1584 Energy & Fuels 2006, 20, 1584-1590

Study of Pressure and Temperature Effects on Asphaltene Stability

in Presence of CO2
Sylvain Verdier,† Hervé Carrier,*,‡ Simon I. Andersen,†,§ and Jean-Luc Daridon‡
Kemiteknik, Danmarks Tekniske UniVersitet, DK-2800 Kgs. Lyngby, Denmark, and Laboratoire des Fluides
Complexes, UMR 5150, UniVersité de Pau et des Pays de l’Adour, BP 1155, 64013 PAU Cedex, France

ReceiVed December 22, 2005. ReVised Manuscript ReceiVed March 22, 2006

In the prolific literature about asphaltenes, the effects of temperature and pressure on their stability are
subjects of discussion. A new high-pressure cell, requiring a very small amount of sample and with wide
working conditions, has been built in order to study the asphaltene phase behavior after injection of various
gases and precipitants. A filtration technique is used to conclude on the effects of temperature, pressure, and
composition. The precipitant used in this work is CO2. Two crude oils (from South America and the Middle
East) were studied up to 383 K and 60 MPa. It was found for both oils that asphaltenes were more soluble
when temperature was decreased and pressure was increased in the presence of a gas component. These effects
were discussed with simple principles of thermodynamics.

Introduction weight aromatics and insoluble in low-molecular-weight alkanes.

Problems related to asphaltenes flocculation during oil
recovery (reservoir plugging), production (deposits in production
wells, generally at the depths corresponding to the bubble point),
or transportation (transport of mixtures of fluids of different
origins and, thus, of different compositions) are still topical
questions.1 Many theories and models were developed to
describe and predict asphaltene precipitation, using the Flory-
Huggins theory,2-7 micellization models,8,9 scaling equations,10
or advanced equations of state such as SAFT,11-13 to name a
few. However, in many cases, it remains a fitting exercise and,
as Porte et al. reported it,14 their capacities to predict the
behavior of asphaltenic fluids are generally poor.
These difficulties are partly due to the fact that asphaltenes
are still defined as a solubility class:1 soluble in low-molecular-
* Corresponding author e-mail: herve.carrier@univ-pau.fr.
† Danmarks Tekniske Universitet.
‡ Université de Pau et des Pays de l’Adour.
§ Present address: Haldor Topsoe A/S Ny Møllevej 55, DK-6800, Kgs
Lyngby, Denmark.
(1) Speight, J. G. The Chemistry and Technology of Petroleum; Marcel
Dekker: New York, 1999.
(2) de Boer, R. B.; Leerloyer, K.; Eigner, M. R. P.; van Bergen, A. R.
D. SPE Prod. Facil. 1995, 55-61.
(3) Burke, N. E.; Hobbs, R. D.; Kashou, S. F. J. P. T. 1990, 1440-
1446.
(4) Hirschberg, A.; deJong, L. N. J.; Schipper, B. A.; Meijer, J. G. SPE
J. 1984, 283-293.
(5) Wang, J. X.; Buckley, J. S. Energy Fuels 2001, 15, 1004-1012.
(6) Lindeloff, N.; Heidemann, R. A.; Andersen, S. I.; Stenby, E. H. Pet.
Sci. Technol. 1998, 16, 307-321.
(7) Andersen, S. I.; Speight, J. G. J. Pet. Sci. Eng. 1999, 22, 53-66.
(8) Fahim, M. A.; Al-Sahhaf, T. A.; Elkilani, A. S. Ind. Eng. Chem.
Res. 2001, 40, 2748-2756.
(9) Victorov, A. I.; Firoozabad, i. A. AIChE J. 1996, 42, 1753.
(10) Rassamdana, H.; Dabir, B.; Nematy, M.; Farhani, M.; Sahimi, M.
AIChE J. 1996, 42, 10-22.
(11) Ting, P. D.; Hirasaki, G. J.; Chapman, W. G. Pet. Sci. Technol.
2003, 21, 647-661.
(12) Wu, J.; Prausnitz, J. M.; Firoozabadi, A. AIChE J. 1998, 44, 1188-
1199.
(13) Buenrostro-Gonzalez, E.; Lira-Galeana, C.; Gil-Villegas, A.; Wu,
J. AIChE J. 2004, 50, 2552-2570.
(14) Porte, G.; Zhou, H.; Lazzeri, V. Langmuir 2003, 19, 40-47.
Thus, the generic word “asphaltene” gathers entities forming a
continuum but belonging to fractions of distinct physical
properties, and fundamental interrogations persist on their exact
natures (size, molar mass, composition, and molecular arrange-
ment) and on the laws governing their behavior, such as
phenomena of aggregation and precipitation.
Pressure and Temperature Effects. In particular, the
influence of temperature on asphaltene stability is subject to
controversy. Andersen and Birdi15 reviewed its various effects:
increase in solubility with temperature,16 decrease,17,18 or an
increase followed by a decrease.19 In ref 15, the authors found
a minimum in solubility at 298 K, with the temperature varying
between 277 and 373 K using precipitants from n-C5 to n-C8.
Gonzalez et al.20 modeled the data published by Jamaluddin et
al.21 with PC-SAFT. They fitted their model to the few
experimental points and found a maximum in stability with
respect to temperature: below 394 K; asphaltenes are more
soluble when temperature is increased, and above this, the
opposite effect is seen. At low temperatures, the authors explain
that asphaltenes become unstable because of differences in the
interaction energies between asphaltene molecules and solvent
(crude oil) molecules. As temperatures increase over 427 K,
they assume that the asphaltene solution demixes as a result of
the large thermal expansivity of the solvent compared to that
of the asphaltene.
As for the effect of pressure, opinions tend to agree:22-24 if
one supports the lyophilic model14 and the widespread asphalt-
(15) Andersen, S. I.; Birdi, K. S. Fuel Sci. Technol. Int. 1990, 8, 593-
615.
(16) Ali, L. H.; Al-Ghannam, K. A. Fuel 1981, 60, 1043-1046.
(17) Mitchell, D. L.; Speight, J. G. Fuel 1973, 52, 149-152.
(18) Hotier, G.; Robin, M. ReV. Inst. Fr. Pet. 1983, 38, 101-120.
(19) Rogacheva, O. V.; Gubaidullin, V. Z.; Gimaev, R. N.; Danlilyan,
T. D. Colloid J. USSR 1984, 46, 715-717.
(20) Gonzalez, D. L.; Ting, P. D.; Hirasaki, G. J.; Chapman W. G. Energy
Fuels 2005, 19, 1230-1234.
(21) Jamaluddin, A. K. M.; Joshi, N.; Iwere, F.; Gurpinar, O. Proc. SPE
Int. Pet. Conf. Exhib. Mex. 2002, 427-436.
(22) Lhioreau, C.; Briant, J.; Tindy, R. ReV. Inst. Fr. Pet. Ann. 1967,
22, 797-806.
(23) Fotland, P. Fuel Sci. Technol. Int. 1996, 14, 3131-326.

10.1021/ef050430g CCC: $33.50 © 2006 American Chemical Society

Published on Web 05/02/2006
Pressure and Temperature Effects on Asphaltene Stability
Figure 1. Onset of precipitation of three crude oils in the presence of
CO2 as a function of temperature (9, oil 1; 2, oil 2; and b, oil 3) (data
from Idem and Ibrahim25).
ene phase envelope, the one-phase zone is located at a higher
pressure than the two-phase region (asphaltene phase + crude
oil).
The temperature and pressure effects of CO2 on asphaltene
stability have not been extensively studied in the literature. Idem
and Ibrahim25 state that, in the presence of CO2, asphaltene
stability in crude oils improves with temperature for two of the
three different samples they studied. However, they compare
volumes at different temperatures (from 300.4 to 337.7 K) and
they observe different trends. The density of CO2 varies between
882.9 and 633.1 kg/m3 at 17.2 MPa within this temperature
range.26 Thus, on a mass-based scale, it is seen that asphaltenes
are less stable with temperature, since less CO2 is required to
initiate precipitation (Figure 1). Kokal et al.27 studied the
influence of various gases on two oils and found opposite results
for the CO2 injection: the Suffield oil was more stable with a
temperature increase, whereas the Lindbergh oil was not. They
explain these effects by the competition between temperature
(affecting the solubility parameter of asphaltenes) and composi-
tion (influencing the solubility of the solvent).
To quantify the impact of temperature and pressure on the
asphaltene stability in the presence of a gas component as
precipitant, an experimental setup based on isobaric filtration
was developed in this work. The apparatus was then used to
assess the stability conditions of two different stock tank oils
in the presence of CO2.
Asphaltene Precipitation as a Phase Transition. The nature
of asphaltene precipitation is a major concern. Is it a liquid/
liquid equilibrium, a solid/liquid equilibrium, a sol-gel transi-
tion, a glass transition? It is a first- or second-order transition?
Fenistein and co-workers28 explain that asphaltene flocculation
is a transition between a solvated aggregation and a compaction
process (compact structures were seen by radiation scattering
techniques with high n-heptane contents). Asphaltene deposits
are solid. Hence, is asphaltene precipitation a solid-liquid
equilibrium? Precipitation is defined by the International Union
of Pure and Applied Chemistry (IUPAC) as “the formation of
a solid phase within a liquid phase”.29 It is indeed modeled such
as one.6 Nonetheless, as Sirota states it,30 this phase separation
can be seen thermodynamically as a liquid-liquid phase sep-
aration, which can be understood in the context of the solution
(24) Hammami, A.; Phelps, C. H.; Monger-McClure, T.; Little, T. M.
Energy Fuels 2000, 14, 14-18.
(25) Idem, R. O.; Ibrahim, H. H. J. Pet. Sci. Eng. 2002, 35, 233-246.
(26) NIST website: http://webbook.nist.gov/chemistry/.
(27) Kokal, S. L.; Najman, J.; Sayegh, S. G.; George, A. E. J. Can. Pet.
Technol. 1992, 31, 24-30.
(28) Fenistein, D.; Barre, L.; Frot, D. Oil Gas Sci. Technol. 2000, 55,
123-128.
(29) Clarke, J. B.; Hastie, J. W.; Kihlborg, L. H. E.; Metselaar, R.;
Thackeray, M. M. Pure Appl. Chem. 1994, 66, 577-594.
(30) Sirota, E. B. Energy Fuels 2005, 19, 1290-1296.
Energy & Fuels, Vol. 20, No. 4, 2006 1585
theory of molecules. The solidlike character of the asphaltene-
rich phase formed during precipitation is only due to the fact
that asphaltenes are below their glass-transition temperature.
Glass temperatures were indeed measured by differential scan-
ning calorimeter and reported between 393 and 403 K.31 This
issue is nonetheless controversial and actively debated.
As for the question about first-order and second-order tran-
sitions, the classification about phase transitions is not unique.
From a thermodynamic point of view, a first-order transition
corresponds to a change in volume and entropy (thus, a latent
heat) and a second-order transition corresponds to a change in
heat capacity Cp, thermal expansivity RP, and isothermal
compressibility κT. The heat of precipitation of asphaltenes, if
any, is rather small, since several teams tried to measure it but
with no success so far. Thus, a break in Cp, RP, and κT should
be expected, as was the case, for instance, for the precipitation
of poly(N-vinylcaprolactam) in water (with molar weights
ranging from 21 000 to 1.5 × 106 g‚mol-1).32 Such measure-
ments are currently tried with recombined live oils and will be
presented in the future if confirmed.
Le Châtelier’s Principle. Effects of both pressure and
temperature can be explained by Le Châtelier’s principle. Henri
Le Châtelier stated 33 that ”eVery change of one of the factors
of an equilibrium occasions a rearrangement of the system in
such a direction that the factor in question experiences a change
in a sense opposite to the original change.”
The equilibrium we are interested in is the following one:
asphaltene (solution) a asphaltene (precipitated) (R1)
Andersen and Speight7 listed two other reactions:
The aggregation:
asphaltenesi + asphaltenesl a asphaltenesi+l (R2)
The interaction with the resins:
asphaltenes + resins a asphaltenes - resins (R3)
Aggregation only takes place at low concentration (<100
ppm34-36). Hence, equilibrium (eq R2) can be neglected, since
the onset conditions are investigated here. As for the interactions
with resins, they can be seen as part of the asphaltene continuum.
If pressure is increased, the position of equilibrium will
move so that the pressure is reduced again, i.e., the number of
molecules decreases or the volume is reduced. Experiment-
ally, it is seen that the solubility of asphaltenes in oil increases
with increasing pressure. Thus, it means that the system de-
creases its volume when pressure is increased, i.e., the volume
of the two-phase region is larger than that of the one-phase
region. To the authors’ knowledge, there is no experimental
evidence of a gain in volume during precipitation. However,
by means of various equations of state (EOS; CPA37 and
SAFT38), an increase of 10 cm3 per mole at 400 K was
(31) Zhang, Y.; Takanohashi, T.; Sato, S.; Saito, I. Energy Fuels 2004,
18, 283-284.
(32) Laukkanen, A.; Valtola, L.; Winnik, F. M.; Tenhu, H. Macromol-
ecules 2004, 37, 2268-2274.
(33) Le Chatelier, H. L. Ann. Mines 1888, 13, 157.
(34) Andreatta, G.; Bostrom, N.; Mullins, O. C. Langmuir 2005, 21,
2728-2736.
(35) Merino-Garcia, D. Calorimetric investigation of asphaltene self-
association and interaction with resins. Ph.D. Thesis, Technical University
of Denmark, Department of Chemical Engineering, Lyngby, Denmark, 2004.
(36) Castillo, J.; Hung, J.; Fernandez, A.; Mujica, V. Fuel 2001, 80,
1239-1243.
(37) Knudsen, L. B. Modelling of asphaltene precipitation. Master’s
Thesis: Technical University of Denmark, Department of Chemical
Engineering, Lyngby, Denmark, 2001.
1586 Energy & Fuels, Vol. 20, No. 4, 2006
calculated between the onset and the bubble point as follows,
RTZ1
V1phases ) (1)
P
RT
V2phases ) (x Z + xasphalteneZasphaltene) (2)
P oil oil
where V is the molar volume, T is the temperature, P is the
pressure, x is the mole fraction, and Z is the compressibility
factor.
The difference V2phases - V1phases gives the volumetric varia-
tions due to asphaltene precipitation, and the increase due to
asphaltene is ∼50% of the total change.
If temperature is increased, Le Châtelier’s principle states that
the position of equilibrium (R1) will move so that the temper-
ature is reduced again. If the reaction is exothermic, the
equilibrium will go to the left side when temperature is
increased, i.e., asphaltenes will be more soluble. If not, the
asphaltenes will be less soluble. As was said previously, both
stabilizing and destabilizing effects are found in the literature.
Could it be that some asphaltene precipitations are exothermic
and some others are endothermic? Is it due to the solvent
properties or to the asphaltenes themselves? If the results about
a maximum in stability with respect to temperature is correct,
it would mean that asphaltene precipitation is first endothermic
below 298 K and then exothermic above. The authors are not
aware of any calorimetric evidence of heat of precipitation of
asphaltenes, except for one attempt made on a live oil.39 In that
study, a slight exothermic signal was observed during pressure
depletion, though the signals are not that clear. One could
intuitively believe that asphaltene precipitation should be
exothermic since more bonds are created than broken, but
binding can be endothermic as well. For instance, examples of
aggregation of polymers and surfactants 40 or polypeptides and
proteins41 are well-described in the literature, not to mention
the sol-gel transitions. Experimental proofs are still needed to
be able to conclude anything about asphaltenes, though.
Le Châtelier’s principle can also be explained by equations
as shown in Appendix 1 (influence of pressure and temperature
on the equilibrium constant). The effect of temperature on the
equilibrium is related to the heat of reaction, and the effect of
pressure is related to the molar volume of asphaltene in the
different phases. Note that Le Châtelier’s principle could not
be used to discuss the experimental results of this work since
there was no evidence of volumetric or calorimetric changes.
Reversibility. When pressure is smaller than the lower-
pressure onset or higher than the upper-pressure onset, asphalt-
enes are likely to go back to solution. As Hammami et al.
suggested,24 asphaltene precipitation is generally reversible, but
the kinetics of redissolution vary significantly depending on the
physical state of the system. Some authors claim that the
asphaltene composition has a key role in the reversibility issue,42
but it is not clearly explained or proved. It was also said that
asphaltene precipitation is less likely to be reversible for crude
(38) Christensen, A. A.; Hadsbjerg, C.; Vestager-Tybjerg, P. C. A study
of the perturbed chain statistical associating fluid theory. Midterm Project,
Technical University of Denmark, Department of Chemical Engineering,
Lyngby, Denmark, 2005.
(39) Stachowiak, C.; Grolier, J.-P. E.; Randzio, S. L. Energy Fuels 2001,
15, 1033-1037.
(40) Dai, S.; Tam, K. C. J. Phys. Chem. B 2001, 105, 10759-10763.
(41) Dzwolak, W.; Ravindra, R.; Lendermann, J.; Winter, R. Biochemistry
2003, 42, 11347-11355.
(42) Leontaritis, K. J.; Amaefule, J. O.; Charles, R. E. SPE Prod. Facil.
1994, 9, 157-164.
Verdier et al.
Figure 2. Scheme of the asphaltene cell (1, thermostat; 2, high-pressure
cell; 3, pressure gauge; 4, thermometer; 5, pressure gauge; 6, injection
pump; 7, thermostat; 8, balance; 9, crude oil sample; 10, vacuum pump;
11, filter; 12, magnetic stirrer; and 13, thermometer).
oils subjected to conditions well beyond those of the precipita-
tion onset.23 The hysteresis between asphaltene precipitation and
redissolution has also been studied in the literature.24,43,44 This
hysteresis may be due to the precipitation factor itself (composi-
tion, temperature, or pressure). Indeed, the hysteresis observed
with the temperature-induced precipitation43 seems more im-
portant than when the effects of pressure are studied.24 However,
since different oils were investigated, it seems risky to conclude.
Note that hysteresis is likely to be linked to deposition. Actually,
if asphaltenes are deposited, their redissolution will take much
longer. It is interesting to note that complete reversibility can
be obtained after sonication.45
Experimental Section
A simplified scheme of the experimental setup used to study
asphaltene stability with addition of gas is shown in Figure 2.
The experimental device consists of three main parts: a PVT
cell (used to mix the crude oil and the precipitant), a filtration
part (enabling filtration under pressure), and an injection cell.
The filtration cell is a piston cell able to function under a
pressure of 70 MPa from 253 to 473 K and allowing the
homogenization of the fluids by means of a magnetic stirrer.
The injection cell is also a piston cell with an operating pressure
of 70 MPa, a maximum temperature of use of 423.15 K, and a
total volume of 50 cm3.
PVT Cell. The PVT cell is a 2.6-13 cm3 mobile piston cell,
designed to work under a maximum pressure of 70 MPa and
up to 473 K. This cell was machined so that one can mix and
homogenize the fluids by means of a magnetic stirrer (the
presence of the agitator imposes an incompressible volume of
2.6 cm3). Figure 3 shows a scheme of this cell. Note that the
incompressible volume is not a dead volume, since the whole
interior of the cell is stirred. Two sapphire windows, associated
to a camera, enable a perfect cleaning of the cell. The cleaning
procedure is as follows:
• The cell is filled with toluene, and stirring is switched on.
• The cell is emptied, and if the toluene is not colorless, the
operation is repeated.
(43) Andersen, S. I. Fuel Sci. Technol. Int. 1992, 10, 1743-1749.
(44) Peramanu, S.; Singh, C.; Agrawala, M.; Yarranton, H. W. Energy
Fuels 2001, 15, 910-917.
(45) Mohamed, R. S.; Loh, W.; Ramos, A. C. S.; Delgado, C. C.;
Almeida, V. R. Pet. Sci. Technol. 1999, 17, 877-896.
Pressure and Temperature Effects on Asphaltene Stability
Figure 3. Sketch of the PVT cell (1, magnetic stirrer; 2, moving piston;
3, pressure gauge; 4, sapphire window; and 5, magnet).
Figure 4. Sketch of the filter holder.
• Once it is done, the inside of the cell is checked with the
camera through the sapphire windows to see whether asphaltene
particles are sticking on the inner walls. If that is the case, tolu-
ene is injected until all the deposited asphaltenes are dissolved.
The temperature of the system, controlled using a Huber
Unistat DC cryothermostat, is determined by a probe (Pt 100,
with an accuracy of 0.1 K). Three valves are connected to this
cell and are used to introduce the crude oil and the precipitant
and to filter the mixture, respectively. A Kulite pressure gauge
(HEM 375), operational between 1 and 100 MPa and compen-
sated in the temperature range 298.15-505.15 K, measures the
pressure within 0.1 MPa. Moreover, this transducer is a flush
pressure gauge, which considerably reduces dead volumes.
High-Pressure Filter. The inlet part of the filtering system,
which consists of a 0.5 µm porosity filter (Swagelok) fixed in
a filter holder that can stand up to 100 MPa, is connected to
the PVT cell, whereas the outlet part is connected to a manual
high-pressure pump (Figure 4). Therefore, before filtration starts
and to avoid asphaltene precipitation caused by pressure
depletion, it is filled with nitrogen up to the pressure of the
mixture. This last pump enables isobaric transfers of the fluids
through the filter during the filtration. Pictures of the filter before
and after precipitation are presented in Figure 5.
Injection Cell. The last part of the setup is an injection cell.
Its operating pressure is 70 MPa, the maximum temperature is
423.15 K, and the total volume is 50 cm3. The volume injected
per round was determined after calibration versus temperature
and pressure with n-heptane.26 It was found to be equal to 0.7608
cm3. This cell is equipped with a sliding gauge, which gives
Figure 5. Filter before precipitation (on the left) and after (on the right).
Energy & Fuels, Vol. 20, No. 4, 2006 1587
Table 1. SARA Analysis (Weight %) and Degree API of the Two
Studied Crude Oils
South American crude oil Middle East crude oil
saturates 35% 34%
aromatics 24% 41%
resins 32% 16%
asphaltenes 9% 9%
degree API 27 29
access to its volume with a precision of 0.01 round (7.6 mm3).
The temperature of the injection cell is kept constant within
0.1 K using a cryothermostat Huber Unistat DC. A similar
temperature probe is used (PT 100, precision of 0.1 K). An
operational pressure gauge Kulite (HEM 375), operating
between 0 and 100 MPa, is used for pressure determination
(uncertainty below 0.1 MPa).
Experimental Procedure. Prior to any study, high vacuum
is made in the filtration cell and in all the connecting lines.
Prior to any study, high vacuum is made in the filtration cell
and in all the connecting lines. The sample is stirred for half an
hour before injection in the PVT cell. The weighted asphaltenic
oil is introduced at atmospheric pressure in the cell, regulated
at the desired temperature. The oil is then pressurized by dis-
placement of the piston. The precipitant, maintained at the tem-
perature and pressure of the study, is then injected in the filtra-
tion cell where the mixture is continuously stirred, at constant
pressure. Once the system is stable (no need to modify the
volume to keep the pressure constant), the mixture is filtered
at the studied pressure and temperature. Hence, the filter is
closely analyzed to see whether traces of asphaltenes can be
detected on the filter. It is important to notice that the filtration
is operated by displacement of the mixture through the filter at
constant pressure (∆P < 1 bar). A new filter is used for each
experimental run to preserve a constant pore size of the filtration
medium.
The CO2 was provided by Messer, and its purity is 99.998%
(in volume). This study has been conduced with two asphaltenic
crude oils: one from South America and the other one from
the Middle East. Some properties of the two investigated crude
oils are presented in Table 1 (SARA analysis and degree API).
The aromatic and resin contents differ, whereas the other
properties are very similar.
Results and Discussion
The first study was made on the South American crude oil
with a single composition (19 wt % CO2, 81 wt % crude oil).
The onset curve and the bubble-point curve from 293.15 up to
383.15 K are given in Figure 6. The bubble point was
determined by means of the PV curve of the mixture. Figure 7
shows one of them at 353.15 K. To determine it more accu-
rately, isothermal compressibility κT ()-1/V (∂V/∂P)T ≈
- 1/V(∆V/∆P)T) was plotted with respect to pressure (Figure
8). There was no volumetric evidence of the asphaltene
1588 Energy & Fuels, Vol. 20, No. 4, 2006
Figure 6. Asphaltene phase envelope of the South American crude
(2, onset curve; and 9, bubble point).
Figure 7. PV curve of the South American crude oil at 353.15 K.
Figure 8. Isothermal compressibility at 353.15 K of the South
American crude oil.
precipitation.Indeed, the equipment should be much more
accurate in terms of volume to be able to detect any sign of
precipitation.
As for the precipitation envelope, small pressure steps
combined with filtrations were carried. Very little sample is
required for each experiment (5 g of crude usually), and this is
one of the major advantages of this high-pressure system.
However, with the first crude oil, only two points were obtained
because there was no more available oil. Furthermore, the effect
of temperature is not visible on this plot. Nonetheless, stability
was studied at 20 MPa and up to 383 K for the same crude oil.
Figure 9 clearly shows that less CO2 is required to precipitate
asphaltenes when temperature is increased, i.e., the higher the
temperature, the less soluble are the asphaltenes.
The second crude (from the Middle East) was also investi-
gated, and its phase envelope was determined for a fixed CO2
content (18% in weight), as seen in Figure 10. The same
conclusions were found:
• The higher the pressure, the more soluble are the asphalt-
enes.
• The higher the temperature, the lower is the solubility.
Hence, the two investigated oils seem to behave in the same
way with respect to pressure and temperature.
For the South American crude oil, the redissolution was
observed for all the investigated conditions and the kinetics was
quite fast (a few hours at high pressure were sufficient after
Verdier et al.
Figure 9. Influence of temperature on the onset (South American crude
oil at 20 MPa).
Figure 10. Asphaltene phase envelope of the Middle East crude oil
(18% CO2) (9, no precipitated asphaltenes; b, precipitated asphaltenes;
and 2, bubble point).
the depletion). As for the crude oil from the Middle East, it
was not seen, even after a 72 h continuous mixing. The resin
content could be an explanation (32% for the South American
crude oil and 16% for the Middle East one). Indeed, resins are
assumed to peptize asphaltenes and keep them in solution.14
CO2 as a PrecipitantsUse of the Solubility Parameter.
Asphaltenes can be either described as lyophobic colloids
peptized by resins (solvent-hating) or as lyophilic colloids
solvated by the liquid medium (solvent-loving). Precipitation
is due, in the first case, to a depeptization and, in the second
one, to a variation of solubility. Since the second approach is
believed to be the correct one,14 solubility parameters δ can be
used to explain why CO2 is a precipitant.
The regular solution theory states that two compounds with
close δ are soluble, a concept well-known as “like dissolves
like”. The Flory-Huggins equation can be used, as Hirschberg
and co-workers suggested.4 After several simplifications, the
maximum volume fraction of soluble asphaltenes in the crude
φmax
a is expressed as follows,
[( )]
Va Vl Vl
φmax ) exp 1 - - (δa - δl)2 (3)
a
Vl Va RT
where V is the molar volume, δ is the solubility parameter, R is
the gas constant, and T is the temperature. The subscripts a and
l, respectively, refer to the asphaltenes and the liquid medium.
The solubility parameter is defined by eq 4,
-Ur(T,P)
δ2 )
V(T,P)
) ∫V∞(∂U
∂V )
dV (4)
where U is the internal energy, Ur is the residual energy, and V
is the molar volume.
With the Peng-Robinson equation of state (PR EOS), it
becomes46
(46) Verdier, S.; Duong, D.; Andersen, S. I. Energy Fuels 2005, 19,
1225-1229.
Pressure and Temperature Effects on Asphaltene Stability Energy & Fuels, Vol. 20, No. 4, 2006 1589

δ2 )
x2
4b(a-T
da
dT
ln
)[ (
V(T,P) + b(x2 + 1)
V(T,P) - b(x2 - 1) )] 1
V(T,P)
(5)

where a is the attractive term of the PR EOS and b is the

covolume.
As Porte et al.14 stated it, precipitation is due to dispersion
forces. Hence, a cubic equation of state such as PRswhich
properly evaluates dispersion forcessis sufficient. Experimental
densities26 are used in order to counteract the poor volumetric
description of the cubic EOS. As seen in Figure 11, the
variations of δCO2 with pressure and temperature are quite
impressive. Note that pure CO2 is in a supercritical state at the
studied temperatures and pressures. Figure 11. Solubility parameter of CO2 as a function of pressure at
The solubility parameter of the solvent (crude oil + gas) different temperatures (calculated every 10 K, starting at 293.15 K for
follows a mixing rule in terms of volume: the top curve).

δoil ) φdeadoilδdeadoil + φgasδgas
The solubility parameter of a dead oil47 is usually ∼18 MPa1/2.
Therefore, when a solvent such as carbon dioxide is injected,
the solubility parameter of the liquid medium is decreasing,
which induces a decrease of solubility and, hence, asphaltene
precipitation.
To evaluate the effect of temperature on solubility, one can
take the logarithm of φmax given in eq 3 and its derivative with
a
respect to temperature:
(6) the solubility parameter of both asphaltenes and oil as function
of temperature, it would be possible to predict the influence of
temperature on asphaltene solubility. However, any measure-
ment of solubility parameter is indirect. Hence, δ of pure
compounds are commonly reported within 0.3 MPa1/2, which
is too high to perform proper predictions.49 Besides, one should
keep in mind that this theory has been developed for nonasso-
ciated compounds. That is the reason such relationships should
be used with care and perspective.
Conclusion

(∂ ln φmax
∂T
a
) Va
) (RP,a - RP,l) +
Vl
Both temperature and pressure effects were studied on two
recombined crude oils, and the same trends were observed:

[ ]
P
Va 1 ∂(δa - δl)/∂T
(δa - δl)2 - RP,a - 2 (7)
RT T δa - δl
where Rp is the isobaric thermal expansivity.
Simple calculations can easily be made with average proper-
ties for the liquid medium, and the key parameters turn out to
be the temperature dependence of the solubility parameters of
the oil and the asphaltenes. Barton48 suggested the following
linear relationship:
δ(T) ) δ0 - m(T - T0)
The coefficient m is listed for pure compounds (p 304 in ref
49) and varies between 2.00 × 10-2 and 3.00 × 10-2
MPa1/2‚K-1 for the studied hydrocarbons (2.70 × 10-2 for
n-pentane, 1.83 × 10-2for n-nonane, and 1.98 × 10-2 for
n-decane, for instance). As for asphaltene, its temperature-
dependent coefficient has been fitted to titration experiments
by Hirschberg et al.4 and was found to be equal to 2.1 × 10-2
MPa1/2‚K-1. It was also calculated by means of a computer-
assisted structure-elucidation software,49 and it was much smaller
this time (4 × 10-3 MPa1/2‚K-1). The first term of eq 2 is within
10-3, whereas the second one is 10-1. Hence, it is assumed to
be negligible. In this case, the solutions satisfying (∂ ln
a /∂T)P ) 0 are either δa ) δl or (ma - ml) ) /2(1/T -
φmax 1
asphaltenes are more soluble when temperature is decreased and
when pressure is increased. This work was possible thanks to a
new high-pressure cell using a filtration technique. Its main
advantages are the following ones: a small sample is required
(5 g), the injection of the precipitant is done at the conditions
under investigation, the sample is mixed continuously, and the
dead volume is almost nonexistent.
The opposite effects seen in the literature can be explained
by means of Le Châtelier’s principle and solubility parameters.
Nonetheless, this last approach is based on the assumption that
no specific interactions occur between the components, which
(8) is in direct opposition to the tendency of asphaltenes to
aggregate.7 Thus, this simple model and its related “fitting”
parameters should be used with care and perspective. As for
Le Châtelier’s principle, experimental evidence about heat of
precipitation and change in volume are still necessary and
equilibrium (eq R2)sthe asphaltene/resin interactionsmight not
be negligible as it was assumed in this work.
The next steps are the injection of other gases and a
calorimetric study of asphaltene precipitation.
Acknowledgment. S.V. thanks the staff of the Laboratoire des
Fluides Complexes for the various and fruitful stays in Pau.
Appendix 1

RP,a)(δa - δl). Therefore, according to this model, temperature Let us consider a component A in equilibrium between two
increases the maximum solubility if phases.

11 δa - δl AR a Aβ
(ma - ml) > (
2T )
- RP,a (δa - δl) ≈
2T
(9)

(48) Barton, A. F. M. CRC Handbook of solubility parameters and other

If it was possible to measure properly and accurately enough cohesion parameters; CRC Press: Boca Raton, FL 1991.
(49) Diallo, M. S.; Strachan, A.; Faulon, J. L.; Goddard, W. A., III. Pet.
(47) Rogel, E. Energy Fuels 1997, 11, 920-925. Sci. Technol. 2004, 22, 877-899.
1590 Energy & Fuels, Vol. 20, No. 4, 2006 Verdier et al.

At the equilibrium, the chemical potentials are equal: Table 2. Effect of Increasing Temperature and Pressure
increase in T increase in P
µAR(T,P,nR) ) µBR(T,P,nβ)
∆h0A <0 r
∆h0A >0 f
µR,0
A (T,P) + RT ln [aA(T,P,n )] ) R
∆V0A <0 f
∆V0A >0
A (T,P) + RT ln [aA(T,P,n )]
µβ,0 β r

[ ]
Table 3. Effect of Increasing Temperature and Pressure in Terms
aA(T,P,nβ) of Asphaltene’s Solubility
(µβ,0
A (T,P) - µR,0
A (T,P)) + RT ln )0 increase in T increase in P
aA(T,P,nR)
hprecipitation < 0 increase solubility
hprecipitation > 0 decrease solubility
(gβ,0
A (T,P) - gR,0
A (T,P)) + RT ln KA ) 0 VAdeposit < VAsolution decrease solubility
VAdeposit > VAsolution increase solubility
R,0 R,0
A (T,P) - hA (T,P)] - T[sA (T,P) - sA (T,P)] +
[hβ,0 β,0
Pressure Effect.
RT ln KA ) 0

| [ ]
R,0 R,0
∂ ln KA 1 A - hA )
∂(hβ,0 A - sA )
∂(sβ,0
-[hβ,0 - hR,0 + T[sβ,0 - sR,0 ) - +T
A (T,P) A (T,P)] A (T,P) A (T,P)] ∂P T RT ∂P ∂P
ln KA )
RT
Furthermore, we have

|
Let us investigate the pressure and temperature effects on the
∂h
equilibrium constant. ) V(1 - RPT)
Temperature Effect. ∂P T

∂ ln KA
| )
∆h0A
-
1 ∂∆hA 1 ∂∆sA
+
0 0 ∂s
∂P T|) -RPV
∂T P RT 2 RT ∂T R ∂T
where Rp is the isobaric expansivity and V is the molar volume

| ( ) ( )
So, it becomes
∂ ln KA ∆h0A 1 ∂h0,β
A ∂h0,R
A 1 ∂s0,β
A ∂s0,R
A
) - - + -
∂T P RT 2 RT ∂T ∂T R ∂T ∂T ∂ ln KA
|
1
) [-Vβ,0 R,0 R,0
A (1 - Rp ) + VA (1 - Rp ) +
β,0

( )
∂P T RT
∂ ln KA
∂T
|P
)
∆h0A
RT 2
-
1 0,β
(c - c0,R
RT p p )+
1
R T
-
T
c0,β
p c0,R
p
)
∆h0A
RT 2
T(-Rβ,0 β,0 R,0 R,0
p VA + Rp VA )]

∂ ln KA
|
1 R,0
) [V - VA ] )
β,0
- ∆V0A
∂ ln KA
∂T | P
)
∆h0A
RT2
∂P T RT A RT
If ∆V0A is negative (smaller molar volume in phase β than in
This relationship is known as the Van’t Hoff equation. If the phase R), an increase in pressure will shift the equilibrium to
the right side (see Table 2).In terms of asphaltene’s solubility,
reaction is endothermic, ∆h0A is negative, so the equilibrium
the results are shown in Table 3.
shifts to its left side. If the reaction is exothermic, the equilibrium
shifts to its right side. EF050430G