SPE 81004

SPE 81004
Hydrocarbon/Solvent Treatment for Inhibiting Paraffin and Suspending Asphaltenes in
Oil Wells
Gale J. Campbell, SPE and John M. Griffin, SPE /Chemex, Inc.
Copyright 2003, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the SPE Latin American and Caribbean Petroleum
Engineering Conference held in Port-of-Spain, Trinidad, West Indies, 2730 April 2003.
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Abstract
A blend of polymeric hydrocarbons within a solvent solution
(HIS-polymer) has been developed (patent pending) that
enhances the flow capacity of oil wells adversely effected by
(a) high viscosity, (b) tubular and rock matrix plugging due to
precipitation of paraffin and asphaltene.
Theoretical mechanisms contributing to observed flow
increase following application of HIS-polymer in field
conditions include (a) preferential wetting of matrix surfaces
by HIS-polymer, (b) reduction of relative permeability to
water and increase of relative permeability to oil, (c) stabilizing interfacial tension, (d) generation of heat which disperses
paraffin and asphaltenes sufficiently for them to enter flow
stream, (e) inhibition of paraffin precipitation, (f) deasphalting
heavy crudes through solvent action, (g) dispersing and
inhibiting the onset of asphaltene precipitation.
Long-term benefit of treatment (exceeding 9 months) is
explained by preference for polymeric hydrocarbon to wet
previously water-wet matrix. Verification of same is reported
using dual-drop-dual-crystal technique in which a 500 ppm
concentration of HIS-polymer was observed to convert both a
water-wet quartz and calcite to a polymeric hydrocarbon-wet
surface.
Field treatment by bullheading through tubing into
formation and over displacing with diesel or lease crude is
reported. This treatment was for a 15 API oil in eastern
Venezuela and resulted in a three-fold production increase
from 104 barrels of oil per day (BOPD); production was
sustained for an excess of 60 days. Tripling of production in a
west Texas stripper well is also included. The HIS-polymer
benefits operators by replacing diluents that have been
historically used to decrease pressure of heavy oil laden
flowlines.

Introduction
Deposition of asphaltenes and paraffins causes plugging of
production lines, oil tubulars, and the formation face in and
around the sandface. Paraffin damage from the formation to
the refinery is also problematic. Paraffin deposition costs oil
companies hundreds of millions of dollars per year in removal
costs and more in lost production.1 Preponderance of
asphaltenes exists in southern Mexico, the West Texas and
Alaska producing regions of the United States, Alberta,
Canada, and the Norwegian sector of the North Sea.2
World reserves of heavy oil occur in order of greatest to
least in Orinoco basin of eastern Venezuela, former Soviet
Union, Canada, Africa, United States, non-Venezuelan Latin
American countries, Asia, and Western Europe.3 Venezuelas
Orinoco basin contains 42-billion tones or more than double
the former Soviet Union. Mississippi and Western Alabama
also produce heavy oils, e.g., the Lower Tuscaloosa in Lamar
County, Mississippi yields a 17API oil.
Paraffin and asphaltene constituents. A majority of crude
oils that are >20 API contain a significant portion of paraffin
or n-alkane components.
Paraffins >C20H42 are the
components that cause deposition or congealing oil in crude
oil systems. Paraffins are straight chain linear structures
composed entirely of carbon and hydrogen with the largest
chain detected by Barker et al.1 to be C103H208.
Houchin and Hubdon4 have defined asphaltene and
paraffin deposits as a mixture of linear and branched-chain
hydrocarbons generally ranging from C18H38 to C60H122.
Most deposited paraffin also contains other organic and
inorganic matter such as crude oil, gums, resins, asphaltenes,
sand, silt, metal oxides, and water. Quantification of
asphaltene fraction of a crude oil is determined by
precipitating it with the addition of n-pentane or some similar
low molecular weight paraffin solvent. Asphaltic materials are
thought to be a colloidal dispersion permeated by adsorbed
maltene molecules.
Treatment of paraffins is handled by two methods:
solvency and/or dispersion. While solvents dissolve paraffins
by breaking down the crystal lattice, dispersants prevent their
agglomeration. Pour point testing was conducted on the HISpolymer to determine impact on crude oil. This provided an
indirect method for measuring the crystallization of crudes
associated with paraffin content.
Barker et al.1 has divided solvents for dissolving
paraffins into two general classes: aliphatic and aromatic.

Common aliphatic solvents are diesel, kerosene and

condensate. Common aromatic solvents are xylene and
toluene. The HIS-polymer consists of several components.
For paraffin treatment, two components were developed and
are distinct from those previously available. One component
is a branched-chain aliphatic while the other is neither
aliphatic nor aromatic.
Background
Treatments composed of asphaltene inhibiting chemicals have
been squeezed into perforations or into sands completed in
open hole. Production improvements and lengthening of time
between remedial well cleanouts have been reported using an
activator and asphaltene inhibitor mixed in diesel and
displaced with lease crude oil.2 Similarly, a proprietary
paraffin-asphaltene chemical exothermally reacts upon contact
with saltwater. This reaction occurs downhole yielding an
These
increase of 40F (22C) and lasts for 2-hours.5
treatments, of course, were ineffective against inorganic scale,
other organic deposits, or iron oxides.
A delayed exothermic reaction has also been reported in
which two aqueous salt solutions are combined at the surface
to produce large, predictable quantities of nitrogen gas and
heat at a predetermined depth.6
A pre-flush to the HIS-polymer discussed herein has
succeeded in producing a 30F (17C) temperature increase.
In this application two proprietary chemicals are combined at
the surface for an immediate exothermic reaction.
Experimental Investigation
Operators had reported benefits of using xylene treatments
downhole albeit with temporary benefits to crude production.
Reports by a west Texas operator that treatment using HISpolymer had kept production elevated for over six months
suggested an operative mechanism different than conventional
solvents. It was hypothesized that the HIS-polymer (hydrocarbon/solvent treatment) rather than residing between the matrix
grains, actually adhered to them. Once this adhesion occurred,
the HIS-polymer would slowly disperse into the production
well stream.
I. Jar Test. To test this hypothesis, a drop of crude oil was
released into a lease saltwater environment. This environment
was a glass bottle filled with saltwater, and consequently, wet
by the saltwater. As expected, the oil drop was unable to
adhere to the water-wet glass surface. Alternately, a single
drop of the HIS-polymer was injected into the same water-wet
glass environment. Immediately upon rising due to a slight
gravity difference to the water-wet glass surface, the HISpolymer contacted the glass surface and permanently adhered.
It was concluded that the HIS-polymer preferentially wets a
previously water-wet surface. This experiment motivated a
more rigorous evaluation using the dual-drop-dual crystal
technique.7
II. Dual-drop-dual crystal technique. In the dual-drop-dual
crystal (DDDC) technique, the crude oil drop to be tested is
released into the fluid environment (saltwater) after aging the
crystals (quartz and calcite) in a 500 ppm concentration of the
HIS-polymer.8 The buoyancy forces are used to drain the

SPE 81004

water film between the crude oil drop and mineral crystal
surface to obtain adhesion equilibrium before measuring
advancing and receding contact angles with respect to aging
time. Two separate crude oil drops on two parallel crystal
surfaces are mingled after aging in a concentration of the HISpolymer. Among the wettability measurements established so
far, the DDDC technique is the solitary one that includes the
effect of adhesion in a quantitative and reproducible manner
for characterizing reservoir wettability through contact
angles.7
The wettability is characterized by a quantitative
measurement of the advancing contact angle according to the
convention:
Water Advancing Contact Angle
0-70 degrees
Water-wet
70-120 degrees
Intermediate-wet
120-180 degrees
Oil-wet
Nomenclature for interpreting the photographs from the
DDDC apparatus are shown here:

While the case histories included herein are both in sandstone

(predominantly quartz matrix), the HIS-polymer also has
potential in carbonate (predominantly calcite matrix)
reservoirs. Consequently, quartz and calcite surfaces were cut,
polished and used to represent sandstone and carbonate
reservoir rocks, respecttively. The hydrocarbon phase was nhexane as it yielded the required water-wet base-case with
quartz surface immersed in deionized water (DIW).
The quartz and calcite surfaces to be used in the
experiments were equilibrated separately in deionized water
for 18 hours before being mounted in the DDDC cell. The cell
was then filled with deionized water and two separate drops of
n-hexane were then placed on the substrates. The two drops
were then allowed to age under the influence of buoyancy for
four hours. The lower surface was turned upside-down to
begin the measurements of advancing and receding contact
angles at various time intervals.8
For studying the effect of the HIS-polymer on
wettability, the above tests were repeated with quartz and
calcite surfaces that were previously equilibrated with the
HIS-polymer. Equilibration was done by immersing crystals
for 28 hours in deionized water containing 500 ppm of the
HIS-polymer.
Quartz-Deionized Water-Hexane System. Figure 1 depicts
the photographs of drops indicating the final contact angles as
the drop moved on the lower surface for the deionized waterhexane-quartz system. This movement of the drop is essential
to satisfy the definition of the advancing and receding contact
angles. Figure 1A represents the situation when the system

SPE 81004

was not exposed to the HIS-polymer while Figure 1B

corresponds to quartz surfaces that had been equilibrated with
the HIS-polymer and hence are presumed to contain an
adsorbed layer of the HIS-polymer on the surfaces.
Figure 2 is a plot of the advancing and receding contact
angles corresponding to the experiment shown in Figure 1.
Both the photographs and the plot of Figure 2A indicate a
weakly water-wet nature of this solid-fluids system with an
advancing angle of 67 degrees, which was shown to be quite
reproducible in Figure 2 by a repeat experiment. The plot of
Figure 2B and the corresponding photograph in Figure 1B
indicate an oil-wet nature with an advancing angle of 127
degrees. These results clearly indicate that the quartz surfaces
have been modified in their wettability characteristics from a
weakly water-wet state to an oil-wet state when exposed to the
HIS-polymer.8
Quartz-Deionized Water-Hexane System. Figure 3A is a
photograph of the calcite-deionized water-hexane system
before the calcite surfaces were exposed to the HIS-polymer,
and Figure 3B shows the drop on the calcite surfaces after
exposure to the HIS-polymer. The results for these tests are
plotted in Figure 4A and 4B respectively. As can be seen, the
initial intermediate-wettability of the calcite surface (with
advancing angle of 97 degrees) has been modified by the
polymer to a strongly oil-wet nature having an advancing
angle of 146 degrees.
Table 1 summarizes the results of all four experiments.
Included also in this table are the interfacial tensions (IFT)
measured between the n-hexane and deionized water with and
without the HIS-polymer on the substrate.
These
measurements were made using the computerized drop-shapeanalysis technique by capturing the images of the profile of
the hexane drops emerging from the needle at the bottom of
the optical cell and iteratively fitting the profiles with the
Laplace equation of capillarity. As can be seen from Table 1,
the measured interfacial tensions agree closely with the value
of 48.8 dynes/cm reported in the literature for this fluids pair,
and that the presence of the HIS-polymer on the solid surfaces
did not affect the interfacial tension. This appears to indicate
that the HIS-polymer adsorbed on the surfaces during the
soaking period does not release any surface active components
into the water- or hydrocarbon-phase within the duration of
these tests.
Analysis of wettability testing. These preliminary results
indicate the ability of the HIS-polymer to wet the matrix
surface at the concentration tested. Whether the matrix was
rendered permanently altered to oil-wet for those surfaces
contacted was beyond the scope of these tests. Reversal of
wettability from water-wet to oil-wet has been discussed in the
literature, however. Such a reversal has been reported as
being favorable to oil recovery.
Rao et al.9 reported a favorable trend of increasing oil
recovery with increasing oil-wetness on miscible flood oil
recovery on cores from three reservoirs in Alberta, Canada.
Pedrera et al.10 studied gravity drainage in one meter long
laboratory cores and focused on wettability effect on gravity
drainage. It was observed in their core investigation that final
oil recovery increased when the core was being oil-wet. The

DDDC wettability testing was to explain the longevity of the

HIS-polymer field treatment.
Viscosity reduction testing. The HIS-polymer can be applied
though (a) bullheading or otherwise squeezing into the
productive pay zone, (b) injecting down the tubing-casing
annulus or via a capillary/injection string so the chemical is
combined with the produced fluid for production back up the
tubing, or (c) injected at the surface into the flowline for
reduced flowline pressure and decreased tubing head pressure.
The latter two applications are currently practiced using
a lighter gravity oil (diluent), e.g., 27 API, to mix with the
dense more viscous crude oil, e.g., 9 API (Table 2). An
investigation was initiated to determine the effectiveness of
replacing diluent with the HIS-polymer. The heavy crude was
mixed with the lighter crude and addition of HIS-polymer was
done by taking 25 mL of heavy crude oil and mixing with
varying percentages of lighter crude at 75F. This mixture
was stirred by hand in a beaker. Field application should be
done by adding HIS-polymer to diluent before adding to the
heavy crude. Viscosity of the resulting mixtures were
measured using a Cole-Parmer Rotational Viscometer 98936
with a TL 7 spindle. Heating was done in a Lauda Brinkman
RM 6 Temperature Control Unit.
While diluent usage could be reduced by 50%, it was
recommended to the operator that diluent be reduced only by
30% to sustain the API gravity at levels required while
substantially saving on volumes of diluent required.
In separate testing, the pour point of the heavy crude was
reduced by 12F through addition of HIS-polymer in a 16API
gravity undiluted crude from El Tigre, Venezuela (Table 3).
This has the advantage of allowing flow even with colder
temperatures.
Declining production of lighter gravity oil (20API) used
as diluent for pipeline pumping of 13API heavy oil meant a
South American operator needed a diluent substitute (Table 4).
Testing of whether the HIS-polymer could replace the
declining supply of 20API oil was conducted on a similar,
available crude, i.e., 12API California crude (Figure 5). A
twenty nine per cent reduction in viscosity occurred (from
4,750 centipoise, cP to 3,390 centipoise) for the case with 30%
diluent at 1,000 ppm HIS-Polymer. At 100 ppm HIS-Polymer
and 30% diluent, a 17% viscosity reduction resulted (from
4,750 cP to 3,920 cP). Economics have not yet been
evaluated.
Application
Field Trials. Bullheading (pumping from surface utilizing
existing production tubing) into the formation was simplified
in the two case histories discussed here as the wells were
vertical. Diverter technology would be beneficial for horizontal wells.11,12
West Texas Case History. The HIS-polymer was injected
down the tubing-casing annulus in Powell Lease 28 Well 10 in
Schleicher County in west Texas. Prior to treatment, the well
was pumped at a rate of 5 barrel oil per day with 50% bottom
sediment and water. The treatment regime consisted of one
drum (55-gal) of HIS-polymer followed by two drums of light

hydrocarbon and displaced with clean lease crude so as to

place treatment back into matrix. After shut-in for 48 hours,
production increased to 14 barrel oil per day. After six
months, production continued at 10 barrel oil per day. The
longevity of the treatment is partially explained by its
adsorption onto to matrix surfaces through preferential wetting
as described earlier.
Paraffin had previously inhibited the flow line, however,
flow lines have since been kept free following treatment.
Eastern Venezuela Case History. Four drums (220-gal) of
HIS-polymer was mixed with 440-gal of a light hydrocarbon
and the mixture displaced with diesel to the end of 3-1/2 inch
tubing equipped at 3600-ft with an electrical submersible
pump with no check valve. The casing valve was closed and
the HIS-polymer bullheaded with more diesel as displacing
fluid into the formation through screen and liner into eighty
feet of perforations at 5440-ft. The mixture was over
displaced.
The 15.2API crude contained 9% asphaltenes and 6%
paraffin. Production prior to treatment had fallen to 104 barrel
of oil per day. Following treatment and a 48 hour shut-in,
production peaked at 334 barrel of oil per day (Figure 6). A
production increase was sustained for an incremental
production increase of at least 6,000 barrels of oil.
Conclusions
Based upon the experimental investigation presented:
1) It has been hypothesized that longevity of the HISpolymer is explained by preferentially wetting a
previously water-wet sandstone. Testing done employing
the dual-drop-dual-crystal (DDDC) technique on both
quartz and calcite crystals supports this claim.
2) DDDC testing indicated quartz surfaces were modified in
their wettability characteristics from a weakly water-wet
state to an oil-wet state when exposed to the HISpolymer.
3) DDDC testing also indicated that the HIS-polymer
adsorbed onto the quartz/calcite surfaces during the
soaking period and did not release any surface active
components into the water- or hydrocarbon-phase for the
duration of these tests.
4) Concentrations of HIS-polymer of 1,000 ppm show reduction of heavy oil viscosity of
a) 67% for the case with 60% 9API & 40% 27API
from 3,990 cP to 1,320 cP.
b) 29% for the case with 70% 9API & 30% 27API
from 4750 cP to 3390 cP.
5) Concentrations of HIS-polymer of 100 ppm show reduction of heavy oil viscosity of 17% for the case with 30%
diluent (4,750 cP to 3,920 cP).
6) A three-fold production increase resulted following HISPolymer treatment in a 15.2API oil well yielding at least
6,000 barrels of incremental oil.

SPE 81004

Acknowledgements
The authors wish to thank Robert Pierro of Chemex, Inc. for
conducting and interpreting results of pour point and viscosity
reduction laboratory studies.
References
1.

Barker, K.M., Newberry, M.E., and Yin, Y.R.: Paraffin

Solvation in the Oilfield, paper SPE 64995 presented at the
2001 SPE International Symposium on Oilfield Chemistry,
Houston, February 13-16.
2. Cenegy, L. M.: Survey of successful world-wide asphaltene
inhibitor treatments in oil production fields, paper SPE 71542
presented at the 2001 SPE Annual Technical Conference and
Exhibition, New Orleans, September 30-October 3.
3. Molero de Blas, L. J.: Pollutant formation and interaction in the
combustion of heavy liquid fuels, PhD thesis, University of
London, 1998.
4. Houchin, L.R. and Hudson, L.M.: The Prediction, Evaluation,
and Treatment of Formation Damage Caused by Organic
Deposition, paper SPE 14818 presented at the 1986 Seventh
SPE Symposium on Formation Damage Control of the Society
of Petroleum Engineers, Lafayette, February 26-27.
5. Steward, R. & Ford, D.R.: Unique chemical removes paraffin
damage, stimulates production, World Oil (March 2002) 84-85.
6. Mitchell, T.I., Donovan, S.C., Collesi, J.B., and McSpadden,
H.W.: Application of a Chemical Heat and Nitrogen
Generating System, paper SPE 12776 presented at the 1984
Society of Petroleum Engineers of AIME 1984 California
Regional Meeting, Long Beach, April 11-13.
7. Rao, D.N. and Girard, M.G.: A new technique for reservoir
wettability characterization, The Journal of Canadian
Petroleum Technology Volume 35, No. 1 (January 1996).
8. Rao, D. N.: Wettability effects of HIS-Polymer, Louisiana
State University Craft & Hawkins Department of Petroleum
Engineering, Correspondence of Laboratory Investigation, 29
May 2002.
9. Rao, D., Girard, M., and Sayegh, G.: Impact of miscible
flooding on wettability, relative permeability, and oil recovery,
SPE Reservoir Engineering (May 1992) 204-212.
10. Pedrera, B, Bertin, H., and Augustin, A: Wettability Effect on
Oil Relative Permeability During a Gravity Drainage, paper
SPE 77542 presented at the SPE Annual Technical Conference
and Exhibition, San Antonio, September 29-October 2.
11. Mackay, E.J., Sorbie, K.S.: An evaluation of simulation
techniques for modeling squeeze treatments, paper SPE 56775
presented at the 1999 SPE Annual Technical Conference and
Exhibition, Houston, October 3-6.
12. Menzies, N.A. and Mackay, E..J.: Modeling of gel diverter
placement in horizontal wells, paper SPE 56742 presented at
the 1999 SPE Annual Technical Conference and Exhibition,
Houston, October 3-6.

Metric Conversion Factors

1 barrel = 0.159 cubic meter
1 foot = 0.3048 meters
1 gallon = 3.785 liters

SPE 81004

Table 1. Summary of Dual-Drop Dual-Crystal test results

Liquid 1

Liquid 2

Rock Substrate

L1L2
IFT*
48.9

Advancing
Angle

Receding
Angle

Deionized
Hexane
Quartz
65
17
Water
Deionized
Hexane
Quartz coated with HIS49.0
127
8
Water
polymer (500 ppm)
Deionized
Hexane
Calcite
49.0
97
18
Water
Deionized
Hexane
Calcite coated with HIS49.1
146
30
Water
polymer (500 ppm)
*L1-L2 IFT The interfacial tension [dynes/cm] between the two liquids, i.e., deionized water and hexane

Table 2. Viscosity reductions for eastern Venezuela heavy crude

HIS-polymer [ppm]

Viscosity [cP]
@ 70F
(21C)
62,560
56,360

Viscosity [cP]
@ 120F
(49C)
5,275
4,500

0 ppm in 83% 9API, 17% 27API

crude oil
1000 ppm in 83% 9API, 17%
27API crude oil

30,710

3,200

19,500

2,050

0 ppm in 60% 9API, 40% 27API

crude oil
1000 ppm in 60% 9API, 40%
27API crude oil

3,990

800

1,320

480

0 ppm in 9API crude oil

1000 ppm in 9API crude oil

Table 3. Pour points of 16API El Tigre, Venezuela heavy crude

HIS-polymer
concentration [ppm]
Crude oil with 0% diesel
Crude oil with 15%
diesel
Crude oil with 50%
diesel

Pour point
1000
2000

4000

68
62

62
56

58
47

56
44

40

30

28

26

Table 4. Viscosity reductions for South American heavy crude

HIS-polymer [ppm]
0 ppm in 13API crude oil
1000 ppm in 80% 13API, 20% 20API
crude oil
1000 ppm in 70% 13API, 30% 20API
crude oil

Viscosity [cP] @
98.5F (37C)
29,390 cP
9,200
3,390

SPE 81004

Figure 1: Photograph of DDDC tests with DIW-HexaneQuartz System with and without HIS-polymer

Figure 3: Photograph of DDDC tests with DIW-HexaneCalcite System with and without HIS-polymer

Figure 2: Dynamic contact angle vs. Time for DIW-Hexane

A. Quartz (top)
B. Quartz coated with 500 ppm HIS-polymer
(bottom)

Figure 4: Dynamic contact angle vs. Time for DIW-Hexane

A. Calcite (top)
B. Calcite coated with 500 ppm HIS-polymer
(bottom)

SPE 81004

100,000

Viscosity [cP]
@ 37C

All samples were heated to

37C prior to mixing

10,000

1,000
0

100

400

1000

HIS-Polymer [ppm]

No diluent

20% diluent

30% diluent

Figure 5 HIS-Polymer reduces viscosity of 12API California

crude consisting of 0, 20%, & 30% 20API diluent

350
300
250
200
150
100
50
0

HIS-polymer injected 13 March

23
-F
e
2 7 b -0
2
-F
eb
3 - -0 2
M
ar
7 - -0 2
M
a
1 1 r-0
-M 2
a
1 5 r-0
-M 2
a
1 9 r-0
-M 2
a
2 3 r-0
-M 2
a
2 7 r-0
-M 2
a
3 1 r-0
-M 2
ar
-0
2

Barrels of Oil Per Day

Eastern Venezuelan Test Well

o
15.2 API Gravity

Figure 6 - Production improvement following HIS-polymer application