SPE 18892

Asphaltene Deposition: A Comprehensive Description of Problem

Manifestations and Modeling Approaches
by K.J. Leontaritis,● U. of Illinois
SPE Member
“Now with ARCO Oil & Gas Co.

Copyright 1989, Society of Petroleum Engineers, Inc.

This paper wae prepared for presentation at the SPE Production Operetiona Sympoeium held in Oklehoma City, Oklahoma, March 1S-14, 1989.

Thie paper wae selected for preeerdation by an SPE Program Committee following review of information contained in en abetracl aubmiffeu by the author(a). Contents of the pqw,
as preeented, hava not been reviewed by the society of Petroleum Engineare and are eubjeot to Sorrestion by the euthor(e). The material, es presented, dose not neaasaarily reflaof
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~BSTRAC T asphaltenes different engineers and researchers have.

The so-called “asphaltene problem” manifests itself in
almost all the facets of production, processing, and
transportation of petroleum, Due to the multiplidty of
the engineering discipi.ines involved in the above
processes an interdisciplinary approach is beat suited
for seeking fundamental understanding of and
solutions to the problem.
This paper gives a detailed description of how the
asphaltene problem manifests itself in the field. It
discusses in-situ formation damage deep in the
reservoir matrix and near the wellbore, subsurface and
surface production facilities problems, and refining,
blending, and transportation problems due to
asphaltene flocculation and deposition. The molecular
and colloidal asphaltene models are described and
recommendations are made as to the preferred
physical model, Existing, published analytical
asphaltene models based on either molecular or
colloidal nature of asphaltenes are presented and
analyzed, A preferred modeling approach based on the
colloidal physical model is recommended. The
colloidal model permits and supports calculations
based on both reversible equilibrium thermodynamics
and irreversible colloidal flocculation as well.
INTRODUCTION
The expression “Asphaltene Deposition Problem”
means different things to different people,. primarily
because of the variation in vantage points related to
——
References and illustration at end of paper.
This paper refers to work done by the author prior to
his affiliation with Arco Oil and Gas Company.
For instance, for the reservoir engineei it may mean
formation damage and in-situ pluggin~; for the
production engineer, near well formation damage and
subsurface +ind surface equipment plugging and
malfunctions; for the refining engineer, distillation
column ind equipment pluggage and tankage capacity
loss, as well as catalyst deactivation; for the
transportation engineer, pipeline pluggage and capacity
loss; and finally, for the asphalt production spechdist,
blending and asphalt quality headaches. Whatever
one’s vantage point the bottom line of the “asphaltene
problem” is exactly what it says, problems! The
literature on the asphaltene flocculation field
experiences and research is extensive
[1,2,3~,5,6,7J3,9,10,11,12,13,14,15,16,17,18)].
By no means
all the existing literature is cited here due to space
limitations,
One of the most intriguing questions related to
the asphaltene problem is, what the asphaltenes
themselves are! Not long ago, some experimental
work using field ionization mass spectrometry (FIMS)
was reported [19]where the authors tasted somedoubt
as to the existence of asphaltenea in crude oil as its
heaviest component, as most researchers feel, hence,
they used the title for their papex “Asphaltenea Where
Are You?”. Since FIMS may be destructing the
asphaltene micelles and, thus, measuring their
properties in a completely non-aggregated state, which
wo.:ld not reflect their natural state in the oil, a
participant of the symposium where the above paper
was Ix&g presented suggested to the authors that a
more appropriate title for their paper might have been
“Asphaltenes, What Have You Done with Them?”.
The above transaction. highlights the elusiveness of
asphaltenes; because the one group of adentista could
not find them where they were supposed to be whaeas
the other was asking them what they did with them.
The goal of this paper is two fold first, present the
scope of the asphaltene problem and hopefully
demonstrate that asphaltenes are for real, and second,
give an overview of the industrial and academic
efforts underway for providing solutions to the
problem. It is frustrating as well as tantalizing to a
saentist or engineer to be invplved in the quest to find
a solution to a problem in which the main culprit is
not even clearly defined and understood.
ASPHALTENE PROBLEM MANIFESTATIONS
Formation DamaPe
Formation damage due to asphaltene flocculation
and deposition can take place either. deep in the
reservoir matrix or near the wellbore. The two cases
are discussed separately next,
1, DeeD in the Reservoir Matrix
It is generally accepted [lA,6,11aOZl,22,23,24,25&]
that asphaltene flocculation may take place because of
either reservoir fluid temperature, pressure and
composition changes or electrokinetic effects due to
streaming potential generation during reservoir fluid
flow. Usually, in the case of normal reservoir
production, no significant changes in temperature are
encountered. Furthermore, although a gradual
pressure drop during the production life of- the
reservoir in most cases doea occur, a drop in the
pressure is generally accepted to act in a way that
inhibits asphaltene flocculation [1,4,6,11,15,20,21,22,23].
Hence, as the reservoir becomes older asphaltene
problems are expected to diminish (indeed, in all cases
known to the author they did). Consequently, only two
dominant mechanisms of asphaltene flocculation may
be considered likely to occur in the reservoir, by
composition change and/or by electrokinetic effect%
i. Flocculation Due To Composition Changes
Two common ways that the composition of a
reservoir fluid (deep in the reservoir “matrix) changes
are by normal depletion during which the lighter
cdtnponents of the reservoir fluid are produced in
higher proportion (i.e., during primary production by
dissolved gas drive) and injection of fluids for
enhanced oil recovery (EOR).
The reservoir fluid composition change during
primary oil production is nearly always towards the
direction that results in a drop of both the GOR and the
API gravity, Both of these composition trends have as
a consequence a drop in the asphaltene flocculation
tendency of the reservoir fluid. The above are, of
course, general trends and may not occur with every
oil. Hence, generally speaking, even if asphaltene
deposition is omurring during primary production of a
reservoir, the asphaltene problems should be expected
to diminish as production progresses with time, while
keeping everything else constant.
It appears then that the only feasible way a non-
asphaltene prone reservoir could get into asphaltene
flocculation and deposition problems deep in the
reservoir matrix by the route of composition change is
by secondary or tertiary oil recovery (EOR). In
secondary recovery a fluid is inja%ed in the reservoir
with the purpose of primarily maintaining the
pressure during production. Depending on the nature
(i.e., composition) of the injected fluid, asphaltene may
start flocculating and depositing in the pores and
passages of the reservoir matrix (see Fig. 1), thus
resulting in severe and possibly irreversible formation
damage. A similar situation may occur in tertiary oil
recovery, where chemicals and/or misdble solvents
are added to the formation thus altering the
composition of the reservoir fluid (for that matter, any
composition changing process employed has the
potential of resulting in asphaltene flocculation).
In miscible EOR a displadng fluid (e.g., propane,
C02, NGL, etc.) is injected into the formation with the
purpose of mixing completely with the reservoir oil
and carry it to the surface. Ideally, in miscible recovery
all of the accessible oil is recoverable due to complete
miscibility between the miscible solvent and the
r~oir oil. It .$sthis property of the miscible solvent,
which makes it a favorable candidate for EOR that also
gives it the potential of causing asphaltene flocculation
in the reservoir and suhequent in-situ deposition and
pore plugging.
It has been amply demonstrated that most (if not
all) of the familiar miscible solvents can cause
asphaltene flocculation. The cpestion that has not been
convincingly answered yet ,is how much of” the
flocculated material will actually deposit in-situ and
what are the consequences. This is basicly a dynamic
problem (flow related) and depends on the specific
flowing system (fluid and media). There is an inherent
difficuhy in trying to answer the above questions
because, first, these answers cannot be easily
generalized and should be tailored obtained for a
particular system and, second, simulating actual
reservoir conditions in the laboratory is very difficult.
The mechanism of the oil displacement process and a
number of other factors (e.g., related to the asphaltene
flocculation mechanism, the geometry of the mass
media, etc.) will dictate the magnitude of the in-situ
deposition.
It is important to note that flocculation and in-
situ deposition are two separate phenomena. It is
possible to have flocculation without substantial in-
situ deposition, provided that the flow dynamics and
the nature of the flocculated material are such that
permit. erosion and/or carrying of the deposit by the

flowing fluid (the deposits may accumulate, however,
in the production wells and separators). Needless is
say that the flocculated materials contain sizable
amount of entrapped oil which, if deposited in the
reservoir with the asphaltenes, will not be recovered,
Ironically, the entrapment of oil by the flocculating
asphaltenes gives them fluidity and acts against
deposition, Because the flocculation is essentially
irreversible, dropping the pressure of the flocculated
system may result in initiation of the deposition
process (this is possible in well tubings).
Nettability reversal of the reservoir rock caused
by asphaltene flocculation and deposition is also a
distinct possibility. As Figure 2 shows, the highly polar
and heavier than water flocculating asphaltene
micelles may diffuse through the water and be
adsorbed onto the rock thus making it oil wet. This
should affect oil recovery adversely, because the
permeability to oil is expected to diminish and
residual saturations to increase.
ii. Flocculation Due To Electrokinetic Effects
It has been shown that ‘asphaltenes carry an
intrinsic charge. This charge has been considered partly
responsible for the stability of the asphaltene-resin
micelles [4,14,20zl~# 24]. Hence, as the rnicelles are
aggregating and ready to flocculate from a volubility in
oil standpoint, the similar charges on the micelle
kernels prevent them from doing so (refer also to a
related discussion h later sections). At this point two
things may happen to cause flocculation of the
micelles; first, a further composition change (i.e.,
addition of a flocculant) that would make the micelles
even less soluble in the oil and, as a result, cause the
opposing electrical charges be overcome by the van der
Waal-London attractive (dispersion type) forces
and/or, second, generation of a streaming potential
due to flow (or application of an external potential)
large enough to neutralize the electrical charges and
disturb the force balance between the micelles thus
causing them to flocculate.
The first route of flocculation is possible to occur
deep in the reservoir matrix and was discussed in the
previous section. The second mechanism of
flocculation is also possible to occur in the reservoir.
Two very important factors in this case are the velocity
of the flowing reservoir fluid and its composition
(which dictates the volubility of the asphaltene micelles
in it). Other factors that influence the electrokinetic
process are the zeta-potential of asphaltenes, their size,
temperature, transport properties of the oil (i.e.,
ViSUWity), and Other [4,14,20~1~,23,2427,28,29~]. ThiS
topic has been discussed in more detail in other
publications of the author [20,2~ and is briefly dealt
with later in this paper,
ear The Well fire
As discussed above, asphaltene flocculation due to
the streaming potential generated by the flowing
reservoir fluid is possible, However, there seems to be
a certain threshold in fluid velocity beyond which
asphaltene flocculation may occur. This threshold for
different fluids, conduit mass medium, and geometry
has not been adequately studied to date. However, we
do know that the higher the velocity of the fluid the
higher the generated streaming potential and as a
result the more severe the asphaltene flocculation
[4,20,22,23,24,27], In a producing reservoir matrix
higher velocities occur near the wellbore, where all the
produced fluids converge, Consequently, reservoir
asphaltene problems caused by electrokinetic effects are
expected to concentrate near the well bore, provided
that the volubility of the micellea in oil is favorable to
(or near) flocculation. In these cases properly designed
matrix acidization jobs can restore full well production
rate by cleaning up the deposited asphaltenes and,
thus, eliminating the formation damage[12,17,1821,271.
This appears to be a fairly routine process, although
costly, as the author can confirm from personal
experience.
In the production of reservoir fluids containing
sizable amount of asphaltenes excessively large
drawdowns must be avoided, because large drawdowns
result in higher fluid velocities deeper in the
formation, which in turn may cause formation
damage that is very difficult to remove. When
opening a well into production for the first time or
after a workover, it is customary to go through an
initial cleanup period at which time the well is
directed to the cleanup facilities. Any debiis, mud, and
cleaning or workover fluids that have entered the
formation or sit in the sump or tubing of the well
must be cleaned out before the well is placed on
production. For asphaltenic oils this step is very
crucial, because the flow rate during cleanup must be
large enough to remove all undesirables from the
vicinity of the well while at the same time being small
enough to avoid asphaltene flocculation and resulting
formation damage, Excessive pressure reduction (or
drawdown) should also be avoided because it promotes
deposition of flocculated asphaltenes.
Well Problems
In the well asphaltene deposition may manifest
itself in many ways, but the most obvious one is 10ssof
production. Higher and higher choke settings are
required to maintain the same production level until
the choke is fully open and the production losses
cannot be compensated by oping the choke further.
Eventually, the well may “bridge” and stop flowing
completely or continue flowing at an extremely small
flow rate in a rather “burping” way where the flow
starts and stops at different time intervals on its own
volition,
4 Asphaltene Deposition: A Comprehensive Description of
Problem Manifestations and Modeling Approaches
Complete plugging of the well is very undesirable
because the cost of asphaltene cleanup to restore
production is very large. A customary method of
cleanup in this case is “bailing” by wireline, This
cleanup method is slow and costly, especially if the
asphaltene plug in the well tubing is very hard and
long. However, other techniques such as drilling the
asphaltene plug inside the tubing or hydroblasting
through it (e.g., by using a coiled tubing unit) have
been used with, of course, a much higher cleanup cost,
due to the normally high mobilization cost of these
units. These type of cleanup operations create also
other kind of Iegistical problems. For instance,
depending on how soft or hard the asphaltene plug is a
very large amount of washings may need to be
disposed of. In the case of offshore operations this can
be a very big problem, especially near beaches or tourist
areas. In this case a mobile barge or standby small
tanker would be of big help, as the author confirms
from personal experience.
The most desirable and recommended alternative
is to undertake well asphaltene cleanup operations
before the well plugs up completely, In general the
wells must be monitored daily to detect production
losses. In this case wireline scraping can be used
successfully while the well effluent is flowing to the
cleanup facilities, and as a result carrying the
asphaltene scrapings with it. This method may be very
effective in onshore operations. However, in offshore
operations the logistical problem of disposing of the
crude oil-asphaltene scrapings needs to be considered
carefully. Routing the well to the production separator
while scraping asphaltene deposits could result in
serious production problems. Alternatively, a solvent
(e.g., xylene) bath and wash of the tubing followed by
s~aping while the well is flowing may bean acwptable
reined y.
Pluggage of downhole safety valves (DHSV) and
their actuation mechanism is another serious problem
caused by asphaltene flocculation and deposition.
Malfunction of the DHSV’S has the potential of
resulting in very serious consequences. DHSV’Sleft in
service for long periods without checking their
operation in wells where asphaltene deposition is
occurring are bound to malfunction. The same holds
for other valves of the x-mass tree, e.g., the hydraulic
master the wing valve and other. Needle’ valves on
the top of x-mass trees for isolation ai pressure gauges
that measure tubing head pressures are particularly
susceptible to asphaltene plugging (although one
would thing that flocculating micelles would not reach
that dead space), There have been cases, known to the
author, where the operator removed the pressure
gauge believing that the needle valve was closed with
subsequent blowing of the asphaltene plug resulting in
the well shootrng 150 atmospheres asphalvmic sour
crude oil high into the air,
SPE 18892
Surface facilitim
In the production surface facilities asphaltene
flocculation and deposition causes tremendous
problems. What actually happens is that flocculated
asphaltenes deposit on just about everything the crude
oil comes in contact with. The biggest impact of this
problem is on safety and process control and
monitoring equipment. For instance, level control and
or indication equipment as well as sight glasses on
production separators and other vessels plug up and as
a result the equipment overflow. The consequences of
this may vary in importance and intensity, High
pressure safety devices may not actuate and if safety
relief valves are also plugged by asphaltene deposits
and fail to open, when needed, the results may very
well be catastrophic. Thus failure of safety and process
monitoring and control devices is a major problem
caused by asphaltene deposition.
In general, it may be said that all vessels and pipes
or even more broadly all production wells and
equipment internals are susceptible to asphaltene
plugging. As a result, identification and prediction of
the asphaltene flocculation potential of a crude prior to
design and construction of the production and
processing facilities is absolutely essential. There we
various equipment design techniques that may be used
to alleviate or minimize the effects of asphaltene
deposition, if it is expected a priori that asphaltene
flocculation will occur. This emphasizes the
importance of modeling efforts that have as a purpose
prediction of the phase behavior of asphaltenea in
crude oil.
The design techniques referred to above for
processing asph altenic crude oils dqmtd on the extend
of operations in the production facilities and other
factors. Detailed description of these design techniques
is beyond the scope of this paper. However, an example
of such a.techniq’s is designing vessel bridles in a way
that permits frequent on stream flushing or cleaning
by the operator without requiring maintenance
personnel to get involved, Also, parallel vessel
operation or provision of spare equipment where
economically feasible is another design remedy. This,
of course, just scratches the surface of the process
design concerns that are to be addressed if the crude oil
has been shown to be prone to asphaltene flocculation.
Evidently, it is of utmost importance for the
prospective developer and producer of a new oil
discovery to know whether the oil would undergo
asphaltene flocculation prior to being produced or later
during processing. This kind of information would
spark a number of design changes starting from the
reservoir, weils, production, and processing facilities.
Designing the above facilities for the case of no
asphaltene flocculation and finding out later that
asphaltenes flocculate is a very &atly problem that may
even threaten the economic recovery of the field. It is
SPE 18892 K. J. Leontaritis
sounder and more economical to design the
production facilities for asphaltene flocculation (if that
happens to be the case) the first time around rather
than trying to retrofit later. On the other hand,
overdesigning the facilities to handle an asphaltene
problem that would never materialize is also an
economic no-no, Hence, it is obvious that the best
alternative is to have a way to reliably predict
asphaltene flocculation in order that proper planning
and design is done at the beginning,
In offshore production operations the “skimpile”
and /or the oily water clean-up system are very
important and at the same time troublesome to
operate systems. Oily water coming from the vessel
drains and/or from cleaning the platform decks must
be carefully de-oiled and cleaned before it is disposed of
into the sea or re-injected. Flocculated asphaltenes,
because they are surface active and their density is
greater than water’s, cause serious problems in the
operation of these equipment (usually the main
principle of operation in these equipment is based on
the gravity difference of the fluids being separated,
with water, of course, being heavier than oil).
Refininp and Trans~ort ation Fac ilitiq
A uarallel may be drawn between the asphaltene
problems during production and refining, because of
the similarity of some of the processing steps and
equipment. All problems mentioned about
instrumentation for the production side apply to the
refining side as well, provided that the crude oil is
asphaltenic and asphaltene flocculation is possible at
the processing conditions of the oil and its derivatives,
For instance, asphaltene flocculation that would
cause plugging in tower and vessel internals is a very
distinct possibility. A crude oil stabilizer once in a
while (e.g., every two to four months, depending on
the asphaltene deposition severity) needs to be taken
out of service for cleaning. The clean-up method may
be hot water washing, steaming, solvent circulation
and wash, or whatever means have been deemed
appropriate for cleaning the stabilizer. This may be a
very costly operation, especially if the tower is
normally run at full capacity and it is not possible to
make up the production losses with the available
equipment. If it is known a priori (i.e., during the
process design step) that asphaltene flocculation would
be a very distinct possibility, a number of provisions
could be made in the original design to either prevent
the asphaltene problem or else permit stabilizer
cleaning without production losses (e.g., provide over-
capacity in the stabilkr and storage facilities to permit
making up for the lost throughput or provide a second
stabilizer running in parallel). Whatever the decision,
in general, it is much cheaper to provide these extra
facilities during the original design and construction
than any time after corninissioning and startup.
5
Similar reasoning applies to other processing
equipment, i.e., heat exchangers, pumps, heaters,
filters, etc... A frequent problem with pumps is
plugging of the cyclone separator that supplies fluid
from the discharge to the pump seals, hence, resulting
in premature pump failure. Also suction strainers plug
up very often and, as a result, onstream redundancy in
this case may be justifkd. There is virtually no limit to
the number of design changes and provisions that
could be made to alleviate the asphaltene problem, if it
is known a priori that asphaltenes will be flocculating
during the production and processing of the crude oil.
It was suggested recently [31] that asphaltene
flocculation may be the main culprit of crude unit heat
exchanger train fouling. Thus, eliminating or
minimizing asphaltene flocculation in this heat
exchanger train could result in hundreds of thousands
of dollars annual savings for the petroleum refiners.
ASPHALTENEPHYSICALMODEL
General Considerations
As it was demonstrated in the previous section
the asphaltene problem is very serious and real and,
with the trend of the oil industry toward heavier more
asphaltenic oils, bound to get worse. The most
important and nagging question in the minds of most
researchers of the asphaltene problem (and certainly to
the author) is what is the true state of asphaltenes in
the original oil? or how do asphaltenes exist in the oil
before any attempt is made to separate them?
The answer to the above question is very crudal
in our quest to understanding and predicting the phase
behavior of asphaltenes. It would be the ultimate of
good luck if one were to develop a model that predicts
asphaltene phase behavior without having accurate
knowledge of how asphaltenes exist in the oil and the
mechanism by which they flocculate. Hence, one
should start by asking what appears to be a pertinent
question at this point, what is known to date about the
nature of asphaltenes in the original oil?
There has been a number of experimente.~ since
the 1930’swho tried to provide an answer to the above
question [4,6,7,8,9,10,11,12,13, 14,24,25,32, 33s4351.
Unfortunately, no one has been able to demonstrate
convincingly and beyond any reasonable doubt what is
the state of asphaltenes as they originally exist in oil.
Nevertheless, the information compiled so far by the
plethora of researchers on the topic of asphaltenes does
point in a certain direction that suggests the “most
probable” state of asphaltenes in the original oil.
Some of the most important facts on asphaltenes
generated over the years by various experimenters
referen~d above are
i. Asphaltenes have an intrinsic charge that may
be positive or negative depending on their oil
source. If asphaltenes are placed under the
6. Asphaltene
.. . ..-Deposition:
. A Comprehensive Description of
l’romem Manifestations and Modeliruz Ammoaches *’–-––
influence of an external ekwtrical field they
migrate to the oppositely charged electrode.
ii. Resins act as peptizing agents for the
asphaltenes, They are highly polar and, hence,
attracted by the charged asphaltene kernels (i.e.,
rnioellecenters). They concentrate around the
surface of the asphaltenes forming a protective
layer, Resins and asphaltenes together, as
described above, may be trolledmicelles. These
micelles are separate molecukwentities of the
crude oil and subject to all thermodynamic
changes the rest of the components undergo.
However, the addition of an adequate amount
of a flocculant, e.g., a paraffin like n-pentane,
causes partial or total destruction of the rrdcelle
and may result in irreversible flocculation of the
asphaltenes,
iii, Substantially high streaming potentials have
been measured between the inlet and outlet of
tubes and corepluga through which asphaltene
containing oils or solutions have flowed. In one
case, the generated streaming potential was
considered responsible for flocculation of the
suspended asphaltenea [241.
iv. Both asphaltenes and resins exist in the oi! in a
polydisperse state and, as a result, molecular
weight distributions are used to describe them.
v. Asphaltenes and resins have a tendency to
aggregate with each other. The degree of
aggregation depends on the oil composition (i.e.,
solvent power of oil).
Although a number of other experimental
observations and conclusions have been made the
above five appear to be accepted by the overwhelming
majority of asphaltene reaeiychers. Hence, a physical
model describing the state of asphaltenes in oil must
incorporate and explain the above five observations.
Qnerallv Ameed As~halten e Phvsical M odel
In this section a physical model of the asphaltene
resin oil system is described. This model is a natural
cultivation of the five observations discussed in the
previous section, The basic concept embodied in the
model is that asphalt~es exist in the oil in colloidal
suspension, stabilized by resins adsorbed on their
surface (see Figure 3). Pfeiffer and S@ [36], in 1940,
were the first researchers to propose an asphaltene
physical model for bitumens similar to the one shown
in Figure 3 (although Nellesteyn (37) was first to
propose the colloidal nature of bitumens). Later,
Witherspoon et al. [13] contended that baaed on their
uhracentrifuge data of Illinois basin oils the Pfeiffer
and Seal model for bitumens was applicable to oils as
well. More experimental work followed that
pinpointed to the applicability of the Pffeifer and Saal
model for asphaltenes in oil. Recently (20,27) the
model was revived and utilized to formulate a
thermodynamic-colloidd model for predicting the
phase behavior of asphaltenes. One important point,
not fully explained by Pfeiffer and Saal, is whether
SPE 1-
aspha!tenea in their natural state are polydisperse.
Pfeiffer and %al depicted asphaltenea in their original
state as monodisperae, although they did raise the
question of polydispersity. Many recent investigators
believe that asphaltenes in the original oil are
pdydisperse [8,9,19a#2647#34].
The short range steric intermolecular repulsive
forces between resin molecules adsorbed on different
asphaltene kernels keeps them from flocculating.
There is also another weaker and of longer range
repulsive force present between the asphaltene
particles because of their similar electrical charge, This
repulsive force can be overcome or neutralized by
mechanical (large pressure drop, agitation) or electrical
(opposing streaming potential) means.
Since the asphaltene-resin-oil system appears to
be a colloidal suspension, as Figure 3 indicates, it is
behooving to investigate whether colloidal science
techniques can be applied hereto predict the stability of
the system. To date, there exist two theories that
account for the stability of colloidal dispersiona, the
“DLVO Theory” and the “5teric Stabilization Theory”
[28,291.The DLVO theory is applicable to electrolytic
systems, where stabilization is due to the electrical
double-layer. The steric stabilization theory is
applicable to systems where the dispersed phase
(particulate phase) is stabilized by repulsive
interactions between molecules adsorbed on the
surface of the suspended particles, Based on what is
known to date about the mture of the asphaltenes and
other constituents of the petroleum fluids it is believed
that the colloidal asphaltene dispersions in oil belong
in the latter (steric) category.
However, the young steric stabilization theory
does not offer as of now any means to produce
quantitative results. As a result, either the steric
stabWzation theory would have to be extended or a
new theory permitting full quantitative treatment of
the asphaltene-resin-oil system would have to be
proposed.
$g
AJYT C L MODELS OF ASPHALTENE
%
To date, there have been two different
fundamental approaches to the development of
analytical models predicting asphaltene flocculation.
One is the “Molecular-Thermodynamic” approach
[25,26,381 and the other is the “Thermodynamic-
Colloidal” approach [20x71, The underlying principles
“ of each of these approaches are discussed next.
]jolecular-1’hermodvnarnic A~r.woach
One of the first molecular-thermodynamic
modeling efforts for predicting the asphaltene phase
behavior, was published by Fussel [38]. ?ussel
attempted to describe the phase behavior of asphaltic
M
SPE 18892 K. J. Leontaritis
systems by using the equation of state approach. Her
model, which was baaed on the Redlick-Kwong EOS,
used a simultaneous calculation of vapor-liquid and
liquid-liquid equilibria to predict the phase behavior of
asph.altic crudea. Fussel considered the flocculating
asphaltenes as a separate “heavy liquid phase in
thermodynamic equilibrium with the light liquid and
vapor phases. An inherent weakness of Fussel’s
method is that the extended corresponding states
theory (which is embodied in the R-K EOS) is known
not to address accurately highly polar (i.e., asphaltene
phase) and dissimilar in constituent size systems.
Fussel’s work was followed by Hirschberg et al.’s
(25) proposal which considered the asphaltene entities
as monodisperse polymeric molecules, as a result
polymer theories (i.e., the Flory-Huggins model) were
used to describe the “molecular” behavior of
asphaltenes. Hirschberg and his co-workers proposed a
molecular-thermodynamic liquid model for describing
asphaltene phase behavior in reservoir crudes upon
changes in pressure, temperature, and composition.
The main concept which separates this model from the
colloidal model is that asphaltenes are molecules
dissolved in the oil like any ‘other molecule (see Figure
4). The amount dissolved in the oil is a function of the
thermodynamic conditions of the system.
Furthermore, the process of precipitation and
redissolution is considered to be complete reversible
depending on the thermodynamic state of the system.
As a result, conventional thermodynamic phase
equilibrium methods may be utilized (possibly using
an EOS) to predict the phase behavior of asphaltenes in
the liquid oil. This is similar to Fussel’s method except
that the Flory-Huggins theory [39,40] is utilized to
perform the liquid-liquid equilibrium calculation
between the oil and asphaltene phases.
Hirschberg et al. instead of using a full three phase
model (as Fussel had previously done) chose a
combination of a vapor-liquid and liquid-liquid model,
by assuming that VLE and LLE are independent of each
other. The liquid phase composition was calculated
first by performing VLE calculations, using the Soave
EOS [41], and assuming no asphaltene precipitation.
Then, the Flory-Huggins model was used, based on a
number of simplifying assumptions, to calculate the
amount of asphaltenes precipitated from the liquid oil
phase, provided (i.e., assuming) that the newly formed
asphaltene phase does not affect the vapor-liquid
equilibrium phase split. This assumption may be too
severe, especially for highly uspludticsystems in which
the liquid oil composition changes drastically after
flocculation of asphaltenes.
An apparent improvement to Hirschberg et al.’s
approach was proposed by Kawanaka and Mansoori
[341. Their contribution was to extend Hirschberg’s
method to the so called “polydisperse” case, where
asphaltenes are considered to be a component of the
crude oil that has a molecular weight distribution
-
7
rather than being of a single size. The polydisperse
polymer theory ef Scott and Magat [42,43]was used in
place of the Flory-Huggins theory to calculate the
asphaltene-oil solid-liquid phase equilibria. One subtle
difference between the two approaches is that in the
Hirschberg et al. model the flocculation of asphaltenes
is determined by an LLE calculation, whereas in the
Kawanaka and Mansoori model the flocculation of
asphaltenes is determined by a solid-liquid
equilibrium, Hence, implicitly, Hirschberg et al.
considered the asphaltene pkwe as a liquid whereas
Kawanaka and Mansoori considered it a solid,
Nevertheless, both in Hirschberg et al,’s and Kawanaka
and Mansoori’s model the asphaltene flocculation
process is necessarily taken as reversible,
The molecular thermodynamic approach to
asphaltene flocculation is a well rounded technique
that utilizes the conventional thermodynamic
methods for phase equilibria, The main handicap of
the method seem to lie in that it doea not take into
account, sufficiently, the physical model that was
described in the previous section (2a) which has been
derived over the years and ia based on actual
experimental observations. Namely, this method doea
not t*e into account the effect of resins on asphaltene
phase behavior. Furthermore, it treats asphaltene
flocculation as a molecular reversible phenomenon
which is opposite to the majority of available
experimental and field data. This model, it maybe said,
is more suitable to be app!!.d when predhking asphalt
phase separation th?.3 a tbaltene flocculation and.
deposition.
Asphalt separating from crude oil is a heavy
liquid phase, e.g., the asphalt phase obtained from the
propane crude deasphalting process. It has been
proposed [l,ll&,44] that in asphalt (and bitumens in
general) the asphaltene-resin micelles are still in tact,
i.e., not destroyed. Hence, hi crude oil deasphalting the
asphaltene-resin micelles simply precipitate from the
original oil mixture essentially unaltered together with
the intermicellar liquid (which contains oil and
propane among other) as another “liquid phase. Since
the micelles are still in tact and as a result act l% the
rest of the molecules and are soluble in oil, addition of
oil to this asphalt liquid phase (i.e., changing its
composition, or even its temperature and pressure) is
expected to result in complete mixing (44). Hence, the
process of asphalt precipitation as a separate phase may
be considered as being very close to reversible,
especially near the onset of flocculation. This may be
the case when a heavy second liquid phase reportedly
separates reversibly in high pressure cells when oil is
mixed with light paraffins, C02. etc.
As it will be made evident in the next section the
reversibility or irreversibility of asphaltene
flocculation depends on the state of the asphaltene
resin micelles during flocculation. If the micelles
separate from the oil essentially as they are in their
8 Asphaltene Deposition A Comprehensive Description of
Problem Manifestations and Modelimz Arwroaches
original state then the flocculation process may be
reversed by simply changing the thermodynamic state
of the system (i.e., by changing the temperature,
pressure, and composition). As mentioned before, hi
this case, it should rather be more suitable to talk of
asphalt phase separation than asphaltene flocculation.
Thermodvnamic<ol16idal Amx’each
Recently, based on the colloidal nature of
I layer of the micelle is stripped deep enough and
asphaltenes, a thermodynamic-colloidal model (T-C
Model) of asphaltene flocculation was proposed, as
depicted in Figure 5, for predicting the phase I#tavior
of asphaltenes in crude oil and its derivatives [20,271.
The basic principle behind the formulation of the T-C
Model is that the transfer of peptizing agents (i.e.,
resins) from the asphaltene phase to the oil phase and
vice versa is responsible for the aggregation of
asphaltene micelles and their flocculation into larger
entities which causes them to drop out of suspension.
The highly polar centers (i.e., kernels) of the
asphaltene micelles have a natural tendency to attract
each other (i.e., aggregate), grow in 8* (i.e.~flocculate)~
and, as a result, drop out of soiution or suspension.
However, the outer layer of an asphaltene micelle
the peptizkg layer or resins) serves as a stabilizer
(i.e.,
which due to steric repulsion with the outer layer of
different rnicelles keeps it from flocculating (see Figure
6). As Pfeiffer and Saal imagined 50 years ago, there is a
smooth transition in terms of physical and chemical
properties from the inner side of the peptizing layer to
the outer edges. For example, the highly polar resin
molecules tend to concentrate at the inner side of the
peptizing layer, whereas the less polar outside.
The size of the asphaltene micelle and the
thickness of the peptizing layer at the onset depends on
a number of factors, e.g., nature of asphaltenes and
resins, composition of oil (or solvent power of oil),
temperature, pressure, and other, Whether the
asphaltene micelles remain peptized or flocculate
depends on the solvent properties of the oil at the
prevailing thermodynamic conditions. A pertinent
question at this point is, at the existing equilibrium
distribution of peptizhtg agents between the asphaltene
and oil phases is the solvent power of the liquid oil
phase large enough to keep the asphaltene micelles
from flocculating? or, in different terms, are the steric
repulsion forces between the asphaltene micelle outer
layers large enough to oppose the attractive forces
between the inner and highly polar micelle centers
(i.e., he kerneh)? The pr-s of flocculation may be
described as follows (see Figure ~
a. As a certain crude oil or bitumen sample is
titrated against a flocculant (i.e., n-heptane) two
important changes with respect to asphaltene
micelle flocculation are occuming
i. the solvent power of the oil changes in a
way that the outer layers of peptizing
agents are transferred to the oil phase.
I
.-
SPE 1SS92
ii. the asphaltene mioelle overall polarity (or
sromatiaty) or tendency to flocculate
increases because the oil phase is
becoming less polar (or less aromatic)
whereas the asphaltene phase is becoming
more polar (or more aromatic).
b. At the onset of asphaltene flocculation the outer
the solvent power of the oil has been Iowerwl to
the point that the altered micelles may now
attach to each other grow in size and drop out of
suspension.
It is evident from the above description that the
micelle size at the onset of flocculation is a function of
the flocculant used during titration. The original T-C
Model, in order to keep the mathematics simple,
treated the nature and size of the asphaltene micelle at
the onset as a function of temperature only. This
assumption may be acceptable for flocculant like
normal heptane and heavier paraffins with which the
maximum amount of flocculated asphaltenes is
essentially constant. For flocculant equivalent to
lighter paraffins, however, the nature and size of
flocculated asphaltene micelles is a function of both
temperature and type of flocculant and as a result the
assumption needs to be relaxed, In the important case
of predicting asphaltene flocculation during gas EOR
the miscible injectants often used are equivalent to
normal paraffins lighter than heptane. As a result, -in
these cases the T-C Model would require as input
experimental onsets of the oil with lighter paraffins as
well (i.e., n-C3, n-C4, n-CS), in order to relax the
assumption that the micelle size is independent of the
flocculant.
The T-C Model has been described in more detail
previously in the referenced publications of the
author. In brief, the model utilizes conventional
macroscopic thermodynamb and the equation of state
approach to perform VLE equilibrium calculations for
establishing the liquid phase from which asphaltenes
may flocculate. Next the model uses the
thermodynamic equality of the chemical potentials
between phasea at equilibrium to determine the split of
peptizing agents (i.e., resins) between the oil and
asphaltene phases, Speafically, at equilibrium, !~~
chemical potential of the resin in the oil phase is equal
to its chemical potential in the asphaltene phase, i.e.:
Aaphakona Phaw OHPh-
~R@n = kaaifl 1
In the T-C Model the chemical potential of the
resin in the 011phase is calculated by considering the
resins as large polymeric molecules, hence, invoking
the Flory-Huggins statistical thermodynamic polymer
theory [25#9#1. The following equation is baaed on
the above theory
 . 7
~MR Mn- (PR)r,f
=ln(@)n+l-~+Xn
m= RT 2 asphalt~zweoccurs without significant thermodynamic
Where @m volume fraction of resin in the liquid
Vn,VM,molar’volume of resin and liquid
mixture respectively
~ = (vfi~(&&)2, Hory-Hu@M
interaction parameter
& volubility parameter
Equation 2, which is derived from the F1ory-
Huggins theory, is based on a number of assumptions,
such as:
i. a monodisperse polymer solution behaves
like a chain, i.e., having mobile segments of
equal size to and behaving as a solvent
molecule
ii. the lattice theory of liquids is invoked
iii. the polymer is amorphous (i.e., non-
qtalline)
iv, the system is athermal (i.e., mixing of solvent
and polymer is without energy effects)
It should be noted here that the main reason for
using the Flory-Huggins model to do the resin
chemical potential calculations is simplicity. In fact,
utilizing a polydisperse polymer theory, e.g., the Scott
and Magat theory, may prove to be more accurate,
assuming that the required input data of the model
could be obtained accurately. Another possible choice is
the use of a cubic equation of state. This, however, is
not recommended because cubic equations of state are
normally based on the extended corresponding states
theory which is known not to be accurate for systems
with heavy, highly dissimilar, and polar
molecules.l%e choice of the method for calculating the
resin chemical potential is left to the individual
engineer. Not enough work haa been done in this area
to tilt the balance one way or another, from the
author’s viewpoint. For a more detailed description of
the recommended procedure for calculating the onset
of asphaltene flocculation the reader is directed to the
original publication of this work [20Z71.
Since asphaltenes are known to carry an intrinsic
similar charge [4,14,20,21,22Z3,24,27],their colloidal
suspension stability should be influenced by the
strength of this charge. Figure 8 depicts the process
through which the charge of asphaltenes could
influence the onset of asphaltene flocculation. Since
the opposing electrical force is considered to& weak
aqd long range, it is not expected to play a role in the
flocculation process if the system is far from the onset.
However, if the system is close to the onset it is
possible to have flocculation caused exclusively by
electrokinetic effects. That is, generation of streaming
potential due to flow large enough to cancel the charge
on the asphaltenes and cause them to flocculate
[4,1440,Z23,24XI. In those cases where flocculation of
change in the produced fluids, such as in early stages of
primary production with small drawdown, asphaltene
deposition caused by electrokinetic eff- is possible.
CONCLUSIONS AND RE~ED FUT~
RESEARC~
It should be evident that predicting asphaltene
phase behavior is a very difficult undertaking.
However, as often emphasized in this paper and in
previous literature, the importance of the task of
identifying the state of asphaltenes in the original oil
and the mechanism of flocculation as they relate to
asphaltene phase behavior prediction cannot be over-
emphasized. It is clear that selecting the molecular or
colloidal physical model of asphaltene flocculation
leads to entirely different scientific methods or
approaches for pre@cdng asphaltene phase behavior. If
Pffeifer and Saal’s original physical model depicts
correctly the state of asphaltenes in petroleum then the
T-C Model is bound to give more accurate and realistic
asphaltene phase behavior predictions. If asphaltenes
exist in oil in molecular state then molecular
thermodynamic models would make more accurate
predictions.
Hence, the accuracy of the mathematical models
described in this paper d~ds lirgely not only on
their intricate details but on how accurately the
physical models they are baaed on reflect the real state
of asphaltenes in petroleum as well, That is why at this
time it is more important to work diligently toward
establishing the real state of asphaltenes than do more
mathematical modeling that is based on uncertain
foundations, This type of research appears to be more
of the basic type rather than applied and should be
tuned toward generating high quality experimental
data on asphaltene structure and phase behavior using
contemporary analytical techniques,
As it has been hopefully demonstrated in this
paper the asphaltene deposition problem is real and
has affected seriotily the economics of petroleum
recovery, production, and processing worldwide. With
the expected trend of the petroleum industry toward
heavier and more asphaltic crudes the economics of
petroleum recovery, production, and processing is
bound .to get worse, The economic recovery of oil from
some reservoim, even during primary pn?ductiow has
been seriously challenged by the asphaltene deposition
problem. The petroleum industry is being forced to
direct more attention and capital to the research of
asphaltene deposition because of the threat it poses to
the economic recovery of oil. Those companies that
take the lead in this process will be affected the least by
the adversities of the problem. The impact of the
10 Asphaltene Deposition: A Comprehensive Description of
Problem Manifestations and Modeling Approaches
solution(s) to asphaltene deposition wil! be industry-
wide affecting the economics of oil from the reservoir
all the way to its final destination,
REFERENCES
1. Bossier, R. B. and Crawford, P. B.: “MisciblePhase
Floods May Precipitate Asphalt”. Oil and Gas J.,
Feb. 23,1959,57, pp.137-145.
2. David, A,: “Asphaltene Flocculation During
Solvent Simulation of Heavy 011s”:American
Institute of Chemical Engineers, Symposium
Series,69, no. 127,1973,pp. 56-58.
3. Orr, F. M,, Yu, A. D., and Lien, C. L.: “Phase
Behavior of COZand Crude Oil in Low
Temperature Reservoirs” Sodety of Petroleum
Engin@rs, paper no. 8813,presented at the
SPE/DOE 1st Joint Symposium on EOR, Tulsa,
April 20-23,1980.
4. Preckshot, G, W., Delisle,N. G., Cottrell, C. E. and
Katz, D, L,: “AsphaMcSubstances in Crude Oils”,
Transactions, American Institute of Mining,
Metallurgical, and Petroleum Engineers, 151,1943,
pp.188-1940
5. Shelton, D. A. and Yarborough, L,: “Multiple
Phase Behavior in Porous Media During C02 or
Rich Gas Flooding”, Journal of Petroleum
Technology, 1977,p. 1171,
6. Sachanen, A, N.: “The Chemical Constituents of
Petroleum”, Reinhold Publishing Corp,, 1945.
7. S>ight, J. G. and Moschopedis, S. C.: “On the
Molecular Nature of Petroleum Asphaltenes”.
Chemistry of Asphaltenes, J. W. Bunger and N. C,
Li (Editors), American Chemical Sodety, Wash.,
D.C,, 1981,pp.1-15.
8. Boduszynski, M. M.: “Asphaltenes in Petroleum
Asphalts”. The Advances in Chemistry Series,
No.195 1981, p. 119.
9. Long, R. B.: “The Concept of Asphaltene”. The
Advances in Chemistry Serim, No. 1951981, p. 17.
10, Yen, T. F,: “Present Status of the Structure of
Petroleum Heavy Ends and its Significance to
Various Technical Applications”. Pre-prints ACS,
Div. Pet. Chem,, 17(4),1972,p. 102,
11. Pfeiffer, J., editon “TheProperties of Asphaltic
Bitumen”. Elsevier Publishing Company, 1950.
12. Leontaritis, K. J. and Mansoori, G. A., 1988.
Asphaltene Deposition in Oil Recovery. A Sufiey
of Field Experiences and Research Approaches,
International Journal of Petroleum Science and
SPE 18892
..
Engineering, p. 229, Aug. 1988,Elsevier Publishers
B. V., Amsterdam, The Netherlands.
13. Ray, B. R., Witherspoon, P, A. and Grim, R, E. : “A
Study of the Colloidal Characteristics of
Petroleum Using the Ultracentrifuge”. J. Phys.
Chem. 61,1296,1957.
14. Katz, D. L. and Beu, K. E.: “Nature of Asphaltic
Substances”. Ind. of Engin. Chemistry, 37, p.195,
1945.
15. Haskett, C, E. and Tartera, M.: “ARactical
Solu:ion to the Problem of Asphaltene Deposits -
Hassi Messaoud Field, Algeria”.J. Pet. Tee,, April,
1%5, pp. 387-391,
16. Tuttle, R. N.: “High Pour-point and Asphaltic
Crude Oils and Condensates”. J. Pet. Tech. June,
*llQq
,,., p. 1192.
17. Von Albrecht, C., salathiel, W. M., and Nierode,
D. E.: “Stimulation of Asphaltic Deep Wells and
Shallow Wells in Lake Maracaibo, Venezuela”.
Advances in Methods of Increasing Well
Productivity and Injectivity. Oil Sands, June 1977,
PD7 (l), pp,55-62.
18. Moore, E. W., Growe, C. W., and Hendrickson, A.
R,: “Formation, Effect, and Prevention of
Asphaltene Sludges During Stimulation
Treatments”. J. i et. Tech., Sept. 1965,pp 1023-1028.
19. Boduszynsld, M. M., McKay,J. F. and Latham, D.
R.: “Asphaltenes, Where Are You?”.Proc.
Association of Asphalt Paving Technologists
Technical Sessions. Louisville, Ky, Vol. 49, Feb.
18-20,1980.
20. Leontaritis, K. J, and Mansoori, G. A.: “Asphaltene
Flocculation During Oil Production and
Processing A Thermodynamic-Colloidal Model”.
Pmt. 1987SPE Inter. Symp. on Oilfield Chem., San
:&torr Tetis, (Jam),paper SPE No.16258,pp.
-.
21. Adalialis, S.: “Investigation of Physical and
Chemical Criteria as Related to the Prevention of
Asphalt Deposition in Oil Well Tubings”. MSC
thesis, Petroleum Engineering Department,
Imperial College of the University’of London,
London, September, 1982.
22. Lichaa, P. M. and Herrera, L.: “Electricaland Other
Effects Related to the Formation and Revention
of Asphaltenes Deposition”, Society of Petroleum
Engineers Journal, SPE paper no. 5304,1975.
23. Lichaa, P. M.: “Asphaltene Deposition Problem in
Venezuela Crudes - Usage of Asphaltenes in
 .,

SPE 18892 K. J. Leontaritis 11

Emulsion Stability”. Oil Sands, June 1977,pp.609-
624.
24. Dykstra, D., Beau, K.E.,and Katz, D.L.:Oil and Gas
J.,43,p.~, 1944.
25. Hirschber& A., DeJon&L. N. J., Schipper, B. A.
and Meijers, J. G.: “Influenceof Temperature and
Pressure on Asphaltene Flocculation”. Society of
Petroleum Engineers Journal, June 1984,24(3),
283-293,
35. Koots, J.A. and Speight, J.C,: “Relationof
Petroleum Resins to Asphshenes”. Fuel, 54,1975,
p. 179.
36. Pfeiffer, J. P. and Said, R. N, J,: “Asphaltic Bitumen
as a Colloid System”,J. Phys. Chem. 1940,44,
139.
37. Nellensteyn, F. j.: ‘The Colloidal Structure of
Bitumens”. The Science of Petroleum, Oxford
University Press, vol. 4,2760,1938.

26. Kawanaka, S., Park, S, J,, and Mansoori, G, A.: 38. Fussel, L. T.: “A Techrdque for Calculating
“The Role of Asphaltene Deposition in EOR Gas Muhiphase Equilibria”.SPE J. Aug. 1979,pp. 203-
Flooding A Predictive Technique”. SPE Paper No. 208.
17376.Proc. EOR Symposium of SPE,Tulsa, Ok,
April 17-20,1988, 39. Flory, P.J.: “Principles of Polymer Chemistry”. N.
Y., Cornel University Press, 19536
27. Leontaritis, K J,: “Asphaltene Deposition A
Thermodynamic-Colloidal Model”. Dksertation
for the degree of Doctor of Philosophy in
I 40. Huggins, M. L.:J. Phys. Chem. 9,440,1941.

Chemical Engineerin& March, 1988. University of
Illinois, Chicago, Illinois.
28, Shaw, D. J.: “Introduction to Colloid and Surface
Chemistry”, 3rd edition, Butterworths, London,
1980.
29. Voyutsky, S.: “Colloid Chemistry”. MIR
Publishers Moscow, 1975,English Translation
1978.
30. Addington, D.V,: “Physid and Chemical
Behavior of Liquified Coal in Solids Separation”.
Departriient of Energy project DOE-ET-10550-6/
82010073, final report of the period A, Oct. 1,1976-
Nov. 30,1979.
31. Dickakian, G.and Seay, S,: “Asphaltene
precipitation primary crude exchanger fouling
mechanism, Oil & Gas Journal, Vol. 47, May 7,
1988,pp.47-50,
41. Soave, G.: “Equilibrium Constants From a
Modified Redlich Kwong Equation of State”.
Chem. Eng. Science,Vol. 27, pp.1197-1203.
42, Scott, R. L and Magat, M.: “TheThermodynamics
of High-Polymer Solutiorw I. The Solubtity and
Fraction of a Polymer of Heterogemxwa
Distribution”. J. Chem. Phys., Vol. 13, No. 5,1945,
ps72.
43. Scott, R L ‘The Thermodynamics of High-
Polymer Solutions II. The Volubility and Fraction
of a Polymer of Heterogeryous Distribution”. J.
Chem. Phys., Vol. 13, No. 5,1945, p.178.
44. Vink, D. J, Ames, A. M., David, R. A., and Katz, D.
L.: “Multiple Phase Hydrocarbon Systems”. Oil &
Gas J. Nov. 21,1940.

32. Swanson, J.: “A Contribution to the Physical

Chemistry of the Asphalts”, J. Phys, Chem., 46, p.
141,1942.

33. ‘ %nger, T,G, and Fu, J.C.: “TheNature of C02-

Induced Organic Deposition”.SPE paper no. 16713,
bznd ~nu~ ‘rechnical conference and Exhibition
of The Society of Petroleum Engineers, Dallas,
Texas, Sept. 27-30,1987.

34. Lamtaritis, K.J. and Manwori, G,A.: “Use of High

Performance Liquid Chromatography and Gel
Permeation Chromatography for Characterization
of Resins and Asphaltenes” Intern. J. of
Petroleum Sdence and Engineering (to appear
soon).
 s= 18$92

.,:,
Q
‘/,
;.j ‘.,
,.,. 0,~ W&f
,.,. ‘/ ‘.
,

h~’
.,. ‘.,

4
r
,, gmln
‘/’, ,

,,, ‘
.’. , -011
/ ‘,:,
,
,’,
,\
;:;:
:.

flg.1 . in.Siiu Aaplwllorn IM@llon Fig. 2. AaplUIIOIWSsdsettwd on tha rock cuiaa wtbbllify chm?gos

~- .
,,
..:..
o-b.
Fig. 3- Pep!izatlon of Asphaltenes With Resins
 .
.

WE 18892

‘/ql\, a.;’
I
---- ---- -.
0–0 --0 lo\
0 -! Legmk
-Q I -* O rninmoleculeg
● uomtk molecules
— p~c, naphthcnic, and olefinic molecules

&@akllepallicl.orKemd9

Fig. 4- Molaoular-lhorrnodyMmlc Model Fig. 5- Thermodynamic-cdioiddModel

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Fig.6 - Asphaltmra-l?esin Micello

 SPE 18892 “

p=-!?!?

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Fig. 7-The addition of ● ffoooufant cauae8 thinning of

tha paptlzlng Iay.r wound the aapfraltanawaain mlcalle.

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F24