SPE 93156
Development and Evaluation of High-Temperature Conformance Polymer Systems
J. Vasquez, SPE, E.D. Dalrymple, SPE, L. Eoff, and B.R. Reddy, SPE, Halliburton Energy Services, and
F. Civan, SPE, U. of Oklahoma
Copyright 2005, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the 2005 SPE International Symposium on Oilfield
Chemistry held in Houston, Texas, U.S.A., 2 – 4 February 2005.
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presented, have not been reviewed by the Society of Petroleum Engineers and are subject to
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Abstract
Conformance polymer systems have been successfully applied
for many years to control undesired water production from
hydrocarbon wells. However, currently available polymer
systems present a number of limitations for high-temperature
conformance applications (> 300oF). Based on laboratory
research, this paper documents the results of the development
and evaluation of polymer gel systems used as sealants to shut
off water production in high-temperature environments. The
polymer systems were evaluated by their effectiveness to:
(a) provide adequate gel time for placement (up to 400oF), (b)
limit permeability to water at temperatures up to 375oF in
sandpack flow experiments, and (c) provide long-term thermal
stability in sandpack flow experiments at elevated temperature
(up to one-year study).
A commercially available polymer system that has been
successfully used in field applications (up to 275oF) has been
modified to extend its applicability up to 375oF. Recently
developed base polymer, crosslinker, and retarder were tested
successfully to extend the temperature range of applicability
of this polymer system. Discussed are: (1) methodology used
for gelation time measurement of polymer systems at elevated
temperatures, and (2) laboratory results regarding gelation
time of crosslinked polymer systems when varying
temperature, base polymer concentration, crosslinker
concentration, retarder concentration, salinity of mixing brine,
and/or pH of solution.
Additionally, this paper discusses and describes the
dynamic flow through porous media experiments performed to
simulate high-temperature / high-pressure reservoir conditions
to evaluate the performance of polymer systems at elevated
temperatures (up to 375oF). Specifically, this paper details:
(1) the physical laboratory equipment and test conditions used
for dynamic flow studies, (2) experimental procedure
regarding short-term and long-term testing, and (3) the effect
of temperature versus permeability reduction over time.
Introduction
Excessive water production from hydrocarbon reservoirs is
one of the most serious problems in the oil industry. Watercut
greatly affects the economic life of producing wells and
unwanted water production is estimated to cost the petroleum
industry about $45 billion a year (although accurate records of
water production are difficult to obtain).1,2 These costs include
the expense to lift, dispose, or reinject this water, as well as
the capital cost of surface facility construction, water
treatment, and efforts to ensure that environmental regulations
are met.1
Remediation techniques for controlling water production,
generally referred to as conformance control, include the use
of polymer systems to reduce or plug permeability to water.
This paper mainly discusses water control in high-temperature
environments for treating hydrocarbon-producing wells to
reduce water production for applications in which water and
hydrocarbon zones are clearly separated. The principle of
operation of this technique is to pump the polymer system into
the formation around the wellbore and allow it to propagate
through the rock matrix. In-situ gelation takes place, plugging
pore spaces and channels, thus limiting undesired water flow.3
A variety of techniques for controlling water production
have been attempted by the oil industry. Earlier attempts to
reduce water production included mechanical isolation,
squeeze cementing, solid slurry (clay) injection, and oil/water
emulsion. More successful results have been obtained with in-
situ polymerized systems, crosslinked polymeric solutions,
and silicate-based gels.4
Polymer gel systems have emerged over the last decade as
one of the most effective tools for controlling water
production. One of the most widely used polymer systems
employs polyacrylamides (PAm’s) or acrylamide co-polymer
and chromium [Cr(III)] as a crosslinker.5 Cr((III) has been
extensively used because of its high success rate and relatively
low cost. However, the short gelation times of this system at
elevated temperatures limit their application to low- to
moderate-temperature reservoirs.6 Another polymer system
widely used is a water-based gel based on
phenol/formaldehyde crosslinker for homo-, co-, and ter-
polymer systems containing acrylamide. The loss of phenol by
partitioning into crude oil with which it comes into contact has
been identified as an important issue for that polymer system.8
The toxicity issues associated with formaldehyde and phenol
have been addressed by other researchers.9
Systems based on polyethyleneimine (PEI) crosslinker and
a base copolymer of acrylamide and t-butyl acrylate (PAtBA)
have been reported to propagate deep into the matrix and to
2 SPE 93156
provide excellent thermal stability. Although polymer systems
using organic crosslinkers such as this have been successful in
field applications, some features need improvement for high-
and low-temperature applications. For example, gel times are
short at high temperatures and systems require high crosslinker
concentrations at low temperatures.10-11
Present Study
The success of a particular polymer system is measured in
terms of its capability to provide predictable and adequate gel
times, reduce water permeability significantly, and provide
thermal stability for a long period of time. The challenge for
high-temperature applications is mainly the capability to
provide longer gelation times and acceptable thermal stability.
This paper presents the results from a laboratory evaluation
that evolved to address these issues and it is a continuation of
the investigation published in SPE 80904.11
The scope of this study was divided into two major
laboratory evaluations: the gelation time measurement of each
system as a function of the base polymer, crosslinker, retarder,
salinity of mixing brine, and/or pH of solution at elevated
temperatures; and secondly, dynamic sandpack flow
experiments up to 375oF to test the effectiveness of each
polymer system.
Description of Polymer Systems
The primary components of the polymer systems presented in
this paper are a low-molecular-weight base polymer and an
organic crosslinker. A commercially available system for low-
and medium-temperature range was modified to extend its
applicability to high temperatures by replacing the base
polymer with a recently developed base polymer, chemically
modifying the crosslinker, and adding a gel time retarder. The
following polymer systems were investigated during this
laboratory evaluation:
• Polymer System-I (a commercially available
system): The base polymer is a copolymer of
acrylamide and t-butylacrylate (PAtBA). The organic
crosslinker is a low-toxicity material based on
polyethyleneimine (PEI). The amine groups on PEI
react with the amide (and probably with the ester
groups) to form an amide linkage. Due to the
presence of multiple amine groups on the PEI and
ester/amide groups on the PAtBA, this results in a
crosslinked, three-dimensional gel.
• Polymer System-II (recently developed base
polymer): The base polymer is a sterically hindered
mixture of acrylamide, acrylamido-2-methylpropane
sulfonic acid (AMPSA), and N, N-dimethyl
acrylamide (N,N-DMA). The same organic
crosslinker (PEI) for Polymer System-I was used.
• Polymer System-III (recently developed
crosslinker): PAtBA was crosslinked with a
derivatized polyethyleneimine (d-PEI). In the d-PEI
some of the amine groups have been converted to
amides. This conversion was performed to delay
gelation time and provide equal or better thermal
stability than Polymer System-I.
• Polymer System-IV (recently developed retarder):
The base polymer and crosslinker are PAtBA and
PEI, respectively. A polyamino acid was added to the
system to delay gelation time.
The general crosslinking mechanism for each system is
illustrated by Fig. 1.
Gelation Time Characterization of Polymer Systems
Gelation time is one of the most important characteristics of a
polymer system. Gelation time defines the amount of time
available to the operator before the pumping pressure of the
polymer system significantly increases when applied in the
field. A reasonable gelation time must be known to allow safe
pumping of the polymer system through tubulars and into the
near-wellbore zone.
Gelation Time Experimental Procedure. Three methods
were used in this study to measure gelation times. A particular
method was selected depending upon the testing temperature.
1. Brookfield Viscosity Method
About 40 mL of a specific polymer system were
placed in a 50 mL graduated cylinder. The graduated
cylinder was inserted into a preheated,
thermostatically-controlled mineral oil heating bath
to reach testing temperature. In addition, 10 mL of
mineral oil were placed on top of the testing sample
to prevent evaporation. The solution was stirred at 20
rev/min with a Brookfield viscometer (Model DV-
II+) with a No.2 spindle and the viscosity changes
were monitored as a function of time. This method
defines gelation time as the time required for a
polymer system to begin building viscosity. If the
increase in viscosity while crosslinking is nearly
linear, the inflection point of the curve corresponds
quite closely to the time when the viscosity begins to
build and can be defined as ‘gel time’.7 Figure 2
shows a typical plot of viscosity versus time for
Polymer System-I (gelation time is approximately 14
hours at 185oF). Gel time measurements were
performed with this method for testing temperatures
up to 200oF.
2. Sealed-Tube Method
A 16-mm × 150-mm borosilicate glass tube with a
cap was filled with a specific polymer system
composition to approximately one-third its volume.
The tube was purged with nitrogen and the screw cap
was sealed with a high-temperature silicone sealant.
A TEFLON® plug was used inside the cap as well.
The tube was placed inside a heavy steel container,
and the container was placed in a preheated oven set
at the test temperature. The steel container was taken
out periodically and the tube removed for
observation. This method defines the gelation time as
the time required for a polymer system to reach
specified gel strength and relies upon the visual
evaluation of the researcher.7 This happened very
rapidly, generally in less than one hour after the
gelation process had begun. Gel time measurements
SPE 93156
were performed with this method for testing
temperatures from 200oF to 325oF.
3. Brookfield High-Pressure PVS Viscosity Method
The High-Pressure PVS Rheometer is a dynamic
coaxial cylinder, controlled shear rate rheometer that
allows viscosity measurements under pressure at
temperatures where evaporation is a problem
(Brookfield model DV-II+ viscometer has this
limitation). Approximately 30 mL of solution were
placed in the sample cup. The bob/spindle sample
cup code used was PVS-B5-D (BOB 1). The outer
cylinder is driven by a stepper motor at a speed of 20
rev/min. Fig. 3 shows a typical plot of viscosity vs.
time for Polymer System-III (gelation time is
approximately 13 hours at 300oF). This method uses
the same gelation time definition as the Brookfield
viscosity method. Gelation time measurements were
performed with this method for testing temperatures
from 200oF to 375oF.
Results and Discussion. Availability of gelation time curves
allows to assign a temperature range of applicability to each
polymer system depending upon reservoir conditions
(reservoir depth, length of the interval to be treated,
bottomhole conditions, injection rate of preflush fluid, and
shut-in time program, among others).1
Gelation times for Polymer System-I are short at
temperatures higher than 250oF and do not exceed 4 hours.
The short gel times are thought to be due to increased reaction
rate of the PEI amine groups with the polymer ester/amide
groups. To make this polymer system work at higher
temperatures, a preflush phase would be required to cool down
the zone to ~ 250oF so that the polymer system can be placed
before gelling. Figs. 4 through 6 show the gelation time curves
for Polymer System-I at different temperatures. For low
temperatures (< 200oF), a high concentration of crosslinker
(PEI) is needed to obtain an adequate gelation time. For high
temperatures, the use of high PAtBA concentrations is
recommended to obtain a more thermally stable gel.
Figs. 7 through 10 show the gelation time curves for
Polymer System-II at different temperatures. Excellent
gelation times and extremely good gel quality was obtained in
the temperature range from 250oF to 350oF. The crosslink in
this system is believed to be taking place at the acrylamide
portion of the polymer, based on the fact that a copolymer of
2-acrylamido-2-methylpropane sulfonic acid/N,N-DMA
would not crosslink with PEI. The extension in gel times at the
elevated temperatures is therefore most likely due to the steric
hindrance provided by the bulky acrylmido propane sulfonate
and dimethyl acrylamido groups. Gelation time of polymer
system was very sensitive to the pH of solution (particularly
between 10 and 12) and to the variation of the salinity percent
of the mixing brine.
The replacement of PEI by d-PEI resulted in excellent
gelation times up to 400oF. Figs. 11 and 12 show gelation time
curves for Polymer system-III. It is believed that the extension
in the temperature range is due to the conversion of some of
the PEI amine groups to amide groups. Before crosslinking
can take place, these amide groups must be hydrolyzed back to
3
the free amine, thus resulting in the delay in crosslinking time.
As with the other systems, strong ringing gels were observed.
Figs. 13 through 15 show the gelation time curves for
Polymer System-IV. By adding the polyamino acid to Polymer
System-I, the temperature range of applicability is expanded
from 250oF to 300oF. In this system, the polyamino acid is
believed to form a complex with the PEI, thus temporarily
blocking the amine groups and extending the crosslink times.
Again, good gel quality was observed.
The modification of Polymer System-I by either the
substitution of the base polymer or modification of the
crosslinker, or addition of a retarder, expands the temperature
range of applicability of the current commercial system
allowing the elimination of the cooling preflush stage and
simplifying job design and execution. Excellent gel quality
was observed in each system. Polymer System-III provides the
broadest temperature range of applicability.
Dynamic Sandpack Flow Experiments
Tests were conducted to evaluate the effectiveness of the
polymer systems to limit permeability to water and to provide
long-term thermal stability at elevated temperature.
Physical Laboratory Model. The experimental system was
designed to test three sandpacks for long-term flow tests.
Fig. 16 illustrates the experimental equipment used to simulate
high-temperature and high-pressure reservoir conditions.
Before water and kerosene were injected into the sandpacks,
the fluids were filtered through a 2.0-µm filter to remove any
particulate matter from the fluids. After flowing through a
check-valve, water and kerosene flowed through a coiled-
tubing heating bath to reach test temperature.
During the experiments, differential-pressure transducers
recorded pressure drop along the core using a Honeywell
Smart Box. Two pressure transducers with different pressure
ranges were set to provide better accuracy on the pressure
differential readings (pressure ranges of 0 to 100 psi and 0 to
3,000 psi).
After flowing through the sandpacks, the fluid temperature
was decreased by forcing the exiting fluids flow through a
cooling coil. Finally, fluids exited the system through a
backpressure regulator, holding a system pressure of
approximately 200 psi.
Test Conditions. The established parameter for the
experiments, such as gradients of pressure, temperature, and
flow rates, correspond to typical values found during high-
temperature field operations:
• Sandpacks: Sand was packed in 21.5-cm long, 1.5-
cm inside diameter Monel tubes. Table 1 shows the
mixture formulations used to pack the Monel tubes.
Oklahoma No. 1 sand was sieved to obtain 70-170
mesh size. 2% KCl brine was added to the mixture to
prevent silicate flour and bentonite from layering
together. 100-mesh screens were placed at the top
and bottom of the tube.
• Temperature: Treating and testing temperature
varied depending upon the gelation time of the
polymer system being tested, up to 375oF.
4 SPE 93156
• Back-pressure: 200 psi
• Flow rates: Different flow rates were used
depending upon the stage of the experiment, as
shown in Table 2.
• Displacement water: 2% KCl
• Displacement oil: Kerosene
Experiment Phases. The overall test was conducted in three
phases:
a. Core Preparation
Sandpack tubes were saturated with water at testing
temperature. Formation damage by clay/water
interaction was minimized by using 2% KCl water.
Water was flowed until a stable pressure drop was
recorded, at which point, the absolute permeability of
the sandpack was calculated. Next, 25 mL of
kerosene were injected into the sandpack at testing
temperature.
Finally, 2% KCl water was injected again to
reach residual oil saturation. At this condition, the
effective permeability to water at residual oil
saturation kwro was calculated. The effective
permeability to water at residual oil saturation kwro
and the “treated effective permeability” within the
sandpack were calculated using Darcy’s flow
equation (Eq. 1):
qµ L
K= ……………………………..….(1)
A ∆P
where K is the permeability in mD, q is the flow rate
in mL/min, µ is viscosity at temperature in cP, A is
the cross-sectional area of the sandpack in cm2, L is
the length of the sandpack in cm, and ∆P is the
differential pressure along the sandpack in psi.
Sufficient water was injected to obtain stable flow. At
this point the sandpack was considered ready to be
treated.
b. Polymer System Saturation and Shut-in Period
Ten pore volumes of a specific polymer system
formulation were injected into the sandpack in
normal flow direction. Depending on testing
temperature and the gelation time of the polymer
system at that temperature, treating temperature was
decreased to provide an adequate gelation time while
avoiding any premature gelation. This was
particularly the case for measuring thermal stability
in Polymer System–I, which required precooling
before placement.
At the end of the treatment placement, sandpack
was shut-in overnight to allow for gelation as
temperature was elevated to the original test cell
temperature at a rate of approximately 20oF/hr.
Sandpack cells were then held at testing temperature
for aging studies to evaluate their effectiveness in
exposure at elevated temperatures.
c. Evaluation of Treatment Effectiveness
This phase had two objectives. The first objective
was to determine permeability by attempting flow of
water through the core at the same differential
pressure used before treatment (recorded when
measuring kwro). Differential pressure was slowly
ramped up in 10-psia increments (holding ∆P for
10 min before each increment) up to 100 psi until
measurable flow occurred.
The second objective was to evaluate the long-
term sealant properties of each polymer system at
testing temperature. The objective of the extended
flow test was to evaluate the effectiveness of the
polymer system in reducing permeability as a
function of time. The percent permeability reduction
(PPR) is given by Eq. 2:
⎛ Kf ⎞
PPR = 100 ⎜⎜1 − ⎟⎟ ………………....…..(2)
K
⎝ i ⎠
where the subscript i indicates the initial permeability
at residual oil saturation conditions and the subscript
f indicates the final permeability after the sandpack
was treated. Each week the procedure described in
the first objective of this phase was repeated and the
regained permeability values were reported.
Results and Discussion. Four dynamic sandpack flow
experiments were performed evaluating each polymer system.
Table 3 shows a detailed description of the formulation used
for each polymer system. Table 4 shows a summary of the
results from sandpack flow experiments regarding the
effectiveness of the polymer systems in reducing permeability
at high-temperatures. During the sandpack flow experiments,
each polymer system showed good injectivity and good
permeability reduction. The effective permeability to water
was significantly decreased after the gelation of each
treatment in the porous media. Differential pressure was
ramped up to 100 psi without observing any water flow (100%
permeability reduction).
Fig. 17 shows the results for the extended flow tests.
Aging test results show that these polymer systems can
effectively reduce permeability to water at 350oF for a
reasonable period of time. Polymer System-I at 350oF showed
a PPR of approximately 88% over a year. Polymer System-II
also proved to be thermally stable, showing approximately
97% permeability reduction after one year. Polymer Systems-
III and -IV are currently being evaluated and have shown
better percent permeability reduction than Polymer Systems-I
and -II up to this point. Polymer System-III allows extension
of the temperature range of applicability up to 375oF (without
a preflush stage to cool the formation).
Laboratory Observations. ‘Sandpack’ flow experiments are
the preferred method over ‘core’ flow experiments for the
laboratory evaluation of ‘high-temperature’ conformance
polymer systems. At the beginning of the study, core flow
experiments were the proposed method to evaluate these
conformance polymer systems.11 However, core flow
SPE 93156
experiments presented problems associated with the collapse
of the overburden pressure system caused by the failure of the
silicone sleeves used for maintaining overburden pressure at
350oF. On numerous occasions, silicone sleeves were replaced
when their chemical composition broke down because of
temperature, interaction with chemicals (oil or polymer
system), or a combination of both. Because the silicone
sleeves were constantly replaced, experimental results might
not have been representative of the true capabilities of the
polymer systems. The authors decided to eliminate overburden
pressure by using sandpacks in Monel tubes instead of core
samples. Fig. 18 shows a comparison of the results obtained
with a sandpack and a core sample. Results obtained with a
core sample might mislead the results about the effectiveness
of Polymer System-I to provide thermal stability at 350oF.
Conclusions
Based on the study conducted in this paper, the following
points summarize the results:
• Polymer System-I, a commercially available system,
can provide long-term sealant capabilities at high-
temperatures (up to 350oF).
• Polymer Systems-I through -IV showed excellent
permeability reduction and good thermal stability in
sandpack flow experiments. No injectivity problems
were observed. Table 1 summarizes the temperature
range of applicability for each polymer system.
• PAtBA crosslinked with d-PEI can provide adequate
gelation times from 250oF to 400oF. This system
showed the widest temperature range of applicability
and provides excellent permeability reduction up to
375oF.
• Dynamic ‘sandpack’ flow experiments are the
preferred method over ‘core’ flow experiments for
the laboratory evaluation of ‘high-temperature’
conformance polymer systems because of the
problems associated with the collapse of the
overburden pressure system in core tests.
• Understanding the effects of parameters such as base
polymer concentration, crosslinker concentration,
retarder concentration, salinity of mixing brine,
and/or pH of solution, in controlling polymer
system’s gelation time allows one to design a specific
formulation to suit a particular high-temperature
application. On the other hand, gel quality needs to
be monitored simultaneously.
Aging tests for Polymer Systems-III and -IV will continue and
regain-permeability values up to a year will be reported.
Nomenclature
A Cross-sectional area, cm2
AMPSA Acrylamido-2-methylpropane sulfonic acid
d Diameter, cm
d-PEI Derivatized polyethyleneimine
K Permeability, mD
Kf Final permeability, mD
Ki Initial permeability, mD
KCl Potassium chloride
5
kwro Effective permeability to water at residual
oil saturation, mD
L Core length, cm
N, N-DMA N, N-dimethyl acrylamide
PAA Polyamino acid
PAtBA Polyacrylamide t-butyl acrylate
PEI Polyethyleneimine
PPR Percent permeability reduction
Q Flow rate, mL/min
t Time, days
T Temperature, oF
∆P Pressure drop along the core, psi
Greek Symbols
∆ Change, drop
∆P Pressure drop along the core, psi
µ Viscosity, cP
Subscripts
f Final
i Initial
o Oil
w Water
Acknowledgements
The authors thank Halliburton Energy Services, Inc. for
permission to publish this work. The support from Halliburton
Energy Services, Inc. and the Mewbourne School of
Petroleum and Geological Engineering at The University of
Oklahoma is greatly appreciated.
References
1. Halliburton, “Conformance Technology Manual,” Halliburton
Energy Services Publication F-3373. Houston, Texas,
106 pages, 1996.
2. Curtice, R. and Dalrymple, E.: “Just the cost of doing
business?” World Oil Magazine, Volume 225, No. 10. Gulf
Publishing Company, Houston, Texas, October 2004, pages 77-
78.
3. Dalrymple, D., Tarkington, J. and Hallock, J.: “A Gelation
System for Conformance Technology,” paper SPE 28503
presented at the 1994 SPE Annual Technical Conference and
Exhibition, New Orleans, 25-28 September.
4. Prada, A., Civan, F. and Dalrymple, D.: “Evaluation of Gelation
Systems for Conformance Control,” paper SPE 59322 presented
at the 2000 SPE/DOE Improved Oil Recovery Symposium,
Tulsa, Oklahoma, 21-23 March.
5. Sydansk, R.: “Acrylamide-Polymer/Chromium (III) Carboxylate
Gels for Near-Wellbore Matrix Treatments,” paper SPE/DOE
20214 presented at the 1990 Enhanced Oil Recovery
Symposium, Tulsa, Oklahoma, 22-25 April.
6. Bartosek, M., Mennella, A. and Lockhart, T.: “Polymer Gels for
Conformance Treatments: Propagation of Cr(III) Crosslinking in
Porous Media,” paper SPE/DOE 27828 presented at the 1994
SPE/DEO Ninth Symposium on Improved Oil Recovery, Tulsa,
Oklahoma, 17-20 April.
7. Hardy, M., Botermans, W. and Smith, P.: “New Organically
Crosslinked Polymer System Provides Competent Propagation
at High Temperature in Conformance Treatments,” paper SPE
39690 presented at the 1998 SPE/DOE Improved Oil Recovery
Symposium, Tulsa, Oklahoma, 19-22 April.
8. Albonico, P., Bartosek, M., Malandrino, A., Bryant, S., and
Lockhart, T.: “Studies on Phenol-Formaldehyde Crosslinked
Polymer Gels in Bulk and in Porous Media,” paper SPE 28983
6 SPE 93156

presented at the 1995 SPE International Symposium on Oilfield
Chemistry, San Antonio, Texas, 14-17 February.
9. Moradi-Araghi, A.: “Application of Low-Toxicity Crosslinking
Systems in Production of Thermally Stable Gels,” paper SPE
27826 presented at the 1994 SPE/DOE Symposium on Improved
Oil Recovery, Tulsa, Oklahoma, 17-20 April.
10. Reddy, B.R., Eoff, E., Dalrymple, D., Black, K., Brown, D. and
Rietjens, M.: “A Natural Polymer-Based Crosslinker System for
Conformance Gel Systems,” paper SPE 75163 presented at the
2002 SPE/DOE Improved Oil Recovery Symposium, Tulsa,
Oklahoma, 13-17 April.
11. Vasquez, J., Civan, F., Shaw, T., Dalrymple, E., Eoff, L., Reddy,
B.R. and Brown, D.: “Laboratory Evaluation of Conformance
Polymer Systems,” paper SPE 80904 presented at the 2003 SPE
Production and Operations Symposium held in Oklahoma City,
Oklahoma, 23-25 March.
12. Dovan, H., Hutchins, R. and Sandiford, B.: “Delaying Gelation
of Aqueous Polymers at Elevated Temperatures Using Novel
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SPE International Symposium on Oilfield Chemistry, Houston,
Texas, 18-21 February.
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in the North Sea: Testing a New Polymer-Gel System in the
Heather Field UKCS Block 2/5”, SPEPF, May 1996, page 108.

Table 1—Sandpack Mixture Formulation

Component Amount
Oklahoma No.1 sand 97 g
Silica flour 1.5 g
Bentonite 1.5 g
2% KCl brine 2.0 mL

Table 2—Typical Flow Rates for

Sandpack Flow Experiments
Flow rate
Phase
(mL/min)

Water saturation 10

Oil saturation 10

Polymer system saturation 2

Evaluation of effectiveness of
2
polymer system
Filling lines and cleaning of
30
system

Table 3—Polymer System Formulations for

Dynamic Sandpack Flow Experiments

Polymer System Formulation

7% active PAtBA, 1.32% active PEI,

I
2% KCl
7% active A/AMPSA/N,N-DMA,
II
2% active PEI, 10% KCl
7% active PAtBA, 2% active d -PEI,
III
2% KCl
7% active PAtBA, 0.65% active PEI,
IV
2% active PAA, 2% KCl
SPE 93156 7

Table 4—Summary of Dynamic Sandpack Flow Experiments

at High Temperature
Polymer System I II III IV
Testing temperature, °F 350 350 375 350
Treating tem perature, °F 175 300 375 300
Liquid absolute permeability, mD 547.7 951.3 734.5 852.2
Water effective permeability at Sor, mD 234.2 331.7 314.8 395.8
Final permeability, mD 0.49 0 0 0
Perm eability reduction, % 99.8 100 100 100

Table 5—Temperature Range of Applicabilitya

Adequate
Polymer System Thermal Stability
Gelation Time
I 175 to 250 oF Up to 350 oF
II 250 to 350 oF Up to 350 oF
III 250 to 400 oF Up to 375 oF
IV 250 to 300 oF Up to 350 oF
a
For each polymer system according to its capability to
provide adequate gelation time and thermal stability.

Figure 1—General crosslinking mechanism for polymer systems (X = O, N; R = C(CH3)3, C(CH3)2, NH2, CH2SO3H, N(CH3)2).
8 SPE 93156

35000

Viscosity, cP 28000

21000

14000

7000

0
0 200 400 600 800 1000
Time, min
Figure 2—Typical gelation time curve using Brookfield viscosity method (Polymer System-I: 7% active PAtBA, 1.5% active PEI, in 7% KCl;
gelation time approximately is 14 hours at 185°F).

Figure 3—Typical gelation time curve using Brookfield High-Pressure PVS Viscometer (Polymer System-III: 7% active PAtBA, 1.5% active
d-PEI, in 2% KCl; gelation time approximately is 12 hours at 300°F).
SPE 93156 9

Figure 4—Polymer System-I, PAtBA crosslinked with PEI: gelation time vs. crosslinker concentration at various temperatures
(7% active PAtBA, in 2% KCl).

Figure 5—Polymer System-I, PAtBA crosslinked with PEI: gelation time vs. polymer concentration at various temperatures
(1% active PEI, in 2% KCl).
10 SPE 93156

Figure 6—Polymer System-I, PAtBA crosslinked with PEI: gelation time vs. salinity percent of mixing brine at various temperatures
(5% active PAtBA, 1% active PEI).

Figure 7—Polymer System-II, Acrylamide/AMPSA/N, N-DMA crosslinked with PEI: gelation time vs. crosslinker concentration at various
temperatures (7% active Acrylamide/AMPSA/N,N-DMA, in 10% KCl, pH = 11).
SPE 93156 11

Figure 8—Polymer System-II, Acrylamide/AMPSA/N, N-DMA crosslinked with PEI: gelation time vs. polymer concentration at various
temperatures (2% active PEI, in 10% KCl, pH = 11).

Figure 9—Polymer System-II, Acrylamide/AMPSA/N, N-DMA crosslinked with PEI: gelation time vs. pH of solution at various temperatures
(7% active Acrylamide/AMPSA/N,N-DMA, 2% active PEI, in 10% KCl).
12 SPE 93156

Figure 10—Polymer System-II, Acrylamide/AMPSA/N, N-DMA crosslinked with PEI: gelation time vs. salinity percent of mixing brine at various
temperatures (7% active Acrylamide/AMPSA/N,N-DMA, 2% active PEI, pH = 11).

Figure 11—Polymer System-III, PAtBA crosslinked with d-PEI: gelation time vs. crosslinker concentration at various temperatures (7% active
PAtBA, in 2% KCl).
SPE 93156 13

Figure 12—Polymer System-III, PAtBA crosslinked with d-PEI: gelation time vs. pH of solution at various temperatures (7% active PAtBA,
2% active d-PEI, in 2% KCl).

Figure 13—Polymer System-IV, PAtBA crosslinked with PEI + polyamino acid: gelation time vs. retarder concentration at various
temperatures (7% active PAtBA, 0.65% active PEI, in 2% KCl).
14 SPE 93156

Figure 14—Polymer System-IV, PAtBA crosslinked with PEI + polyamino acid: gelation time vs. pH of solution at various temperatures
(7% active PAtBA, 0.65% active PEI, 2% polyamino acid, in 1% KCl).

Figure 15—Polymer System-IV, PAtBA crosslinked with PEI + polyamino acid: gelation time salinity percent of mixing brine at various
temperatures (7% active PAtBA, 0.65% active PEI, 2% polyamino acid).
SPE 93156 15

Figure 16—Experimental setup for dynamic sandpack flow tests.

16 SPE 93156

100

90
% permeability reduction

80

Polymer System-I

Polymer System-II
70
Polymer System-III

Polymer System-IV

60
0 100 200 300 400
Cumulative time at testing temperature, days

o
Figure 17—Summary of aging tests results (Sandpack treated with Polymer System-III has been only 15 days at 375 F).

Figure 18—Polymer System-I, PAtBA crosslinked with PEI: Aging test comparison between a sandpack flow test and a core flow test
(7% active PAtBA, 1.32% active PEI, in 2% KCl at 350°F).