Controlling Asphaltene Deposition
in Oil Wells
D.C. Thomas and H.L. Becker, Welchem Inc., and R.A. Del Real Soria, Petroleos Mexicanos
Summary
The deposition of asphaltenes in oil producing fonnations and pro-
duction systems has caused problems for years. Selection of chemi-
cal control agents in the past has been limited to bulk dissolution
studies on samples retrieved from production systems. Until recent-
ly, the accepted way to treat these problems has been through the use
of xylene, toluene or other aromatic solvents. This method requires
the use oflarge amounts of these solvents, as well as a high frequen-
cy of treatment. This paper describes the results of field testing and
application of asphaltene control chemicals, and the use of laborato-
ry tests to select asphaltene deposition removal and prevention
chemicals.
Preliminary dispersant and solvency tests are conducted by an as-
phaltene dispersant test in hexane. Chemicals which provide prom-
ising results in dissolving and dispersing asphaltenes in the non-sol-
vent medium of hexane are selected as candidates for field
application, or for additional testing in a core flow deposition re-
moval test.
The core flow test apparatus provides a method to introduce as-
phaltene fouling into a core and study its removal by the use of
chemical agents. Using core samples and asphaltenes from the pro-
duction resource under consideration allows the selection of the best
removal chemical.
Introduction
Asphaltenes are eomplex hetroatomic polar macro-cycles contain-
ing carbon, hydrogen, sulfur, and oxygen. They are large and highly
aromatic in nature, and occur in crude oils as stabilized micelles.
Resins and maltenes, which are molecular precursors of the asphal-
tenes, act to stabilize a dispersion of asphaltene particles. The as-
phaltenes are surrounded by the resins and maltenes polar heads,
while their increasingly aliphatic tails extend into the hydrocarbon
(oil) phase. When mechanical or chemical forces become sufficient-
ly great, these stabilizing species are lost and the asphaltene particle
becomes susceptible to interaction with a similarly destabilized as-
phaltene leading to flocculation and precipitation. These destabiliz-
ing factors include: streaming potential caused by the fluid flow in
the porous media of the fonnation which destabilizes asphaltenes by
electrical potential, mechanical factors, and by the addition of for-
eign agents. These agents can be acid or other stimulation or work-
over fluids, and recovery assist additives such as C02 or other mis-
cible gases. These materials can destabilize the asphaltenes by
changing the pH or the solubility characteristics of the crude oil. lA
Because the asphaltene particle is polar, it may take on a charge
by induction resulting in secondary aggregation. As aggregation
proceeds, accumulations of asphaltene macro-particles appear.
Bubble point effects are important because they represent the chem-
ical stripping mechanism of destabilization. As the pressure drops
below the bubble point, light ends encounter the aliphatic tails of the
resins and maltenes causing a momentary imbalance in the charac-
ter of the surrounding media. This momentary imbalance is suffi-
cient to cause a stripping of the resins and maltenes and cause desta-
bilization. Meehanical processes facilitate this action in several
ways, but the most important of these is the movement of the crude
from one pressure zone to another lower pressure zone. Miscible
Copyright 1995 Society of Petroleum Engineers
Original SPE manuscript received for review March 21, 1993. Revised manuscript received
Sept. 2. 1994. Paper accepted for publication Oct. 17. 1994. Paper (SPE 25483) first pres-
ented at the 1993 SPE Production Operations Symposium held in Oklahoma City. March
21-23.
SPE Production & Facilities, May 1995
floods aggravate the problem by introducing higher concentrations
of light ends to the system. I ,3.4
Laboratory Testing
Laboratory testing conducted for development of effective treat-
ment chemicals and selection for field application consisted of three
types of tests. For selection of chemicals used primarily for asphal-
tene dispersant applications, a dispersant type test is used. This test
consists of first preparing a stock solution of five grams of deposit
dissolved into 100 mL of xylene. One hundred milliliters of hexane
is added to 100 mL graduated cylinders with the desired chemical
dispersant in each. One milliliter of the asphaltene stock solution is
added and the cylinder is mixed well. After standing for one hour,
a 10 mL sample is thieved from the 70 mL level and mixed with 30
mL of xylene. Transmittance at 640 nm is measured and compared
to other chemical products performance. The chemical product with
the least transmittance is considered to suspend the most asphaltene
into the hexane. 5
A more severe version of the dispersant test can be used for selec-
tion of asphaltene dispersants and solvents. In this test, a pellet of
the asphaltene deposit is fonned by placing two grams of the asphal-
tene in a pellet press and forming a pellet at high pressure. The pellet
is made to avoid differences in surface area and cracks that may be
present in the pieces of asphaltene deposit used for testing. These
factors may influence results of this test. One hundred milliliters of
hexane is placed in 100 mL cylinders and mixed with the desired
chemical. The asphaltene pellet is placed in the cylinder and al-
lowed to stand for a period of time. The amount of asphaltene dis-
persed into the hexane indicated by a darkening layer in the hexane
is read from the graduated cylinder. The chemical which provides
the most dispersed asphaltene in the shortest time is selected. This
test helps select chemicals that can penetrate deposits and disperse
them. This test can be used to screen chemicals for testing on the
core flow test.
The core flow test is used to select the most appropriate chemical
product for removal of asphaltene deposits from fonnation materi-
als and to help restore relative penneability. This test equipment
shown in Fig. 1, consists of a Hasler core holder, high pressure liq-
uid chromatographic gradient pump, flow through spectrophotome-
ter, pressure transducer, and computerized data recording system.
For the core tests either a field core or a standard Berea core is used.
The core test is conducted at room temperature in this study. Testing
conducted at higher downhole temperatures would be expected to
provide similar results, but with lower total permeability loss num-
bers since the asphaltenes would be expected to be more soluble in
xylene at the higher temperatures. After establishing a water wet
condition and determining the effective penneability of an undam-
aged core using xylene as the eluent, or continuous phase, damage
is accomplished by loading 75 mL of a I % dispersion of asphaJtene
to the core via the xylene continuous phase.
The asphaltene dispersion is made by grinding up an asphaltene
deposit and adding it to xylene. If no deposit is available, asphaJtene
is precipitated from the field crude oil sample by hexane. When the
xylene/asphaltene dispersion is fully charged to the core, the xylene
carrier solvent is allowed to wash through several core volumes to
establish a baseline for xylene removal of the asphaJtene deposit.
Since many asphaltenes are not soluble in xylene under the condi-
tions of the test, this baseline represents the best removal that xylene
can achieve for the asphaltene under investigation, and is defined as
the zero removal point. While more asphaltenes would be expected
to soluble in xylene under higher downhole temperatures, this worst
119
 Pressure Pressure
80mb Transducer
Original Perm.
Xylene Base
Product 38

i I I
Product 2

I I

•
Product 31

Core
Discharge
Fig.1-Core test device.
case test should be representative of relative results expected in field
operations.
The selected chemical product is then applied to the core at vari-
ous rates. Usually one pore volume is used initially for squeeze sim-
ulation treatments. The product can be applied into the xylene flush
to determine the effect of the chemical in flow through deposit re-
moval. The flow in the core can be reversed to apply the chemical
treatment from the discharge side of the core. This would simulate
a squeeze application from the well bore in a field treatment. The
core can be shut in for several hours if desired for soaking, and the
flow is reestablished using xylene.
The pressure and flow rate in the core is measured and stored in
the data gathering system. Transmittance of the effluent from the
core is measured at 430 nm by a flow through spectrophotometer.
By comparison of a Beer's Law plot of transmittance vs. concentra-
tion plotted by standard dilutions ofthe asphaltene in xylene disper-
sions to the effluent readings, the quantity of asphaltenes deposited,
removed, and remaining on the core is determined.
The asphaltene charge is reintroduced to the core after each run
to foul the core. The xylene base is reestablished and the core treated
with another chemical product.
Relative permeability is determined by the flow and pressure
measurements taken during the test. When plotted along with the as-
phaltene removal the best product for treatment can be determined.
Typical results shown in Fig. 2 describe the original permeability
using xylene (original perm), the reduction in permeability caused
by the asphaltene fouling the core, and represents the best perme-
ability that can be achieved by xylene cleanout alone (xylene base)
and the amount of asphaltene removed and resulting restoration of
permeability by each product tested.
In many treatments the addition of a mutual solvent will increase
the improvement in relative permeability. Fig. 3 shows the effect of
adding an appropriate amount of mutual solvent on permeability in
the core flow test. However, increasing the mutual solvent content
can in many cases decrease the amount of asphaJtene removal. The
mutual solvent can cause water wetting of the asphaltene particles
preventing the oil soluble solvent/dispersant from effectively con-
tacting the deposit.
I I
Product 3
o 20 40 60 80 100 120 140
mD & % Removal
_ Permeability mD _ % Asphaltene Removal
Fig. 2-Results of core flow test.
The xylene used in the core test as the continuous carrier phase
will remove some asphaltene deposit itself. To make the test more
severe during chemical testing and development, hexane can be
used as the carrier phase. The hexane will not remove any deposit,
and will cause the asphaltene to remain precipitated. Results oftest-
ing show the selected chemical will still remove the asphaltene de-
posit, and increase the relative permeability even when hexane is
used as the carrier fluid. Results are shown in Fig. 4.
Field Application
When well production is reduced due to asphaltene deposition, the
most common action is to perform a cleanup treatment using high
aromatic content solvents. To be effective, the solvent used must be
able to solubilize the asphaltenes and retain them in solution
throughout the production system. If the asphaltenes are not re-
tained in solution, then re-precipitation may occur anywhere desta-
bilizing factors are experienced. ,
Once asphaltene deposition does occur, it can be very costly in
terms of downtime, deferred production, and pump replacements,
as well as costly additional remedial removal and/or stimulation
treatments. Therefore it is important to optimize the chemical treat-
ing program to decrease the workover frequency on any problem
well.
Selection of the appropriate treating product depends on where
the problem occurs, what causes it, and the desired application. In
addition, the laboratory tests used to make the product selection also
depend on the extent of the problem and the preferred chemical ap-
plication method. Typical field application methods include well-
bore and formation cleanup, formation squeeze, or continuous in-
jection to prevent or retard further deposition.
Application of the selected chemical products in field treatments
is indicated where asphaltene deposition problems are causing pro-
duction operation problems. This is especially important where pro-
duction has been reduced by induced asphaJtene destabilization fac-
tors such as miscible floods. AsphaJtene deposition in miscible

Original Perm . • 11.rl--1--T--r-l Original Perm.

Xy lene Base
Asphaltene

Product 1

Mutual SIProduct 1
Mutual S/Product 1

o 50 100 150 200 250 300 o 100 200 300 400 500 600
mD & % Removal mD & % Removal

_ Permeability mD _% Asphaltene Removal _ Permeability mD _ % Asphaltene Removal

Fig. 3-Mutual solvent effect. Core flow test with xylene. Fig. 4-Mutual solvent effect Core flow test with hexane.

120 SPE Production & Facilities. May 1995

Original Perm.
Xylene Base
Product #1

Product #3
1
Product #4
~
Product #2
1
Product #38
o 50 100 150 200 250
mD & % Removal Weil l Well 2 Well 3
_ Permeability mD _ % Asphaltene Removal _ Initial _Before Treat After Treat _21 Months

Fig. 5-Case History 1. southeastern Mexico core test. Fig. 6-Case History 1 production history, southeastern Mexico.

floods that are produced by electric submersible pumps present an
especially severe situation due to destabilization by both solvent
changes, and extreme mechanical shear and pressure drop in the
pump. Application of the products discussed herein has been suc-
cessful in these types of production applications.
Field Treatments
Case History #1. A flowing well in the southwestern region of
Mexico had been developed to a depth of 19,600 ft with one zone
of completion occurring at 19,029 ft. The bottomhole temperature
of this well was close to 200°C. The well was producing 4,700 bbl
of oil per day when it was first completed, but after nine months of
production the rate had fallen to 436 bbl of oil per day. Mechanical
treatment of the well showed that asphaltene deposition in the tub-
ing was responsible for the production falloff.
Previous treatments consisted primarily of xylene and various ad-
ditives. The results of these treatments lasted various time periods,
usually around six months, and the producer desired more effective
treatments with longer treatment life. Dispersant testing and core
flow testing studies in the laboratory using crude oil and tubing de-
posit samples indicated that the use of a combination solvent and
dispersant would remove the asphaltene deposits from the tubing
and- damage from the formation and restore permeability. The re-
sults of the laboratory core flow test are shown in Fig. 5.
To treat the well it was necessary to clean the asphaltenes from the
tubing and then treat the formation to remove any damage and to
help reduce future deposits. Coiled tubing was used to add diesel as
the well fluids were displaced to a flare. When the coiled tubing
reached the asphaltene restriction at 15,748 ft, the mixture of 90%
xylene and 10% (about 275 gal) of Product 1 were pumped through
a high pressure spray nozzle attached to the end of the coiled tubing.
The treatment was successful in removing the asphaltene deposit in
the tubing with one pass of the coiled tubing. After the restriction in
the tubing had been removed, the formation was treated using coiled
tubing to squeeze 1,100 gal of a mutual solvent followed by 1,100
gal of Product 3 mixed 10% in xylene. Nitrogen was used to squeeze
the fluids into the formation to a distance of8 radial ft from the well-
bore. The well was shut-in and allowed to soak for 4 hours.
After 4 hours, the well was brought back on production and was
making 4,800 bbl of oil per day. Periodic checks over the next 21
months showed production to drop gradually to 3,500 bbl per day.
A second well in the same region of southwestern Mexico, with
a depth of 17,000 ft and a production zone of 50 ft, had plugged off
completely to the top of the Christmas tree with asphaltenes. Labo-
ratory testing using the dispersant and core flow tests indicated that
the same products used for the previous well could be used for this
application. Since the tubing was completely plugged, coiled tubing
could not be used to treat the well. A hot oil truck was connected to
the well and a mixture of xylene and 10% Product I was surged into
the top of the Christmas tree. After several hours the asphaJtene was
removed to a depth of 11,500 ft, and the treatment was allowed to
soak 24 hours.
The well was returned to production and oil production went from
zero to 3,400 bbl per day. This well has remained in production for
21 months experiencing a gradual decline to 2,900 bbl per day.
A third well in the same region of southwestern Mexico with a
similar depth to the two previous wells, also had asphaltene deposits
in the tubing restricting production from the original rate of 2,600
bbl per day to 280 bbl per day. Laboratory testing on a deposit from
this well indicated the same treatments as used on the previous wells
would be effective. The well was treated as described for the first
well to remove the deposit from the tubing and restore permeability.
After treatment, the production of this well went to 1,400 bbl per
day, with production rates over the following year remaining at
1,300 bbl per day. Fig. 6 shows the production history of these Mex-
ico area treatments.
Case History #2. A well in Southern Louisiana had exhibited a rap-
id falloff in production from 406 bbl oil per day to 53 bbl oil per day.
Treatments with xylene restored production to 101 bbl oil per day
for short time periods with a steady decline to 66 bbl oil per day.
Laboratory testing using the dispersant test showed Product 2 would
provide appropriate treatment. The well was treated using 440 gal
of Product 2 with a 440 gal mutual solvent preflush. A coiled tubing
unit was used to place the treatment to the top perforation and dis-
placed with nitrogen. The well was shut in overnight. The initial pro-
duction after the well was reopened increased to 152 bbl oil per day.
The well has stabilized at 91 bbl oil per day for 5 months (Fig. 7).
Case History #3. A C02 flood in the Permian Basin area is experi-
encing asphaJtene and paraffin plugging in the near well bore area
and tubing of flowing wells. Deposits from the wells contain an al-
most equal amount of both asphaltene and paraffin. Traditional
treatments using hot oil, acid, or hot water had been employed for
some time. These treatments were becoming less effective resulting
in typical production rates of just 6 bbl oil per day. Testing selected
Product 3 for use. Treatments consisted of a wellbore/formation
cleanup using 200 gal of a mutual solvent preflush, followed by 824
gal of Product 3 squeezed into the well with 400 bbl of lease crude
followed by one tubing volume of water.
P rod Hct2lrea! Wo nl
Month
Fig. 7-Case History 2, southern Louisiana field treatments.

SPE Production & Facilities. May 1995 121

 120 Barrel~. ~e~ 1?~1. ______ ._.__________ ~ ______ ._. ____ _
100
80
60
40
._-- . - -- - --- -~.-.
Month
Fig. 8-Case History 3. west Texas field treatments.
Following this treatment. well production was returned to the typ-
ical pre-deposit production levels of 83 bbl oil per day. This treat-
ment lasted for almost 6 weeks. The cost of the chemical treatment
was less than $7,000 U.S. compared to the acid treatment cost of
$20,000 U.S.,with payback occurring in less than one week.
Since the initial success of the treatments, the application method
was changed from the squeeze application to a more economical
dump and soak method. To treat the wells, 55 gal of a mutual sol-
vent, followed by 793 gal of Product 3 are batched into the annulus
and flushed with 77 bbl of crude oil and allowed to soak for 16 hours.
The treated wells have responded to treatment with this application
with production returning to pre-deposit levels. The results for three
wells are presented in Fig. 8. This program now treats nine wells and
the program is being expanded to 42 wells.
In addition to the well treatments, continuous addition of Product
3 into surface production vessels is controlling asphaltene deposits
and interface problems caused by asphaltene solids.
Case History #4. A major miscible flood project in Alberta, Canada
has been subject to severe asphaJtene deposition problems after the
breakthrough of the miscible flood front. As such, many of the wells
required high content aromatic solvent formation squeezes, well-
bore cleanouts, andlor pump and tubular cleanouts to maintain pro-
duction levels. The asphaltene problem was so bad in some wells
that the frequency of treatments in one case was about every 16
hours. Although the sol vent treatments were deemed successful, the
program required frequent use of high volumes of solvents. This
generated a need to reduce the cost of the asphaltene treatment con-
trol programs.
One of the most severe problems being experienced in the subject
miscible flood project was re-precipitation of asphaltenes in the
electrical submersible pumps and wellbores following solvent
formation squeezes and tubul ar and pump cleanouts. It was theo-
rized the asphaltenes that were being solubilized by the solvent were
not staying in solution throughout the high pressure drop and shear
rate regimes of the pumping system and re-depositing. Dilution of
the solvent by the produced fluids also contributed to the severity of
the re-deposition problem.
% Absorbance
80 ~~~~~.------.------,------.
60
20 - l - - - -
a a
Blank A B F Blank
Product (5000 ppm)
. 3 Hours .24 Hours
Fig. 9-Case History 4 asphaltene solvent test, Alberta, Canada
miscible flood.
122
In an effort to provide a cost effective alternative for treating this
problem, solvency and dispersant tests described previously were
used to screen a number of products to determine their effectiveness
for asphaltene deposition control (Figs. 9 and 10).
Based on this testing, the treatment designed for this problem was
initial wellbore/formation cleanup using Product F followed by
continuous injection of Product G to just above the pump intake via
a capillary injection string.
Typical formation treatments consist of spotting Product F across
the perforated interval and squeezing 15-40 gal per foot into the
formation and allowed to soak for 2-24 hours. The well is then
placed on production.
Once the deposit has been removed with Product F, preventative
action is required to mitigate further deposition and flow restriction
problems. This is accomplished by continuous treatment with Prod-
uct G through a capillary injection string downhole, at the wellhead
or into the flowlines and surface facilities as necessary. For this ap-
plication, a treating rate of 250-5000 ppm (based on oil production)
is required. The actual rate used can be determined by the lab proce-
dures previously described in conjunction with field optimization.
Five wells in this field were treated using the above described pro-
cedure to keep the wells producing and to reduce operational prob-
lems. The cost of this chemical treating program compared with the
original solvent cleanup program is considerably less. The cost ef-
fectiveness of this treatment regime for 1991 is compared to the
1990 solvent only treatments in Fig. 11. As shown, the total cost of
continuous injection of Product G along with occasional remedi al
Product F cleanup treatments is between 50 % to 80 % less than the
cost of solvent cleanup alone 6
Case History #5. A 16 in. pipeline, 12 miles long is used for gather-
ing and transportation of production from several fields in Mexico.
Two hundred fifty barrels of asphaltic oil and 800 bbl of condensate
per day were added at the beginning of the pipeline. An additional
7,450 bbl of oil and 2,500 bbl of water were added to the line before
it reached the treating battery. The line experienced asphaltene de-
posits requiring pigging every 2 to 3 months. Interface buildup in the
dehydration vessel and problems with dehydration of the crude oil
were also attributed to asphaltenes.
Injection of 60 ppm of Product 4 continuously into the condensate
at the beginning of the pipeline eliminated routine pigging of the
line. After the treatment had been used for some time, the interface
and dehydration problems were eliminated also.
Conclusions
The use of specifically designed laboratory tests for selecting as-
phaltene treatments can provide cost effective solutions for the con-
trol of production asphaltene problems. These solutions include
properly selected chemicals and appropriately designed application
of the selected chemicals.
Acknowledgments
We wish to thank WeJchem Inc . for permission to publish this paper.
We also wish to thank the WeJchem Technology Center and Wel-
20
G c o E
Product (500 ppm)
. 3 Hours .24 Hours
Fig. 1O-Case History 4 asphaltene dispersant test, Alberta,
Canada miscible flood.
SPE Production & Facilities. May 1995
 SI Metric Conversion Factors
200 ~--~--~-------,-------,-------.-------,
A x 1.0* E-OJ =nm
bbl x 1.589 873 E-OJ =m 3
150
ftx 3.048* E-01 =m
of CF-32)/1.8 =oC
100
gal x 3.785412 E-03 =m3
in. x2.54* E+OO =cm
50
*Conversion factor is exact. SPERE
o
2 3 4 5
Well
Don C. Thomas is currently International Marketing Manager for
Baker Performance Chemicals Inc. in Houston, TX. He has held
.-Aromatic Solvent . Product G + F various R&D, product management, and marketing positions in
several production chemical companies during the last 20
Fig. 11-Case History 4 annualized treatment cost aromatic sol- years, specializing in product and application development.
vent VS. chemical. He holds a BS degree in chemistry from Southern Illinois Universi-
ty. H.L. Becker has held various R&D pOSitions in several produc-
chem Canada Ltd. for their assistance in testing and gathering field tion chemical companies during the last 20 years, specializing
data. in product and application R&D. He holds a BS degree in chem-
istry from the University of California. Becker is currently an inde-
pendent consultant specializing in test equipment develop-
References ment for production chemical applications. R.A. Del Real Soria
I. Newberry, M.E. and Barker, K.M.: "Formation Damage Prevention joined Petroleos Mexicanos in Villa hermosa , Mexico as a petro-
Through the Control of Paraffin and Asphaltene Deposition," SPE 13796. leum engineer in 1986 working in field operations and the
1985, 53-6\. technology group. He was involved in asphaltene problems for
2. Leontaritis, KJ. and Mansoori, G.A.: "Asphaltene Flocculation During more than three years during this time. Del Real is presently an
Oil Production and Processing: A Thermodynamic Colloidal Model," Auxiliary Engineer in the reservoir administration group. Del Real
SPE 16258, 1987, 149-158. holds a BS degree in petroleum engineering from the Instituto
3. Akbar. S.H. and Saleh, A.A.: "A Comprehensive Approach To Solve As- Politecnico Nacional in Mexico City.
phaltene Deposition Problems in Some Deep Wells," SPE 17965,
377-384.
4. Monger, T.G. and Trujillo, D.E.: "Organic Deposition During C02 and
Rich-Gas Flooding," SPE 18063,63-73.
5. Stephenson, W.K.: "Producing Asphaltenic Crude Oils: Problems And
Solutions," Petroleum Engineer International, June 1990,24-31.
6. Becker, H.L., Thomas, D.C., Doddridge, W.R., and McDougall, D.B.:
"Asphaltene Deposition Control Using Chemical Control Agents," CIM
92-70, 1992. Thomas Becker Del Real

SPE Production & Facilities, May 1995 123