SPE

Society of Petroleum Engineers

SPE 21000

Polymer Treatment for Water Control in High-Temperature

Production Wells
N. Kohler and A. Zaitoun, Inst. Franyais du Petrole
SPE Members

Copyright 1991, Society of Petroleum Engineers, Inc.

This paper was prepared for presentation at the SPE International Symposium on Oilfield Chemistry held in Anaheim, California, February 20-22, 1991.

This paper was selected for presentation by an SPE Program Committee following review.of informatio~ contained in an abstract submitted by the author(s). Contents of the paper,
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recent years. But injecting a polymer solution into a production

ABSTRACT
A polymer treatment based on the use of a nonionic high-
molecular-weight polysaccharide has been proposed for water
control in high-temperature production wells_ This polymer
has excellent viscosifying power in all types of reservoir
brines, high shear resistance and good thermal stability. Its
ability to decrease the relative permeability to brine without
affecting the relative permeability to hydrocarbons is
demonstrated for both matricial sandstone and limestone
reservoirs.
The superiority of this polysaccharide based water control
treatment over other competitive processes seems obvious as
soon as the reservoir temperature exceeds 70-75°C. With
specially designed additives, treatments at temperature up to
120-130°C may be proposed. Moreover, because of its high
shear resistance and its strong shear-thinning behavior this
polysaccharide can be pumped at high injection rates with a
slight wellhead pressure increase. Shut-in times of the wells
treated may thus be considerably reduced.
INTRODUCTION
Control of water production in oil or gas producing wells
by using polymers or gels has received renewed attention in
References and illustrations at end of paper
well is risky, especially if there is no possibility of zone
isolation. Polymers must be selective, i.e. they have to
reduce water production without affecting oil or gas
production.
Single high-molecular-weight water soluble
polyacrylamides have been proposed for the treatments of
production wells when the water and hydrocarbon zones are
not easily distinguishable. 1 Treatments using either
hydrolyzed or unhydrolyzed prolyacrylamides have already
been successfully tested both in lab experiments and in the
field. 2,3 In two-phase flow experiments it has been shown
that relative permeabilities to water may be efficiently reduced
while oil or gas relative permeabilities seem to be very little
affected by the presence of polymer in the porous matrix.
However it is well known that, due to thermally induced
hydrolysis and also oxidative degradation, treatments based on
polyacrylamides fail if the reservoir conditions become severe,
i.e. if the hardness level of the produced brine is too high and
4
overall if the reservoir temperature exceeds 75°C.
Alternative treatments based on thermally stable gels have
been recently proposed to overcome these unfavorable
environmental conditions. 5,6 They generally imply ionic or
covalent crosslinking reactions taking place either during or
following implementation into the reservoir. Although such
systems may act as permanent barriers in fissured reservoirs or

37
2 POLYMER TREATMENT FOR WATER CONTROL IN HIGH-TEMPERATURE PRODUCTION WELLS
if water and hydrocarbon production zones are clearly
separated, their use in matricial sandstone or limestone
formations may cause considerable risk of well impairment and
lack of selectivity.? Furthermore their use is generally limited
in harder brines due to additional crosslinking with calcium and
magnesium ions present in these brines.
In a previous paper8 we demonstrated that uncrosslinked
high-molecular-weight nonionic water soluble polysaccharides
are able to reduce the permeability to water in both sandstones
and sandpacks without affecting to a great extent the
permeability to oil. Although this behavior may be a general
rule for different types of polysaccharides including anionic
ones,9,10 one of the most efficient polymer is a nonionic
glucan type of polymer, Polysaccharide G, with strong shear-
thinning properties, excellent brine compatibility and good
thermal stability. Based on this polysaccharide, a new water
control process was meanwhile developed and its
performances have been tested in the lab.
The aim of this paper is to describe the efficiency of this
process in various environmental conditions and to show its
limits of maximum efficiency. It is shown that treatments using
polysaccharides cover a field of application that is
complementary to that of polyacrylamide based ones.
MATERIALS AND FLUIDS
Polymer solutions
Polysaccharide G is a nonionic glucan type of polymer
available in powder form. Its macromolecular dimensions and
characteristics in solution as determined by light scattering and
visosimetry are the following: molecular weight '"
6
5 x 10 daltons, intrinsic viscosity'" 7000 cm 3/g and
molecular length", 1.7 f.lm. Like other polysaccharides
from the same familyl1 its configuration in solution is a rod-
like triple helix.
The following lab procedure was used to prepare
Polysaccharide G solutions. The powder form of
polysaccharide was dispersed directly in the brine with the help
of a Hamilton Beach mixer with preconcentrate homogeneized
by agitation during 20 minutes. The concentrated polymer
solution was then diluted to the final concentration and left to
mature for two hours by gentle stirring with a magnetic
stirrer. Before use in stability studies or core flow
38
SPE 21000
experiments, the resulting solution was subjected to a quick
quality test performed with 8 f.lm Millipore filters (diameter
2
142 mm) under a pressure of 10 kPa. The time required to
filter 1 liter of solution was recorded, and a viscosity loss of
less than 5% (y = 10 s-1) was taken as a quaJity criterion.
Unless otherwise stated, for long conservation of
Polysaccharide G solutions, 2 gIL of commercial
formaldehyde was generally added to avoid bacterial
contamination.
The viscosities of polymer solutions were measured at shear
rates ranging between 0.1 and 120 s-1 using a Contraves
LS 30 viscosimeter.
Porous media
The core material used throughout this study was chosen to
cover a wide range of permeabilities. Table 1 gives their
mineral composition as estimated by X-ray diffraction and their
specific area obtained by nitrogen or krypton adsorption. One
reservoir core was used for high temperature relative
permeability measurements after being cleaned by Soxhlet
extraction and reconditioned with both reservoir brines and oil.
The consolidated limestone and sandstone cores were 4 cm
in diameter and 6 to 8 cm long. They were fitted with a
Vitton rubber sleeve and mounted in a Hassler cell. A pressure
3 3
of 2 x 10 to 4 x 10 kPa was imposed on the sleeve to
achieve lateral core tightness.
Sand C was a natural sand from which the fines had
previously been eliminated by several cycles of washing and
decantation with distilled water under ultrasonic
conditions. The dried sand was packed in a stainless steel
holder 3.5 cm in diameter and about 15 cm long.
Fluids
The following brines were used throughout this study:
10 gIL KCl solution, essentially to prevent clay migration in
clayey sandstones,
synthetic seawater containing 30 gIL NaCI and
3 gIL CaCI2.2H20,
• synthetic reservoir brine with 130 gIL TDS, reconstituted
with 118.6 gIL NaCl, 8.5 gIL CaCI2.2H20,
2.35 gIL MgC12.6H20 and 0.4 gIL KCl.
SPE 21000 N. KOHLER and A. ZAITOUN
The brines were fIltered through a 0.22 J.lm Millipore filter
prior to their use in flow experiments. Also, before each
polymer injection, we ascertained that there was a good
stability between the core material and the injected fluid.
As the oil phase we used either a petroleum jelly/dodecane
9/1 by weight mixture having a viscosity of 12.8 mPa.s at
60°C or a 2/1 by weight mixture having a viscosity of
8.8 mPa.s at 36°C and 4.5 mPa.s at 60°C.
In the experiment with a reservoir core, a crude oil was
used with a viscosity of 2.7 mPa.s at 95°C.
EXPERIMENT AL CONDITIONS AND
PROCEDURES
Thermal stability in solution
Since in fIled tests of water control treatments it is not
conceivable to purify the polymer solutions to any great extent
and to carefully exclude the dissolved oxygen, all our thermal
stability studies were performed with raw biopolymer solutions
prefiltered only to eliminate undissolved polymer particles and
some aggregates. The dissolved oxygen content was
decreased by subjecting the polymer solutions placed in sealed
glass cylinders to several alternating cycles of oxygen-free
nitrogen flush and vacuum. An oxygen content of about
10 ppb, measured using the colorimetric technique marketed
by Chemetrics Inc., could thus be obtained and the individual
ampoules could be flame sealed. To minimize acid catalyzed
hydrolysis of the polysaccharide's acetal groups, we added a
pH buffer to all solutions subjected to high temperatures.
Powdered calcium carbonate (200 gIL) was used throughout
our experiments, according to the recommendations of Seright
and Henrici,12 to maintain solution pH between 7
and 8. Periodically a test tube was opened and its oxygen
content, pH and viscosity were measured at room
temperature. The initial polysaccharide viscosimetric
reference curve was obtained by sacrificing one ampoule where
the polymer solution was in contact with the buffer during a
few hours at the testing temperature in order to satisfy polymer
adsorption requirements.
Results were recorded as the time necessary to reach a
viscosity decrease of 50 percent compared to the initial value
(1 = 10 s-I).
39
3
Flow experiments
Equipment:
Our experimental flow equipment comprised a positive-
displacement pump, a guard fIlter, a Hassler cell containing the
core, and a fraction collector, all arranged in series. The
system including one or two buffer cells for the fluids, was
thermostated in an oven at the testing temperarure with an
accuracy of ± 1°C. The pressure drop across the core was
measured using pressure transducers. Cumulative volumes
of displaced fluid during two-phase flow experiments were
followed in a graduated test cell directly collecting the
effluent. The two-fluids were injected through the same core
face.
Adsorption-Retention:
Polymer adsorption-retention experiments were performed
according to the previously described experimental
procedure. 13 Two polymer slugs containing a tracer (50 ppm
of KI) separated by a brine slug were injected at low rates (less
than 2 mid) through the core and the effluent tracer and
polymer concentration were followed versus injected pore
volumes. The delay of the first polymer front with regard to
the second one gives a measurement of adsorption.
Residual resistance factor (RRF) and resistance factor (RF):
The residual resistance factor to brine was experimentally
determined by the equation:
RRF= !::.P/M'o (1)
where !::.P0 and !::.P are respectively the pressure drop through
the core measured during brine flow at a given shear rate 1 and
a given saturation state of the core Sw before and after polymer
adsorption. Note that the !::.P value was obtained after
displacement of all free polymer from the core as checked by
viscosimetric measurement of the effluents.
The resistance factor RF was defined as the ratio of the
pressure drop during polymer solution flow through the core to
the pressure drop during brine flow !::.Po'
The effect of thermal aging on RRF values after
Polysaccharide G adsorption was checked in the following
way: two 1 gIL Polysaccharide G solutions in synthetic
seawater containing respectively no additive and 30 gIL of
4 POLYMER TREATMENT FOR WATER CONTROL IN HIGH-TEMPERATURE PRODUCTION WELLS
commercial formaldehyde were injected at lOO°C and
Sw = lOO% through two different Berea sandstones having
close characteristics (k = 0.143 11m2, <p = 0.17 and
k = 0.149 11m2, <p = 0.17). Seawater was then injected
until no more polymer was detected in the effluents, and RRF
values were determined at lOO°C for each core.
By a peristaltic pump, synthetic seawater containing no
formaldehyde was then recirculated in a closed system through
each core, and the differential pressure was recorded daily
during 10 days at lOO°C. Thus RRF variations with time
could be calculated.
The oven temperature was then progressively increased to
120 and 130°C and the differential pressure was noted daily.
Corrections based on brine viscosity variations with
temperature were made and RRF variations were evaluated.
Shear stability:
To evaluate the shear resistance inside porous medium of
Polysaccharide G solutions, a Vosges sandstone core was
saturated at 35°C with synthetic sea brine and its permeability
and porosity were measured (k = 3.35 11m2, <p = 0.31). A
1 gIL Polysaccharide G solution was then injected at constant
pressure through the core. For progressively increasing
pressure values, the resistance factor developed inside the
porous medium and effluent flow rates were measured. The
effluent viscosity was measured for each experiment and
compared to the injected one. Average shear rates inside
porous medium were calculated2 using the equation:
Y= 4 vir (2)
where v = Q/A <p (I-Sor) is the superficial velocity of the
aqueous phase, Q the flow rate, A the core section, <p the
porosity and Sor the residual oil saturation.
The average pore radius was taken as
(3)
assuming that residual oil acts as a solid towards the water
phase, diminishing the available porosity from <p to <p(1 - Sor),
and the permeability from k to k krw.
40
SPE 21000
Water/oil relative permeability:
Water/oil relative permeability measurements were
performed using the unsteady-state Welge method. 8 The
displacing fluid was injected through the core at a constant
flow rate of 0.5 L/h, and both pressure drop and cumulative
volumes of displaced fluid in the effluent were
monitored. Flow rates were sufficiently high so that end
effects could be neglected at the outlet face of the core and the
following condition could be fulfilled:
Illv>1 (4)
where I is the core length in cm, 11 the viscosity of the injected
fluid in mPa.S and v the superficial velocity in
crn/min. Relative permeability curves were determined during
displacement of water by oil (drainage).
Note that both the setting in place of the polymer and RRF
measurements were performed at much lower shear rates than
that used in relative permeability measurements. The reason is
that our measurements had to be performed at constant Sw
values to be reliable; by imposing too high shear rates a risk
indeed exists of modifying the saturation state of the core by
expelling an additional quantity of oil.
The effect of thermal aging at 120°C in oiVwater relative
permeabilities in the presence of adsorbed polymer was tested
in the following experimental conditions. A Vosges sandstone
(k = 1.55 11m2, <p = 0.24) mounted in a Hassler cell was
successively saturated at 60°C with a lO gIL KCI brine
containing 3 weight % of commercial formaldehyde and a 9/1
by weight petroleum jelly/dodecane mixture in order to
determine the initial relative permeability curves. Low shear
injection (y = 68 s-l) of a 1 gIL Polysaccharide G solution
also protected by 3 weight % of commercial formaldehyde
was then performed, and the oiVwater relative permeabilities
were measured in the presence of adsorbed polymer. The
core was shut-in and placed in an oven at 120°C during
6 days. After this time a new set of oiVwater relative
permeability curves was obtained at 60°C. The experiment
was renewed with a second aging period of 90 days at 120°C
followed by the final oiVwater relative permeability
measurements. In all cases the brines used contained
3 weight percent of formaldehyde.
SPE 21000 N. KOHLER and A. ZAITOUN
RESULTS AND DISCUSSION
General characteristics
The Polysaccharide G used throughout this study was a
nonionic polysaccharide produced by fennentation of glucose
by fungi of the genus Sclerothinia. Like other glucan type
polymers from the same family, 11,14 its molecular structure
consisted of single glucopyranose groups attached to every
third unit of the glucopyranose backbone.
When dissolved in water, Polysaccharide G is an extremely
stiff chain . There is strong evidence that this polymer is
triple-stranded in solution. Nevertheless its persistence length
of 180 nm shows that this polysaccharide is not truly a rigid
rod but instead seems to be a very stiff coil or a wonn-like
chain. 8
Since it is a nonionic polymer, the viscosity in solution of
Polysaccharide G is virtually insensitive to salinity
changes. Figure 1 shows that this polymer is very effective
as a viscosifier of seawater even at low polymer
concentrations. This behavior is undoubtedly due to its high
molecular weight and stiffness.
The strong shear thinning properties of Polysaccharide G
solutions also imply that, under the high shear conditions
prevailing around the wellbore, this polymer will have very
low viscosities, thus favoring reduced wellhead pressures and
high injection rates.
Shear resistance
The apparent stiffness of the Polysaccharide G molecule
also explains the high shear tolerance of this polymer in
solution. The results given in Table 2 show that for
increasing shear rates the resistance factor RF inside the core
diminishes according to the polymer pseudoplastic behavior in
solution and also that effluent viscosity loss (measured at a low
shear rate of 0.05 s-l) is minimized and is no greater than
10% for shear rates as high as 6900 s-l.
Similar results were found with the same core at 80°C and
shear rates up to 5000 s-l.
Thus for field applications high pumping rates can be used
without any significant viscosity loss of the injected solutions.
41
5
RRF levels and Polysaccharide G adsorption-
retention
Adsorption of Polysaccharide G molecules on reservoir
rocks is expected to be high due to their nonionic
nature. This was already demonstrated by us 13 in flow
experiments through sandspacks where polymer adsorption
increased tremendously with the clay content of the
sand. Low shear injection of 1 gIL of Polysaccharide G
solutions in synthetic seawater through a sandpack containing
12 weight % of kaolinite was found to give both high levels
of polymer retention and correspondingly high RRF values.
Polymer retention was due to the difficulty for the large size
Polysaccharide G molecules to pass through the reduced pore
constrictions under low shear conditions.
In another set of experiments,z,8 RRF values after polymer
adsorption were found to increase considerably as a
consequence of the presence of residual oil. The explanation
for this behavior was that an adsorbed polymer layer at the
pore wall more effectively restrains the flow of water when the
flow cross-section available to this phase is reduced by oil
droplets trapped in front of pore throats.
Table 3 summarizes the results obtained for
Polysaccharide G solutions while flowing through cores
having various calculated average values of pore radii as a
consequence either of their mineral composition or their clay
content. For each porous medium parallel experiments were
perfonned in the presence or not of an oil phase.
It can be seen that Polysaccharide G adsorption-retention
levels exceed 100 Ilg/g in all cases and do not vary to any
great extent in the presence of residual oil saturation.
RRF values were found to depend greatly on the
characteristics of the porous media used. When pore sizes are
high compared to the polymer molecular length, RRF values
remain low independently of the presence of oil or not. This
is the case for the experiments with clay-free sandpack C
where adsorption of the semi-rigid polysaccharide molecules
takes place in a flat configuration on the mineral surface giving
a reduced hydrodynamic thickness of the adsorbed polymer
11
layer.
On the contrary, if available pore sizes are on the same
order of magnitude as the molecular length, propagation of
6 POLYMER TREATMENT FOR WATER CONTROL IN HIGH-TEMPERATURE PRODUCTION WELLS
polymer solutions under low shear conditions becomes
difficult and retention phenomena- lead to high RRF values.
This is the case in both experiments with Lavoux limestone and
also with oil-containing Vosges sandstone. Note that for
water control operations these retention phenomena may easily
be minimized by reducing the injected polymer concentration
and/or by increasing polymer injection rates.
Thermal stability in solution
Glucan-type polymers are recognized to have excellent
14
thermal stability. Kalpacki et al. reported that under certain
test conditions scleroglucan solutions show little or no
viscosity loss at 100°C over 720 days. This behavior was
attributed to the triple helix structure of the polymer in
solution. For the same polymer, Rivenq et al. ll have shown
that at a temperature of about 125°C a structural change from a
rod-like to a random coil configuration could be
observed. They concluded that the scleroglucan molecule is
expected to maintain its excellent viscosifying properties up to
about 130°C.
In both of the above studies these results were obtained
under strictly anaerobic conditions with polysaccharide
solutions carefully purified by different techniques in order to
eliminate all impurities that may induce or favor polymer
degradation. The origin of thermal degradation of
polysaccharides is generally related to the presence of
hydrolyzable acetal functional groups. Different parameters 14
have been found to act on the kinetics of thermal hydrolysis,
i.e. solution pH, polymer structure, presence of impurities and
free oxygen.
The aim of our thermal stability studies was to check the
effect of long term aging at high temperature on
Polysaccharide G viscosity in solution under experimental
conditions compatible with its use for water control
treatments. Thus raw Polysacharide G solutions were used
only after having been subjected to prefiltration in order to
eliminate undissolved polymer particles and some
aggregates. Experiments in sealed ampoules were performed
at three different temperatures, first at 95°C with the
Polysaccharide G being dissolved in a 130 gIL reservoir
brine, then at 100 and 120°C with polymer solutions in
synthetic seawater.
Figure 2 shows that only a small viscosity decrease was
42
SPE 21000
observed after 72 days of thermal aging at 95°C with a 1 gIL
Polysaccharide G solution in the high salinity reservoir brine
in the presence of 2 gIL of commercial formaldehyde.
Table 4 summarizes the results of the thermal stability
studies performed at the three test temperatures. Our
experiments show that unprotected Polysaccharide G solutions
have very fast viscosity decay at all temperatures. A
significant improvement in thermal stabilization is obtained by
adding various concentrations of mono- and
15
dialdehydes. Especially formaldehyde in high
concentration seems very effective, with the general trend
being to increase its concentration progressively with
increasing reservoir temperature.
The ability of formaldehyde to act both as a biocide and
oxygen inhibitor has already been proven during long term
aging at 50°C of polyacrylamide solutions. 16 Formaldehyde
was thought to act as a free radical scavenger.
Core flow experiments at high temperature
It has been shown above that RRF values obtained after
Polysaccharide G adsorption depend greatly on the
characteristics of the porous media used and on the presence or
not of a residual oil saturation. However during flow
experiments through Berea sandstones with a scleroglucan
ll
broth, Rivenq et al. found that both polymer adsorption
levels and RRF values decreased when the testing temperature
increased from 30 to 90°C.
Our core flow experiments with Polysaccharide G
solutions show that high RRF levels can also be obtained at
higher reservoir temperatures.
Figure 3 shows, for example, the evolution with shear rate
of RRF values obtained after injection through a 0.05 11m2
reservoir core of a 1 gIL Polysaccharide G solution in
130 gIL TDS brine. The test temperature in this experiment
was 95°C.
Figure 4 gives the results of the corresponding oil/water
relative permeability measurements. The presence of an
adsorbed polymer layer reduces the relative permeability to
water without affecting the relative permeability to oil. Thus
the polysaccharide treatment remains efficient at high
temperature.
SPE 21000 N. KOHLER and A. ZAITOUN 7

This statment is also confmned by the discontinuous two- behavior of its solutions and also its resistance to the high
phase flow experiment including a long term aging period at shear conditions prevailing around the wellbore.
120°C performed on a more permeable Vosges sandstone
(k = 1.55 Ilm2). Figure 5 shows that the relative 2. Polysaccharide G molecules may give appreciable RRF
permeability to brine (10 gIL KCI) is hardly affected by the values to water when adsorbed in porous media. The levels
two successive aging periods of respectively 6 and 90 days at obtained are mainly governed by the characteristics of the
120°C, while the kro values are sligthly improved during this reservoir rocks treated and particularly by their clay content and
time. Let us note that in this test all fluid injection was the ratio between pore sizes and molecular length.
performed at 60°C and that both injected polymer solution and
the 10 gIL KCI brine contained 3 weight % of commercial 3. Water control treatments based on Polysaccharide G
formaldehyde. injection in production wells are selective. They reduce the
relative permeability to water without affecting the relative
Thus the ability of adsorbed Polysaccharide G molecules to permeability to oil.
reduce water flow without affecting oil flow is maintained after
a three month aging period at 120°C. 4. The use of Polysaccharide G based treatements is of
particular interest in high salinity and high temperature
The assumption that the high temperature stabilization effect reservoirs. All the basic polymer properties are preserved in
induced by the presence of formaldehyde is related to some such severe environmental conditions. Thus their field of
bonds formed with the Polysaccharide G molecule is enhanced application is quite complementary to that of polyacrylamide
by the two comparative flow experiments in Berea sandstones. based treatments.
Figure 6 shows that RRF values obtained after adsorption of a
1 gIL Polysaccharide G solution in synthetic seawater and in 5. For temperatures exceeding 95-WO°C and up to about
the presence of 30 gIL of commercial formaldehyde remain l30°C, it is strongly recommended in lab or field experiments
quite stable at 100 and 120°C and show only a slight decrease to add increasing quantities of mono- or dialdehydes to
at l30°C. On the contrary, RRF values obtained after injection, Polysaccharide G solutions for the long-term preservation of
in the same experimental conditions, of an unprotected their main properties.
Polysaccharide G solution were found to decrease drastically
already at 100°C. Let us note that, in these experiments NOMENCLATURE
injection and recirculation of synthetic seawater was done in a
closed system after the removal of free formaldehyde. Thus A core cross-section
the good stability of the RRF values toward the continuous k permeability
flow of water at high temperature after adsorption of kro oil relative permeability
formaldehyde protected Polysaccharide G molecules tends to krw water relative permeability
indicate that some bonds exist between the polymer and the I core length
protecting aldehyde. AP pressure drop of brine after polymer adsorption
AP0 pressure drop of brine before polymer adsorption
CONCLUSIONS Q flow rate through the core
r average pore radius
The following conclusions can be drawn from the present RF resistance factor
study: RRF residual resistance factor
Sor residual oil saturation
1. Polysaccharide G is a nonionic high-molecular-weight
Sw water saturation
poly-saccharide which behaves in aqueous solutions as a rod-
v superficial velocity
like triple helix. The nonionic nature as well as the relative
y shear rate
stiffness and high molecular length of the polymer fully explain
Il dynamic viscosity
its very high viscosifying power, which is insensitive to the
<p porosity
nature of dissolved salts, the pseudo-plastic or shear-thinning

43
8 POLYMER TREATMENT FOR WATER CONTROL IN HIGH-TEMPERATURE PRODUCTION WELLS
ACKNOWLEDGMENTS
This research was supported in part by the Association de
Recherche sur les Techniques d'Exploitation du Petrole
(ARTEr) and in part by an EEC-Contract No. TH03-
307/89. The authors wish to acknowledge the contribution of
J. Behot, F. Sivade and R. Tabary who performed
laboratory experiments.
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SPE 21000
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Symposium on Oilfield Chemistry, San Antonio, Texas,
February 4-6.
14. Kalpakci, B., Jeans, Y.T., Magri, N.F. and Padolewski,
J.P., "Thermal Stability of Scleroglucan at Realistic
Reservoir Conditions," paper SPE/DOE 20237 presented
at the 1990 SPE/DOE Seventh Symposium on EOR,
Tulsa, Oklahoma, April 22-25.
15. Patent Application filed in France, No. 89/17161,
December 21, 1989.
16. Knight, B.L.; "Reservoir Stability of Polymer
Solutions," J. Pet Tech" pp. 618-626, May 1973.
 TABLE I: CHARACIERISTICS OF ROCK SAMPLES TABLE2:SHEARSTABILITYOFIg!LPOLYSACCHARIDEGSOL~~ 2. 100.,
(Vosges sandstone (k = 3.35 J..I.ltl2), synthetic seawater. 35°C)

Nature Penneabi1ity Mineral composition in weight % Specific

range area Applied6P Measured flow rate Calculated shear rate Resistance factor Effluent viscosity
(11m2) Quanz Clay Others (m2/g) (mPa.s)
(kPa) Q(cm3/h) )\S-I) RF 1=0.5s- 1

Vosges 0.5 - 2.1 80 7 13 0.89

sandstone (mainly illite) (mainly feldspars) 56 295 100 55.4 539"
100 1239 419 23.6 538
Berea 0.13 - 0.18 80 5 15 1.2 350 6120 2068 20.5 532
sandstone (mainly kaolinite) (feldspars, dolomite 600 9840 3326 17.8 515
siderite) 900 20640 6976 12.7 500

Lavoux 0.09 - 0.14 0 0 100 0.50

limestone (calcite) * Equal to viscosity of injected solution

Sand C 4.8 - 5.6 100 0 0 0.34

TABLE 3: COMPARATIVE FLOW EXPERIMENTS OF POLYSACCHARIDEG SOLlIT10NS

wrrn AND wrrnOUT AN OIL PHASE

T Porous Core Porosity Water W_ Average Polymer Polymer RRF

("C) medium penneability saturation relative pore concentration adsorption at1= I s-1
(11m2) pemneabi1ity radius (gIL) (I1gig)
(11m)

36 Vosges 1.35 0.22 1.0 1.0 7.0 1.0 400 2.6

sandstones

36 Vosges 1.13 0.23 0.69 0.12 2.6 1.0 650 35

sandstone

60 SandC 5.6 0.41 1.0 1.0 10.5 1.0 135 2.7

60 SandC 4.8 0.42 0.78 0.5 7.7 1.0 120 4.2

60 Lavoux 0.14 0.24 1.0 1.0 2.1 0.5 465 > 30

limestone

60 Lavoux 0.12 0.24 0.74 0.075 0.63 0.5 455 > 30

limestone

TABLE 4: THERMAL STABILITY OF I GIL POLYSACCHARIDE G SOLUTIONS

(Time in days to reach 50% viscosity loss)

Added Aldehyde
Test No. T=95°C T=IOO"C T= 120°C
Reservoir Seawater Seawater
Nature Concentration brine
gIL

I - - <7 <7 <3

2 Formaldehyde 2 < 100 <30 < 15

3 Formaldehyde 10 > 100 < 100 < 100

4 Formaldehyde 30 > 100 > 100 > 100

5 Glyoxal 10 > 100 < 100

6 Glyoxal 30 > 100 > 100

7 GlutaraJdehyde 10 >60 < 15

8 Glutaraldehyde 30 > 100 < 100

45
 SPE !. ttl'

POLYSACCHARIDE G
SYNTHETIC SEAWATER
TEMPERATURE 3SoC

~
iii
o
u
:>
C/) 102 r-......-____
w
> O.S giL
,
3a:
w
,,'
"
10 "",,,
""," ...

1 10
SHEAR RATE (s-')

Fig. 1-Viscosity of Polysaccharide G solutions vs. concentration.

POLYMER 1 giL
BRINE 130 giL TDS
TEMPERATURE 9SoC

-Initial
103 • After 72 days at 95°C

~
iii
0
(.)
102
en
:>
w
>
f=
:5w 10'
a:

10° 10'
SHEAR RATE (S-')
Fig. 2-Stability of Polysaccharide G solution at 95°C.

46
 SANDSTONE 0.05 p.m2
SPE 21001
POLYMER 1 giL
BRINE 130g/L TDS
CRUDE OIL 2.7 mPa.S
TEMPERATURE 95°C

3
>- 10
!::
en
0
()
en
5> 2
w 10
>
i=
:5w
a::

SHEAR RATE (S-')

Fig. 3-Residual resistance factor following Polysaccharide G Injection through a reservoir sandstone core.

SANDSTONE 0.05 p.m2

POLYMER 1 giL
BRINE 130g/L TDS
CRUDE OIL 2.7 mPa.S
TEMPERATURE 95°C

>-
~ ~
::i ::i
a5 0.4- 0.4 a5
<t <t
W w
2 2
a:: a::
w w
0. 0.3 0.3 0.
w w
> >
i=
:5w
a:: 0.2
'\,
-; 0.2
~
w
a::
.....
o Before polymer ~--+------M
,
;--0.15 a::
w

0.1
,\ After polymer
I 0.1 i
I
I

0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90

WATER SATURATION
Fig. 4-Modlflcation of oil/water relative penn.abilitles Induced by Polysaccharide G adsorption In 8 sandstone core.

47
kro THERMAL STABILITY 120°C krw

1.00 1.00

o After polymer t = 0 day

~ t= 6 days
::::i
iii 90_
t=_
......._ _ _ _ _ days
---'0.75
0.75~
:E
a: ~
w ::::i
0. iii
W ~
> w
:E
~
0.50w
a:
~ 0.50
a: w
....I >
~
(5
w
a:
a:
w
0.25 ~ 0.~5
0.052 3:
0.01
0.012
~0.02

0.1 0.4 0.6 0.8

WATER SATURATION
Fig. 5-Effect of aging at 120°C on oil and water relative permeablllties.

2
BEREA SANDSTONES 0.140Jim
POLYSACCHARIDE G 1 giL
SYNTHETIC SEAWATER

I I I
100°C I 120°C I 130°C I
~-------~I-------I I
I
I
J
I I
10 -------t-------I-----t- - - - - - - - -
I I
I 30 giL Formaldehyde
~~~~~ ~

I
I
J

~ ~
a: I
a: I
....I I
~ I
E
z
0.5 r - - - - - + - - 1 - - - + I

/NO
I I

~ 1 adrtive

I I
I I
I
I
II
I
I
I
I
I
o ~------~------~----~-----------
10 20 30
TIME (days)
Fig. 6-Effect of increasing temperature on residual resistance factor.
48