Energy & Fuels 2004, 18, 667-673 667

Solubility Parameters of Crude Oils and Asphaltenes

F. Mutelet,† G. Ekulu,‡ R. Solimando,† and M. Rogalski*,‡
Laboratoire de Thermodynamique des Milieux Polyphasés, Ecole Nationale Supérieure des
Industries Chimiques, Institut National Polytechnique de Lorraine, 1 rue Grandville, BP 451,
F-54001 Nancy Cedex, France, and Laboratoire de Thermodynamique des Milieux Polyphasés,
Université de Metz, 1, Boulevard Arago, CP 87811, 57078 Metz Cedex 3, France

Received September 18, 2003. Revised Manuscript Received January 23, 2004

Results obtained with flocculation threshold experiments and with inverse gas chromatography
were used to validate the use of the solubility parameter approach to asphaltene flocculation
phenomena. It was found that values of solubility parameters obtained with both methods are
in good agreement. The global solubility parameter of the crude oils was factorized in terms of
Linear Solvation Energy Relationship (LSER) coefficients corresponding to a given fluid. Results
confirm the validity of the three-dimensional solubility parameter proposed by Hansen to deal
with petroleum fluids.

Introduction gas of the same material at the same temperature, and

V is the molar volume of the solute. ∆E of volatile
Crude oil asphaltenes are compounds classified by
compounds may be derived from the heat of vaporiza-
their solubilities in n-alkanes. Asphaltene precipitation
tion. It was shown that the onset of flocculation occurs
causes damage in producing reservoirs and wellbores.
when the solvent solubility parameter overcomes the
The deposits can clog tubings and reduce effective
value characteristic for a given crude oil.3-5 The use of
hydrocarbon permeability by blocking the pore throats.
the Hildebrand model is justified when interactions are
Asphaltene precipitation has been considered to be a
dominated by dispersive forces. Nevertheless, this model
very serious problem facing the oil industry for many
was often used to predict solubility of polar and as-
years. The economic recovery of the oil of many oil fields
sociating compounds. In this case, the solubility param-
around the world has been threatened considerably.
eter should take into account other types of interactions.
Nevertheless, due to the complexity of the asphaltene
The concept of dissociating the attractive intermolecular
aggregation processes, trustworthy methods to predict
potential into several parts corresponding to nonpolar
the flocculation onset are still lacking. The best results
and different types polar interactions is based on
were obtained with various versions of the method
perturbation theories, but an empirical use of it may
initially proposed by Hirschberg et al.1 and based on
be justified by the quality of results obtained only.
the concept of Hildebrand’s solubility parameters.
Indeed, a single molecule, because of its structure, may
Hildebrand’s theory of nonelectrolyte solubility2 has
exhibit interactions that are an additive result of two
been frequently used to elaborate thermodynamic mod-
or three different kinds of polar contributions. The
els predicting asphaltene precipitation.3,4 Hildebrand
practical importance of this concept appears while
stated that the maximum solubility is observed when
dealing with the phase equilibria of multicomponent
the solute and solvent cohesive energy densities are
systems. Indeed, phase equilibria are dependent not
identical. He defined the solubility parameter indicating
only on these global intermolecular interactions between
the relative solvency behavior of a specific solvent. This
components but also on the sums of composite polar
solubility parameter is derived from the cohesive energy
interactions. While the total cohesive energy densities
density of the solvent and is given by
of two compounds are similar, the addends that make
1/2 up those individual totals may be different. These slight
δ) (∆EV) (1) disparities in polar contributions result in considerable
differences in phase behavior. If these component dif-
where ∆E denotes the difference between the internal ferences are taken into account, quantified, and included
energy of the condensed material and that of an ideal in solubility theory, the prediction of solubility behavior
is more accurate.
* Corresponding author. E-mail: rogalski@sciences.univ-metz.fr. The most used extension of the multicomponent
† Institut National Polytechnique de Lorraine.
‡ Université de Metz.
solubility parameter was introduced by Hansen et al.6,7
(1) Hirschberg, A.; deJong, L. N.; Schipper, B. A.; Meijer, J. G. Soc. The Hildebrand parameter was divided into three
Pet. Eng. J. 1984, 24, 283-293.
(2) Hildebrand, H. J.; Scott, R. L. The Solubility of Nonelectrolytes; (5) Teixeira, M. A. G. Prepr. Pap.sAm. Chem. Soc., Div. Pet. Chem.
van Nostrand: Princeton, NJ, 1950. 2001, 46, 114-116.
(3) Wang, J. X.; Buckley, J. S. Energy Fuels 2001, 15, 1004-1012. (6) Hansen C. M. J. Paint Technol. 1967, 39, 505-511.
(4) Mannistu, K. D.; Yarranton, H. W.; Masliyah, J. H. Energy Fuels (7) Hansen, C. M.; Beerbower; A. Encyclopedia of Chemical Technol-
1997, 11, 615-622. ogy; Wiley: New York, 1971; pp 889-910.

10.1021/ef0340561 CCC: $27.50 © 2004 American Chemical Society

Published on Web 03/09/2004
668 Energy & Fuels, Vol. 18, No. 3, 2004
components with accounting for the dispersive forces,
the polar interactions, and hydrogen bonding. The value
of each component was determined empirically on the
basis of a number of experimental observations.
In this paper, we propose an alternative approach.
We divide global solubility parameters into contribu-
tions accounting for different intermolecular forces using
the Linear Solvation Energy Relationship (LSER)
concept.8-11 The LSER model was mostly used to
represent the solute transfer between two phases and
supposes that the corresponding free energy changes
may be partitioned using the following linear form:
log SP ) constant +
F(effective dispersion interactions) +
F(effective dipolarity/polarizability) +
F(effective hydrogen bond basicity) +
F(effective hydrogen bond acidity) (2)
For transfer processes occurring between the liquid
and gas phase, Abraham and al.8-11 proposed an em-
pirical form of eq 2:
log SP ) c + rR2 + sπH
2 + a ∑RH2 + b∑ βH2 +
l log L16 (3)
The independent variables in eq 3 are the solute excess
molar refraction (R2), the effective solute dipolarity/
polarizability (πH 2 ), the effective solute hydrogen bond
acidity (∑RH
2 ), the effective solute hydrogen bond ba-
sicity (∑βH
2 ), and the solute gas-liquid partition coef-
ficient on n-hexadecane at 25 °C (log L16). The coeffi-
cients c, r, s, a, b, and l are not simply fitting coefficients,
because they reflect complementary properties of the
solvent phase. The r-coefficients reflect the tendency of
the phase to interact with gaseous solutes through
dispersive-type interactions via electron pairs and π
electrons. The coefficient s is a measure of the phase
dipolarity/polarizability. The coefficient a represents the
complementary property to solute hydrogen bond acidity
and it is a measure of the hydrogen bond basicity.
Likewise, the coefficient b is a measure of the phase
hydrogen bond acidity. Finally, the coefficient l is a
combination of the work needed to create a cavity in
the phase and the general dispersion interaction energy
between solute and solvent phase.
Descriptors used in eq 3 are appropriately scaled and
may be assessed by relatively easy experiment.12,13
Some recent studies confirmed that the partitioning of
molecular interactions proposed in LSER can by justi-
fied on the ground of the quantum chemistry calcula-
(8) Abraham, M. H.; Grellier, P. L.; McGill, R. A. J. Chem. Soc.
Perkin Trans. 2 1987, 797-803.
(9) Abraham, M. H. Chem. Soc. Rev. 1993, 110, 73-83.
(10) Abraham, M. H.; Whiting, G. S. J. Chem. Soc., Perkin Trans. 2
1990, 1451-1460.
(11) Abraham, M. H.; Whiting, G. S.; Dohertu, R. M.; Shuely, W. J.
J. Chromatogr. 1991, 587, 213-228.
(12) Mutelet, F.; Rogalski, M. J. Chromatogr. A 2003, 988, 117-
126.
(13) Mutelet, F.; Rogalski, M. J. Chromatogr. A 2001, 923, 153-
163.
(14) Murray, J. S.; Politzer, P.; Famini, G. R. J. Mol. Struct.
(Theochem) 1998, 454, 299-306.
(15) Rassamdana, H.; Dabir, B.; Nemati, M.; Farhani, M.; Sahimi,
M. AIChe J. 1996, 42, 10-22.
(16) Donaggio, F.; Correra, S.; Lockhart, T. P. 3rd International
Conference on Petroleum Phase Behavior and Fouling, 2002.
Mutelet et. al.
tions.14 We assumed that the LSER decomposition is
adequate for representing the solubility parameter of
crude oils and petroleum fractions. The LSER model
applied to petroleum systems makes it possible to
factorize the global interaction potential and to quantify
contributions due to various molecular forces. Thus, it
allows comparing not only the dispersion interactions
of various oils but also their polarity and the basicity/
acidity balance.
When a set of solutes with well characterized polarity,
basicity/acidity, and dispersion interactions is used in
chromatographic experiments, retention times of solutes
may be used to determine c, a, b, r, s, and l coefficients
in eq 3. This method was used to determine LSER
coefficients of asphaltenes and of the crude oils.
On the other hand, solubility parameters of these
materials were determined using the methods described
below.
Solubility parameters of simple compounds can easily
be calculated from the physical and chemical properties
of a pure liquid. Solubility parameters of defined
mixtures may be calculated on the basis of data for the
single components. For solid materials and complex
mixtures, it is not possible to determine solubility
parameters directly, and they should be obtained by
indirect methods. The usual method is to dissolve a
material in different solvents with known solubility
parameters and record the solubility. Another method,
often used with polymer materials, is based on the
inverse chromatography experiments. In this case, the
investigated material is deposited in the chromato-
graphic column as a stationary phase. Retention times
of solutes, the solubility parameters of which are known,
are recorded and are used to determine the solubility
parameter of the stationary phase. In the present study,
both methods were used to determine solubility param-
eters of asphaltenes and of crude oils. A comparison of
results obtained with two different methods makes it
possible to validate the use of the solubility parameter
approach to asphaltene flocculation phenomena.
Next, correlation in terms of LSER descriptors was
performed with the view to establish a multidimensional
characterization of solubility parameters.
The LSER characterization of the material makes it
possible to determine more precisely the nature of
molecular interactions than the Hansen method does,
and offers a new method to establish solubility param-
eters of complex materials.
Experimental Section
Materials. All experiments were carried out using two
crude oils supplied by the TotalFinaElf. These oils, called here
F1(West Africa) and F2 (Europe), contained, respectively, 11%
and 10.4% of asphaltenes. Asphaltenes F1 and F2 were
precipitated with n-heptane at a solvent-to-oil ratio of 40 mL/
g. Asphaltenes were allowed to settle for 16 h and separated
on sintered glass filters by vacuum filtration. Precipitated
asphaltenes were extracted with toluene. Then the solvent was
evaporated, and the precipitate was dried at 60 °C. The
asphaltenes so obtained were further washed with aliquots of
n-heptane until the supernatant liquid was colorless. This
procedure is believed to remove most coprecipitated non-
asphaltene components.
Molecular weight of both crude oils was estimated using
results of chromatographic analysis assuming that the molec-
Solubility Parameters of Crude Oils and Asphaltenes
Figure 1. Flocculation threshold data of crude oils F1, F2,
F3, and F4.
Figure 2. Asphaltenes recovery (masph./mcrude oil) as a function
of the amount of n-heptane (mn-heptane/mcrude oil).
ular weight of asphaltene is 1000 g/mol. Densities of F1 and
F2 oils were measured at 298.15 K using the Anton Paar DMA
602 density meter and were 0.95510 and 0.95201 g/cm3,
respectively.
Flocculation Experiments. The flocculation threshold of
crude oils F1 and F2 was determined using the usual optical
method. Measurements were performed for a series of toluene/
crude oil mixtures using n-heptane as precipitant. Results are
presented in Figure 1.
Asphaltenes F1 were fractionated by precipitation with an
increasing ratio of n-heptane. The fractions obtained were
treated in the same way as described above. Figure 2 il-
lustrates the percentage recovery of asphaltenes as a function
of the amount of n-heptane per one gram of the crude oil. The
asymptotic character of this relationship indicates that the
effect of the n-heptane/crude oil ratio on the amount of
deposited asphaltenes is strong at the early flocculation stage
and weakens with increasing amount of the flocculent. It was
shown by Rassamdana et al.15 that the size and the properties
of deposited asphaltene aggregates obtained on the sharp part
of the flocculation curve depend on the amount of n-heptane.
In this study, we worked with asphaltenes obtained within
the flat part of this curve, using a significant excess of
n-heptane. Almost all amounts of asphaltenes are deposited
at these conditions, and the global composition of asphaltenes
should be nearly identical in all samples. In this case, all
differences of the precipitate properties would be due to
asphaltene-n-heptane interactions.
Inverse Gas Chromatography. Inverse chromatography
experiments were carried out using a Shimadzu GC 14 gas
chromatograph equipped with a heated on-column injector and
a flame ionization detector. The injector and detector temper-
atures were kept at 523 K during all experiments. Helium flow
rate was adjusted to obtain adequate retention times. Exit gas
flow rates were measured with a soap bubble meter. The
temperature of the oven was measured with a Pt 100 probe
and controlled to within 0.1 K. A PC directly recorded detector
signals, and corresponding chromatograms were obtained
using Borwin 2.1 software. Stationary phases used with
packed columns were prepared by soaking in 10% crude oil/
Energy & Fuels, Vol. 18, No. 3, 2004 669
cyclohexane solution. After evaporation of the cyclohexane
under vacuum, the support was equilibrated at 323 K during
6 h. The columns prepared in this way were coated with the
part of crude oils less volatile than C9 fractions. The weight
of the packing material was calculated from the weight of the
packed and empty column and was checked during experi-
ments. The injected volumes of the sampled vapor were 0.1
µL. All other chemicals were obtained from commercial sources
and used as received. All support materials used in the packed
column studies were purchased from Supelco.
Results and Discussion
Determination of Hildebrand’s Solubility Pa-
rameters Using Flocculation Threshold Data. Solu-
bility parameters obtained using flocculation threshold
data were calculated with the method proposed by
Donaggio et al.16 Donaggio applied to asphaltenic crude
oils the Θ condition concept elaborated by Flory17 for
polymer solutions and identified Θ conditions with the
flocculation threshold. When interactions between non-
neighboring monomer units in polymeric asphaltenes
are repulsive, asphaltenes swell the “good” solvent with
respect to the noninteraction situation. Θ conditions
occur when interactions between monomer units and
solvent molecules become comparable. In the presence
of the “bad solvent”, monomer units attract each other
and the resulting contraction leads to a compact con-
formation of aggregates which could flocculate. The
flocculation occurs when the value of the χ parameter
is 0.5, and that allows calculation of solubility param-
eters of the oil and of asphaltenes according to eq 4:
(δasph. - δoil) + (Φtoluene + Φn-heptane) × δoil )
x
0.5RT
+ (Φtolueneδtoluene + Φn-heptaneδn-heptane) (4)
v1
where δasph. and δoil are, respectively, the solubility
parameters of the asphaltenes and of the oil after
flocculation of asphaltenes; φtoluene and Φn-heptane are
molar fractions of toluene and n-heptane, and v1 is the
molar volume of the overall solvent mixture.
Solubility parameters δasph. and δoil were used to
calculate the solubility parameter of the crude oil.
Indeed, according to Hildebrand’s theory, the solubility
parameter of the mixture of two mutually soluble liquids
is proportional to the volume fraction of each liquid that
can be written as follows:
( )
Φoilδoil + Φasph.δasph.
δcrude oil ) (5)
Φoil + Φasph.
where Φasph. and Φoil are, respectively, the molar fraction
of asphaltenes and of the crude oil after flocculation of
asphaltenes.
Estimated solubility parameters are reported in Table
1.
Determination of Hildebrand’s Solubility Pa-
rameters δIC Using Inverse Gas Chromatography.
Determination of the Crude Oil Solubility Parameter
δIC
crude oil. The retention data determined with inverse
chromatography experiments were used to calculating
Hildebrand’s solubility and LSER parameters. We have
(17) Flory, P. J. Principles of Polymer Chemistry; Cornell University
Press: Ithaca, 1953.
670 Energy & Fuels, Vol. 18, No. 3, 2004 Mutelet et. al.

Table 1. Crude Oil Solubility Parameter δ (cal/cm3)1/2 a Table 2. LSER Descriptors and Solubility Parameter
δasph.(cal/cm3)1/2 of Asphaltenes at 323 K Obtained from
crude
IC D the Crude Oil F1 Determined
oils δcrude oil δcrude oil δD
oil δD
asph.
Crude Oil F1 +
F1 7.03 7.00 6.42 15.6
6 volumes
F2 7.65 7.72 6.99 15.4
of toluene c r s a b l δasph.
F3 7.95 8.69 8.82 15.7
F4 8.085 10 volumes C7 -3.63 0 0.60 1.060 0.100 0.920 12.60
F5 10.03 10.07 9.6 16.0 11 volumes C7 -3.02 0 0.590 0.998 0.102 0.830 12.32
F6 9.845 10.33 8.9 16.1 12 volumes C7 -3.04 0 0.623 1.160 0.109 0.804 12.00
a δIC
13 volumes C7 -2.94 0 0.580 0.980 0.090 0.820 11.59
crude oil: determined with eq 8 using retention data obtained
with inverse gas chromatography (IC) at 323 K. δD D
oil, δasph.:
estimated value of solubility parameter of oil and of asphaltenes
D
using Donaggio’s Method at 298 K. δcrude oil: solubility parameter
of crude oil calculated using eq 4.

used retention data of fluids F1 and F2 determined in

this work and of fluids F3, F4, F5, and F6 determined
previously.18 According to the Flory-Huggins theory,
the parameter χ ∞12 characterizing interactions between
the solute and the stationary phase obtains using the
following expression:

χ ∞12 ) ln
( 273.15Rv2
V 0g P 01 V1 ) - P1
(B11 - V1)
RT
(6)

> In eq 6, R is the gas constant, v2 is the specific volume
of the stationary phase, and V 0g is the probe-specific
retention volume. B11 is the second virial coefficient of
the solute in the gaseous state, and P 01 is the probe
vapor pressure at temperature T (K). The values of P 01
and B11 have been taken from literature.19 The molar
volume of the solute, V1, was calculated using the liquid
density taken from TRC Tables.19
If it is assumed that the interaction parameter can
be expressed as a function of the solubility parameters
of the probe and of the stationary phase:
v10 × (δ1 - δ2)2
χ)
RT
where v10 is the molar volume of the solute, and δ1 and
δ2 are solubility parameters of the solute and of the
stationary phase, respectively. Then, the solubility
parameter of the stationary phase δ2 can be calculated
by fitting χ ∞12 and δ1 to the following equation:
Figure 3. Solubility parameter of asphaltenes δasph. as a
function of the ratio of the amount of n-heptane (mn-heptane/
mcrude oil) used to induce the flocculation.
Calculated values of solubility parameters are given
in Table 1. Values of solubility parameters obtained
from inverse chromatography measurements are in good
agreement with values calculated using Donaggio’s
method and flocculation threshold data.
Determination of the Asphaltene Solubility Parameter
δIC
asph.. The same method was applied to determining
solubility parameters of asphaltenes deposited from the
crude oil F1, using different amounts of n-heptane but
(7) always much higher than the amount corresponding to
the flocculation threshold. Results are presented in
IC
Table 2. It may be observed that values of δasph.
decrease with an increasing amount of n-heptane. This
relationship is linear as shown in Figure 3. When the
straight line in Figure 3 is extrapolated to the amount
of n-heptane corresponding to the flocculation threshold
of the crude oil F1, we find that the value of the

( ) ( )
δ21 χ ∞12 2δ2 δ22
- ) δ1 -
RT V1 RT RT
If the left-hand side of eq 8 is plotted against δ1, a
straight line having a slope of 2δ2/RT and an intercept
of - δ22/RT is obtained. The solubility parameter of the
stationary phase δ2 can be calculated from the slope or
the intercept of the straight line. The agreement of both
δ2 values confirms the applicability of the method to the
considered system. The inverse chromatography is
currently used to characterize molecular interactions in
macromolecular systems.20-22
(18) Mutelet, F.; Ekulu, G.; Rogalski, M. J. Chromatogr. A 2002,
969, 207-213.
(19) Thermodynamics Research Center, Texas Engineering Experi-
ment Station, The Texas A.& M. University System: College Station,
April 1987.
(20) Voelkel, A.; Fall J. J. Chromatogr. A 2002, 982, 245-254.
(21) Voelkel, A.; Grzeskowiak, T. Colloids Surf., A: Physicochemical
and Engineering Aspects 2002, 208, 177-185.
solubility parameter at this concentration is 14.6 (cal/
D
(8) cm3)1/2. This value may be compared with δasph. ) 15.6
(cal/cm )3 1/2 obtained with this oil using flocculation
threshold data and Donaggio’s model. When one takes
into account a significant difference of temperature
between the two experiments, results obtained with
both methods may be considered as very similar. This
conclusion is important for the comprehension of the
flocculation process. Indeed, the similar value of solubil-
ity parameter of asphaltenes in solution and in the
deposited state means that the flocculation implies no
significant change of the asphaltene aggregate state. A
decrease of the solubility parameter value with an
increasing amount of n-heptane may be interpreted as
a confirmation of the hypothesis that n-heptane mol-
ecules participate in the formation of asphaltene ag-
gregates.
(22) de Schaefer, C. R.; de Ruiz Holgado, M. E. F.; Arancibia, E. L.
J. Colloid Interface Sci. 2001, 239, 222-225.
Solubility Parameters of Crude Oils and Asphaltenes Energy & Fuels, Vol. 18, No. 3, 2004 671

Table 3. LSER Descriptors of Probes Used To of hydrogen bond donor sites. This discussion shows that
Characterize Crude Oils and Asphaltenes LSER analysis affords detailed analysis of interactions
solutes R2 π2H ΣR2H Σβ2H log L16 characteristic for a given system.
n-hexane 0 0 0 0 2.668 Asphaltenes of the Crude Oil F1. As was stated above,
n-heptane 0 0 0 0 3.173 samples of asphaltenes of the crude oil F1 were obtained
n-octane 0 0 0 0 3.677 using different amounts of n-heptane but always much
n-nonane 0 0 0 0 4.182 higher than the amount corresponding to the floccula-
cyclohexane 0.305 0.1 0 0 2.964
1-hexene 0.078 0.08 0 0.07 2.572 tion threshold. LSER parameters of these fractions were
benzene 0.61 0.52 0 0.14 2.768 determined by the method described above and are
toluene 0.601 0.52 0 0.14 3.325 presented in Table 1. The polarity “s” and the hydrogen
ethylbenzene 0.613 0.51 0 0.15 3.778 bond basicity “a” of asphaltene are much higher than
ch2cl2 0.387 0.57 0.1 0.05 2.019
chcl3 0.425 0.49 0.15 0.02 2.48 corresponding parameters of the oil. While asphaltenes
ccl4 0.458 0.38 0 0 2.833 are a more polar fraction of the oil, this result is not
1-butanol 0.224 0.42 0.37 0.48 2.601 surprising. Nevertheless, the hydrogen bond acidity “b”
2 methyl-1-propanol 0.217 0.39 0.37 0.48 2.413 of asphaltenes is lower; that indicates that acid species
2-propanol 0.212 0.36 0.33 0.56 1.764
present in the oil do not precipitate with asphaltenes.
2 pentanone 0.143 0.68 0 0.51 2.755
methyl ethyl ketone 0.166 0.7 0 0.51 2.287 Moreover, it was found that the more acid oil F1,
triethylamine 0.101 0.15 0 0.79 3.04 Table 1, is also more stable with respect to flocculation,
pyridine 0.631 0.84 0 0.52 3.022 Figure 1. Therefore, the stability of asphaltenes in
thiophene 0.687 0.57 0 0.15 2.819 solution can be enhanced by petroleum acids and resins.
nitropropane 0.242 0.95 0 0.31 2.894
trifluoroethanol 0.015 0.6 0.57 0.25 1.224 This confirms the old theory attributing to resins a
diethyl ether 0.041 0.25 0 0.45 2.015 crucial role in stabilizing the asphaltene micelles.24-28
hexafluoro-2-propanol -0.24 0.55 0.77 0.1 1.392 In the case of a high excess of n-heptane, chemical
1,4-dioxane 0.329 0.75 0 0.64 2.892 properties of asphaltenes precipitated with different
ratios of n-heptane are very similar. Decreasing values
Table 4. LSER Descriptors of Crude Oils Determined at of thecoefficient l, characterizing dispersion forces, with
323 K an increasing amount of n-heptane, indicate that ag-
crude gregates contain not only asphaltenes but also some
oils c r s a b l r n F amount of n-heptane that increases with n-heptane total
F1 -2.64 0 0.320 0.700 0.172 0.842 0.993 22 607 concentration.
F2 -2.33 0 0.594 0.943 0.087 0.826 0.994 22 598 Relation between Hildebrand’s Solubility Pa-
rameter and LSER Descriptors. Global solubility
parameter of the crude oils was factorized in terms of
LSER Characterization of Crude Oils and As- LSER coefficients (a, b, r, s, l) corresponding to a given
phaltenes. Crude Oils F1 and F2. The retention data fluid.The resulting relationship is as follows:
of 26 solutes determined with inverse chromatography
experiments were used to calculate LSER coefficients δcrude oil ) -2.51s - 2.60a - 3.91b + 16.00l (9)
of crude oils. LSER parameters of these solutes are
given in Table 3. Retention data were obtained with s.d ) 0.354; r2 ) 0.979; n ) 6
fluids F1 and F2; F3 and F4 were used as stationary
phases in chromatographic columns. For each crude oil, Equation 9 shows that the solubility parameter is
coefficients c, r, s, a, b, and l of eq 3 oils were obtained determined mainly with dispersion interactions. This
by multiple linear regression of retention data. Values finding is important because it confirms the validity of
of crude oil LSER coefficients are reported in Table 4. Hildebrand and Flory theories to deal with the problem
They afford information about the chemical properties of asphaltene flocculation. The acidity-basicity balance
of a given crude oil. Thus, it can be observed that the in the fluid cannot be neglected, but it plays a secondary
crude oil F1 is more acid than crude oil F2. The polar role only. A large basicity lowers the oil solubility
character of F2 is evidenced by the value of the polar- parameter and increases its stability with respect to the
izability parameter twice larger than the value found flocculation. This analysis confirms the fact that the
with fluid F1. Dispersive interactions are considered three-dimensional factorization of the solubility param-
with parameters “r” and “l”. The “l” term expressing eter proposed by Hansen6,7 is adequate to describe
general dispersion interactions is large with both fluids molecular interactions occurring in the petroleum fluids.
studied, and that reflects the high ratio of heavy Nevertheless, LSER offers a better insight into the
molecules. The “r” term expressing partly the oil polarity spectrum of molecular forces. In the case of the crude
vanishes, as was reported previously by Selves et al. oil F1, LSER analysis makes it possible to separate the
and Mutelet et al.18,23-24 This result is surprising in the hydrogen bonding contribution into the acidity and the
case of highly aromatic oils. Indeed, dispersion forces basicity terms. Moreover, this analysis allows estimat-
and n-π interactions present in aromatic systems result
usually in high values of the excess molar refractivity, (23) Selves, J. L.; Abraham, M. H.; Burg, P. Fluid Phase Equilib.
R2. The fact that the “r” parameter is equal to zero in 1998, 148, 69-82.
(24) Burg, P.; Selves, J. L.; Colin, J. P. Anal. Chim. Acta 1995, 317,
the case of crude oils may be due to formation of 107-125.
aggregates through n-π and π-π interactions. Signifi- (25) Gonzalez, G.; Middea, A. Colloids Surf. 1991, 42, 207-217.
cant values of “s” and “a” indicate the presence of (26) Chang, C.-L.; Fogler, H. S. Langmuir 1994, 10, 1749-1757.
(27) Chang, C.-L.; Fogler, H. S. Langmuir 1994, 10, 1758-1766.
polarizable hydrogen bond acceptor (basic) sites. The low (28) De Boer, R. B.; Leerlooyer, K.; Eigner, M. R. B.; Van Bergen,
values of coefficients “b” and “r” indicate a small number R. D. SPE Prod. Fac. 1995, 2, 55-61.
672 Energy & Fuels, Vol. 18, No. 3, 2004
Figure 4. General linear relationship determining the ratio
of the solvent (mtoluene/mcrude oil) and of the antisolvent (mn-heptane/
mcrude oil) at the flocculation threshold. Results were obtained
with flocculation onset data of five crude oils.
ing a quantitative contribution of every molecular
interaction influencing physical properties of the system
studied.
Prediction of the Flocculation Onset of Crude
Oils Using Hildebrand’s Solubility Parameter.
According to Figure 1, concentrations of the solvent
(mtoluene/mcrude oil) and of the antisolvent (mn-heptane/
mcrude oil) are linearly related for a given fluid. On the
basis of this result, we looked for an empirical correla-
tion, making it possible to establish a general linear
form to estimating flocculation threshold condition. As
can be seen in Figure 4, all experiment points obtained
with five crude oils may be represented with the unique
straight line crossing the origin of the graph. The
corresponding equation is
mn-heptane mtoluene
) 1.3683
mcrude oil mcrude oil
s.d. ) 1.14; r2 ) 0.920; n ) 28
While the regression coefficient is 0.92, we conclude that
eq 10 is significant and expresses qualitatively a rela-
tionship between amounts of the solvent and antisolvent
at the flocculation threshold. According to this result,
the flocculation onset occurs at a constant ratio of the
solvent and antisolvent with all the crude oils studied.
In the next correlation, we proposed to differentiate
the crude oils with their solubility parameters. The best
relationship giving the flocculation threshold composi-
tion as a function of the solubility parameter of the oil
was found to be
mn-heptane
mcrude oil
) [
mtoluene Fn-heptane δtoluene - 7.96
mcrude oil Ftoluene 7.96 - δn-heptane
+ ]
[ ]
Fn-heptane 7.96 - 1.09δcrude oil
(11)
Fcrude oil δn-heptane - 7.96
s.d. ) 0.610; r2 ) 0.965; n ) 28
Equation 11 was established with flocculation threshold
data of 5 fluids diluted with toluene. The training set
used in calculations contained 28 data points. Equation
11 states that in the general straight line, eq 11, the
slope is independent of the crude oil properties and the
intercept is a weak function of the crude oil solubility
parameter. According to eq 11, flocculation results
Mutelet et. al.
obtained with different fluids might be represented as
a series of parallel straight lines. This model allows us
to estimate flocculation threshold concentration with an
average deviation of 16%. This result is far from the
experimental accuracy, but it cannot be improved using
correlation based on the solubility parameter only.
Equation 11 may be presented in the following
equivalent form:
δfloc ) δC7ΦC7 + δtolueneΦtoluene + δcrude oilΦcrude oil )
7.96 - 0.09δcrude oilΦcrude oil (12)
Equation 12 shows that highly diluted crude oils floc-
culate at the constant value of the solubility parameter
of the mixture.
Rough correlation of the flocculation onset given with
eqs 10 and 11 should be considered as a qualitative
estimation of the oil propensity to flocculate. In any case,
they afford quantitative estimates of the flocculation
onset.
Conclusions
It was demonstrated that Hildebrand’s solubility
parameter of crude oils might be factorized in terms of
LSER coefficients determined by inverse chromatogra-
phy experiments. Results obtained showed that the
solubility parameter is determined mainly with disper-
sion interactions. Therefore, Hildebrand and Flory
theories are an adequate model for dealing with the
problem of asphaltene flocculation. The acidity and the
basicity of the oil play a secondary role but cannot be
neglected. Indeed, a large basicity lowers the oil solubil-
ity parameter and increases its stability with respect
(10) to the flocculation. The LSER model offers an insight
into the intensity and the nature of molecular forces
involved in flocculation processes. Moreover, inverse gas
chromatography data might be used to calculate directly
the solubility parameter of the crude oil or of asphalt-
enes. Indeed, we found that solubility parameters of
crude oils that were determined with the inverse gas
chromatography agree well with these obtained using
flocculation threshold data. Moreover, similar values of
the asphaltene solubility parameter were found with
both methods despite differences of the asphaltene state.
While during flocculation experiments, asphaltenes are
dissolved in the oil, they are present as a solid precipi-
tate in the chromatographic column. Similar values of
solubility parameters suggest that the physical state of
asphaltenes does not change during the solution-
precipitate transition.
On the other hand, an agreement of solubility pa-
rameters obtained using two different experiments
confirms the validity of the theory used to interpret
experimental data. Therefore, we consider that the
Hildebrand and Flory theory is an adequate model to
represent the flocculation of asphaltenes.
At last, the inverse gas chromatography made it
possible to determine the influence of the n-heptane
excess on the properties of flocculated asphaltenes.
Results obtained suggest the inclusion of n-heptane into
asphaltene aggregates. This phenomenon is enhanced
by increasing amounts of n-heptane.
Results obtained justify using inverse gas chroma-
tography characterization and as a complementary
Solubility Parameters of Crude Oils and Asphaltenes
method to study properties of crude oils. We prepare a
project of chromatographic characterization of a series
of crude oils from various origins that were well
characterized with the usual chemical methods. It will
be interesting to compare the H/C ratio and aromaticity
of oils as well as the number of aromatic rings and the
Energy & Fuels, Vol. 18, No. 3, 2004 673
type of alkyl chains attached to the aromatic ring with
solubility and LSER parameters.
Acknowledgment. The authors acknowledge the
financial support of CNRS, TotalFinaElf, and IFP.
EF0340561