SPE

Society of Petroleum Engineers

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 was prepared for presentation at the SPE Production Operations Symposium held in Oklahoma City, Oklahoma, March 13-14, 1989.

This paper was selected for presentation by an SPE Program Committee following review of information contained in an abstract submitted by the author(s). Contents of the paper,
as presented, have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material, as presented, does not necessarily reflect
any position of the Society of Petroleum Engineers, its officers, or members. Papers presented at SPE meetings are subject to publication review by Editorial Committees of the Society
of Petroleum Engineers. Permission to copy is restricted to an abstract of not more than 300 words. Illustrations may not be copied. The abstract should contain conspicuous acknowledgment
of where and by whom the paper is presented. Write Publications Manager, SPE, P.O. Box 833836, Richardson, TX 75083-3836. Telex, 730989 SPEDAL.

ABSTRACT asphaltenes different engineers and researchers have.

For instance, for the reservoir engineer it may mean
The so-called "asphaltene problem" manifests itself in formation damage and in-situ plugging; for the
almost all the facets of production, processing, and production engineer, near well formation damage and
transportation of petroleum. Due to the multiplicity of subsurface and surface equipment plugging and
the engineering disciplines involved in the above malfunctions; for the refining engineer, distillation
processes an interdisciplinary approach is best suited column and equipment pluggage and tankage capacity
for seeking fundamental understanding of and loss, as well as catalyst deactivation; for the
solutions to the problem. transportation engineer, pipeline pluggage and capacity
loss; and finally, for the asphalt production specialist,
This paper gives a detailed description of how the blending and asphalt quality headaches. Whatever
asphaltene problem manifests itself in the field. It one's vantage point the bottom line of the "asphaltene
discusses in-situ formation damage deep in the problem" is exactly what it says, problems! The
reservoir matrix and near the wellbore, subsurface and literature on the asphaltene flocculation field
surface production facilities problems, and refining, experiences and research is extensive
blending, and transportation problems due to [1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18)]. By no means
asphaltene flocculation and deposition. The molecular all the existing literature is cited here due to space
and colloidal asphaltene models are described and limitations.
recommendations are made as to the preferred
physical model. Existing, published analytical One of the most intriguing questions related to
asphaltene models based on either molecular or the asphaltene problem is, what the asphaltenes
colloidal nature of asphaltenes are presented and themselves are! Not long ago, some experimental
analyzed. A preferred modeling approach based on the work using field ionization mass spectrometry (FIMS)
colloidal physical model is recommended. The was reported [19] where the authors casted some doubt
colloidal model permits and supports calculations as to the existence of asphaltenes in crude oil as its
based on both reversible equilibrium thermodynamics heaviest component, as most researchers feel, hence,
and irreversible colloidal flocculation as well. they used the title for their paper: "Asphaltenes Where
Are You?". Since FIMS may be destructing the
INTRODUCTION asphaltene micelles and, thus, measuring their
properties in a completely non-aggregated state, which
The expression "Asphaltene Deposition Problem" would not reflect their natural state in the oil, a
means different things to different people, primarily participant of the symposium where the above paper
because of the variation in vantage points related to was being presented suggested to the authors that a
more appropriate title for their paper might have been
References and illustrations at end of paper. "Asphaltenes, What Have You Done with Them?".
This paper refers to work done by the authm· prior to The above transaction highlights the elusiveness of
his affiliation with Arco Oil and Gas Company. asphaltenes, because the one group of scientists could

599
2 Asphaltene Deposition: A Comprehensive Description of SPE 18892
Problem Manifestations and Modeling Approaches

not find them where they were supposed to be whereas deposition is occurring during primary production of a
the other was asking them what they did with them. reservoir, the asphaltene problems should be expected
to diminish as production progresses with time, while
The goal of this paper is two fold: first, present the keeping everything else constant.
scope of the asphaltene problem and hopefully
demonstrate that asphaltenes are for real, and second, It appears then that the only feasible way a non-
give an overview of the industrial and academic asphaltene prone reservoir could get into asphaltene
efforts underway for providing solutions to the flocculation and .deposition problems deep in the
problem. It is frustrating as well as tantalizing to a reservoir matrix by the route of composition change is
scientist or engineer to be involved in the quest to find by secondary or tertiary oil recovery (EOR). In
a solution to a problem in wqich the main culprit is secondary recovery a fluid is injected in the reservoir
not even clearly defined and understood. with the purpose of primarily maintaining the
pressure during production. Depending on the nature
ASPHALTENE PROBLEM MANIFESTATIONS (i.e., composition) of the injected fluid, asphaltene may
start flocculating and depositing in the pores and
Formation Damage passages of the reservoir matrix (see Fig. 1), thus
resulting in severe and possibly irreversible formation
Formation damage due to asphaltene flocculation damage. A similar situation may occur in tertiary oil
and deposition can take place either deep in the recovery, where chemicals and/or miscible solvents
reservoir matrix or near the wellbore. The two cases are added to the formation thus altering the
are discussed separately next. composition of the reservoir fluid (for that matter, any
composition changing process employed has the
1. Deep in the Reservoir Matrix potential of resulting in asphaltene flocculation).

It is generally accepted [1,4,6,11,20,21,22,23,24,25,26] In miscible EOR a displacing fluid (e.g., propane,

that asphaltene flocculation may take place because of C02, NGL, etc.) is injected into the formation with the
either reservoir fluid temperature, pressure and purpose of mixing completely with the reservoir oil
composition changes or electrokinetic effects due to and carry it to the surface. Ideally, in miscible recovery
streaming potential generation during reservoir fluid all of the accessible oil is recoverable due to complete
flow. Usually, in the case of normal reservoir miscibility between the miscible solvent and the
production, no significant changes in temperature are reservoir oil. It is this property of the miscible solvent,
encountered. Furthermore, although a gradual which makes it a favorable candidate for EOR, that also
pressure drop during the production life of· the gives it the potential of causing asphaltene flocculation
reservoir in most cases does occur, a drop in the in the reservoir and sub-sequent in-situ deposition and
pressure is generally accepted to act in a way that pore plugging.
inhibits asphaltene flocculation [1,4,6,11,15,20,21,22,23].
Hence, as the reservoir becomes older asphaltene It has been amply demonstrated that most (if not
problems are expected to diminish (indeed, in all cases all) of the familiar miscible solvents can cause
known to the author they did). Consequently, only two asphaltene flocculation. The question that has not been
dominant mechanisms of asphaltene flocculation may convincingly answered yet ,is how much of the
be considered likely to occur in the reservoir, by flocculated material will actually deposit in-situ and
composition change and/or·by electrokinetic effects. what are the consequences. This is basicly a dynamic
problem (flow related) and depends on the specific
i. Flocculation Due To Composition Changes flowing system (fluid and media). There is an inherent
difficulty in trying to answer the above questions
Two common ways that the composition of a because, first, these answers cannot be easily
reservoir fluid (deep in the reservoir ·matrix) changes generalized and should be tailored obtained for a
are by normal depletion during which the lighter particular system and, second, simulating actual
co1nponents of the reservoir fluid are produced in reservoir conditions in the laboratory is very difficult.
higher proportion (i.e., during primary prdduction by The mechanism of the oil displacement process and a
dissolved gas .drive) and injection of fluids for number of other factors (e.g., related to the asphaltene
enhanced oil recovery (EOR). flocculation mechanism, the geometry of the mass
media, etc.) will dictate the magnitude of the in-situ
The reservoir fluid composition change during deposition.
primary oil production is nearly always towards the
direction that results in a drop of both the GOR and the It is important to note that flocculation and in-
API gravity. Both of these composition trends have as situ deposition are two separate phenomena. It is
a consequence a drop in the asphaltene flocculation possible to have flocculation without substantial in-
tendency of the reservoir fluid. The above are, of situ deposition, provided that the flow dynamics and
course, general trends and may not occur with every the nature of the flocculated material are such that
oil. Hence, generally speaking, even if asphaltene permit erosion and/or carrying of the deposit by the

600
SPE 18892 K. J. Leontari tis 3

2. Near The Well Bore

~owing fluid (the deposits may accumulate, however,
In the production wells and separators). Needless to As discussed above, asphaltene flocculation due to
say that the -flocculated materials contain sizable the streaming potential generated by the flowing
amount of entrapped oil which, if deposited in the reservoir fluid is possible. However, there seems to be
reservoir with the asphaltenes, will not be recovered. a certain threshold in fluid velocity beyond which
Ironically, the entrapment of oil by the flocculating asphaltene flocculation may occur. This threshold for
asphaltenes gives them fluidity and acts against different fluids, conduit mass medium, and geometry
deposition. Because the flocculation is essentially has not been adequately studied to date. However, we
irreversible, dropping the pressure of the flocculated d? know that the higher the velocity of the fluid the
system may result in initiation of the deposition higher the generated streaming potential and as a
process (this is possible in well tubings). result the more severe the asphaltene flocculation
[4,20,22,23,24,27]. In a producing reservoir matrix
Wettability reversal of the reservoir rock caused higher velocities occur near the wellbore, where all the
by asphaltene flocculation and deposition is also a produced fluids converge. Consequently, reservoir
distinct possibility. As Figure 2 shows, the highly polar asphaltene problems caused by electrokinetic effects are
and heavier than water flocculating asphaltene expected to concentrate near the well bore, provided
micelles may diffuse through the water and be that the solubility of the micelles in oil is favorable to
adsorbed onto the rock thus making it oil wet. This (or near) flocculation. In these cases properly designed
should affect oil recovery adversely, because the matrix acidization jobs can restore full well production
permeability to oil is expected to diminish and rate by cleaning up the deposited asphaltenes and,
th~s, eliminating the formation damage[12,17,18,21,27].
residual saturations to increase.
This appears to be a fairly routine process, although
costly, as the author can confirm from personal
ii. Flocculation Due To Electrokinetic Effects experience.

It has been shown that asphaltenes carry an . In the production of reservoir fluids containing
intrinsic charge. This charge has been considered partly Sizable amount of asphaltenes excessively large
responsible for the stability of the asphaltene-resin drawdowns must be avoided, because large drawdowns
micelles [4,14,20,21,22,23,24]. Hence, as the micelles are result in higher fluid velocities deeper in the
aggregating and ready to flocculate from a solubility in formation, which in turn may cause formation
oil standpoint, the similar charges on the micelle damage that is very difficult to remove. When
kernels prevent them from doing so (refer also to a opening a well into production for the first time or
related discussion in later sections). At this point two ~f~e; a workover, it is customary to go through an
things may happen to cause flocculation of the Imhal cleanup period at which time the well is
micelles; first, a further composition change (i.e., directed to the cleanup facilities. Any debris, mud, and
addition of a flocculant) that would make the micelles cleaning or workover fluids that have entered the
even less soluble in the oil and, as a result, cause the formation or sit in the sump or tubing of the well
opposing electrical charges be overcome by the van der must be cleaned out before the well is placed on
Waal-London attractive (dispersion type) forces pro~uction. For asphaltenic oils this step is very
and/ or, second, generation of a streaming potential crucial, because the flow rate during cleanup must be
due to flow (or application of an external potential) large enough to remove all undesirables from the
large enough to neutralize the electrical charges and vicinity of the well while at the same time being small
disturb the force balance between the micelles thus enough to ayoid asphaltene flocculation and resulting
causing them to flocculate. formation damage. Excessive pressure reduction (or
drawdown) should also be avoided because it promotes
The first route of flocculation is possible to occur deposition of flocculated asphaltenes.
deep in the reservoir matrix and was discussed in the
previous section. The second mechanism of Well Problems
flocculation is also possible to occur in the reservoir.
Two very important factors in this case are the velocity In the well asphaltene deposition may manifest
of the flowing reservoir fluid and its composition itself in many ways, but the most obvious one is loss of
(which dictates the solubility of the asphaltene micelles production. Higher and higher choke settings are
in it). Other factors that influence the electrokinetic required to maintain the same production level until
process are the zeta-potential of asphaltenes, their size, the choke is fully open and the production losses
temperature, transport properties of the oil (i.e., cannot be compensated by opening the choke further.
viscosity), and other [4,14,20,21,22,23,2427,28,29,30]. This Eventually, the well may "bridge" and stop flowing
topic has been discussed in more detail in other completely or continue flowing at an extremely small
publications of the author [20,27] and is briefly dealt flow rate in a rather "burping" way where the flow
with later in this paper. starts and stops at different time intervals on its own
volition.

601
4 Asphaltene Deposition: A Comprehensive Description of SPE 18892
Problem Manifestations and Modeling Approaches

Complete plugging of the well is very undesirable Surface facilities

because the cost of asphaltene cleanup to restore
production is very large. A customary method of In the production surface facilities asphaltene
cleanup in this case is "bailing" by wireline. This flocculation and deposition causes tremendous
cleanup method is slow and costly, especially if the problems. What actually happens is that flocculated
asphaltene plug in the well tubing is very hard and asphaltenes deposit on just about everything the crude
long. However, other techniques such as drilling the oil comes in contact with. The biggest impact of this
asphalte~e plug inside the tubing or hydroblasting
problem is on safety and process control and
through 1t (~.g., by using a coiled tubing unit) have monitoring equipment. For instance, level control and
been used w1th, of course, a much higher cleanup cost, or indication equipment as well as sight glasses on
due to the normally high mobilization cost of these production separators and other vessels plug up and as
units. These type of cleanup operations create also a result the equipment overflow. The consequences of
other kind of legistical problems. For instance, this may vary in importance and intensity. High
depending on how soft or hard the asphaltene plug is a pressure safety devices may not actuate and if safety
v~ry large amount of washings may need to be
relief valves are also plugged by asphaltene deposits
disposed o~. In the case of offshore operations this can and fail to open, when needed, the results may very
be a very b1g problem, especially near beaches or tourist well be catastrophic. Thus failure of safety and process
areas. In this case a ~obile barge or standby small monitoring and control devices is a major problem
tanker would be of b1g help, as the author confirms caused by asphaltene deposition.
from personal experience.
In general, it may be said that all vessels and pipes
The most desirable and recommended alternative or even more broadly all production wells and
is to undertake well asphaltene cleanup operations equipment internals are succeptible to asphaltene
before the well plugs up completely. In general the plugging. As a result, identification and prediction of
wells must be monitored daily to detect production the asphaltene flocculation potential of a crude prior to
losses. In this case wireline scraping can be used design and construction of the production and
successfully ~h~le the well effluent is flowing to the processing facilities is absolutely essential. There are
cleanup fac1ht1es, and as a result carrying the various equipment design techniques that may be used
aspha.lten~ scrapings with it. This method may be very to alleviate or minimize the effects of asphaltene
effective m onshore operations. However, in offshore deposition, if it is expected a priori that asphaltene
operations the legistical problem of disposing of the flocculation will occur. This emphasizes the
crude oil-asphaltene scrapings needs to be considered importance of modeling efforts that have as a purpose
car~fully. Ro.uting the well to the production separator
prediction of the phase behavior of asphaltenes in
whlle scrapmg asphaltene deposits could result in crude oil.
serious production problems. Alternatively, a solvent
(e.g., .xylene? bath and wash of the tubing followed by The design techniques referred to above for
scrapmg whlle the well is flowing may be an acceptable processing asphaltenic crude oils depend on the extend
remedy. of operations in the production facilities and other
factors. Detailed description of these design techniques
Pluggage of downhole safety valves (DHSV) and is beyond the scope of this paper. However, an example
their actuation mechanism is another serious problem of such a technique is designing vessel bridles in a way
caused by asphaltene flocculation and deposition. that permits frequent on stream flushing or cleaning
Malfunction of the DHSV's has the potential of by the operator without requiring maintenance
resulting in very serious consequences. DHSV's left in personnel to get involved. Also, parallel vessel
servic~ fo~ long periods without checking their
operation or provision of spare equipment where
operat~on m wells where asphaltene deposition is
economically feasible is another design remedy. This,
occurrmg are bound to malfunction. The same holds of course, just scratches the surface of the process
for other valves of the x-mass tree, e.g., the hydraulic design concerns that are to be addressed if the crude oil
master the wing valve and other. Needle valves on has been shown to be prone to asphaltene flocculation.
the top of x-mass ~rees for isolation of pressure gauges
that m~asure tub1ng head pressures are particularly Evidently, it is of utmost importance for the
succeptlble to asphaltene plugging (although one prospective developer and producer of a new oil
would thing that flocculating micelles would not reach discovery to know whether the oil would undergo
that dead space). There have been cases, known to the asphaltene flocculation prior to being produced or later
author, where the operator removed the pressure during processing. This kind of information would
gauge believing that the needle valve was closed with spark a number of design changes starting from the
subsequent blo~ing of the asphaltene plug resulting in reservoir, wells, production, and processing facilities.
the well shootmg 150 atmospheres asphaltenic sour Designing the above facilities for the case of no
crude oil high into the air. asphaltene flocculation and finding out later that
asphaltenes flocculate is a very costly problem that may
even threaten the economic recovery of the field. It is

602
SPE 18892 K. J. Leontaritis 5

sounder and more economical to design the . Similar .reasoning applies to other processing
production facilities for asphaltene flocculation (if that e.qu1pment, 1.e., heat exchangers, pumps, heaters,
happens to be the case) the first time around rather f1lters, etc... A frequent problem with pumps is
than trying to retrofit later. On the other hand, plugging of the cyclone separator that supplies fluid
~rom the discharge to the pump seals, hence, resulting
overdesigning the facilities to handle an asphaltene
problem that would never materialize is also an m premature pump failure. Also suction strainers plug
u~ very often and, as a result, onstream redundancy in
economic no-no. Hence, it is obvious that the best
alternative is to have a way to reliably predict th1s case may be justified. There is virtually no limit to
asphalt~ne ~occulation in order that proper planning
the number of design changes and provisions that
and des1gn 1s done at the beginning. ~ould be mad~ to. alleviate the asphaltene problem, if it
1s k~own a pr10n t?at asphaltenes will be flocculating
In offshore production operations the "skimpile" durmg the production and processing of the crude oil.
~nd/ or the oily water clean-up system are very It was suggested recently [31] that asphaltene
1mportant and at the same time troublesome to flocculation may be the main culprit of crude unit heat
ope.rate systems. Oily water coming from the vessel ex.c~a~g~r train fouling. Thus, eliminating or
drams and/ or from cleaning the platform decks must m1n1m1z1ng asphaltene flocculation in this heat
?e carefully de-oiled and cleaned before it is disposed of exchanger train could result in hundreds of thousands
mto the sea or re-injected. Flocculated asphaltenes, of dollars annual savings for the petroleum refiners.
because they are surface 'active and their density is
greater than water's, cause serious problems in the ASPHALTENE PHYSICAL MODEL
op.er~tion of the~e equipment (usually the main
prmc1ple of operahon in these equipment is based on General Considerations
th: gravity difference of the fluids being separated,
w1th water, of course, being heavier than oil). As it was demonstrated in the previous section
th: asphaltene problem is very serious and real and,
w1th the trend of the oil industry toward heavier more
Refining and Transportation Facilities asphaltenic oils, bound to get worse. The most
important and nagging question in the minds of most
A parallel may be drawn between the asphaltene researchers of the asphaltene problem (and certainly to
probl~m.s d~uing production and refining, because of the a~t~or) is. what is the true state of asphaltenes in
the .s1mllanty of some of the processing steps and the ongmal ml? or how do asphaltenes exist in the oil
equ1pment. All problems mentioned about before any attempt is made to separate them?
instrumentation for the production side apply to the
refining side as well, provided that the crude oil is . The answer to the above question is very crucial
asphaltenic and asphaltene flocculation is possible at m our quest to understanding and predicting the phase
the processing conditions of the oil and its derivatives.
behavior of asphaltenes. It would be the ultimate of
good luck if one were to develop a model that predicts
For instance, asphaltene flocculation that would
asphaltene phase behavior without having accurate
c~u~e pluggi~g. i~ tower and vessel internals is a very knowledge of how asphaltenes exist in the oil and the
d1st1nct poss1b1hty. A crude oil stabilizer once in a
mechanism by which they flocculate. Hence, one
while (e.g., every two to four months, depending on
should start by asking what appears to be a pertinent
the asphaltene deposition severity) needs to be taken
question at this point, what is known to date about the
out of service for cleaning. The clean-up method may
nature of asphaltenes in the original oil?
be hot water washing, steaming, solvent circulation
and wash, or whatever means have been deemed
There has been a number of experimenters since
appropriate for cleaning the stabilizer. This may be a
the 1930's who tried to provide an answer to the above
very costly operation, especially if the tower is
question [4, 6, 7, 8, 9, 10, 11, 12, 13, 14, 24, 25, 32, 33,34,35].
normally run at full capacity and it is not possible to
Unfortunately, no one has been able to demonstrate
make up the production losses with the available
convincingly and beyond any reasonable doubt what is
equipment. If it is known a priori (i.e., during the
the state of asphaltenes as they originally exist in oil.
process design step) that asphaltene flocculation would
Nevertheless, the information compiled so far by the
be a very distinct possibility, a number of provisions
plethora of researchers on the topic of asphaltenes does
could be made in the original design to either prevent
point in a certain direction that suggests the "most
the asphaltene problem or else permit stabilizer
probable" state of asphaltenes in the original oil.
cleaning without production losses (e.g., provide over-
capa.city in the stabilizer and storage facilities to permit
Some of the most important facts on asphaltenes
makmg up for the lost throughput or provide a second
generated over the years by various experimenters
stabilizer running in parallel). Whatever the decision,
referenced above are:
in general, it is much cheaper to provide these extra
i. Asphaltenes have an intrinsic charge that may
facilities during the original design and construction
be positive or negative depending on their oil
than any time after commissioning and startup.
source. If asphaltenes are placed under the

603
6 Asphaltene Deposition: A Comprehensive Description of SPE 18892
Problem Manifestations and Modeling Approaches

influence of an external electrical field they asphaltenes in their natural stale are polydisperse.
migrate to the oppositely charged electrode. Pfeiffer and Saal depicted asphaltenes in their original
ii. Resins act as peptizing agents for the state as monodisperse, although they did raise the
asphaltenes. They are highly polar and, hence, question of polydispersity. Many recent investigators
attracted by the charged asphaltene kernels (i.e., believe that asphaltenes in the original oil are
micelle centers). They concentrate around the polydisperse [8,9,19,20,26,27,34].
surface of the asphaltenes forming a protective
layer. Resins and asphaltenes together, as The short range steric i11-termolecular repulsive
described above, may be called micelles. These forces between resin molecules adsorbed on different
micelles are separate molecular entities of the asphaltene kernels keeps them from flocculating.
crude oil and subject to all thermodynamic There is also another weaker and of longer range
changes the rest of the components undergo. repulsive force present between the asphaltene
However, the addition of an adequate amount particles because of their similar electrical charge. This
of a flocculant, e.g., a paraffin liken-pentane, repulsive force can be overcome or neutralized by
causes partial or total destruction of the micelle mechanical (large pressure drop, agitation) or electrical
and may result in irreversible flocculation of the (opposing streaming potential) means.
asphaltenes.
iii. Substantially high streaming potentials have Since the asphaltene-resin-oil system appears to
been measured between the inlet and outlet of be a colloidal suspension, as Figure 3 indicates, it is
tubes and coreplugs through which asphaltene behooving to investigate whether colloidal science
containing oils or solutions have flowed. In one techniques can be applied here to predict the stability of
case, the generated streaming potential was the system. To date, there exist two theories that
considered responsible for flocculation of the account for the stability of colloidal dispersions, the
suspended asphaltenes [24]. "DL VO Theory" and the "Steric Stabilization Theory"
iv. Both asphaltenes and resins exist in the oil in a [28,29]. The DLVO theory is applicable to electrolytic
polydisperse state and, as a result, molecular systems, where stabilization is due to the electrical
weight distributions are used to describe them. double-layer. The steric stabilization theory is
v. Asphaltenes and resins have a tendency to applicable to systems where the dispersed phase
aggregate with each other. The degree of (particulate phase) is stabilized by repulsive
aggregation depends on the oil composition (i.e., interactions between molecules adsorbed on the
solvent power of oil). surface of the suspended particles. Based on what is
Although a number of other experimental known to date about the nature of the asphaltenes and
observations and conclusions have been made the other constituents of the petroleum fluids it is believed
above five appear to be accepted by the overwhelming that the colloidal asphaltene dispersions in oil belong
majority of asphaltene researchers. Hence, a physical in the latter (steric) category.
model describing the state of asphaltenes in oil must
incorporate and explain the above five observations. However, the young steric stabilization theory
does not offer as of now any means to produce
Generally Agreed Asphaltene Physical Model quantitative results. As a result, either the steric
stabilization theory would have to be extended or a
In this section a physical model of the asphaltene new theory permitting full quantitative treatment of
resin oil system is described. This model is a natural the asphaltene-resin-oil system would have to be
cultivation of the five observations discussed in the proposed.
previous section. The basic concept embodied in the
model is that asphaltenes exist in the oil in colloidal ANALYTICAL MODELS OF ASPHALTENE
suspension, stabilized by resins adsorbed on their FLOCCULATION
surface (see Figure 3). Pfeiffer and Saal [36], in 1940,
were the first researchers to propose an asphaltene To date, there have been two different
physical model for bitumens similar to the one shown fundamental approaches to the development of
in Figure 3 (although Nellesteyn (37) was first to analytical models predicting asphaltene flocculation.
propose the colloidal nature of bitumens). Later, One is the "Molecular-Thermodynamic" approach
Witherspoon et al. [13] contended that based on their [25,26,38] and the other is the "Thermodynamic-
ultracentrifuge data of Illinois basin oils the Pfeiffer Colloidal" approach [20,27]. The underlying principles
and Saal model for bitumens was applicable to oils as of each of these approaches are discussed next.
well. More experimental work followed that
pinpointed to the applicability of the Pffeifer and Saal ~1olecular-Thermodynamic Approach
model for asphaltenes in oil. Recently (20,27) the
model was revived and utilized to formulate a . 'One of the first molecular-thermodynamic
thermodynamic-colloidal model for predicting the modeling efforts for predicting the asphaltene phase
phase behavior of asphaltenes. One important point, behavior, was published by Fussel [38]. ;Fussel
not fully explained by Pfeiffer and Saa], is whether attempted to describe the phase behavior of asphaltic

604
SPE 18892 K. J. Leontaritis 7

systems by using the equation of state approach. Her rather than being of a single size. The polydisperse
model, which was based on the Redlick-Kwong EOS, polymer theory of Scott and Magat [42,43] was used in
used a simultaneous calculation of vapor-liquid and place of the Flory-Huggins theory to calculate the
liquid-liquid equilibria to predict the phase behavior of asphaltene-oil solid-liquid phase equilibria. One subtle
asphaltic crudes. Fussel considered the flocculating difference between the two approaches is that in the
asphaltenes as a separate "heavy liquid" phase in Hirschberg et al. model the flocculation of asphaltenes
thermodynamic equilibrium with the light liquid and is determined by an LLE calculation, whereas in the
vapor phases. An inherent weakness of Fussel's Kawanaka and Mansoori model the flocculation of
method is that the extended corresponding states asphaltenes is determined by a solid-liquid
theory (which is embodied in the R-K EOS) is known equilibrium. Hence, implicitly, Hirschberg et al.
not to address accurately highly polar (i.e., asphaltene considered the asphaltene phase as a liquid whereas
phase) and dissimilar in constituent size systems. Kawanaka and Mansoori considered it a solid.
Nevertheless, both in Hirschberg et al.'s and Kawanaka
Fussel's work was followed by Hirschberg et al.'s and Mansoori's model the asphaltene flocculation
(25) proposal which considered the asphaltene entities process is necessarily taken as reversible.
as monodisperse polymeric molecules, as a result
polymer theories (i.e., the Flory-Huggins model) were The molecular thermodynamic approach to
used to describe the "molecular" behavior of asphaltene flocculation is a well rounded technique
asphaltenes. Hirschberg and his co-workers proposed a that utilizes the conventional thermodynamic
molecular-thermodynamic liquid model for describing methods for phase equilibria. The main handicap of
asphaltene phase behavior in reservoir crudes upon the method seem to lie in that it does not take into
changes in pressure, temperature, and composition. account, sufficiently, the physical model that was
The main concept which separates this model from the described in the previous section (2a) which has been
colloidal model is that asphaltenes are molecules derived over the years and is based on actual
dissolved in the oil like any other molecule (see Figure experimental observations. Namely, this method does
4). The amount dissolved in the oil is a function of the not take into account the effect of resins on asphaltene
thermodynamic conditions of the system. phase behavior. Furthermore, it treats asphaltene
Furthermore, the process of precipitation and flocculation as a molecular reversible phenomenon
redissolution is considered to be complete reversible which is opposite to the majority of available
depending on the thermodynamic state of the system. experimental and field data. This model, it may be said,
As a result, conventional thermodynamic phase is more suitable to be applied when predicting asphalt
equilibrium methods may be utilized (possibly using phase separation than asphaltene flocculation and
an EOS) to predict the phase behavior of asphaltenes in deposition.
the liquid oil. This is similar to Fussel's method except
that the Flory-Huggins theory [39,40] is utilized to Asphalt separating from crude oil is a heavy
perform the liquid-liquid equilibrium calculation liquid phase, e.g., the asphalt phase obtained from the
between the oil and asphaltene phases. propane crude deasphalting process. It has been
proposed [1,11,36,44] that in asphalt (and bitumens in
Hirschberg et al. instead of using a full three phase general) the asphaltene-resin micelles are still in tact,
model (as Fussel had previously done) chose a i.e., not destroyed. Hence, in crude oil deasphalting the
combination of a vapor-liquid and liquid-liquid model, asphaltene-resin micelles simply precipitate from the
by assuming that VLE and LLE are independent of each original oil mixture essentially unaltered together with
other. The liquid phase composition was calculated the intermicellar liquid (which contains oil and
first by performing VLE calculations, using the Soave propane among other) as another "liquid" phase. Since
EOS [41], and assuming no asphaltene precipitation. the micelles are still in tact and as a result act like the
Then, the Flory-Huggins model was used, based on a rest of the molecules and are soluble in oil, addition of
number of simplifying assumptions, ~o calculate the oil to this asphalt liquid phase (i.e., changing its
amount of asphaltenes precipitated from the liquid oil composition, or even its temperature and pressure) is
phase, provided (i.e., assuming) that the newly formed expected to result in complete mixing (44). Hence, the
asphaltene phase does not affect the vapor-liquid process of asphalt precipitation as a separate phase may
equilibrium phase split. This assumption may be too be considered as being very close to reversible,
severe, especially for highly asphaltic systems in which especially near the onset of flocculation. This may be
the liquid oil composition changes drastically after the case when a heavy second liquid phase reportedly
flocculation of asphaltenes. separates reversibly in high pressure cells when oil is
mixed with light paraffins, C02. etc.
An apparent improvement to Hirschberg et al.'s
approach was proposed by Kawanaka and Mansoori As it will be made evident in the next section the
[36]. Their contribution was to extend Hirschberg's reversibility or irreversibility of asphaltene
method to the so called "polydisperse" case, where flocculation depends on the state of the asphaltene-
asphaltenes are considered to be a component of the resin micelles during flocculation. If the micelles
crud~ oil that has a molecular weight distribution separate from the oil essentially i:lS they are in their

605
8 Asphaltene Deposition: A Comprehensive Description of SPE 18892
Problem Manifestations and Modeling Approaches

original state then the flocculation process may be ii. the asphaltene micelle overall polarity (or
reversed by simply changing the thermodynamic state aromaticity) or tendency to flocculate
of the system (i.e., by changing the temperature, increases because the oil phase is
pressure, and composition). As mentioned before, in becoming less polar (or less aromatic)
this case, it should rather be more suitable to talk of whereas the asphaltene phase is becoming
asphalt phase separation than asphaltene flocculation. more polar (or more aromatic).
b. At the onset of asphaltene flocculation the outer
Thermodynamic-Colloidal Approach layer of the micelle is stripped deep enough and
the solvent power of the oil has been lowered to
Recently, based on the colloidal nature of the point that the altered micelles may now
asphaltenes, a thermodynamic-colloidal model (T-C attach to each other grow in size and drop out of
Model) of asphaltene flocculation was proposed, as suspension.
depicted in Figure 5, for predicting the phase behavior
of asphaltenes in crude oil and its derivatives [20,27]. It is evident from the above description that the
The basic principle behind the formulation of the T-C micelle size at the onset of flocculation is a function of
Model is that the transfer of peptizing agents (i.e., the flocculant used during titration. The original T-C
resins) from the asphaltene phase to the oil phase and Model, in order to keep the mathematics simple,
vice-versa is responsible for the aggregation of treated the nature and size of the asphaltene micelle at
asphaltene micelles and their flocculation into larger the onset as a function of temperature only. This
entities which causes them to drop out of suspension. assumption may be acceptable for flocculants like
The highly polar centers . (i.e., kernels) of the normal heptane and heavier paraffins with which the
asphaltene micelles have a natural tendency to attract maximum amount of flocculated asphaltenes is
each other (i.e., aggregate), grow in size (i.e., flocculate), essentially constant. For flocculants equivalent to
and, as a result, drop out of solution or suspension. lighter paraffins, however, the nature and size of
flocculated asphaltene micelles is a function of both
However, the outer layer of an asphaltene micelle temperature and type of flocculant and as a result the
(i.e., the peptizing layer or resins) serves as a stabilizer assumption needs to be relaxed. In the important case
which due to steric repulsion with the outer layer of of predicting asphaltene flocculation during gas EOR,
different micelles keeps it from flocculating (see Figure the miscible injectants often used are equivalent to
6). As Pfeiffer and Saal imagined 50 years ago, there is a normal paraffins lighter than heptane. As a result, .in
smooth transition in terms of physical and chemical these cases the T-C Model would require as input
properties from the inner side of the peptizing layer to experimental onsets of the oil with lighter paraffins as
the outer edges. For example, the highly polar resin well (i.e., n-C3, n-C4, n-CS), in order to relax the
molecules tend to concentrate at the inner side o.f the assumption that the micelle size is independent of the
peptizing layer, whereas the less polar outside. flocculant.
The size of the asphaltene micelle and the The T-C Model has been described in more detail
thickness of the peptizing layer at the onset depends on previously in the referenced publications of the
a number of factors, e.g., nature of asphaltenes and author. In brief, the model utilizes conventional
resins, composition of oil (or solvent power of oil), macroscopic thermodynamics and the equation of state
temperature, pressure, and other. Whether the approach to perform VLE equilibrium calculations for
asphaltene micelles remain peptized or flocculate establishing the liquid phase from which asphaltenes
depends on the solvent properties of the oil at the may flocculate. Next the model uses the
prevailing thermodynamic conditions. A pertinent thermodynamic equality of the chemical pote~tials
question at this point is, at the existing equilibrium between phases at equilibrium to determine the split of
distribution of peptizing agents· between the asphaltene peptizing agents (i.e., resins) between the oil and
and oil phases is the solvent power of the liquid oil asphaltene phases. Specifically, at equilibrium, the
phase large enough to keep the asphaltene micelles chemical potential of the resin in the oil phase is equal
from flocculating? or, in different terms, are the steric to its chemical potential in the asphaltene phase, i.e.:
repulsion forces between the asphaltene micelle outer
layers large enough to oppose the attractive forces Asphaltene Phase Oil Phase
between the inner and highly polar micelle centers
(i.e., the kernels)? The process of flocculation may be
J..l Resin =J..l Resin 1
described as follows (see Figure 7): In the T-C Model the chemical potential of the
a. As a certain crude oil or bitumen sample is resin in the ml phase is calculated by considering the
titrated against a flocculant (i.e., n-heptane) two resins as large polymeric molecules, hence, invoking
important changes with respect to asphaltene the Flory-Huggins statistical thermodynamic polymer
micelle flocculation are occurring: theory [25,39,40]. The following equation is based on
i. the solvent power of the oil changes in a the above theory:
way that the outer layers of peptizing
agents are transferred to the oil phase.

606
SPE 18892 K. J. Leontaritis 9

on the asphaltenes and cause them to flocculate

[4,14,20,22,23,24,27]. In those cases where flocculation of
2 asphalt~nes occurs withou~ significant thermodynamic
change m the produced fluids, such as in early stages of
prima:~ production with small drawdown, asphaltene
Where: <l>R, volume ~action of resin in the liquid
deposition caused by electrokinetic effects is possible.
VR, Ym, molar volume of resin and liquid
mixture respectively
XR = (vR/RT)(5m-5R)2, Flory-Huggins
interaction parameter CONCLUSIONS AND RECOMMENDED FUTURE
a, solubility parameter RESEARCH

It should be evident that predicting asphaltene

Equation 2, which is derived from the Flory-
Huggins theory, is based on a number of assumptions, phase behavior is a very difficult undertaking.
such as: However, as often emphasized in this paper and in
previous literature, the importance of the task of
i. a monodisperse polymer solution behaves identifying the state of asphaltenes in the original oil
like a chain, i.e., having mobile segments of and the mechanism of flocculation as they relate to
equal size to and behaving as a solvent asphaltene phase behavior prediction cannot be over-
molecule emphasized. It is clear that selecting the molecular or
ii. the lattice theory of liquids is invoked colloidal physical model of asphaltene flocculation
iii. the polymer is amorphous (i.e., non- leads to entirely different scientific methods or
crystalline) approaches for predicting asphaltene phase behavior. If
i v. the system is a thermal (i.e., mixing of solvent Pffeifer and Saal's original physical model depicts
and polymer is without energy effects) correctly the state of asphaltenes in petroleum then the
T-C Model is bound to give more accurate and realistic
It should be noted here that the main reason for asphaltene phase behavior predictions. If asphaltenes
using the Flory-Huggins model to do the resin exist in oil in molecular state then molecular
ch~~!cal potential calculations is simplicity. In fact,
thermodynamic models would make more accurate
uhhzmg a polydisperse polymer theory, e.g., the Scott predictions.
and Magat theory, may prove to be more accurate,
assuming that the required input data of the model Hence, the accuracy of the mathematical models
could be obtained accurately. Another possible choice is described in this paper depends largely not only on
the use of a cubic equation of state. This, however, is their intricate details but on how accurately the
not recommended because cubic equations of state are physical models they are based on reflect the real state
normally based on the extended corresponding states ~f as~h~tenes in .petrolE!um as well. That is why at this
theory which is known not to be accurate for systems hme It IS more Important to work diligently toward
with heavy, highly dissimilar, and polar establishing the real state of asphaltenes than do more
molecules.The choice of the method for calculating the mathematical modeling that is based on uncertain
resin chemical potential is left to the individual foundations. This type of research appears to be more
engineer. Not enough work has been done in this area of the basic type rather than applied and should be
to tilt the balance one way or another, from the tuned toward generating high quality experimental
author's viewpoint. For a more detailed description of data on asphaltene structure and phase behavior using
the recommended procedure for calculating the onset contemporary analytical techniques.
of asphaltene flocculation the reader is directed to the
original publication of this work [20,27]. As it has been hopefully demonstrated in this
paper the asphaltene deposition problem is real and
Since asphaltenes are known to carry an intrinsic has affected seriously the economics of petroleum
similar charge [4,14,20,21,22,23,24,27], their colloidal recovery, production, and processing worldwide. With
suspension stability should be influenced by the the ~xpected trend of the petroleum industry toward
strength of this charge. Figure 8 depicts the process heavier and more asphaltic crudes the economics of
through which the charge of asphaltenes could petroleum recovery, production, and processing is
influence the onset of asphaltene flocculation. Since bound .to get worse. The economic recovery of oil from
the opposing electrical force is considered to be weak some reservoirs, even during primary production, has
and long range, it is not expected to play a role in the been seriously challenged by the asphaltene deposition
flocculation process if the system is far from the onset. problem. The petroleum industry is being forced to
However, if the system is close to the onset it is direct more attention and capital to the research of
possible to have flocculation caused exclusively by asphaltene deposition because of the threat it poses to
electrokinetic effects. That is, generation of streaming the economic recovery of oil. Those companies that
potential due to flow large enough to cancel the charge take the lead in this process will be affected the least by
the adversities of the problem. The impact of the

607
10 Asphaltene Deposition: A Comprehensive Description of SPE 18892
Problem Manifestations and Modeling Approaches

solution(s) to asphaltene deposition will be industry- Engineering, p. 229, Aug. 1988, Elsevier Publishers
wide affecting the economics of oil from the reservoir B. V., Amsterdam, The Netherlands.
all the way to its final destination.
13. Ray, B. R., Witherspoon, P. A. and Grim, R. E. : "A
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Petroleum Using the Ultracentrifuge". J. Phys.
1. Bossler, R. B. and Crawford, P. B.: "Miscible-Phase Chern. 61, 1296, 1957.
Floods May Precipitate Asphalt". Oil and Gas J.,
Feb. 23, 1959, 57, pp.l37-145. 14. Katz, D. L. and Beu, K. E.: "Nature of Asphaltic
Substances". Ind. of Engin. Chemistry, 37, p.l95,
2. David, A.: "Asphaltene Flocculation During 1945.
Solvent Simulation of Heavy Oils". American
Institute of Chemical Engineers, Symposium 15. Haskett, C. E. and Tartera, M.: "A Practical
Series, 69, no. 127, 1973, pp. 56-58. Solution to the Problem of Asphaltene Deposits-
Hassi Messaoud Field, Algeria". J. Pet. Tee., April,
3. Orr, F. M., Yu, A. D., and Lien, C. L.: "Phase 1965, pp. 387-391.
Behavior of C02 and Crude Oil in Low
Temperature Reservoirs" Society of Petroleum 16. Tuttle, R.N.: "High Pour-point and Asphaltic
Engineers, paper no. 8813, presented at the Crude Oils and Condensates". J. Pet. Tech. June,
SPE/DOE 1st Joint Symposium on EOR, Tulsa, 1983, p. 1192.
April 20-23, 1980.
17. Von Albrecht, C., Salathiel, W. M., and Nierode,
4. Preckshot, G. W., Delisle, N. G., Cottrell, C. E. and D. E.: "Stimulation of Asphaltic Deep Wells and
Katz, D. L.: "Asphaltic Substances in Crude Oils", Shallow Wells in Lake Maracaibo, Venezuela".
Transactions, American Institute of Mining, ' Advances in Methods of Increasing Well
Metallurgical, and Petroleum Engineers, 151,1943, Productivity and Injectivity. Oil Sands, June 1977,
pp.l88-194. . PD7 (1), pp.55-62.

5. Shelton, D. A. and Yarborough, L.: "Multiple 18. Moore, E. W., Growe, C. W., and Hendrickson, A.
Phase Behavior in Porous Media During C02 or R.: "Formation, Effect, and Prevention of
Rich Gas Flooding", Journal of Petroleum Asphaltene Sludges During Stimulation
Technology, 1977, p. 1171. Treatments". J. Pet. Tech., Sept. 1965, pp 1023-1028.

6. Sachanen, A. N.: "The Chemical Constituents of 19. Boduszynski, M. M., McKay, J. F. and Latham, D.
Petroleum". Reinhold Publishing Corp., 1945. R.: "Asphaltenes, Where Are You?". Proc.
Association of Asphalt Paving Technologists
7. Speight, J. G. and Moschopedis, S.C.: "On the Technical Sessions. Louisville, Ky, Vol. 49, Feb.
Molecular Nature of Petroleum Asphaltenes". 18-20, 1980.
Chemistry of Asphaltenes, J. W. Bunger and N.C.
Li (Editors), American Chemical Society, Wash., 20. Leontaritis, K. J. and Mansoori, G. A.: "Asphaltene
D.C., 1981, pp.l-15. Flocculation During Oil Production and
Processing: A Thermodynamic-Colloidal Model".
8. Boduszynski, M. M.: "Asphaltenes in Petroleum Proc. 1987 SPE Inter. Symp. on Oilfield Chern., San
Asphalts". The Advances in Chemistry Series, Antonio, Texas, (Jan.), paper SPE No.16258, pp.
No.195 1981, p. 119. 149-158.

9. Long, R. B.: "The Concept of Asphaltene". The 21. Adalialis, S.: "Investigation of Physical and
Advances in Chemistry Series, No. 195 1981, p. 17. Chemical Criteria as Related to the Prevention of
Asphalt Deposition in Oil Well Tubings". MSc
10. Yen, T. F.: "Present Status of the Structure of thesis, Petroleum Engineering Department,
Petroleum Heavy Ends and its Significance to Imperial College of the University of London,
Various Technical Applications". Pre-prints ACS, London, September, 1982.
Div. Pet. Chern., 17(4), 1972, p. 102.
22. Lichaa, P. M. and Herrera, L.: "Electrical and Other
11. Pfeiffer, J., editor: "The Properties of Asphaltic Effects Related to the Formation and Prevention
Bitumen". Elsevier Publishing Company, 1950. of Asphaltenes Deposition", Society of Petroleum
Engineers Journal, SPE paper no. 5304, 1975.
12. Leontaritis, K. J. and Mansoori, G. A., 1988.
Asphaltene Deposition in Oil Recovery. A Survey 23. Lichaa, P. M.: "Asphaltene Deposition Problem in
of Field Experiences and Research Approaches, Venezuela Crudes- Usage of Asphaltenes in
International Journal of Petroleum Science and

608
SPE 18892 K. J. Leontaritis 11

Emulsion Stability ... Oil Sands, June 1977, pp.609- 35. Koots, J.A. and Speight, J.C.: "Relation of
624. Petroleum Resins to Asphaltenes 11 • Fuel, 54, 1975,
p.179.
24. Dykstra, D., Beau, K.E., and Katz, D.L.: Oil and Gas
J., 43, p.79, 1944. 36. Pfeiffer, J.P. and Saal, R.N. J.: .. Asphaltic Bitumen
as a Colloid System.., J. Phys. Chern. 1940,44,
25. Hirschberg, A., DeJong, L. N. J., Schipper, B. A. 139.
and Me~jers, J. G.: .. Influence of Temperature and
Pressure on Asphaltene Flocculation... Society of 37. Nellensteyn, F. J.: .. The Colloidal Structure of
Petroleum Engineers Journal, June 1984, 24(3), Bitumens ... The Science of Petroleum, Oxford
283-293. University Press, vol. 4, 2760, 1938.

26. Kawanaka, S., Park, S. J., and Mansoori, G. A.: 38. Fussel, L. T.: 11 A Technique for Calculating
.. The Role of Asphaltene Deposition in EOR Gas Multiphase Equilibria... SPE J. Aug. 1979, pp. 203-
Flooding: A Predictive Technique... SPE Paper No. 208.
17376. Proc. EOR Symposium of SPE, Tulsa, Ok,
April17-20, 1988. 39. Flory, P.J.: .. Principles of Polymer Chemistry... N.
Y., Cornel University Press, 1953.
27. Leontaritis, K. J.: 11 Asphaltene Deposition: A
Thermodynamic-Colloidal Model ... Dissertation 40. Huggins, M. L.: J. Phys. Chern. 9, 440, 1941.
for the degree of Doctor of Philosophy in
Chemical Engineering, March, 1988. University of 41. Soave, G.: .. Equilibrium Constants From a
Illinois, Chicago, Illinois. Modified Redlich Kwong Equation of State...
Chern. Eng. Science, Vol. 27, pp.1197-1203.
28. Shaw, D. J.: .. Introduction to Colloid and Surface
Chemistry ... 3rd edition, Butterworths, London, 42. Scott, R. Land Magat, M.: .. The Thermodynamics
1980. of High-Polymer Solutions: I. The Solubility and
Fraction of a Polymer of Heterogeneous
29. Voyutsky, S.: ..Colloid Chemistry ... MIR Distribution... J. Chern. Phys., Vol. 13, No. 5, 1945,
Publishers Moscow, 1975, English Translation p.172.
1978.
43. Scott, R. L: 11 The Thermodynamics of High-
30. Addington, D.V.: .. Physical and Chemical Polymer Solutions: IT. The Solubility and Fraction
Behavior of Liquified Coal in Solids Separation ... of a Polymer of Heterogen~us Distribution ... J.
Department of Energy project DOE-ET-10550-6/ Chern. Phys., Vol. 13, No.5, 1945, p.178.
8201 0073, final report of the period A, Oct. 1, 1976-
Nov. 30, 1979. 44. Vink, D. J, Ames, A. M., David, R. A., and Katz, D.
L.: .. Multiple Phase Hydrocarbon Systems ... Oil &
31. Dickakian, G.and Seay, S.: .. Asphaltene Gas J. Nov. 21, 1940.
precipitation primary crude exchanger fouling
mechanism. Oil & Gas Journal, Vol. 47, May 7,
1988, pp.47-50.

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

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

33. Monger, T.G. and Fu, J.C.: ..The Nature of C02-

Induced Organic Deposition ... SPE paper no .. 16713,
62nd Annual Technical Conference and Exhibition
of The Society of Petroleum Engineers, Dallas,
Texas, Sept. 27-30, 1987.

34. Leontaritis, K.J. and Mansoori, G.A.: ..Use of High

Performance Liquid Chromatography and Gel
Permeation Chromatography for Characterization
of Resins and Asphaltenes .. Intern. J. of
Petroleum Science and Et;lgineering (to appear
soon).

609
 SPE 18892

water

asphaltenes

...._ grain

Flg.1 -In-Situ Asphaltene Deposition Fig. 2- Asphaltenes adsorbed on the rock cause wettablllty changes

'-

?
~

~-
Fig. 3 - Peptization of Asphaltenes With Resins

610
 SPE 18892

0 ... 0 .. ~
-~, -1/0,.
o/llt -o 1
~ 0
.
' _j
a- !'0
1
a. '~o, 0 • -
I /.I,,Q....
, .. - /
-0- 0
./,

...

0- 0 ~0
I 0 '
~- Legend:
/
-. I -_. 0 resin molecules
e aromatic molecules
paraHinlc, olaHinlc, and naphthanlc molaeulu _ paraffinic, naphthenic, and olefinic molecules
0 Aromatic molaculu
e- Raaln (polar, aromatlclhataroatom) molaculaa
~ asphaltene particles or kernels
- Asphaltanlc molaculaa

Fig. 4 • Molecular-Thermodynamic Model Fig. 5 - Thermodynamic-Colloidal Model

Fig.6 • Asphaltene-Resin Micelle

611
 SPE 18892

Fig. 7 - The addition of a flocculent causes thinning of

the peptlzlng layer around the asphaltene:-resln micelle.
A

B
c

D E

612
 SPE 188 9 2

.......,_
F3
--..
F3

F1

F1 = F2 + F3

Fig. 8 ·Force Balance on asphaHene micelles showing the effect of electric charge (F1=dispersive aHraction of
asphaHene kernels, F2:steric repulsion of peptizing layers, F3::electrlcal repulsion due to the similar charges).

613