SPE 59703

Asphaltene: To Treat or Not

Harold L. Becker JR, Unichem A Division of BJ Services Company

Copyright 2000, Society of Petroleum Engineers Inc.

This paper was prepared for presentation at the 2000 SPE Permian Basin Oil and Gas
Recovery Conference held in Midland, Texas, 2123 March 2000.
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presented, have not been reviewed by the Society of Petroleum Engineers and are subject to
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Abstract
The work described in this paper has been conducted over
several years under both laboratory and field conditions.
Several field case histories and supporting laboratory
observations are presented to substantiate the conclusions
expressed.
Asphaltenes are often invoked to describe the nature of
organic damage and obstructions found when atypical forms
of organic deposits appear. In fact a majority of problems
studied by this laboratory have been misidentified as
asphaltene when the true problem was due to paraffin wax
deposition. Asphaltenes are poorly understood, consequently
methods aimed at dealing with deposit mechanisms and
chemical prevention present a doubly difficult challenge.
Asphaltene deposition mechanisms and the chemical
structures responsible are less well characterized than those of
emulsion breaking, corrosion protection, and paraffin deposit
control. Since most asphaltene deposits are associated with
paraffin and there exists many proven methods of paraffin
control, in many cases it makes better sense to attack organic
deposit problems with paraffin control products than some
unproven asphaltene inhibitor.
This paper suggests that adequate methods exist today for the
removal and control of paraffin wax damage, and that methods
for the control of asphaltenes are still in a relatively embryonic
state of development. Until the day comes that asphaltenes are
well understood chemically, as are waxes, emulsions,
corrosion, and scale, the hope of economically treating them
will remain a problem for research.

Introduction
Asphaltenes are basically defined as comprising an organic
fraction of crude oil that is insoluble when that oil is placed in
fifty times its volume in pentane.1 This definition is extremely
broad and non-informative, and very little information about
the chemical structure of these pentane insoluble fractions is
gained by this procedure. In fact if the crude oil is not
properly pretreated to remove water and solids, confusion can
arise about the true quantity of asphaltenes that are actually
present. This operational definition of asphaltenes results
from historical observations made by oil industry personnel,
and was never intended to offer a rigorous description of these
substances. One outstanding feature of this method of
isolating asphaltenes is its clear tendency to exclude ionic
and/or polar species possessing strong intermolecular
interactions from solvation by pentane. Hidden within this
feature is the fact that higher molecular weight normal
paraffins tend to aggregate by inductive charge association
through London dispersion forces (Fig.1). Unless the pentane
solution is heated to disrupt these forces of aggregation the
higher normal paraffins will also be included as part of the
precipitated asphaltenes.
Many organic molecules can be classified as ionic and/or
polar. Carboxylic acids and their salts are examples of
naturally occurring organic molecules that can be and are
often found in crude oil (Fig. 2). Additionally, many amines
and anionic amine salts are known to be present in crude oils
(Fig. 3). Although the concentration of these molecules is
usually low in the majority of crude oils produced, they are
often associated with problems in its production.
Asphaltenes, as they are operationally defined, can thus be
thought of as including these molecules.
Further, as
mentioned above, normal paraffins can also be included as
part of the isolated asphaltenes when no heat has been
applied to the pentane oil mixture. Although researchers
attempting to elucidate structural features of asphaltenes
have expended considerable efforts, the basic lack of a clear
definition of these materials hinders progress.2
Vague
descriptions of resins and maltenes are given to describe the
components thought to be responsible for the suspension of
asphaltenes (Fig. 4). Thus, confusion on confusion results
and speculation replaces fact when dealing with the ill-defined
nature of asphaltenes.

HAROLD L. BECKER "JR"

What Do We Really know about asphaltenes?

If we constrain our speculation and concede the operational
definition, we can only say that asphaltenes are those species
present in crude oil that possess a tendency to aggregate
despite the solvation effects of pentane. This definition does
not exclude the carboxylic acids, amines, and their respective
salts. Further, it does not exclude those molecules that
aggregate through London forces of dispersion such as higher
molecular weight paraffins. Thus one or several of the acids,
amines, their respective salts, and paraffins could be
considered asphaltenes. Some additional qualifiers have been
added to the definition of asphaltenes over the years such as
following:
1) Those fractions of crude oil that are insoluble in fifty
times their volume in pentane are intensely colored
species (e.g., black).
2) Those fractions of crude oil that are insoluble in fifty
times their volume in pentane possess polar character.
3) Those fractions of crude oil that are insoluble in fifty
times their volume in pentane migrate in an electric
field.
4) Those fractions of crude oil that are insoluble in fifty
times their volume in pentane are comprised of
molecules that contain heteroatoms (e.g., Nitrogen,
Oxygen, and Sulfur).
Although these qualifiers help in the characterization of
asphaltenes they do little to negate the possibility that
carboxylic acids, amines, their salts, and higher molecular
weight paraffins are included as part of the pentane
precipitated asphaltenes. Intensely colored species often
result from very small quantities of highly conjugated
molecules (repeating units of doubly bonded carbons
separated by two saturated carbons), or metallic complexes
(Fig. 5). Carboxylic acids, amines, and their respective salts
possess polarity and as such they can also migrate in electric
fields (Fig.6). Carboxylic acids, amines, and their respective
salts also include heteroatoms (Fig. 7). Therefore, a case can
be made that what is classified as asphaltene might just as
easily be called heteroatom molecular species inclusion in a
crude oil .
Laboratory Testing
Much of the laboratory work conducted on asphaltenes has
been directed at methods for the solublization or suspension of
these materials. One such method involves the precipitation
of the asphaltenes and resolvation or resuspension of them
in large volumes of incompatible solvent (i.e., pentane). In
this test, a small sample of the crude oil (e.g., 1 c.c.) is placed
in a large volume of pentane (e.g., 50 c.c.) and allowed to
precipitate, whereupon a small quantity (e.g., 1000 PPM) of
suspending agent or test compound is added and the results
of its addition observed. If the test compound is effective,
the precipitated asphaltene will be dispersed and remain
dispersed throughout the pentane. Although this method does
suggest that certain chemical compounds are useful in the

SPE 59703

dispersion of materials that are incompatible with lighter

hydrocarbons, it does little to indicate whether it will be
successful in the actual crude oil system.
Another test procedure involves the employment of core
testing apparatus to simulate some of the reservoir conditions
under which the crude is produced. The test apparatus
consists of high-pressure pump, Hastler core holder, Barea
sandstone core, forward/backward valving, pressure
transducer, U.V./Visible spectrometer, and two-channel
recorder (Fig. 8). Samples of asphaltene collected from the
field or precipitated from the crude are added to xylene and
pumped onto a brine-saturated core while the pressure and
absorbency are measured. Xylene pumping is continued until a
base-line pressure and absorbency is achieved. Once a high
base-line pressure and absorbency are established, chemical
additives are added to the xylene flush and pumped onto the
core. If the additives are effective, they will cause a drop in
pressure and an increase in absorbency greater than the xylene
alone. Testing indicated that various additives were more
effective than xylene alone, and that fatty bi-polar molecules
were among the most effective additives for the removal of
damage.3
Infrared and H1NMR analysis of various field-collected and
laboratory prepared samples of asphaltenes have yielded
spectra that are mostly consistent with those of hydrocarbons.
In fact the absence of functional group adsorption bands in the
infrared indicate that these structures contain less than few
percent heteroatom functionality.
Thus, instrumental
analytical methods have not yet clearly defined or structurally
elucidated many of the attributes of asphaltenes.

Field Problems related to Asphaltenes

What circumstances promote the formation of asphaltene
deposits in the oil field? During the last decade the use of CO2
floods have gained increasing acceptance as a method of
enhancing the recovery of petroleum. CO2 is injected into the
producing formation at pressures above its critical pressure
(e.g., pressures that reduce its gas volume to a volume where it
exists in a liquid state). CO2 is polar but it does not possess a
dipole moment and it cannot act to solvate dipolar species or
non-polar components within crude oil, it can only act as a
diluent. Thus CO2 at critical pressure behaves as pentane does
when mixed with crude oil; it acts as a non-interactive matrix
with charged species and a marginal solvent for low
hydrocarbons. As CO2 breakthrough (the appearance of fluids
at the well bore) occurs, organic deposits begin to obstruct the
flow of reservoir fluids. It is the character of these deposits
that often contributes to the confusion about the nature of
asphaltenes.
These deposits are regularly obtained from
sucker rods, and well tubing and saved for future analysis.
However, they are not generally saved in sealed containers.
The gases have been allowed to escape from the sample and
what is left is a black hard substance very often referred to as
asphaltene.

SPE 59703

ASPHALTENE: TO TREAT OR NOT

Acid treatments to remove inorganic scale obstructions are

common occurrences in the oil field. These acid treatments
are frequently accompanied by the appearance of organic
sludges that, if not controlled, plug perforations and reduce
production. It is commonly accepted that this organic sludge
results from the incompatibility of asphaltenes with acid.
However, from the discussion above, it should be clear that
carboxylic acids or amine salts could also be responsible for
the obstructions resulting from acidification of the formation.
Steam floods have been employed by production companies in
attempt to recover some of the heavier crude oils for many
years. The concept of these efforts is based on the idea that
heavier crude oils are recoverable by viscosity reduction
affected by heating so that they can migrate through restrictive
pore throats to the well bore. However, if asphaltenes are
salts of acids or base, they usually comprise species
possessing melt points that are usually in excess of those
obtainable by steam under pressure. Thus, the nature of the
crude oils obtained by steam flood methods must include those
fractions of crude oil that are rendered mobile by elevated
temperatures. Furthermore, those temperatures must be
obtainable by steam under pressure. So what is the nature of
crude production under steam flood? It should be noted that
polar or charged organic species are among the least likely to
be rendered movable by increased temperature. However, the
polar nature of the water used in the steam infusion can be
considered as a motive media. Thus, it can be seen that
analysis of fluids produced in this way can include both polar
and non-polar species.
Case History I; the Consequences of Misinterpretation
A major oil producer in Mexico had determined that their
production problems were due to an accumulation of
asphaltenes in their production string. Their initial production
was determined to be forty six hundred barrels per day, but
after two days the well would plug off and production would
go to zero. The well had a depth of fifty seven hundred
meters, and a bottom hole temperature of one hundred fifty
degrees centigrade. The production companies technical staff
was certain that with such high well temperatures the
likelihood of paraffin deposits was small. Thus, the deposits
that plugged the well were described as asphaltenes. This
description led to the use of aromatic solvent clean-outs
utilizing expensive coiled tubing units. After a two-day coiled
tubing round trip, the well again began producing at the forty
six hundred barrel per day rate and promptly fell again to zero
after two additional days. Interestingly, laboratory analysis of
deposits removed from the well tubing showed them to consist
of a fifty-fifty mixture of paraffins and asphaltenes. After
several of these coiled tubing procedures, the Production
Company began looking for other methods of controlling
organic deposition.
Several specialty chemical companies were invited to test their
various chemistries for the control of asphaltene deposits. The

Production Company established a criterion for successful

treatment. This criterion required that the wellhead pressure
drop no lower than twenty seven hundred pounds per square
inch from the initial pressure of thirty two hundred pounds per
square inch over a two-month period. All but one of these
specialty chemical companies met with failure and coiled
tubing treatments were resumed after each failure. Solvents,
dispersents, and combinations of solvent and dispersents were
included among the many classifications of treatments
unsuccessfully performed. The only successful treatment
achieved was one that employed the use of a paraffin crystal
modifier treatment. Crystal modifier chemical was added on a
continuous basis down the backside of the well. After twentyseven months of this treatment, the well pressure was found to
be twenty nine hundred pounds per square inch, and the
production had fallen from forty eight hundred barrels per day
to thirty two hundred barrels per day.

Case History II; Organic Deposit Removal

A large production company located in Wyoming had been
conducting CO2 floods for several years and had implemented
a solvent wash program that utilized xylene to remove the
deposits obstructing production. In fact, this company had a
monthly allotment of funds for the purchase of xylene, since it
was found to be so effective in removing organic deposits.
High-pressure pump trucks were used to pump xylene into the
well, and the wells were shut in for twenty-four hours to allow
sufficient contact time of the xylene to break-up the organic
deposits. Some wells were on a monthly schedule, while
others were on weekly or bi-weekly solvent clean-up
schedules. Analysis of solids retrieved from the tubing, and
sucker rods showed that the deposit constituted approximately
a fifty-fifty weight ratio of paraffin to asphaltene just the same
as those reported in Case History I above. Although several
laboratory tests including cold finger, pour point, and viscosity
data indicated that a crystal modifier could be applied
successfully to this field, no field trials were authorized.
Several reasons were given why there was a reluctance to
allow the application of a crystal modifier product in this field.
Perhaps, the most convincing reason involved the poor
physical characteristics of the crystal modifier products (e.g.,
they were known to freeze in the winter, thus rendering them
un-pumpable). This situation meant that they had to switch
treating programs back and forth between the winter and
summer seasons. This also meant that they had to keep on
hand the pressure treating trucks for winter clean-up
procedures. Although this laboratory is strongly disposed to
believe that a crystal modifier application to this field problem
would have met with success, we cannot disapprove of the
producing companies choice to remain committed to remedial
solvent treatment methods. However since the time this
decision was made, substantial improvements have been made
to many of these crystal modifier products. The reliable
winterization of these products has finally been achieved, and
the limitation of seasonal application has been removed.

HAROLD L. BECKER "JR"

Organically soluble crystal modifier products have been

successfully suspended in a highly polar solvent matrix that
allows them to be pumped at temperatures well below zero
degrees F. Given the advances made in crystal modifier
technology, the laboratory results reported in this case history,
and the success reported in Case History I above, it would
appear that application of crystal modifier technology would
have been successful.
Case History III: Steam Floods
A major producing company in California who has been
conducting steam floods for over twenty years recently
noticed (ca., 1999) that their water cuts were going up, and
that their LACT sales were diminishing. For many years this
company and its predecessor had accepted the theory that they
were removing high asphaltene crude from a formation that
had, long ago, spent its natural gas drive. The crude oil
recovered from this formation was found to be extremely
viscous (e.g., 8-10 API Gravity), and intensely colored
(black). The combination of these observations suggested to
both producers that the nature of the crude oil they were
displacing with steam fit with the reported characteristics of
asphaltene. Concurrently, analysis conducted by specialty
chemical companies reported that asphaltenes were present in
the oil samples obtained from the field. Consequently they
settled on asphaltene as the cause of problem deposits
responsible for treater interface problems and were deterred
from examining alternative causes of the diminishing crude oil
sales. During the last several years a number of specialty
chemical companies have been contracted by the producing
company to solve the interface problems. In the majority of
cases, those specialty companies were sidetracked by the
asphaltene issue and failed to satisfy the requirements of the
customer. It was not until very recently (ca., August 1999)
that this laboratory had an opportunity to examine the nature
of the problem.
The viscosity of the crude oils produced from these areas is
very high (e.g., twenty thousand to forty thousand centipoise
at sixty degrees F.). This high crude oil viscosity requires the
provision of special physical treating equipment, such as tube
heat exchangers and high temperature dehydration vessels
capable of maintaining fluid transport. Many steam floods
maintain a down-hole temperature in excess of four hundred
degrees F. in order to assure the mobility of crude oils within
the reservoir. Unique problems abound in such a system, nonthe least important of which is the tightness of the emulsion
formed during the processes of crude oil recovery and its
subsequent treatment. One such problem involved the
plugging of one of the post well heat exchangers by what was
described as asphaltene. Laboratory analysis of the deposit
plugging the heat exchanger revealed that it was mainly fine
sand covered by heavy black crude oil. This finding did not
rule out the possibility that the black crude oil was
asphaltene, however, it also did not rule out the possibility that
the deposit was a high boiling paraffin wax. Thus, a sample of
the deposit was obtained from the heat exchanger and diluted

SPE 59703

fifty-fifty volume to volume with kerosene, divided into

fractions and treated at one thousand parts per million with
various crystal modifier products. Several of these dilute
treated and untreated samples were allowed to reach room
temperature and examined to see if they would flow when
tilted at an angle. All but one of the dilute deposit samples
remained solid (resisted flow when displaced from the upright
position). Once this crystal modifier was indicated as having
potential for inclusion in the field treatment program,
continued testing was performed to examine if it would also
have a beneficial effect on the resolution of interface
problems. This testing revealed a marked improvement in the
water oil interface, and provided additional emphasis for the
incorporation of crystal modifier products in this steam flood
operation.
Conclusion
Specialty chemical companies, indeed, know and employ a
few effective chemical methods for dealing with corrosion,
scale, emulsions, and paraffin problems. However, these
methods are extremely limited and suggest that a high
specificity of product activity is required for an effective
solution to the problem. If the nature of the problem is poorly
defined, as is that of asphaltene and no clear chemical handle
can be used to alter their behavior, then a redefinition of the
problem and its possible solution should be offered.
Asphaltenes, resins, and maltenes offer convenient but
obscure descriptions of problem species.
References:
1

ASTM D-2006, D-2, ASTM STANDARDS PETROLEUM

PRODUCTS, LUBRICANTS, AND FOSSIL FUELS
2
Becker, H.L. (J.R.), Crude Oil Emulsions, Waxes, and
Asphaltenes, PennWell, (1997).
3
Becker, H.L. (J.R.), Thomas, D.C., Raul de Real Ruis,
Asphaltene Formation Damage Remediation, SPE Production
Operations Symposium, Oklahoma City, Oklahoma, 21-23
March 1993.

CH3 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH3

London
Dispersion
Forces

Figure 1: London Dispersion forces producing Wax Crystals

H

O
H
H C
H
H C
H
H C

C O
H
C

H
C

H
H

C
H

C O - M+

H
H C
H
C
=R. H
H
H C

H
C

H
H

H
H

H
H
H
H
H
H

C OO
M++
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
H

C
H
C H
C

H
C H
H
C H

C
H

Where R= aliphatic, cyclic, aromatic, and combinations

Where M+= K+, Na+, and M++= Ca++, Fe++, Zn++ etc.

Figure 2: Organic acid salts commonly present in crude oil

H
H
C

H
H C

=R.

H
H C

H
H

H
H

H C

X-

H
H C

H
H C
H
H C

+ H

H
H

H
H

Where R= aliphatic, cyclic, aromatic, and combinations

Where X-= Chlorine, flourine, bromine, iodine, fatty acid or other organic acid anion

R
2
CH C
H

CH
CH C

2
CH C
H

CH C

CH 2
HC

CH2

C
C

N
H
Fe3+

C
CH2

C
H2 C

CH 2CH

CH

C H2

Aromatic
association
CH2

HC
HC
HC

C
HC
CH
CH

Aliphatic
association

CH C

CH 2CH

CH
C

HC

H3 C

CH 2
HC

CH

CH 2

CH

CH

C H2

H
N

H2C

CH
R

CH2

CH 2
HC

C
H2 C

C
N

HC
HC

C
HC

CH 2CH

HC
C

HC
HC

CH C

CH 2
HC

2
CH C
H

CH C

CH 2
HC

C H2
C

HC

H
H

H2C

CH

CH2

CH2

HC
HC

H3 C

HC
C

C H2
C

CH2

CH

CH

Figure 3: Organic amine salts commonly present in crude oil

Figure 4: Proposed asphaltene structure surrounded by resins

and/or maltenes

H3 C

C H2
C

HC

H2C

C
C

HC

HC
C

H2 C

CH2

HC

CH2

CH
CH

H3 C

C H2
C

HC
N

CH

HC

HC

HC

HC

CH2

CH2

HC

H
N

H2C

HC

N
H
Fe3+

HC

CH2

CH2

CH2

C
HC
C

H2 C

C H2

CH
CH

Conjugated
double bonds

HC

CH2

Metal Complex

Figure 5: Two structural features leading to highly colored species

+ H

H
H
H
H C
H
H C
H
H C

C
H
C

H
H

H
H

C
H

X-

C O - M+
H
H C
H
H C

H
C

H
C

H
H C

H
H

C
H

Figure 6: Organic amine salts migrate in an applied electric field

H3 C

C H2
C

HC

CH2

CH2

C
C

H2C
C

HC
C

CH2

H2 C

C H2

HC

HC

HC

HC

HC

CH

H3 C

C H2

HC

HC

CH
S

HC

H
N

H2C

C
C

CH
R

CH2

CH2

C
C

HC

N
H
Fe3+

HC

CH2

HC
C

H2 C

C H2

HC

CH2

CH
CH
R

R
R

Figure 7: Proposed de-peptized asphaltene di-mer unit

High Pressure Liquid
Chromatography Pump

Duel Channel Recorder

80
Pressure
Meter

Core Sample

Pressure
Transducer

Pressurized Core Holder

Spectrometer
Sample
Reservoir

Figure 8: Core testing device used for studying asphaltenes