Asphaltene Precipitation and Alteration
of Wetting: The Potential for Wettability
Changes During Oil Production
Rashid S.H. Al-Maamari, SPE, Sultan Qaboos U., and Jill S. Buckley, SPE, New Mexico Petroleum Recovery
Research Center, New Mexico Tech
Summary
Wettability controls the distribution and flow of immiscible fluids
in an oil reservoir and thus plays a key role in any oil-recovery
process. Once thought to be a fixed property of each individual
reservoir, it is now recognized that wettability can vary on both
microscopic and macroscopic scales. Polar oil components can
adsorb onto the pore-bounding mineral surfaces by several differ-
ent mechanisms. In this study, we explore a transition in the
mechanism of wettability alteration that relates to the asphaltene
fraction and its stability in the oil phase.
Asphaltene stability was varied by adding n-heptane to samples
of five crude oils. Conditions tested ranged from those in which
asphaltenes were stable to mixtures in which aggregates formed
and separated from the oil. The onset condition—in which the first
asphaltene particles become visible—provides a reference point
with respect to asphaltene stability in each crude-oil sample.
Muscovite mica sheets, treated with brine and with the crude
oil/heptane mixtures, were examined using contact angles between
decane and water as a measure of altered wettability on the oil-
treated surfaces. A significant increase in oil-wet conditions very
near the onset of asphaltene precipitation was observed with four
of the five oils, indicating the potential for wetting changes during
the course of oil production if conditions of asphaltene instability
are approached. Implications of changes in the mechanism of wet-
ting alteration during the course of production from an oil reservoir
are considered.
Introduction
Asphaltenes and Reservoir Wettability. The potential for as-
phaltenes to adsorb onto high-energy mineral surfaces and thus to
affect reservoir wettability has long been recognized. A good sum-
mary of early work is provided by Anderson.1 More recently, there
have been a number of studies of asphaltene adsorption and re-
sulting changes in wetting on smooth surfaces.2–5 What has been
missing in previous studies is a simple measure of the stability or
incipient instability of the asphaltenes, which is needed to distin-
guish between competing interaction mechanisms among these
large, aromatic, somewhat polar molecules and mineral surfaces in
the presence of brine.
COBR Interaction Mechanisms. The polar components in crude
oils can adsorb, in the presence of an aqueous phase, by distinctly
different mechanisms, depending on factors that include brine
composition and the ability of the oil to keep its asphaltenes dis-
persed.6 Additional interactions that may occur between oil com-
ponents and dry surfaces are not relevant in the context of an oil
reservoir in which both aqueous and oleic phases are present.7
Crude oil/brine/rock (COBR) interactions can include the following:
• Ionic interactions that involve ionization of acids and bases at
the oil/water and solid/water interfaces (acid/base, ion-binding,
and other specific interactions are included in this category).
Copyright © 2003 Society of Petroleum Engineers
This paper (SPE 84938) was revised for publication from paper SPE 59292, first presented
at the 2000 SPE/DOE Improved Oil Recovery Symposium, Tulsa, 3–5 April. Original manu-
script received for review 11 July 2000. Revised manuscript received 27 January 2003.
Paper peer approved 14 April 2003.
210
• Surface precipitation interactions that depend mainly on
crude-oil-solvent properties with respect to their asphaltenes.
While these interaction mechanisms have been demonstrated
for specific cases under conditions that clearly should be domi-
nated by one class of mechanisms or the other, little is yet known
about the intermediate conditions and the transition from one set of
mechanisms to another.
We use the refractive index (RI), a readily measured property,
to quantify solvent properties of oil/heptane mixtures as they relate
to asphaltene stability.8–10 RI at the onset of precipitation is de-
noted as PRI. Above that value of RI, asphaltenes remain dis-
persed; below it, they flocculate. The value of PRI depends on both
oil and added precipitating agent (n-heptane in this study). When
the asphaltenes are stable (i.e., RImix>>PRI), we expect that ionic
interactions will dominate. As the onset of precipitation is ap-
proached, a transition to surface precipitation as the primary in-
teraction mechanism should take place.
Alteration of Reservoir Wettability. The effect of recovery pro-
cesses on reservoir wettability has been a recurring theme in the
improved oil recovery literature.11–13 Many interesting questions
have been raised, but few definitive answers have been provided
because it is difficult to isolate the influence of wetting on mea-
surable parameters (e.g., fluid-flow rates, pressure drops) from
other variables. Even in laboratory corefloods, the effects of wet-
ting alteration are complicated and difficult to isolate. Yan et al.14
used asphaltenes dissolved in toluene to effect changes in the
wetting of Berea sandstone cores and the measured rate of water
imbibition to assess the extent of wetting change. In many other
studies, however, wetting states are deduced from endpoint rela-
tive permeabilities,11,13,15 sometimes after the addition of a large
excess of precipitant.16 It is difficult to say conclusively how many
of the changes reported were caused by a reduction of total per-
meability, by cycle-dependent hysteresis in the relative permeabil-
ity curves,17 or by the actual changes in surface properties of the
pore-lining materials.
The trends of wettability alteration demonstrated in this study
have implications for reservoir wettability and changes that might
occur during production.
Experimental Techniques
Materials. Freshly cleaved Muscovite mica was used as the solid
surface. Surfaces were cleaned with a mixture of nine parts 30%
H2O2 and one part of 20% NH4OH in an ultrasonic bath for 30
minutes and then left in the cleaning solution overnight. Finally,
the mica samples were rinsed extensively with double-distilled,
de-ionized water.
Table 1 summarizes the brines used. All solutions were pre-
pared from double-distilled, de-ionized water, with sodium chlo-
ride added to adjust the salinity.
HPLC grade hydrocarbons (heptane, n-decane, and cyclohex-
ane) were purified by passing through dual-packed columns of
activated silica gel and alumina.
Five crude oils were tested (Table 2). Two of these oils (La-
grave and Tensleep) had some aggregates in the laboratory oil
samples. To ensure that the asphaltenes were well dispersed,
␣-methylnaphthalene (␣-MN) was added to these two samples to
make up the initial test “oil.”
August 2003 SPE Reservoir Evaluation & Engineering
Onset of Asphaltene Precipitation. Oil and heptane mixtures
were observed microscopically at a magnification of 45X to de-
termine the onset of asphaltene flocculation. The first appearance
of asphaltic particles with a minimal amount of added precipitant
was selected as the onset.
Refractive Index. RI was measured using an Index Instruments
GPR 11-37 refractometer.
Wettability Tests. Clean pieces of mica were first exposed to a
selected aqueous phase for 1 day, then drained (not dried) and
submerged in crude oil, to which heptane was then added. This
technique has been described in detail previously.18 Some samples
were centrifuged under oil to expedite removal of bulk brine.19
Comparable results were obtained for centrifuged samples and
those that were simply submerged in oil after minimal draining in
air. After the mica had been aged in a crude oil and heptane
mixture for at least 3 weeks at 25°C, it was rinsed with cyclohex-
ane, allowed to dry, and then immersed in decane. A sessile drop
of water was advanced and receded over the mica surface, and
contact angles were measured with a goniometer. The water-
advancing angle was recorded after 2 to 4 minutes. All measure-
ments were performed at ambient conditions of pressure and tem-
perature and are reported for the angle measured through the water
phase. The sequence of wettability alteration and contact-angle
measurements is summarized in Fig. 1.
Results and Discussion
Contact-angle measurements provide an indication of the extent of
wettability alteration as a function of the conditions under which
mica surfaces were exposed to oil. The magnitude of wettability
alteration observed is also affected by the details of test conditions.
It is not expected that the results of these tests should be repre-
sentative of reservoir conditions, but rather that they provide a
Fig. 1—Summary of procedure used to produce oil-treated sur-
faces and to measure contact angles.
August 2003 SPE Reservoir Evaluation & Engineering
means of comparing the wettability-altering potentials of different
oils and surface treatments. Details of water-advancing and water-
receding angles have been presented elsewhere.20,21
Repeatability of measurements can vary dramatically. In most
cases, comparisons of different positions on a single piece of mica
and of averages of different mica samples show reproducibility
within a few degrees. Much greater variability was observed under
some test conditions, especially those in which asphaltenes were
flocculating. The results presented here are averages of measure-
ments on at least two (and sometimes many more) surfaces.
Careful examination of all the conditions with high standard
deviations showed some interesting trends. Standard deviations of
10 to 15 generally encompass cases such as that shown in Fig. 2
for Mars-Yellow maltenes. In these cases, most of the measure-
ments fall near the average, with a few outliers. In other cases, a
wide distribution of angles was measured, as illustrated in Fig. 2
for Mars-Yellow and heptane at onset conditions.
In a few cases, two very distinct trends emerged. The values of
standard deviation when these measurements are averaged are ex-
tremely high. Two examples are shown in Fig. 3 for mica surfaces
pretreated with the pH8 brine, then aged in either Lagrave or
Lagrave plus n-heptane. Averaging makes little sense in either of
these cases; for Lagrave alone, the average advancing angle is
115°±47, and for the onset mixture of Lagrave and n-heptane, the
average is 43°±57. In these special cases, the averages obscure the
coexistence of patches that are clearly water-wet with others that
are quite oil-wet.
Fig. 2—Individual water-advancing angle measurements, sorted
in ascending order. (The order shown is unrelated to chrono-
logical or spatial relationships.) Standard deviations in the
range 10 to 15 often reflect the presence of a few outliers in an
otherwise consistent trend, as shown for maltenes from Mars-
Yellow. Higher standard deviations may indicate a wide distri-
bution of advancing angles, as illustrated for Mars-Yellow and
n-heptane at the onset conditions.
211

Fig. 3—Individual water-advancing angle measurements, sorted
in ascending order. Two distinct trends were observed for La-
grave and its mixture with n-heptane when the mica was pre-
treated with pH8 brine. Some areas are water-wet, whereas oth-
ers are quite oil-wet.
Stable Water Films. In the absence of water, precipitation of
asphaltenes might be expected to convert mineral surfaces to oil-
wet conditions. When water is present, the situation is more com-
plicated. Previous work has established ranges of pH and ionic
composition for which water films are either stable or unstable for
A-93 crude oil and Muscovite mica surfaces.18 Accordingly, two
aqueous-phase compositions were tested:
• pH 8, I⳱1M, for which the water film between mica and
A-93 oil is stable.
• pH 4, I⳱0.01M, for which the water films for mica and A-93
are unstable.
Oil composition was varied by the addition of n-heptane. As
shown in Fig. 4, the existence of a stable water film maintains
water-wet conditions with water-advancing contact angles of less
than 20° for all oil/heptane mixtures. Water-receding angles (not
shown) were generally smaller than water-advancing angles. Even
when sufficient heptane was added to induce flocculation of as-
phaltenes, which occurs for A-93 when the volume fraction of oil
is 0.43 (and that of heptane is 0.57)—as indicated by the vertical
line in Fig. 4—no deviation from water wettability was observed.
Unstable Water Films. When the brine composition was changed
to one that produced unstable water films, a very different picture
of wettability alteration was produced, as shown in Fig. 4. Even
though the mica surfaces were wet when first submerged in the
Fig. 5—Water-advancing contact angles for mixtures of five dif-
ferent crude-oil samples with n-heptane.
212
Fig. 4—Water-advancing contact angles on surfaces treated
with A-93 crude oil. Mica samples pretreated with high-pH brine
have stable water films and remain water-wet; those pretreated
with low-pH brine have unstable water films that break, allowing
alteration of wetting. The extent of wetting alteration is highest
when the asphaltenes are near the onset of precipitation.
oil/heptane mixtures, they became significantly less water-wet af-
ter approximately 3 weeks of aging in oil. Surfaces aged in the neat
oil (fv,oil⳱1) were altered almost to neutral wetting. The addition
of heptane had little effect on the resulting wettability until the
onset conditions were approached. Near the onset, the wetting
alteration jumped to fairly oil-wet conditions.
Many properties change as heptane is added to crude oil. For
example, viscosity decreases, as do the concentrations of all oil
species, including the asphaltenes. These gradual changes have
little or no effect on wettability alteration, which—for the selected
oil/brine/solid ensemble—depends mainly on charged sites at the
oil/brine and solid/brine interfaces. As the onset of asphaltene
flocculation is approached, however, there is a transition from the
ionic interactions to surface precipitation of asphaltenes, resulting
in the jump from neutral to oil-wet surfaces.
Comparison of Crude-Oil Samples. In Fig. 5, wetting alter-
ations induced by all five crude-oil samples and by their mixtures
with n-heptane are compared. In each case, mica surfaces were
first equilibrated with the pH4, I⳱0.01M aqueous solution. Sev-
eral of the oils show the same abrupt increase in water-advancing
contact angles over a narrow range of oil volume fractions, as was
observed for A-93. The effect cannot be documented for Lagrave
because even the neat oil (in this case, a mixture of oil and ␣-MN)
made the mica oil-wet. At the other extreme is Mars-Yellow, for
which only a slight increase can be seen in the near-onset mixtures.
Fig. 6—Water-advancing angles increase rapidly as the onset of
asphaltene precipitation is approached (⌬RI=RImix−PRI=0).
August 2003 SPE Reservoir Evaluation & Engineering
Fig. 7—Pseudoternary phase diagrams based on the CO2/Wasson crude-oil system at 2,000 psi and 105°F.22 Lines of constant RI
were calculated using PVTSim.23 RIoil=1.443. (a) If PRI=1.44, the plait-point composition is unstable with respect to asphaltenes.
(b) If PRI=1.40, the plait point falls in the asphaltene-stable region.
The specific influence of asphaltene flocculation can be seen
most readily in Fig. 6, where data from Fig. 5 are compared on the
basis of the difference between mixture RI and the onset value PRI
for each oil with heptane (Table 2). That difference, denoted as
⌬RI, is a measure of how much higher (asphaltenes stable) or
lower (asphaltenes unstable) RImix is than PRI. The steepest in-
creases in contact angles coincide with the approach of asphaltene
flocculation for all of these oils.
Precipitated Asphaltenes. In mixtures with precipitated asphalt-
enes, judging wettability is often more difficult than it is in mix-
tures in which the asphaltenes are dispersed. Measurements with
precipitated asphaltenes are included in Fig. 6 for Lagrave, A-93,
and Mars-Pink. For the first two oils, oil-wet conditions persist, but
for Mars-Pink, there can be great disparity between one treated
surface and another and even between two sides of the same
sample. Poorly adsorbed layers of deposited asphaltene can some-
times be removed in the rinsing step.
Implications for Reservoir Wettability. During oil recovery,
changes in temperature, pressure, and composition can affect as-
phaltene stability. Decreasing the pressure decreases RI until the
bubblepoint is reached.9 Depending on temperature and composi-
tion, some oils may experience asphaltene destabilization as a
result of depressurization. As this point is approached at any given
place in the reservoir, a change in the mechanism of wetting al-
teration might be expected for oils such as Mars-Pink, Tensleep, or
A-93. If the pressure decreases below the bubblepoint, the lightest
components begin to separate into another phase, leaving the re-
maining oil phase a better solvent for its asphaltenes and returning
rock/fluid interactions to the region of ionic mechanisms.
Miscible or partially miscible gas-injection processes can
change oil composition and potentially destabilize asphaltenes.
Consider, for example, the pseudoternary diagrams for CO2 injec-
tion into the Wasson field,22 shown in Fig. 7. Superimposed upon
the pseudoternary diagram are lines of constant RI, calculated
using PVTSim (Version 11)23 to estimate the properties of CO2
and the light ends; properties of the heavy ends were measured
using a sample of dead oil. The original live-oil composition falls
near the 1.44 iso-RI line.
Two possibilities can be considered for the onset conditions. If
PRI is equal to 1.44 for the n-heptane onset at ambient conditions
(the average value in Table 2 for the onset of precipitation with
n-heptane), PRI at 2,000 psi and 105°F would be close to 1.4, and
precipitation would begin in the single-phase region, as shown in
Fig. 7a. Wettability alteration by the surface-precipitation mecha-
nism might occur over a narrow range of compositions near the
onset condition, but asphaltenes would be removed from the oil
mainly by bulk flocculation.
August 2003 SPE Reservoir Evaluation & Engineering
In Fig. 7b, the effect of a lower value of PRI (1.40 at ambient
conditions) is illustrated. No precipitation would occur until the
overall composition reaches the two-phase envelope. Contact of
original oil with the lighter phase would produce mixtures in both
the unstable and stable regions. Compositions that fall closest to
the onset conditions have the greatest opportunity for causing
wetting alteration; depending on the precise details of the phase
behavior, such a system might experience significant changes
in wetting.
Conclusions
1. Two interaction mechanisms have been demonstrated. Ionic in-
teractions and surface precipitation both can contribute to the
wetting alteration of mineral surfaces exposed to crude oil in the
presence of water. Ionic interactions dominate in oil mixtures in
which asphaltenes are in stable dispersion. Near the onset of
asphaltene flocculation, a sharp transition to surface precipita-
tion can occur, which produces more oil-wet conditions.
2. Stable water films can maintain water-wet conditions in systems
dominated by surface precipitation, just as they can in ionic-
interaction regimes.
3. Once flocculated, asphaltenes may be only poorly adsorbed.
4. Wetting may change in reservoirs if the onset of asphaltene
precipitation is approached by pressure depletion. Additional
opportunities for wetting alteration may occur in gas-injection
processes. Whether and where either wetting alteration or bulk
precipitation occur are complex functions of pressure, tempera-
ture, and composition.
Nomenclature
fv,oil ⳱ volume fraction of oil
M ⳱ ionic strength
PRI ⳱ RI at the onset of asphaltene precipitation
RImix ⳱ refractive index of mixture
RIoil ⳱ refractive index of oil
⌬RI ⳱ RImix – PRI
␪ ⳱ contact angle, degrees
␪A ⳱ water-advancing contact angle, degrees
␪R ⳱ water-receding contact angle, degrees
␳ ⳱ density
{4, 0.01} ⳱ aqueous solution with pH 4 and 0.01 mol/L NaCl
{8, 1} ⳱ aqueous solution with pH 8 and 1.0 mol/L NaCl
Acknowledgments
The authors thank Jianxin Wang for calculations of RI and PRI for
the ternary system shown in Fig. 7.
213
 Support for wettability research at the PRRC comes from
NPTO (DOE), the State of New Mexico, and industrial sponsors,
including the ARTEP consortium (Elf-Aquitaine, Gaz de France,
IFP, and Total), BP, Chevron, Norsk Hydro, and Unocal. Oil
samples were provided by Arco, Elf-Aquitaine, Shell, and the U.
of Wyoming. Support for Mr. Al-Maamari was provided by Sultan
Qaboos U., Oman.
References
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Presence in Some Rock Properties,” SPE Advanced Technology Series
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force microscopy of adsorbed asphaltenes,” Colloids and Surfaces A (3
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Alteration by Crude Oils,” SPEJ (March 1998) 54.
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Their Asphaltenes,” Revue de l’Institut Français du Pétrole (1998) 53,
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of Crude Oils,” Petroleum Science and Technology (1998) 16, Nos. 3
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of the Effect of Mobile Water on CO2-Flood Residual Oil Saturation,”
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13. Patel, P.D., Christman, P.G., and Gardner, J.W.: “Investigation of Un-
expectedly Low Field-Observed Fluid Mobilities During Some CO2
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14. Yan, J., Plancher, H., and Morrow, N.R.: “Wettability Changes Induced
by Adsorption of Asphaltenes,” SPEPF (November 1997) 259.
15. Potter, G.F.: “The Effects of CO2 Flooding on Wettability of West
Texas Dolomitic Formations,” paper SPE 16716 presented at the 1987
SPE Annual Technical Conference and Exhibition, Dallas, 27–30
September.
16. Kamath, V.A., Yang, J., and Sharma, G.D.: “Effect of Asphaltene
Deposition on Dynamic Displacements of Oil by Water,” paper SPE
26046 presented at the 1993 SPE Western Regional Meeting, Anchor-
age, 26–28 May.
17. Hawkins, J.T. and Bouchard, A.J.: “Reservoir Engineering Implica-
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Log Analyst (July–August 1992) 33, 415.
18. Liu, L. and Buckley, J.S.: “Alteration of Wetting of Mica Surfaces,”
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19. Yang, S.-Y. et al.: “Mechanisms for Contact Angle Hysteresis and
Advancing Contact Angles,” J. Pet. Sci. Eng. (December 1999) 24, 63.
20. Al-Maamari, R.S.H.: “Effect of Asphaltene Destabilization on Wetta-
bility,” PhD thesis, New Mexico Inst. of Mining and Technology,
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21. Al-Maamari, R.S.H. and Buckley, J.S.: “Asphaltene Precipitation and
Alteration of Wetting: Can Wettability Change During Oil Produc-
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Recovery Symposium, Tulsa, 3–5 April.
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23. Retrieved from www.calsep.com (2002).
SI Metric Conversion Factors
°F (°F – 32)/1.8 ⳱ °C
psi × 6.894 757 E + 00 ⳱ kPa
Jill Buckley is a senior scientist and head of the Petrophysics
and Surface Chemistry group at the New Mexico PRRC, New
Mexico Tech. e-mail: jill@prrc.nmt.edu. Her research is focused
on rock/fluid interactions and the interfacial properties of
crude oils and their asphaltenes. She holds BS and MS degrees
in chemistry and a PhD in petroleum engineering from Heriot-
Watt U. Buckley is past president of the Soc. of Core Analysts;
she serves on the Editorial Board of SPEJ and has served as a
Review Chairperson for SPEREE. Rashid Al-Maamari is an assis-
tant professor in the Petroleum and Chemical Engineering
Dept. at the Sultan Qaboos U., Oman. e-mail:
rsh@squ.edu.om. He holds a B.Eng. degree from Sultan Qa-
boos U., an MSc, DIC degree from Imperial College, and a PhD
degree from New Mexico Tech, all in petroleum engineering.
August 2003 SPE Reservoir Evaluation & Engineering
‘‘Asphaltene Precipitation and Alteration of Wetting: The Potential for Wettability Changes During Oil Production,’’ by Rashid S.H.
Al-Maamari and Jill S. Buckley, which appeared in the August 2003 issue, contained a misprinted figure. The correct version is included
here:

CO 2
(RI =1.16)

constant RI
lines
tie lines

1.20

Plait point
unstable

1.24
PRI
stable
Heavy ends Light ends
(RI =1.50) 1.48 1.44 1.40 1.36 1.32 1.28 (RI =1.26)
Original oil
(RI=1.443)

(a) If the n-heptane PRI at ambient conditions is 1.44, asphaltene precipitation begins in the single-phase region.

CO 2
(RI =1.16)

constant RI
lines
tie lines

1.20

Plait point
unstable
PRI
1.24

stable
Heavy ends Light ends
(RI =1.50) 1.48 1.44 1.40 1.36 1.32 1.28 (RI =1.26)
Original oil
(RI=1.443)

(b) If the n-heptane PRI at ambient conditions is 1.40, there is the potential for asphaltene precipitation after the phase split.

Fig. 7—Pseudo-ternary phase diagrams based on CO2/Wasson crude-oil system at 2,000 psi and 105°F.22 Lines of constant RI were calculated
using PVTSim.23 RIoil = 1.443. (a) If PRI = 1.44, the plait-point composition is unstable with respect to asphaltenes. (b) If PRI = 1.40, the plait point
falls in the asphaltene-stable region.

December 2003 SPE Reservoir Evaluation & Engineering 367