ASPHALTENE DEPOSITION AND ITS

ROLE IN PETROLEUM PRODUCTION

AND PROCESSING

G. A. Mansoori*, T. S. Jiang, and S. Kawanaka

University of Illinois at Chicago
Chicago, Illinois 60607, U.S.A.
January 1988

ABSTRACT

The need to understand the nature of asphaltene and its role in the production
and processing of crude oil is well recognized around the world as manifested by
the extensive problems resulting from asphaltene depositions. It appears certain
that the trend in the petroleum industry worldwide now and in the future will
involve the exploration, drilling, production, and processing of heavier oils (higher
in asphaltene content), use of gas injection (or re-injection) techniques, and
secondary and tertiary methods for recovering more oil from existing reservoirs.
The subject of asphaltene deposition and its role in the petroleum field is here
analysed and the technical requirements for its understanding are presented. It is
demonstrated that for a comprehensive understanding of this subject the following
topics should be studied: (i) Molecular thermodynamic modeling of phase behavior
of asphaltene + petroleum crude+ injection gas systems and examination of the
resulting successful models against the available laboratory and field data;
(ii) transport phenomena modeling of the flow of crude in porous media containing
asphaltene colloidal particles (m; micelles), colloidal instability which may cause
asphaltene deposition, and wettability alterations due to the adsorption of
asphaltene on the pore walls, and (iii) experimental measurements and simulations
in support of such studies.

(*) Corresponding author, email: mansoori@uic.edu

The Arabian Journal for Science and Engineering, Volume 13, Number 1.
11
 ASPHALTENE DEPO SITIO N AND ITS RO LE IN
PETROLEUM PRO DUCTIO N AND
PROCESSING
G. A. Mansoori, T. S. Jiang, and S. Kawanaka
University of Illinois at Chicago
Chicago, Il linois 60607, U.S.A.

The Arabian Journal for Science and Engineering, Volume 13, Number 1.
18
 G. A. Mansoori, T. S. Jiang, and S. Kawanaka

ASPHALTENE DEPOSITION AND ITS ROLE IN

PETROLEUM PRODUCTION AND PROCESSING

NOTATION r(A) = Rate of production of asphaltene aggre­

gates per unit volume by homogeneous
A = Area on which an integration is per- polymerization or association reaction.
formed. Sw = Union of the pore walls within S.
a = Force per unit volume that fluid exerts T = Temperature.
upon the pore walls contained within S T- = Stress tensor.
in excess of the hydrostatic force. ∆ivap = Internal energy change of vaporization
B = Scalar, vector, or tensor associated with of compound j.
a fluid. u·� = Speed of displacement of Sw directed
B = Local volume average of B for a fluid. into a fluid phase.
(B) = Intrinsic volume average of B for a V = Volume enclosed by S.
fluid. V(f) = Volume of Rco·
b = External force per unit_ mass. Vi = Volume of compound j.
D = Diffusion coefficient. VTA = Total volume of asphaltene.
D*(A) = Function of the porosity and a dimen­ VTAi = Total volume of the i th fraction of
sionless group, as in Equation (40). asphaltene.
Deff = Effective diffusion coefficient. v = Mass-averaged velocity.
Fn(MAi) = Normalized mole distribution of the ith v(A) = Velocity vector of asphaltene aggre­
asphaltene fraction with respect to the gates.
molecular weight of asphaltene. v(A)i = Molar volume of the i th fraction of
Fv(MAi) = Normalized volume distribution of the asphaltene.
ith asphaltene fraction with respect to νB = Molar volume of the mixture of asphal­
the molecular weight of asphaltene. tene free crude oil and solvent.
f = Intermediate parameter defined in w(A) = Mass fraction of asphaltene aggregates
·- Equation (4).
= Identity tensor, which transforms every
special vector into itself.
w�
T
defined by Equation (33).
= Total weight of asphaltene.
= Total weight of the i th fraction of
WAI
d.IV u(c))
(A) = "Effective" mass flux vector with asphaltene.
respect tov.
K = Empirical constant relating to the polar- Greek Letters
ities of compounds.
k = Permeability of the porous medium. α(A) = Net rate per unit volume at which
lo = Characteristic pore size. asphaltenes deposit at the pore walls
MAi = Molecular weight of the ith fraction of within the averaging surface S.
asphaltene. δA = Solubility parameter of asphaltene.
mAi = Segment number of the i th fraction of δ(A) = Property defined by Equation (36).
asphaltene ( = vA;lv8). δB = Solubility parameter of the mixture of
mN = Mole average segment number of asphaltene free crude oil and solvent.
asphaltene. δJ = Solubility parameter of component j.
nTA = Mass flux of asphaltene aggregates with θ = Intermediate parameter defined in
respect to the fixed frame of reference. Equation (17).
ni = Total mole number of asphaltene. μAi = Chemical potential of the ith fraction of
p = Modified pressure defined by Equation asphaltene.
( 47). μoAi = Chemical potential of the ith fraction of
p = Pressure. asphaltene at a standard state.
R = Gas constant. p = Total mass density of a mixture of N
R<r> = Pores that contain fluid within S. components.
r = Coordination number of the segment of pA = Density of asphaltene.
an asphaltene molecule. p(A) = Mass density of asphaltene aggregates.

Th� Arabian Journal for Sewn« and Enginttring, Vol� 13, N�r I. )9
 G. A. Mansoori, T. S. Jiang, and S. Kawanaka
ф = Scalar potential representing the exter­
nal force per unit mass b.
фAi = Volume fraction of the i th fraction of
asphaltene in a phase.
(<f>A)max = Maximum volume fraction of asphal­
tene held by a solvent rich phase.
<f>e = Volume fraction of the mixture of
asphaltene-free crude oil and solvent.
ѱ = Porosity of the porous media.
ξ = Unit normal to Sw pointing into the fluid
phase.
Mathematical Symbols
( ) Refers to an intrinsic volume average.
V = Vector partial differential operator:
i( iJ/iJx) +j(iJ/iJy) + k( iJ/iJz).
div = Dot product of V with a vector: e.g.
div(B) = V·B.
Superscripts
T Refers to whole phases.
L Refers to liquid phase.
S Refers to an asphaltene phase.
Refers to local volume average.
Subscripts
A Refers to asphaltene.
Ai Refers to the i th fraction of asphaltene.
B Refers to asphaltene free liquid.
1. INTRODUCTION AND BACKGROUND
The key to solving many of the technical problems
that face the petroleum and natural gas industries in
our modern technological society today involves an
understanding of the thermodynamic and transport
aspects of these problems. Most of the irreplenish­
able energy resources available are mixtures of
gases, liquids, and solids of varying physical and
chemical properties contained in the crust of the
earth in a variety of geological formations. Know­
ledge of the fluid-phase equilibrium thermodynamic
and transport characteristics of these mixtures is a
primary requirement for the design and operation of
the systems which recover, produce, and process
such mixtures.
There has been extensive progress in the past
several years in the formulation of molecular thermo­
dynamics of mixtures and transport phenomena
modeling of multiphase flow in composite media.
20 Th� Arabian Journal for Sc�na and Enginttring, Vol� JJ, Number I.
This knowledge may now be applied to the under­
standing and prediction of the phase and transport
behavior of reservoir fluids and other hydrocarbon
mixtures. The present review is designed with the
purpose of applying modern theoretical and ex­
perimental techniques of molecular thermodyna­
mics, transport, and electrokinetic phenomena to
develop methods that will predict asphaltene and
asphalt flocculation during the production and pro­
cessing of crude oil.
The mechanisms of gas injection and oil recovery
involved with miscible gas flooding are basically of
three kinds [1-3]: first-contact miscible gas drive;
condensing-gas drive (or the enriched gas drive); and
vaporizing-gas drive (or the high pressure gas drive).
The first and second processes are based on the
injection of hydrocarbons that are soluble in the
residual oil, while the third process involves injection
of a high-density gas, such as high-pressure nitrogen
or carbon dioxide. In the case of the first-contact
miscible process, a typical injection fluid is propane,
which is completely soluble in oil. For the conde­
nsing-gas (drive process, the injection fluid could be a
.
natural gas containing relatively high concentration
of intermediate hydrocarbons, such as ethane, prop­
ane, and butane.
Miscible flooding of petroleum reservoirs by
carbon dioxide, natural gas, and other injection
fluids has become an economically viable technique
for enhanced oil recovery [2, 3]. The most common
problem in petroleum recovery is poor reservoir
volumetric sweep efficiency, which is due to channel­
ing and viscous fingering because of the large
difference between mobilities of the displacing and
displaced fluids. Introduction of a miscible fluid in
the petroleum reservoirs will in general produce a
number of alterations in the flow behavior, phase
equilibrium properties, and the reservoir rock char­
acteristics. One such alteration is asphaltene and wax
precipitation, which is expected to affect productivity
of a reservoir in the course of oil recovery (3-8]. In
most of the instances observed, asphaltene and wax
precipitation may result in plugging or wettability
reversal in the reservoir. The effect of asphaltene
deposition could be positive or negative, depending
on whether it could be controlled and predicted
before it occurs.
The parameters that govern precipitation of
asphaltene and wax appear to b e the composition of
crude and injection fluid and the pressure and
temperature of the reservoir. With alterations in

these parameters, the nature of asphaltene and wax
substances which precipitate will vary. Also, it is a
proven fact that the precipitation of asphaltene is
generally followed by polymerization, or floccula­
tion, of the resulting precipitate, which produces an
insoluble material in the original reservoir fluid
[9-15]. Because of the complexity of the nature of
asphaltic and wax substances, the phenomena of
precipitation and flocculation of these substances are
not well understood. Also in view of the complexity
of petroleum reservoirs, study and understanding of
the in situ precipitation of asphaltene and wax seems
to be a challenging and timely task. Such an
understanding will help to design a more profitable
route for miscible gas flooding projects.
In section 2 of the present report, the nature of
molecular characteristics of asphaltene and wax
deposits from petroleum crudes are presented. Field
experiences with asphaltene and wax deposition and
their related problems are discussed in section 3. In
order to predict the phenomena of asphaltene
deposition one has to consider the use of the
molecular thermodynamics of fluid phase equilibria.
In section 4, predictive approaches on the behavior
of reservoir fluids and asphaltene depositions are
discussed from a molecular thermodynamic point of
view. This includes correlation and prediction of the
effects of temperature, pressure, and composition of
the miscible gas and crude on: the thermodynamic
behavior of fluids; onset of asphaltene and wax
deposition; and the mechanism of asphaltene floccu­
lation. The in situ precipitation and flocculation of
aspbaltene is expected to be quite different from that
in �ontrolled laboratory experiments. This is pri­
manly due to the multiphase flow through the
reservoir porous media and the interactions of the
precipitates with the reservoir material. In section 5,
the transport phenomena modeling of the flow
t�ro �gh porous media with in situ asphaltene deposi­
tion 1s presented. Successful predictive models for
asphaltene deposition and flocculation require · a
number of experimental and laboratory meas­
ure?1 �nts. I � section 6, the experimental techniques
env1S1oned m support of predictive models for
�sphal �ene and wax deposition are discussed. Finally'
I ? section 7' an overview of the asphaltene deposi­
tion problem is presented.
2• NATURE AND CHARACTERISTICS OF
ASPHALTENE
Th � word "asphaltene" was originally coined by
Bousmgault [16] to describe the alcohol-insoluble
' collotdal suspensions in the crude oil (22, 34-39].
11,� Arabian Journal for Sci�ntt and Enoi
G. A. Mansoori, T. S. Jiang, and S. Kawanaka
but essence of turpentine soluble, solids obtained
from the distillation residue of an asphalt. Since
then, the concept of asphaltene has been extended to
define the low-molecular-weight n-paraffin-insoluble
and benzene-soluble fraction derived from various
carbonaceous sources, such as petroleum, coal, and
shale oil [17-29]. Asphaltenes must be classified by
the particular precipitation solvent since different
solvents cause different amounts of precipitation
[30, 31]. In Figure 1, the hypothetical structures for
asphaltenes from different regions of the world are
presented. Figure 2, taken from Yen (28], shows how
the asphaltene particles and the asphaltene micelles
are structured due to the formation of the crystallites
(A) of 'TT'-'TT' associations among asphaltene mole­
cules; on changing the conditions of solutions, the
particles may grow to micelles, or the micelles may
dissociate into particles. Figure 3, taken from
Corbett and Petrossi [31], illustrates the effect of
precipitation solvent on the amount of asphaltenes
precipitated. According to this figure there is very
little difference in the amount of asphaltenes precipi­
tated by n-heptane and heavier a-paraffins.
However, when n-pentane is used, additional mate­
rial with Jess polarity and lower molecular weight is
recovered in addition to n-heptane asphaltenes
[23, 32]. Thus, there are n-pentane asphaltenes,
n-hexane asphaltenes, n-heptane asphaltene, and so
on, depending on the precipitation solvent used.
Recognizing the great complexity of various asphal­
tene fractions, Speight and Moschopedis [33] defined
asphaltenes in terms of elemental composition and
molecular structure as well as by the carbonaceous
source. Table 1, reproduced from their paper, shows
the fundamentally different elemental compositions
of asphaltene fractions precipitated by different
solvents from various sources of petroleum. Long
[23] pro rosed an overall concept of asphaltenes by
cons1denng molecular weight and molecular polarity
as separate properties of the molecules. He demons­
trated that asphaltenes contained a wide distribution
o ! polarities and molecular weights. As shown in
F1gur � 4, petroleum asphaltenes have higher molecu­
l �r weight as well as wider molecular-weight distribu­
tion than coal asphaltenes. Nevertheless, asphaltenes
fro � �t� sources _ lie within a region bounded by
prec1p1tat1on _ Imes in a map of molecular weight
v �rsus polarity of the component as illustrated in
Figure 5.
In the petroleum reservoir' asphaltenes have been
obse �ed to occur as dissolved and as micelles or
o-- ···ng, "-'-·-
..-.. .,.,._- 13, N""81,n- 1. 21
 G. A. Mansoori, T. S. Jiang, and S. Kawanaka

(b)

(c)

Figure 1. Hypothetical Structures for Asphaltenes from (a) Venezuelan Crude Oil, (b) Iraqi Crude Oil, and (c) Califomill
Crude Oil [Speight (1970)].

Measurement of the surface tension indicates that
there exists the critical micelle concentration (CMC)
for dilute solutions of asphaltenes in toluene [38).
With concentration below the CMC, the asphaltenes
in the solution are in a molecular state, while above
the CMC, associates and aggregates of asphaltenes
may form. When resins and asphaltenes are both
present as in petroleums, asphaltenes tend to
associate with resins preferentially over association
among themselves [33, 40). This led Speight and his
co-workers to conclude that single aspbaltene entities
associated with resins molecules could be the domi-
nant species which exist in the colloid al state in a
crud e oil.
3. FIELD EXPERIENCES WITH
ASPHALTENE DEPOSfflONS
Control of asphaltene and wax depositions can be
d ifficult and costly in field experience [10, 41-48].
The kind of precipitates observed can vary from very

22 The Arabian Journal for Science and Engineering, Volume 13, Number 1.
 G. A. Mansoori, T. S. Jiang, and S. Kawanaka

Table 1. Elemental Compositions of Asphaltene Fractions Precipitated by Different Solvents (33).

Precipitating Composition (wt %) Atomic Ratios

Source
Medium C H N 0 s H/C N/C O/C SIC

Canada n-pentane 79.5 8.0 1.2 3.8 7.5 1.21 0.013 0.036 0.035
n-heptane 78.4 7.6 1.4 4.6 8.0 1.16 0.015 0.044 0.038
Iran n-pentane 83.8 7.5 1.4 2.3 5.0 1.07 0.014 0.021 0.022
n-heptane 84.2 7.0 1.6 1.4 5.8 1.00 0.016 0.012 0.026
Iraq n-pentane 81.7 7.9 0.8 1.1 8.5 1.16 0.008 0.010 0.039
n-heptane 80.7 7.1 0.9 1.5 9.8 1.06 0.010 0.014 0.046
Kuwait n-pentane 82.4 7.9 0.9 1.4 7.4 1.14 0.009 0.014 0.034
n-heptane 82.0 7.3 1.0 1.9 7.8 1.07 0.010 0.017 0.036

Figure 2. Microstructure of Asphaltene as Proposed by Yen
/28/. (A) RepresenJs a Crystallite, Including an lntracluster
(G) and Forming a Particle (C); (D) Represents a Mice/le
ConJaining a Metal (M) and a Gap and Hole (F), and (I)
Represents Molecules of Resin Forming a Particle (C). (B) is a
Chain Bundle;(£) is a Weak Link; (H) is an lntercluster; (J)
is a Single Layer; and (K) is a Petroporphyrin.
minor to large amounts depending on the nature of
crude, the cloud and pour points of crude, the nature
of the injection fluid and the operating (or reservoir)
temperature and pressure. Asphaltene and wax
deposition can play a significant role in the produc­
tion history and economics of a reservoir. In Figures
6 and 7 two ternary diagrams are presented in order
to demonstrate the composition of different classes
of crude oils from oil fields all around the world.
According to these figures, concentrations of asphal­
tenes and resins in most of the crude oils are
significantly high.
As discussed in the above section, the asphaltene
fraction of an oil is defined as that part precipitated
Figure 3. Effect of the Molecular Weight of n-Paraffin
Solvents on The Amount of Precipitation of Asphaltene
from Arabian Light Atmospheric Residuum (Corbett and
Pertossi {31/). Similar Effects can be Observed for Other
Petroleum Crudes.
by the addition of a low-boiling (or low molecular­
weight) paraffin solvent such as n-pentane. The
asphaltene fraction generally consists of condensed
aromatic and naphthenic molecules of molecular
weights in the range of several hundred to several
thousand grams per mole. Asphaltenes usually
contain a significant number of heteroatoms of
nitrogen, sulfur, and oxygen. Asphaltenes contain
larger carbon-to-hydrogen ratio than is prevalent in
crude oils. As a result, the low molecular wei ght
paraffin solvents, which contain larger hydrogen-to­
carbon ratios than the crude oils, cause precipitation
of the asphaltene colloids. This is thought to

The Arabian Journal for Sdma and Enginttring, Volume 13, Number I. 23

Figure 4. Comparison of Molecular Weight Distribution of
Coal Asphaltene and Jobo Petroleum Asphaltenes. For
Petroleum Asphaltene the Solid Line Represents the
Vacuum Resid uum While the Dots Represent the Atmos-
pheric Resid uum (Long [23}).
Figure 5. Comparison of Asphaltene Fractions Derived
from Petroleum and Coal in a Spectrum of Molecular
Weight, Polarity, and the Precipitation Solvent. According
to this Figure, Coal Asphaltenes are Generally of Lower
Molecular Weight but Higher Polarity, While Petroleum
Asphaltenes are Comparatively of Lower Polarity but
Higher Molecular Weight.
accompany the removal (dissolution and desorption)
of maltenes, which are the soluble fraction of
asphaltenes. In addition to the precipitative effects of
low molecular weight paraffins, water, carbon diox­
ide, and acids are observed to contribute to the
precipitation of asphaltenes. Carbon dioxide, in
addition to reducing the solubility of asphaltenes,
cause rigid asphaltene film formation on the inter­
face due to its effect on the pH value of the water
present.
24 Tht Arabian Journal for Science and Enginttring, Vo/runt 13, Num�r l.
Asphaltene deposition occurs most readily w� en
the pressure of the crude oils is at the bubble � 1_nt.
That is, maximum amount of asphaltene depos1t1on
is produced at the bubble point if their is asphalten_e
deposition. As a result of this fact, if the reservoar
pressure is higher than the bubble point, asphaltene
deposition may occur at the well or in pipes, since the
pressure decreases during the oil production.
Asphaltene deposition was observed even before
the introduction of enhanced oil recovery projects
during the early period of black oil production, as in
the cases of the Ventura field in California
[21, 41,49) and the Hassi Messaoud field in Algeria
[12, 41, 45). In both of these fields, the crude oil was
highly undersaturated with respect to gas. In the case
of the Ventura field, significant problems existed
during the early production life of the wells.
However, the problems diminished after the bottom­
hole pressure (BHP) fell below the bubble-point was
reached. In addition, during the gas-injection period
of the field, a reduced injectivity, by a factor of 2,
was observed. This seems to be a result of the
origin<\1 mixed wettability or oil wetness (wettability
reversal) due to gas injection. The fact that Hassi
Messaoud crude is a light crude (0API of 45) and has
a low asphaltene content of 0.2 wt% is an indication
of the serious problems which may arise in the
recovery of light crude by miscible gas drives.
Injection of solvents or gases may either increase
or decrease the amounts of asphaltene deposition.
Injection of naphthenes, such as cyclohexane, or
aromatics, such as benzene, may reduce the asphal­
tene deposition because asphaltene is soluble to
these solvents. Therefore, damaged reservoirs by
asphaltene deposition may regain their lives by
adding proper solvents. For instance, xylene injec­
tion has been carried out for the Prinos Field, North
Aegean Sea, Greece [26, 41] to prevent the asphal­
tene deposition problem. On the other hand,
injection of carbon dioxide may result in asphaltene
deposition because of the insolubility of asphaltene
in crude oils with miscible carbon dioxide.
Asphaltene deposition is also observed in well­
acidizing practices. Use of hydrochloric acid as a
well-stimulation fluid can cause severe damage in
wells containing asphaltenic crude oil. This is
because the acid causes the asphaltene to precipitate,
and as a result produce a rigid film, which causes
significant damage to the porous media around the
well bore. Carbon dioxide in the presence of water
also has an acidizing effect on the reservoir.
 G. A. Mansoori, T. S. Jiang, and S. Kawanaka

Figure 6. A Ternary Diagram Categorizing Six Different Classes of Crude Oils According to Their Aromatic, Naphthenic, and
Paraffinic Hydrocarbon Contents. The Dots in This Diagram Represent the Composition of 541 Oil Fields Around the World
(Tissot and Welte {51]).

Figurt 7. A Ternary Diagram Showing the Gross Composition of 636 Crude Oils from Around dae World; �
Hydrocarbons, Aromatic Hydrocarbons, and Asphaltenes plus Resins (Weight % in the Fraction Boiling Above 210-C); for
Construction of the lsofrequency Contours a Triangle Unit of 10:10:10 was Used (Tissot tlNl Wehe {51/).

The Arabian Joumal for Sciola Mil �. Volaw 13, � l.

 G. A. Mansoori, T. S. Jiang, and S. Kawanaka
Injectivities reduced by a factor of three following
gas injection have been observed in a number of
carbon dioxide-injection projects (2] and water­
alternate gas drives (50]. These problems are associ­
ated mostly with field problems rather than well-bore
effects.
Asphaltene precipitation inside the reservoir can
add significantly to field problems, specially if it
occurs deep in the well or in the producing intervals.
Extensive testing shouJd be conducted before the
start of miscible flooding or acidizing of wells that
produce crude oils with high asphaltene contents, to
prevent plugging of the reservoir with precipitated
asphaltene.
4. MOLECULAR THERMODYNAMIC MODEL­
ING OF ASPHALTENE DEPOSITION
Crude petroleum generaJly consists of many hyd­
rocarbon components, from methane up to very
heavy hydrocarbons. There exist also varying
amounts of sulfur, oxygen, and nitrogen-containing
compounds [24, 50). The liquid state of the pet­
roleum crude is a result of a delicate balance between
its con§titutents, which depend upon each other for
solubility. On introduction of a solvent into this
mixture, such as carbon dioxide at high pressures, or
n-pentane, the natural equilibrium of the mixture is
upset and some compounds precipitate. Deposition
of asphaltene from petroleum crude due to the
introduction of a solvent can be understood by the
application of the principles of the thermodynamics
of multicomponent mixtures and phase equilibria. In
the present section, we first introduce a descriptive
account of the asphaltene deposition phenomena,
then use molecular thermodynamic techniques
[52, 56] in order to produce predictive equations for
its quantitative interpretation.
It is understood that asphaltene precipitation is a
general phenomenon common to all complex organic
solutions [24]. Thus, interpretations which are made
for the deposition of petroleum asphaltenes will also
apply to coal-derived liquids, kerogen from shale oil,
bitumen of tar sands, and any other complex solution
of organic compounds.
There are two types of modeling for asphaltene
deposition processes: the solubility model; and the
colloidal model. The colloidal model is based on the
fact that asphaltene is suspended due to the adsorp­
tion of resin on asphaltene and that asphaltene may
have either a positi_ve or a negative charge (41]. This
The Arabian Journal for Science and Engineering, Volume 13, Number l.
model is effective for asphaltenes, the molecular
weights of which are several hundred. The solubility
model uses the statistical mechanical theory, in
which asphaltene is assumed to behave like polymer
molecules, and the rule of heat of mixing. The
solubility model is introduced in this section.
It is generally assumed that two factors are
primarily responsible for maintaining the mutual
solubility of the compounds in a complex mixture
such as petroleum crude. They are the ratio of polar
to nonpolar molecules and the ratio of the high­
molecular-weight to low-molecular-weight molecules
in the mixture [24]. Of course, polar and nonpolar
compounds are basically irnmmiscible, and light and
heavy molecules of the same kind are partially
miscible or immiscible depending on the difference
between their molecular weights. However, in the
complex mixture of petroleum crude all these
compounds are probably mutually soluble so long as
a certain ratio of each kind of molecule is maintained
in the mixture. By introduction of a solvent into the
mixture this ratio is altered. Then the heavy and/or
polar �olecules separate from the mixture, either in
the form of another liquid phase or as a solid
precipitate. Hydrogen bonding and the sulfur and/or
the nitrogen-containing segments of the separated
molecules could start to aggregate (or polymerize)
and as a result produce the irreversible asphaltene
deposits, which are insoluble in solvents.
In order to formulate the necessary model for
prediction of the onset of deposition of asphaltene
from petroleum crude we can take advantage of the
theories of polymer solutions [57-59]. The first
attempt at such modeling is due to Hirschberg and
others [60, 61], in which they utilized the Flory­
-Huggins theory of polymer solutions in order to
predict the onset of asphaltene deposition [62].
However, the Flory- Huggins theory is valid for the
case of homogeneous chain molecules of asphaltene
of uniform molecular weight in a single uniform
solvent. It is a well-known fact that molecules of
asphaltene neither consist of homogeneous chain
molecules, nor can the asphaltene-free crude and the
injection fluid be considered as a single uniform
solvent [63-68]. In reality, asphaltene, and the
asphaltene-free crude, both consist of mixtures of
molecules with a virtually continuous molecular
weight distribution. In order to formulate the
phenomena of asphaltene deposition from petroleum
crude, we can utilize the thermodynamic theory for
polymer solutions consisting of a polymer with

heterogeneous distribution and a solvent. According
to this theory [58], the chemical potential of fraction
( i) of asphaltene in the mixture of asphaltene and
solvent can be shown by the fo llowing expression:
(µA,-µ�,) = RT[ln<l>A,+ 1-(mA,/mN }(l -<l>e)
(1)
In this expression, <I>..., is the volume fraction of the
i th fraction of asphaltene and <l>e is the volume
fraction of asphaltene-free crude such that
(2)
also mA; = v.../v8 where v Ai is the molecular volume
of the i th asphaltene fraction and v8is molecular
volume of asphaltene-free crude. Also we have
(3)
and
where r is the coordination number of the segments
of the asphaltene molecule (about 3 to 4), K is an
empirical constant relating to polarity of substances
in mixture, and 6... and 68 are the solubility
parameters of the asphaltene and asphaltene-free
crude, respectively. The solubility parameter is
related to the internal energy of vaporization by the
following expression
(5)
At the onset of asphaltene deposition fractions of the
asphaltene in the solid precipitate phase and in the
liquid phase are in equilibrium, i.e.
(6)
L
IIs -
r-Ai - II
r-Ai,• - 1'
1· - 2,... .
From this equilibrium condition, by utilizing Equa­
tion (1) we can then write
2
lncf>t+ 1-(mttmt)(l-cf>�)-mt cf>�+ _r m!;(�)
= lncf>t+ 1-(m�/m�)(l-cf>i)
-mt cJ>i+f-mt(cJ>i) . (7)
2 (15)
At this stage we can assume that the solid phase
is free of crude (cf>�= 0). We can assume that
vAi= vt = v Ai and v� = Vi = v 8• As a result of these
assumptions Equation (7) will simplify to the
following form
The Arabian Journal for Sdaa and Enginttring, V� 13, NWflber 1.
G. A. Mansoori, T. S. Jiang, and S. Kawanaka
<l>lJ<I>�; = exp[mA;(l/mi-11mt)
-m...;(1-1/mt)<I>� +m...,f (<1>�) ] . (8)
L 2
Since, in general, the molecular distribution of
asphaltene in the precipitate phase is different from
that in the liquid phase, we can not set mt equal to
mt. In the special case when we set mt= mt= m
and if we assume a unif orm molecular-weight distri­
bution for the asphaltene (<I>�; = <I>�; <l>t= 1), then
we can drive the expression for volume fraction of
asphaltene in the liquid phase according to the
Flory-Huggins theory [60).
Let us now define the total volume distribution of
asphaltene with respect to the molecular weight of
asphaltene:
Fv(M...;) = (1/Vl)(dVL/dMA;) , (9)
where, Vl is the total volume of asphaltene, and
dV' L is the total volume of the i th fraction of
asphaltene, whose molecular weight is between MA ;
and MA;+ dMAi " We can also write for the total
volume of the i th fraction of asphaltene as follows:
dVL = dV�;+dVt = VLdcf>�;+ VSdcf>t, (10)
where VL and Vs are the total volumes of the liquid
phase and the asphaltene phase, respectively.
According to Equations (9) and (10),
F,(MAi) V1 dMAi = v1-dcf>t+ VSdcJ>t . (11)
Equation (8) may be written as a differential form:
def>!; = exp (-mA,-8)dcf>�; , (12)
where
8 = (1-1/m�)cf>i-/L(<l>i)2 - (l/m�-llm1) . (13)
From Equations (11) and (12) we can write:
dcf>t = [Vl/ {V L + VS exp (-m...;8)}]F.(M...;)dMAi. (14)
This expression provides us with the maximum
volume fraction of the i th fraction of asphaltene
remaining in the liquid phase. Assuming we have the
weight distribution of the asphaltene fractions
available as experimental data:
The weight of the i th fraction of asphaltene is
w...; = v.../PAi · Using the average density PA , or
assuming the density is constant, we have the
following from Equations (9) and (15):
F.,(MA;) = Fw(MA;) . (16)
27
 G. A. Mansoori, T. S. Jiang, and S. Kawanaka
That is, for constant density of asphaltene, the
volume distribution with respect to the molecular
weight of asphaltene happens to be the same as the
weight distribution. In order to get the total volume
fraction of asphaltene in the liquid phase, we
substitute Equation (16) into Equation (17) and
integrate over the entire molecular-weight distribu­
tion range; i.e.,
rd<!>�;
r
(<I>.Jmax =
= [Vl!{VL + vsexp(-m A;6)}]Fw(MA;)dMAi · (17)
Hence, for a given weight distribution of asphaltene
fraction, F ..,(MA;), we will be able to integrate
Equation (17) in order to calculate the maximum
volume fraction of asphaltene in the liquid phase at
the onset of its depo<:ition
Suppose the mole distribution of the asphaltene
fraction be provided:
(18)
Then, we obtain
F..,(MAJ = F.(M;,;) = (MA;IMA) Fn(MA;) , (19)
where MA is the average molecular weight of asphal­
tene. For the derivation, the molar volume of the i th
fraction of asphaltene, vA; = dVl/dnL is used and
the constant value of the density of asphaltene PA is
again used. In order to obtain the maximum volume
fraction of asphaltene in the liquid phase, integrate
Equation (14) after the substitution of Equation
(19).
S. TRANSPORT PHENOMENA MODELING
S. 1 Flow Through Porous Media with
Asphaltene Deposition
Fundamentally, there are no special equations
needed to analyze transport processes in a permeable
structure. The usual equations of change are be­
lieved applicable to the fluid phase moving through
an individual pore. The problem is to describe
geometrically the configuration of the pore walls
bounding the flow.
For many purposes, only local averages of concen­
trations, velocities and pressures are important. This
suggests the concept of local volume averaging, in
which the equations of change are averaged over the
immediate neighborhood of each point in the
28 The Arabian Journal for Science and Enginttring, Volume 13, Num/Nr l.
structure. The advantage is that one can avoid
specifying detailed configurations of the pore
geometry. But a price is paid: information is lost that
must be supplied empirically or from an idealized
structural model for the local flow.
In what follows, the local volume-averaged mass­
balance equations for the flow through porous media
with asphaltene deposition will first be established.
The elementary mechanisms which cause the deposi­
tion of asphaltenes in porous media are then
identified. From the basic laws of the colloid and
interface science, the general form of correlations
governing the deposition phenomena will be prop­
osed. With the combination of these deposition
correlations and local averaged mass balance
equations, the general behavior of flow through
porous media with asphaltene deposition can be
described. The pressure drop and its variation with
asphaltene deposition will then be examined by the
local volume-averaged equations of motion.
5.2 Local Volume Averages
Let us begin by thinking of a particular point z in
the porous medium. It makes no difference whether
this point is located in the solid phase, the fluid
phase, or on the solid-fluid phase interface; the
argument remains unchanged. Let us associate with
this point z a closed surface S of arbitrary shape.
We will identify this averaging surface S with every
point in the porous medium with a simple translation
of S without rotation. The characteristic dimension
of S should be sufficiently large that averages over
the fluid enclosed by S vary smoothly with position.
Whenever possible, it should be so small as to be
negligible with respect to the macroscopic dimension
of the porous medium.
Let us define V to be the volume enclosed by S.
We will denote by R(f) the pores that contain the fluid
within S; Ver> is the volume of Rcr>·
Assume that B is some scalar, vector, or tensor
associated with the fluid. We will have occasion to
speak of
B = (1/V) ( BdV (20)
J"<o
as the local volume average of B for the fluid phase,
and
(B) • (1/V<r)) f BdV (21)
�f)
 G. A. Mansoori, T. S. Jiang, and S. Ka wanaka

(30)
as the intrinsic volume average of B f or the fluid a(Al = -(1/V) JP(A)(v<A>-u)·�dA
phase. By dV we indicate that a volume integration is
Sw

to be performed. The local volume average and the
intrinsic volume average are simply related in terms
of the porosity.
"1 = Vc, /V
of the porous medium:
B = "1(B).
The theorems for the local volume averages of a
gradient and of a time derivative [69-72] give
as the net rate per unit volume at which asphaltene
aggregates deposit at the pore walls within the
averaging surface S.
(22) The constitutive equation for the local volume­
averaged mass flux vector iicA> depends on how we
describe diffusion in multicomponent mixtures. If we
(23) assume conditions are such that it is appropriate to
use Fick's first law in analyzing diffusion within the
fluid contained by the permeable structure, we can
express Equation (28) as

(VB)= V(B)-(1/V)JB�dA (24) (31)

where
Sw

(aB!at) = (aBtat)+(l/V) fn u·� dA . (25)

SW
p = L P(A) (32)
The union of the pore walls within S is indicated by A=l

S..,; � is the unit normal to Sw pointing into the fluid is the total mass density of the mixture of N
phase; u·� is the speed of displacement of Sw directed components.
into the fluid phase; dA indicated that an area
integration is to be performed. The theorem for the w<A> = Pc A/P (33)
local volume average of the divergence (72] the mass fraction of asphaltene aggregates,
(div B) = div B- (1/V) fn-� dA
SW
(26)
v = Lw
N

(A) v( A) (34)
A=l
follows immediately.
the mass-averaged velocity, and D should be thought
of as the diffusion coefficient for asphaltene aggre­
gates in the multicomponent mixture. If we assume
5.3 Local Volume Averages of Equation of
that the diffusion coefficient D is a constant, Equa­
Continuity for Asphaltene Aggregates
Let us consider the fluid phase as a multicompo­ tion (24) allows us to write the local volume average
nent mixture. The equation of continuity f or asphal­ of Equation (31) as
tene aggregates in the mixture requires
n(A) = (P(A))v-(p)DVw(A)-6(A ), (35)
ap<Aifat+div ncA) = r <A> , (27)
where we have defined:
in which PcA> denotes the mass density of asphaltene
aggregates, r(A) indicates the rate of production of 6(A) = (p(A))v-(p(A)v)+ (DpVw(A))-(p)D(Vw(A))
asphaltene aggregates per unit volume by
homogeneous polymerization or association reaction -((p)DIV)fwA � dA . (36)
(60], and Sw

If the mass density of asphaltene aggregates is not

n <A> = Pc A> v CA) (28) a strong function of position, the effect of the first
is the mass flux of asphaltene aggregates with respect four terms on the right of Equation (36) can usually
to the fixed frame of reference. In Equation (28) we be discounted. The fifth term on the right of
have define vCA> as the velocity vector of asphaltene Equation (36) may be thought of as mass-density
aggregates. The local volume average of Equation tortuosity vector for asphaltene aggregates that
(27) for the fluid phase takes the form accounts for the twisting and turning of the passages
through which the fluid moves.
dP(A/at+ div n(A) = '(A)-a(A) , (29)
With Equations (23) and ( 35 ), the local volume
where we have introduced average of the equation of continuity for asphaJtene

The Arabian Journal for Science and Enginttring, Volunw 13, Mmt.t,n 1. 29
 G. A. Mansoori, T. S. Jiang, and S. Kawanaka
aggregates in the form of Equation (29) may be
expressed as
a( \Jl(PcA >) )lat+ div((PcA>)v) = rcA>-div(j�1>)-acA> ,
where the vector
j�1> = - <P> D ;<A>-s<A>
should be thought of as "effective" mass flux vector
with respect to v.
With the introduction of local volume-averaged
variables, we have eliminated the necessity for an
explicit description of the microscopic structure of
the pores. However, as in any averaging process,
information has been lost. We are now faced with the
necessity of introducing additional relationships for
6(A) and acA) · Either these additional relationships
could take the form of empirical data correlations or
they could be developed from an idealized structural
model [72-74] for porous medium within any giving
averaging surface S. Slattery [71] gave three exam­
ples of how experimental data can be used to prepare
correlations for 6(A) · For instance, in an isotropic
(nonoriented) porous medium when convection can
be neglected, it is shown that
(39)
with
as a function of the porosity and a dimensionless
group. In Equation (40), /0 can be thought of as a
characteristic pore size. If conditions are such that
Equation (39) applies, the effective mass flux in the
form of Equation (38) can be expressed in terms of
an effective coefficient
as
This is consistent with the common practice in
describing diffusion in a porous medium [74).
By similar arguments we can show that when
convection is important, 6<A> can be expressed as
6(A) = (p)(DD(Al)Vw(A) -,o lVw(A) IDcA2)v )
where, for i = 1, 2;
30 The Arabian Journal for Science and Engineering, Volume 13, Number J.
D(Ai) =
D(Ai) (Npe> v· VwcA/(lvllwcA) I), lo (P)IVw(A )l/(P( A)) ,'1,)
(44)
(37) and
(45)
(38)
S.4 Deposition Mechanisms
When a crude oil containing asphaltenes is flowing
through porous media, precipitation cart occur as
discussed in section 2. The asphaltene aggregates
formed may be brought into contact with the possible
retention site on the pore walls. They either deposit
there or are carried away by the flowing stream. The
deposition process is therefore a sequence of the
following mechanisms:
1. The contacting of asphaltene aggregates with the
retention sites on the pore walls;
2. The fixing of asphaltene aggregates on the sites,
and eventually;
3. The breaking away of previously deposited
I
asphaltene aggregates.
Our objective here is to relate the deposition rate
a(A) of asphaltene aggregates to the various factors
which define the system. The factors considered
should be the experimental parameters which are
measurable and have an effect upon deposition
(40) process. For example, the crude oil is characterized
by its viscosity µ., mass density p artd flow rate v; the
asphaltene aggregates are defined by their concentra­
tion (P(A)) and surface properties; the porous medium
is represented by its porosity -i,, permeability k artd
pore size distribution.
Before asphaltene aggregates deposit on the pore
wall surface, they have to be brought into the
immediate neighborhood of the wall. Possible
(41) mechanisms are hydrodynamic lateral diffusion in the
mass-transfer boundary layer, as well as Brownian
.diffusion due to molecular thermal motion. Once
(42) asphaltene aggregates are brought into the immedi­
ate neighborhood of, or into contact with, the pore
wall, deposition may occur due to the interaction of
asphaltene aggregates with the solid surface or
deposited asphaltenes. There has been evidence
showing the surface activity of petroleum asphaltenes
[38). The van der Waals forces, which are always
(43) attractive, and the electrical forces (electrostatic or
e�ectrokinet�c) which are either attractive or repu
l­
sive according to the physicochemical cond ition
s•
 could be the forces causing the deposition. This
initial deposition can also be viewed as a monolayer
adsorption with a similar picture to that for the
chemisorption of gases [75). However, the heat of
adsorption from solution is usually fairly small, and is
more comparable with heats of solution than with
chemical bond energies. After a monolayer adsorp­
tion has been formed, the deposit can grow through
hydrogen-bonding interaction with resins [33, 40, 60]
or association with other asphaltenes similar to
polymerization [60]. Because of the deposition,
wettability of the surface coated with asphaltenes can
be varied or even reversed. In some cases, the
amount of deposition could be sufficiently large that
plugging of small pores is possible, as discussed in
section 3.
S.S Local Volume-Average Equations of Motion
The local volume average of Cauchy's first law for
an incompressible Newtonian fluid when all inertial
effects are neglected can be written as [70]
V(\jl(P))-µdiv(Vv)+a = 0 . (46)
Here µ is the viscosity of the fluid, P is the modified
pressure
p = p+p<I>' (47)
and
a= (1/V) I (T.-p<j>l.)-�dA, (48)
can be identified as the force per unit volume that the
Sw
fluid exerts upon the pore walls contained within S
beyond the hydrostatic force. In Equation (44), pis
pressure and <I> is a scalar potential representing the
external force per unit mass b by
(49)
In Equation (48), T_ is the stress tensor and I_ is the
identity tensor, which transforms every spatial vector
into itself.
A dimensional analysis shows 'that in Equation
(46), the magnitude of the second term is generally
much smaller than that of a. If we are willing to
neglect the second term in Equation (46) with
respect to a, Equation (46) can be reduced to
-V("1(P)) =a.
(50)
As for 6(A) and a(A)• empirical correlations f or a are
required. For example, in a fixed isotropic (nonor­
iented) porous medium, we may write
Tht Arabian Journal for Sc�nct and Enginttring, VollU'M 13, Numba l.
a = (µlk)v' (5n
in which k is the permeability of the porous medium.
Equation (50) when joined with Equation (51) is
usually referred to as the Darcy's law.
Deposition of asphaltenes will not only change the
porosity but also the permeability k of the porous
formation. The pressure drop across the medium will
therefore vary according to Equations (50) and (51).
How the porosity and permeability of the porous
formation change according to the deposition of
asphaltenes is still under study. However, in order to
obtain the onset point of asphaltene deposition, we
may set the porosity and permeability of the porous
media as constant.
6. DISCUSSION AND CONCLUSIONS
Implementation of the molecular thermodynamics
and transport phenomena modelings of asphaltene
flocculation and its role in petroleum recovery and
processing industries presented in this paper require
a number of experimental measurements [76-78].
Such experiments are in two categories. One consists
of the measurement of the physicochemical charac­
teristics of crude, asphaltene, reservoir core, the
injection gases, and their interactions. The second
category are of the simulation type, trying to mimic
the in situ asphaltene deposition at different temper­
atures, pressures, and other reservoir conditions. Of
the first category, the following are of greatest
importance:
1. Chromatographic analysis of crude oil and asphal­
tene for the purpose of specification of construc­
tion of molecular weight distributions of the
asphaltene-free crude and asphaltene.
2. Measurement of solubility parameters of different
fractions of asphaltene and crude for the purpose
of comparisons with the theoretical prediction
models.
3. Observation and specification of the onset of
asphaltene deposition at different temperatures
and pressures, and with the use of different
injection fluids.
4. Titration experiments for the purpose of measure­
ment of the amount of asphaltene deposition.
5. Development of analytic techniques for the
measurement of the rate of asphaltene
polymerization and/or flocculation.
6. Effect of porosity, wettability, and other reservoir
parameters on the rate of asphaltene deposition
in a porous medium.
31
 G. A. Mansoori, T. S. Jiang, and S. Kawanaka
Of the second category, that of greatest import­
ance is Comprehensive core-flood testing facility for
simulation of the in situ asphaltene deposition at
different temperatures, pressures, core porosity, and
injection fluid to oil ratios.
With the implementation of the models presented
in this report, along with the experimental measure­
ments discussed, the following objectives could be
accomplished:
1. Development of a thorough molecular thermo­
dynamic model for asphaltene deposition and
testing of the model against the laboratory and
field measurements.
2. Development of a comprehensive transport phe­
nomena model of the flow of crude oil containing
asphaltene colloidal particles ( or micelles) in
porous media ii: the course of asphaltene deposi­
tion, studies on colloidal instabilities which may
be the cause of asphaltene deposition, and studies
on wettability alterations due to the adsorption of
asphaltene on surfaces.
3. PhysicochemicaJ property measurements and
laboratory simulations in support of the studies
which will basically consist of:
(i) Measurement of the phase behavior of crude
and injection gas mixtures at high pressures
and at different GOR and temperature
conditions;
(ii) Experimental simulation of miscible gas
flooding of reservoir during the course of
asphaltene deposition and flow through
porous media of asphaltene containing crude
and injection gas.
These experiments will enable the researchers to
develop structural models for porous media ·and
analysis of flow of miscible crude system containing
asphaJtene substances in colloidal states.
The present models are only the beginning of an
effort to try to develop analytical predictive techni­
ques on the phase and transport behavior of
asphaltenes. Any investigation, theoretical or ex­
perimental, into the chemical structure and phase
behavior of asphaltenes in crude oil is hindered by
their complex nature. Despite the large volume of
laboratory work that has been performed since
1930's to establish the physcial and chemical nature
of asphaltenes in oil [77), there are only qualitative
descriptions and hypotheses given as to the physi­
cochemical structure of asphaltenes. A comprehen­
sive model that would describe the phase and
The Arabian Journal for Science and Engineering, Volume 13, Number 1.
transport behavior of asphaltenes in oil must take
into account the fact that there is generally a wide
range of size distribution of asphaltenes in oil and the
plausible speculation that one part of them is
dissolved and the other is in a colloidal state.
ACKNOWLEDGEMENTS
This research is supported by the Chemical
Sciences Division of the Office of Basic Energy
Sciences; U.S. Department of Energy Grant # DE­
FG02-84ER13229.
REFERENCES
[1] R. Simon, A. Rosman, and E. Zana, "Phase Be­
havior of CO2-Reservoir Oil Systems", Society of
Petroleum Engineers Journal, 1978, p. 20.
[2] F. I. Stalkup, "Carbon Dioxide Miscible Flooding,
Past, Present and Outlook for the Future", Journal of
Petroleum Technology, 1979, p. 1102.
[3] F. I. Stalkup, "Miscible Displacement", Society of
Petroleum Engineers Monograph, June 1983.
[4] A. David, "Asphaltenes Flocculation During Solvent
Simulation of Heavy Oils", American Institute of
Chemical Engineers, Symposium Series, 69(127)
(1973), p. 56.
[5] T. G. Monger and A. Khakoo, "The Phase Behavior
of CO,-Appalachian Oil Systems", Society of Pet­
roleum Engineers Journal, (1981), paper no. 10269.
[6] F. M. Orr, A. D. Yu, and C. L. Lien, "Phase Be­
havior of CO2 and Crude Oil in Low Temperature
Reservoirs", Society of Petroleum Engineers, Paper
no. 8813, Presented at the SPEIDOE 1st Joint
Symposium on EOR, Tulsa, April 20-23, 1980.
[7] G. W. Preckshot and others, "Asphaltic Substances
in Crude Oils", Transactions, American Institute of
Mining, Metallurgical, and Petroleum Engineers, 151
(1943), p. 188.
[8] D. A. Shelton and L. Yarborough, "Multiple Phase
Behavior in Porous Media During CO2 or Rich Gas
Flooding", Journal of Petroleum Technology, 1m,
p. 1171.
(9) R. J. Cole and F. W. Jessen, "Paraffin Deposition",
Oil and Gas Journal, 58 (1960), p. 87.
[10) A. Hirschberg, "The Role of Asphaltenes in Com­
positional Grading of a Reservoir's Fluid Column,. ,
Society of Petroleum Engineers Journal, 1984, paper
no. 13171.
(11] E. B. Hunt, Jr., "Laboratory Study of Paraffin
Deposition", Journal of Petroleum Technology, 225
(1962), p. 1259.
[12] C. Lhioreau, J. Briant, and R. Tmdy, ..Influence de
la Pression sur la Flocculation des Asphaltenes",
lnstitut Frtlllfais du Petrole, Rn,ru, 22 (1967), p. 797 .
[13] P. M. Lichaa and L. Herrera, "Electrical and Other
Effects Related to the Formation and Prevention of
Asphaltenes Deposition", Society of Petrokum En­
gineers Journal, 1975, paper no. 5304.

(14] D. A. hock. J. D. Sadbury, nod J. S. Crockett,
"Studies of the Mechanism of Paraffin Deposition nod
Its Control". Joumal of Petroleum Technology, 7(9)
(1955). p. 23.
(15) J. G. Speight. R. G. Long, and T. D. Truwbridge,
"Factor Influencing the Separation of Asphaltenes
from Heavy Petroleum Feedstocks", Fuel, 63(5)
(1984), p. 616.
(16] M. Boussingault, "Memoire sur la Composition des
Bitume ", Annales de Chimie Physique, 64 (1937),
p. 141.
[17] M. M. Boduszyn ki, "Asphaltenes in Petroleum
A phalt's", in Ad,·ances in Chemistry Series, 195
(19 1). p. 119.
[18] E. J. Barth, Asphalt Science and Technology. New
York: Gordon and Breach, 1968.
(19] G. V. Chillinger and T. F. Yen, Bitumens, Asphalts,
and Tar Sands. Amsterdam: Elsevier, 1978.
[20] A. S. Gadzhi-Kasumov and R. V. Adamov,
.. Asphaltene Content in Various Petroleum", Geolo­
giya Nefti i Gaza, 14 (1970), p. 46.
[21] D. L. Katz and K. E. Beu, "Nature of Asphaltic
Substances", Industrial and Engineering Chemistry, 37
(1945), p. 195.
(22] J. W. A. Labout. "Constitution of Asphaltic
Bitumen", in The Properties of Asphaltic Bitumen. ed.
J. Pfeiffer. Amsterdam: Elsevier, 1950.
(23] R. 8. Long, "The Concept of Asphaltene", Advances
in Chemistry Series, 195 (1981), p. 17.
(24] J. F. McKay and others, "Petroleum Asphaltenes:
Chemistry and Composition", Advances in Chemistry
&ries, 170 (1978), p. 128.
(25) J. G. Speight, The Chemistry and Technology of
Petroleum. New York: Marcel Dekker, 1980.
(26] J. G. Speight, "On the Molecular Nature of Pet­
roleum Asphaltenes", Advances in Chemistry Series,
195 (1981), p. 1.
(27) T. F. Yen, G. J. Erdman, and S. S. Pollack,
.. Investigation of the Structure of Petroleum Asphal­
tenes by X-Ray Diffraction", Analytical Chemistry, 33
(1961). p. 1587.
[28) T. F. Yen, .. Present Status of the Structure of
Petroleum Heavy Ends and Its Significance to
Various Technical Applications", Amuican Chemical
Society Division of Petroleum Chemistry (Reprints),
1972, p. 102.
[29) T. F. Yen, ..The Nature of Asphaltenes in Heavy
Oils.. , Pan Pacific Synfuels Conferentt, 2 (1982),
p. 547.
[30) D. L. Mitchell and J. G. Speight, "The Solubility of
Asphaltenes in Hydrocarbon Solvents", Fuel, 52
(1973), p. 149.
[31) L. W. Cobrett and U. Petrossi, .. Differences in Dis­
tillation and Solvent Separated Asphalt Residua",
Industrial and Engineering Chemistry: Product Re­
search and Develop�nt, 17 (1978), p. 342.
[32) L. H. Ali and K. A. AI-Ghannam, "Investigations
into Aspbaltenes in Heavy Crude Oils", Fuel, 60
(1981), p. 1043.
TM Anabion Joumol for Scien« and�. Volunw 13, Nlllnl,a I.
G. A. Mansoori, T. S. Jiang, and S. Kawanaka
[33] J. G. Speight and S. C. Moschopedis, "On t�e
,,
Molecular Nature of Petroleum Asphaltenes , 10
Chemistry of Asphaltenes. ed. J. 'W_· Bunger �nd
N. C. Li. Washington D.C.: Amencan Chemical
Society, 1981, p. 1.
(34) J. Briant and G. Hotier, "Etude de l'etat des Asphal­
tenes dans Jes Melanges d'Hydrocarbures", Institut
Franfais du Petrole, Revue, 38 (1983), p. 83.
[35) G. Hotier and M. Robin, "Action de Divers Diluants
sur Jes Produits Petroliers Lourds", /nstitut Fra�ais
du Petrole, Revue, 38 (1983), p. 101.
[36] W. M. Mazee, "Physical and Chemical Properties of
Petroleum Waxes", Journal of the Institute of Pet­
roleum (London), 44(419) (1958), p. 401.
(37] F. I. Nellansteyn, "The Colloidal Structure of
Bitumens", in The Science of Petroleum, vol. 4. ed.
A. E. Dunston. London: Oxford University Press,
1983.
[38) 0. V. Rogacheva, R. N. Rimaev, V. Z. Gu-
baidullin, and D. K. Khakinov, "Investigation of the
Surface Activity of the Asphaltenes of Petroleum
Residues", Colloid Journal, 42 (1980), p. 490.
[39) A. Wachal, "Dissolving Ability and Selectivity of
Solvents with Respect to Asphaltic Resinous Com­
pounds of Different Molecular Weight", Nafta (KaJo­
wice), 27 (1971), p. 236.
[40] J. A. Koots and J. G. Speight, "Relation of Pet­
roleum Resins to Asphaltenes", Fuel, 54 (1975),
p. 179.
[41] K. J. Leontaritis, G. A. Mansoori, and T. S. Jiang,
"Asphaltene Deposition in Oil Recovery: a Survey of
Field Experiences and Research Approaches",
CAPAMA 86 Proceedings (International Conference
on Advanced Technology), De Kalb, Illinois, April,
1986.
[42) S. H. Collins and J. C. Melrose, "Adsorption of
Asphaltenes and Water on Reservoir Rock
Minerals", Society of Petroleum Engineers Journal,
1983, paper no. 11800.
(43) A. K. Gallyamov and others, "Effect of Asphalt and
Tars on the Deposition of Paraffin Waxes in Oil
Pipeline", Neftyanoe Khozyaistro, 1983, p. 42.
[44) J. W. Gardner, F. M. Orr, and P. D. Patel, "The
Effect of Phase Behavior on CO 2 Flood Displacement
Efficiency", Journal of Petroleum Technology, 33
(1981), p. 2067.
[45) C. E. Haskett and M. Tartera, "A Practical Solution
to the Problem of Aspbaltene Deposits-Hug­
Messaoud Field, Algeria", Journal of Pmokum
Technology, 1965, p. 387.
[46) R. Kb. Khazipor and others, "Selection of Solvents
for the Removal of Organic Scale from Oil Wells",
Neftepromyslovoe Delo, 6 (1982), p. 18.
[47) F. M. Orr, M. K. Silva, C. L. Lien, and M. T. Pel­
letier, .. Laboratory Experiments to Evaluate Field
Properties for CO2 Flooding", Journal of Petroleum
Technology, 1982, p. 888.
(48) M. H. Waxman, C. T. Deeds and P. J. Csomann,
"Thermal Alterations of Asphaltenes in Peace River
 G. A. Mansoori, T. S. Jiang, and S. Kawanaka
Tars", Society of Petroleum £11gi11eers Journal, 1980,
paper no. 9510.
f49] R. N. Tuttle, "High-pour-point and Asphaltic Crude
Oils and Condensates", Journal of Petroleum Tech­
nology, 1983, p. 1192.
[50) M. T. Harvey, J. L. Shelton and C. II. Kelm, "Field
Injectivity Experiences with Miscible Recovery Pro­
jects Using Alternate Rich Gas and Water Injection",
Society of Petroleum Engineers, Paper no. 4738,
Presented at the SPE-AIME Improved Oil Recovery
Symposium, Tulsa, April 22-24, 1974.
[51] B. P. Tissot and D. H. Welte, Petroleum Formation
and Occurrence. New York: Spinger-Verlag, 1978.
[52] J. M. Haile and G. A. Mansoori (eds.), "Molecular
Based Study of Fluids", Advances in Chemistry Series,
204 (1983). p. 1.
[53] S. S. Lan and G. A. Mansoori, "Statistical Thermo­
dynamic Approach to the Prediction of Vapor­
Liquid Equilibria Properties of Multicomponent
Mixtures", International Journal of Engineering Scien­
ce, 15 (1977), p. 323.
[54] G. A. Mansoori and T. W. Leland, "Statistical Ther­
modynamics of Mixtures", Faraday Transactions II,
68 (1972), p. 320.
[55] G: A. Mansoori, "Thermodynamics of Systems at
High Pressures", 7th Thermophysical Properties Sym­
posium Series, 1977, p. 442.
[56] A. R. Massih and G. A. Mansoori, "Conformal
Solution Theory of Polar Fluids", Fluid Phase
. Equilibria, 10 (1983), p. 57.
[57) I. C. Sanchez and R. H. LaCombe, "Statistical Ther­
modynamics of Polymer Solutions", Macromolecules,
11 (1978), p. 1145.
[58) R: L. Scott and M. Magat, "Thermodynamics of
�gh Polym«:r Solutions", Journal of Chemical Phy­
s,cs, 13 (1945), p. 172; R. L. Scott, Journal of
Chemical Physics, 13 (1945), p. 178.
[59] G. A. �ansoori, "Molecular Basis of Activity
Coe �cients", Fluid Phase Equilibria, 4 (1980), p. 61.
[60) A. Hirschberg _ L. �- J. de Jong, B. A. Schipper,
_,
and J. G. Me11ers, 'Influence of Temperature and
Pressure on Asphaltene Flocculation" Publication 61
1!oninklijke Shell Exploratie en Prod�ktie Laborator�
1um, Rijswijk, The Netherlands 1983
[61) A. Hii:schberg and L. Hermans', "As�haltene Phase
Behav10
_ �-A Molecular Thermodynamics Model"'
Publ�cat1on 676, Koninklijke Shell Exploratie en Pro­
t;:�e Laboratorium, Rijswijk, The Netherlands,
[62) P. J. Flory, Principles of Polymer Chemistry. Ithaca,
N.Y.: Cornell University Press 1953
[63) G. Hall and S. P. Harron, "Siz� Char�cterization of
�:trol�um SAs�haltenes and Maltenes"' Advances in
emistry erzes, 195 (1981), p. 137.
[64] F. S.Jacobs and R · H · Filby, "Liquid Chromatog-
raphic Fractionation of Oil-Sand and Crude Oil
Asphaltenes", Fuel, 62 (1983), p. 1186.
[65] L. R. Klienschmith, "Chromatographic Methods for
the Fractionation of Asphalt into Distinctive Groups
of Components", Journal of Research, U.S. National
Bureau of Standards, 54 (1955), p. 163.
[66) H.J. Neuman, "Asphaltenes and Crude Oil Resins",
Erdol und Kohle, Erdgas, Petrochemie, 23 (1970),
p. 496.
[67) B. P. Tissot, "Connaissances Actuelles sur les Pro­
duits Lourds du Petrole", Jnstitut Fran�ais du Petrole,
Revue, 36 (1981), p. 429.
[68) M. A. Wahab and others, "Studies on Resins and
Asphaltenes from Abu Crude Oil, Egypt", Egyptian
Journal of Chemistry, 18 (1978), p. 783.
[69) J. C. Slattery, "Multiphase Viscoelastic Flow
Through Porous Media", American Institute of
Chemical Engineers Journal, 13 (1967), p. 1066.
[70) J. C. Slattery, "Multiphase Viscoelastic Flow
Through Porous Media", American Institute of
Chemical Engineers Journal, 14 (1968), p. 50.
[71) J. C. Slattery, Momentum, Energy, and Mass Trans­
fer in Continua, 2nd edn. Malabar, Florida: Robert E.
Kriger, 1981.
[72) T. S. Jiang, M. H. Kim, V. J. Kremesec, Jr., and
J_. C. Slattery_, "The Local Volume-Averaged Equa­
, t10ns of Motion for a Suspension of Non-Neutrally
Buoyant Spheres", Chemical Engineering Communi­
cations, SO (1987), p. 1.
[73) C. Y. Lim and J. C. Slattery, "Three-Dimensional
Randomized, Network Model for Two-Phase Flo�
Through Porous Media", American Institute of
Chemi �al Engineers Journal, 28 (1982), p. 311.
[74) S. �taker, "Diffusion and Dispersion in Porous
Media", American Instilute of Chemical Engineers
Journal, 13 (1%7), p. 420.
[75] A. W. Adamson, Physical Chemistry of Surfaces 4th
edn. New York: Wiley, 1982.
[76] L. T. yuong, "A Simple and Accurate Experimental
Techmque �o� Measurement of the Onset of Asphal­
tene Depos1t10n from Petroleum Reservoir Fluids"
M�ter Thesis, Chemical Engineering Department''
.
Umversity of Illinois, 1985.
[77] K. J. Leontaritis and G. A. Mansoori , "Asphaltenc
. Dunng
F1occu1at1on . Oil Recovery and Processing.. A
.
Thermodynam1c-Colloidal Model", SPE Pa ,
# !62�8, Proceedings of the 1987 SPE Symposium1:n
O�l Field Chemistry, Society of Petroleum En ine ,
g us
Richardson, Texas, 1987.
[78] G. A. Mansoori, "A Comprehensive Bibliography on
Asphaltene, Asphaltene Deposition and the Roi
e 0f
Asphaltene in Oil Recovery Proce�.. D
' epartmen,
o'
" Chem,ca · l Engme· ermg
· , Universily of Illinois, 1986.
Paper Received 11 March 1985; Revised 18 March 1987.