¼ ,
1 þ FNA xA χA Δ þ FNR xR χR ΔAR
AA
1
χR ¼
1 þ FNA xA χA ΔAR
where Δij = gκijbij[exp(εij/kBT) - 1] (i = A and j = A or R)
characterizes the “association strength” with bij = (bi þ bj)/2, kB
is the Boltzmann constant, g is the contact value of the radial
distribution function of the hard-sphere mixture, and κij and εij
are the association volume and energy parameters, respectively.
To simplify the calculations, g is approximated by that of the pure
hard-sphere fluid as g ≈ (1 - 0.5η)/(1 - η)3, with η = bF/4. The
(40) Wertheim, M. S. J. Stat. Phys. 1984, 35, 19.
(41) Wertheim, M. S. J. Stat. Phys. 1984, 35, 35.
(42) Wertheim, M. S. J. Stat. Phys. 1986, 42, 459.
(43) Wertheim, M. S. J. Stat. Phys. 1986, 42, 477.
(44) Chapman, W. G.; Jackson, G.; Gubbins, K. E. Mol. Phys. 1988,
65, 1057.
(45) Chapman, W. G.; Gubbins, K. E.; Jackson, G.; Radosz, M. Fluid
Phase Equilib. 1989, 52, 31.
(46) Chapman, W. G.; Gubbins, K. E.; Jackson, G.; Radosz, M. Ind.
Eng. Chem. Res. 1990, 29, 1709.
(47) Jackson, G.; Chapman, W. G.; Gubbins, K. E. Mol. Phys. 1988,
65, 1.
cross-associations between asphaltene and pseudo-hydrocarbon
components are assumed negligible, but they can be included
within the same theoretical framework with the introduction of
more adjustable parameters.
3. Results and Discussion
In this work, we study the asphaltene precipitation in seven
live oils. Table 1 provides the concentration of the pure
ð3Þ components and pseudo-hydrocarbon components for these
live oils. It also gives the mole fraction, molecular weight
(MW), and specific gravity (SG) of the hydrocarbon residue.
The asphaltene weight fractions in stock tank oils (STOs) are
also included. The physical parameters TC, PC, ω, and MW of
the pure components, pseudo-hydrocarbon components, and
asphaltene are either directly available or obtained in our
recent work.37,48 They are repeated in Table 2 for the sake of
completeness. For the reservoir fluids A,49,50 C1,36 Y3,36 X1,49
For the Weyburn oil, precipitation is induced by CO2 mix-
ing.51 The common association parameters NA = NR = 4,
ð4Þ κAA = κAR = 0.01, and εAA/kB = 2000 K are also provided in
our recent work for asphaltene precipitation in heavy oils.37
The physical parameters of the “heavy” component are
obtained in two steps. First, for the hydrocarbon residue, on
the basis of its molecular weight and specific gravity, Cavett’s
correlation is used to provide the rough estimation of TC
and PC52 and the normal boiling point TB is estimated using
the interpolation of the generalized properties of petroleum
hexane-plus groups.38 Because the uncertainty in TC estima-
tion is less than that in PC,38 we only adjust PC of the
hydrocarbon residue to match the bubble point pressure
(48) Database of RERI Flash Computation Software Package.
(49) Fahim, M. A. Pet. Sci. Technol. 2007, 25, 949.
(50) Jamaluddin, A. K. M.; Joshi, N.; Iwere, F. Society of Petroleum
Engineers (SPE) International Petroleum Conference and Exhibition,
Villahermosa, Mexico, Feb 10-12, 2002; SPE 74393.
(51) Srivastava, R. K.; Huang, S. S.; Dyer, S. B.; Mourits, F. M.
J. Can. Pet. Technol. 1995, 34, 31.
(52) Cavett, R. H. Proceedings of the American Petroleum Institute
(API) 27th Mid-year Meeting, San Francisco, CA, 1962; Vol. 52, p 351.
2958
Energy Fuels 2010, 24, 2956–2963 : DOI:10.1021/ef9014263 Li and Firoozabadi

Table 2. Common Physical Parameters of Pure Components, Pseudo- Table 4. Non-zero Binary Interaction Coefficients for the Seven Live
hydrocarbon Components, and Asphaltene37,48 Oils38,53
TC (K) PC (bar) ω MW C1-HC N2-HC CO2-HC H2S-HC
N2 126.21 33.90 0.039 28.0 fluid A
CO2 304.14 73.75 0.239 44.0 fluid C1
H2S 373.20 89.40 0.081 34.1 fluid Y3
C1 190.56 45.99 0.011 16.0 fluid X1 0.0289 þ 1.633  0.15
0.1 0.1
C2 305.32 48.72 0.099 30.1 fluid X2 10-4MW
C3 369.83 42.48 0.153 44.1 fluid X3
iC4 407.80 36.04 0.183 58.1 Weyburn oil 0.071
nC4 425.12 37.96 0.199 58.1
iC5 460.40 33.80 0.227 72.2 Table 5. Cross-association Energy between Asphaltene and “Heavy”
nC5 469.70 33.70 0.251 72.2 Molecules εAR for the Seven Live Oils
C6 507.40 30.12 0.296 86.2
fluid A εAR/kB (K) = 665.82 þ 1.0145T
C7 556.48 26.75 0.294 100.0
fluid C1 εAR/kB (K) = 1258.85 - 1.2462T
C8 574.76 25.24 0.418 114.0
fluid Y3 εAR/kB (K) = 422.54 þ 2.0125T
C9 593.07 23.30 0.491 128.0
fluid X1 εAR/kB (K) = 1311.49 - 0.8835T
C10 617.07 21.55 0.534 142.0
fluid X2 εAR/kB (K) = 1219 (303 K)
C11 638.24 19.74 0.566 156.0
fluid X3 εAR/kB (K) = 1500 (303 K), 1420 (353 K), 1400 (403 K)
asphaltene 1474 6.34 2 1800
Weyburn oil εAR/kB (K) = 500 (332 K)

εAR has to be assumed temperature-dependent. Table 5 ex-

Table 3. Physical Parameters of the “Heavy” Component for the
Seven Live Oils
hibits εAR as function of the temperature for the seven live oils.
For the first four oils (fluids A, C1, X1, and Y3), the
TC (K) PC (bar) ω MW coefficients in the correlations are obtained from the measure-
fluid A 823.2 9.8 1.28 332.9 ments of upper onset pressures at the lowest and highest
fluid C1 788.6 11.7 1.28 323.6 temperatures. The upper onset pressures at the other tem-
fluid Y3 689.9 15.7 1.01 276.0
fluid X1 721.3 15.0 0.80 208.5
peratures and lower onset pressures are then predicted. εAR
fluid X2 766.9 10.5 0.99 288.6 either increases (fluids A and Y3) or decreases (fluids C1 and
fluid X3 786.6 9.9 1.11 320.7 X1) with temperature. We are not able to provide a physical
Weyburn oil 746.2 15.9 1.00 220.1 interpretation for this behavior within the frame of our work.
(without considering asphaltene precipitation). The ω is It is possibly due to the complexity of the asphaltene problems
calculated from38 and more likely due to the poor accuracy of the onset
 measurements. As stated in ref 36, “the onset determination
3 log10 ðPC =1:01325Þ
ω ¼ -1 ð5Þ is highly uncertain”. For the other three oils (fluids X2 and X3
7 TC =TB - 1 and Weyburn oil), εAR is estimated from the fitting of the
measured amount of precipitated asphaltenes.
where PC is in bar and TC and TB are in Kelvin. It should be
Solubility parameter of the oil may explain the asphaltene
emphasized that we have used the physical parameters of pure
phase behavior. The solubility parameter of the reservoir fluid
components and pseudo-hydrocarbon components (Table 2)
decreases as the pressure decreases from the reservoir condi-
and the method of estimating the physical parameters of the
tion to the bubble point and makes asphaltene less stable
hydrocarbon residue in many industrial projects, and they
because the oil density decreases. Below the bubble point,
work well for fitting the bubble point pressure at various
there is an increase in density and solubility parameter when
temperatures. Second, the gas/oil ratio (GOR) and then the
the pressure decreases because of the release of light hydro-
asphaltene concentration in live oil can be calculated by
carbons and the oil becomes a better solvent for asphaltene
flashing the oil at room conditions (293.15 K and 1 bar).
again. During depressurization, when the pressure is higher
The physical parameters of the “heavy” component are then
than the upper onset, the solution is in a single-phase region.
obtained from those of the hydrocarbon residue and asphal-
Asphaltene precipitation occurs when the pressure is between
tene through molar averaging, as shown in Table 3. Because of
the upper onset and bubble point and between the bubble
the low mole fraction of asphaltene in live oils, the molar
point and lower onset. The solution is at oil-asphaltene two-
averaging does not affect the prediction of the bubble point
phase equilibrium for the former and at gas-oil-asphaltene
pressures. We let the hydrocarbons (HCs) include C1, C2, C3,
three-phase equilibrium for the latter. When the pressure is
iC4, nC4, iC5, nC5, C6, C7, C8, etc., “heavy” component, and
lower than the lower onset, there is no asphaltene precipita-
asphaltene. The BICs between C1 and HC (except C1),
tion and the solution is in the gas-oil two-phase region. An
between N2 and HC, between CO2 and HC, and between
increase in the temperature decreases the oil density but at the
H2S and HC can be referred to the previous work and are
same time increases the solution entropy, resulting in a
reproduced in Table 4. Other BICs are set to zero.38,53 It
counter balancing effect; i.e., asphaltene precipitation can be
should be mentioned that the BICs between CO2 and HC for
either strengthened or weakened when the temperature in-
the Weyburn oil have to be tuned to fit the bubble point
creases.54,55
pressures for different CO2/oil mixtures. It should also be
Figure 1 presents the asphaltene precipitation envelop for
emphasized that we have tested the method of estimating the
the reservoir fluid A with the plots of bubble point and upper
BICs in many industrial projects. For asphaltene precipitation
and lower onset pressures as a function of the temperature.49,50
in live oils, to match the available experiments, the cross-
The STO has a nC7-insoluble asphaltene content of 1.4 wt %.
association energy between asphaltene and “heavy” molecules
(54) Ting, P. D. Ph.D. Thesis, Rice University, Houston, TX, 2003.
(53) Arbabi, S.; Firoozabadi, A. SPE Adv. Technol., March, 1995, (55) Gonzalez, D. L. Ph.D. Thesis, Rice University, Houston, TX,
139-145. 2008.
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Energy Fuels 2010, 24, 2956–2963 : DOI:10.1021/ef9014263 Li and Firoozabadi

Figure 1. Pressures of bubble point and asphaltene precipitation

upper and lower onsets as function of the temperature for the
reservoir fluid A. Symbols are experiments from refs 49 and 50,
and lines represent calculations.

It should be noted that our predictions are similar to those in

the literature.26 According to our calculations, when the
temperature is lower than 400 K, the temperature change
dramatically affects the upper onset pressure. When the
temperature increases from 300 to 400 K, the upper onset
pressure falls by 1300 bar. The low-temperature region is
important to evaluate the asphaltene precipitation risk during
the production of deep sea reservoirs. When the temperature is
higher than 400 K, the effect of the temperature on the upper
onset pressure becomes weak. In comparison to the upper
onset pressure, the bubble point pressure and lower onset
pressure are weakly dependent upon the temperature. With a Figure 2. Pressures of bubble point and asphaltene precipitation
unified theoretical framework, our model successfully repro- upper and lower onsets as function of the temperature for the
duces the asphaltene precipitation envelop. reservoir fluid X1 with an asphaltene concentration of (a) 0.5 wt
Figure 2 shows the asphaltene precipitation envelop for the % and (b) 0.4 wt %. Symbols are experiments from ref 49, and lines
represent calculations.
reservoir fluid X1 with asphaltene contents in STO of 0.4 and
0.5 wt %. The precipitant used to determine the asphaltene
content in STO is not reported.49 It should be emphasized that
all of the results in Figure 2b are predictions. For this oil,
according to our calculations, the effect of the temperature on
the upper onset pressure is much weaker even at low tempera-
tures compared to the reservoir fluid A. A decrease of the
asphaltene concentration has essentially no effect on the
bubble point pressure but can decrease the upper onset
pressure and increase the lower onset pressure; i.e., asphaltene
becomes more stable. It is interesting that, when the tempera-
ture is higher than 400 K, the asphaltene is less stable as the
temperature increases in the gas-oil-asphaltene three-phase
region but the trend is opposite in the oil-asphaltene two-
phase region. For the higher asphaltene content, i.e.,
Figure 2a, both the upper onset pressure and bubble point
pressure are faithfully captured but the lower onset pressure is
somewhat overestimated. For the lower asphaltene content,
i.e., Figure 2b, the performance for the bubble point pressure Figure 3. Pressures of bubble point and asphaltene precipitation
is still excellent and, for the lower onset pressure, it is also upper onset as function of the temperature for the reservoir fluid
C1. Symbols are experiments from ref 36, and lines represent
improved. However, the upper onset pressure is slightly over- calculations.
estimated. We suspect that experiments of onset pressures
may have large errors especially for the lower onset. In asphaltene content of 3.80 wt % for fluid C1 and 3.25 wt % for
general, the agreement between the experiments and calcula- fluid Y3. The measurements of the lower onset pressure are
tions for the reservoir fluid X1 is satisfactory. not reported. For oil Y3, the upper onset pressure also
In Figures 3 and 4, we examine the effect of the temperature presents strong dependency upon temperature. On the basis
on both upper onset and bubble point pressures for the of our results, when the temperature increases from 300
reservoir fluids C1 and Y3.36 The STO includes nC5-insoluble to 400 K, the upper onset pressure can drop by 1800 bar.
2960
Energy Fuels 2010, 24, 2956–2963 : DOI:10.1021/ef9014263
Figure 4. Pressures of bubble point and asphaltene precipitation
upper onset as function of the temperature for the reservoir fluid
Y3. Symbols are experiments from ref 36, and lines represent
calculations.
Figure 5. (a) Fraction of precipitated asphaltenes and (b) relative
volume of the mixture (bubble point is the reference) as function of
the pressure for the reservoir fluid X2 at 303 K. Symbols are
experiments from ref 22, and lines represents calculations. In panel
a, the calculated bubble point and upper and lower onsets are
marked by thin lines.
Our calculation indicates that, in the oil-asphaltene two-phase
region when the temperature is above 400 K, the asphaltene
precipitation is strengthened as the temperature increases.
This phenomenon also weakly appears for the reservoir fluids
A and C1 possibly because of the counter effect of the
temperature. For the fluids C1 and Y3, our calculations agree
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Li and Firoozabadi
Figure 6. (a) Fraction of precipitated asphaltenes and (b) relative
volume of the mixture (bubble point is the reference) as function of
the pressure for the reservoir fluid X3 at 303, 353, and 403 K.
Symbols are experiments from ref 23, and lines represent calcula-
tions. In panel a, the calculated bubble point and upper and lower
onsets are marked by thin lines.
well with the experiments for both bubble point and upper
onset pressures.
Our work predicts that the plot of upper onset pressure
tends to be parallel to or away from that of the saturation
pressure at high temperatures. This is in agreement with the
theories in the literature.23-26,28 However, some of the the-
ories predict that these two plots may eventually meet.18,56
The difference is possibly due to different reservoir oils. After
a careful literature search, we do not notice any direct experi-
mental evidence to support either of the predictions.
For the reservoir fluids X2 and X3, we study the effect of the
pressure on the amount of asphaltene precipitation.22,23 The
asphaltene content is determined using nC7 titration. The
comparison between measurements and calculations is dis-
played in Figures 5 and 6. The bubble point and upper and
lower onset pressures can be readily seen in the plots. As the
pressure drops, asphaltene precipitation first increases when
the pressure is between the upper onset and bubble point and
then decreases when the pressure is between the bubble point
and lower onset. The maximum precipitation appears at the
bubble point. This behavior can be interpreted from the
solubility parameter, which will be presented later. Our model
correctly captures the effect of the pressure on the asphaltene
(56) Lopez-Chavez, E.; Pacheco-Sanchez, J. H.; Martinez-Magadan,
J. M.; Castillo-Alvarado, F. D.; Soto-Figueroa, C.; Garcia-Cruz, I. Pet.
Sci. Technol. 2007, 25, 19.
Energy Fuels 2010, 24, 2956–2963 : DOI:10.1021/ef9014263
Figure 7. (a) Bubble point pressure at 332 K and (b) fraction of
precipitated asphaltenes at 332 K and 160 bar as function of the
CO2 mole fraction for the Weyburn oil. Symbols are experiments
from ref 51, and lines represent calculations.
precipitation amount particularly in the oil-asphaltene two-
phase region. However, for the reservoir fluid X3, our method
predicts that the asphaltene precipitation disappears too fast
when the pressure is lower than the bubble point; i.e., the lower
onset pressure is overestimated, which is similar to Figure 2.
This is possibly one limitation of our model. Besides, we also
present the comparison between calculations and experiments
for the relative volumes (the ratio between the total volume
and the bubble point volume) during depressurization. There
is a slope change at the bubble point because the vapor phase
vanishes when the pressure is higher than the bubble point.
Again, the agreement is excellent.
For the Weyburn oil, we investigate the asphaltene pre-
cipitation from mixing with CO2.51 Saturates, aromatics,
resins, and asphaltenes (SARA) analysis of STO was con-
ducted using a modified Syncrude method, but the precipitant
is not provided. The asphaltene content of the flashed CO2-
saturated oils is determined by a photometric technique. A
change of 0.1 wt % in asphaltene content in the oil can be
estimated with confidence. Weyburn oil contains a very small
amount of light components. CO2 injection can potentially
improve the oil recovery but may lead to a large amount of
asphaltene precipitation. In Figure 7a, the bubble point
pressure at 332 K is presented for different CO2/oil mixtures.
At a very high CO2 concentration, asphaltene precipitation
occurs at the bubble point. In Figure 7b, the fraction of
precipitated asphaltenes at 332 K and 160 bar is shown as a
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Li and Firoozabadi
Figure 8. Computed solvent solubility parameter and oil phase mass
density for the reservoir fluid X2 at 303 K with pressure between
upper and lower onsets.
function of the overall concentration of CO2 in the mixture. As
expected, as the CO2 overall concentration increases, asphal-
tene precipitation becomes more pronounced. However, at
very high CO2 concentrations, asphaltene precipitation can be
inhibited because of the appearance of the gas phase, which is
reflected by the slope decrease in Figure 7b. The calculations
are in good agreement with the measurements.
As mentioned before, the solubility parameter is normally
used to explain the asphaltene phase behavior. In Figure 8, we
present the solvent solubility parameter and the oil phase
density when the pressure decreases from the upper onset to
the lower onset for the reservoir fluid X2 at 303 K. Here, the
solvent includes all of the components in the oil phase, except
asphaltene. Without asphaltene, the CPA-EOS is reduced to
the PR-EOS and the solvent solubility parameter can be
calculated from5,38
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
  pffiffiffi ffi
1 da vs þ ð1 þ 2Þb
δs ¼ pffiffiffi a-T ln pffiffiffi ð6Þ
2 2bvs dT vs þ ð1 - 2Þb
where vs is the molar volume of the solvent. PR-EOS can
provide accurate predictions for the solubility parameters (we
have tested the solubility parameters of several pure sub-
stances, including nC5, nC6, nC8, benzene, and toluene, at
298 K). From Figure 8, as expected, the solvent solubility
parameter decreases when the pressure drops from the upper
onset to the bubble point because of the decrease of the oil
phase density and then increases when the pressure drops
further from the bubble point to the lower onset because of
evaporation of light components (which causes the increase of
the oil phase density). The minimum of both the solvent
solubility parameter and oil phase density is at the bubble
point where the asphaltene precipitation reaches the maximum.
As a representative, in Figure 9, we show the calculated
composition of both asphaltene and oil phases for the reser-
voir fluid X2 at 303 K and 98.1 bar (bubble point). While some
of the existing models assume that the precipitated phase is
pure asphaltenes and/or the oil phase is pure oil (with no
asphaltenes), our method describes the heterogeneity of both
asphaltene-rich and asphaltene-lean phases. Even though
the asphaltene precipitation reaches the maximum at the
bubble point, the precipitated phase still contains a non-
negligible amount of other species (about 12 wt %) and, at
the same time, there is also a small amount of asphaltenes
remaining in the oil phase (about 1.2 wt %). It can be expected
that, at other precipitation conditions, both the asphaltene
and oil phases should be even more heterogeneous.
Energy Fuels 2010, 24, 2956–2963 : DOI:10.1021/ef9014263
Figure 9. Computed weight fractions of different components in the
asphaltene and oil phases for the reservoir fluid X2 at 303 K and 98.1
bar (bubble point).
4. Conclusions
We apply the CPA-EOS to study the asphaltene pre-
cipitation in several live oils induced by a pressure decrease
and CO2 mixing. The live oils are characterized by
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Li and Firoozabadi
considering the pure components, the pseudo-hydrocarbon
components, and the hydrocarbon residue. The residue
is further divided into the “heavy” component and asphal-
tene. The physical interactions are described by the PR
equation. The polar-polar interactions between asphal-
tene molecules (self-association) and between asphaltene
and “heavy” molecules (cross-association) are described
by the thermodynamic perturbation theory. The physi-
cal parameters of EOS are directly available for the
pure components and pseudo-hydrocarbon components,
from our recent work for asphaltene, and from the fitting
of the bubble point pressures for the “heavy” component.
Some common association parameters are also from
our recent paper.37 Letting the cross-association energy
between asphaltene and “heavy” molecules be temp-
erature-dependent, we successfully reproduce the effect
of pressure and temperature on the bubble point, asphaltene
precipitation amount and onset pressures, and gas-oil-
asphaltene three-phase behavior within a unified theoretical
framework.
Acknowledgment. We are grateful to the financial support
from the industrial members of RERI.