SPE-179657-MS

Permeability Reduction Due to use of Liquid Polymers and Development of

Remediation Options
Varadarajan Dwarakanath, Robert M. Dean, Will Slaughter, Dennis Alexis, David Espinosa, Do Hoon Kim,
Vincent Lee, Taimur Malik, Greg Winslow, Adam C. Jackson, and Sophany Thach, Chevron

Copyright 2016, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Improved Oil Recovery Conference held in Tulsa, Oklahoma, USA, 11–13 April 2016.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents
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any position of the Society of Petroleum Engineers, its officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written
consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may
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Abstract
Polymer flooding by liquid polymers is an attractive technology for rapid deployment in remote locations.
Liquid polymers are typically oil external emulsions with included surfactant inversion packages to allow
for rapid polymer hydration. During polymer injection, a small amount of oil is typically co-injected with
the polymer. The accumulation of the emulsion oil near the wellbore during continuous polymer injection
will reduce near wellbore permeability. The objective of this paper is to evaluate the long-term effect of
liquid polymer use on polymer injectivity. We also present a method to remediate the near well damage
induced by the emulsion oil using a remediation surfactant that selectively solubilizes and removes the
near wellbore oil accumulation. We evaluated several liquid polymers using a combination of rheology
measurement, filtration ratio testing and long-term injection coreflood experiments. The change in
polymer injectivity was quantified in surrogate core after multiple pore volumes of liquid polymer
injection. Promising polymers were further evaluated in both clean and oil-saturated cores. In addition,
phase behavior experiments and corefloods were conducted to develop a surfactant solution to remediate
the damage induced by oil accumulation. Permeability reduction due to long term liquid polymer injection
was quantified in cores with varying permeabilities. The critical permeability where no damage was
observed was identified for promising liquid polymers. A surfactant formulation tailored for one of the
liquid polymers improved injectivity three- to five-fold and confirms our hypothesis of permeability
reduction due to emulsion oil accumulation. Such information can be used to better select appropriate
polymers for EOR in areas where powder polymer use may not be feasible.

Introduction
Over the last ten years there has been renewed interest in polymer EOR due to a combination of high oil
prices and falling polymer costs. Polymer applications range from injection tests offshore in Dalia, Angola
(Morel et al., 2008) to full field deployment of polymer flooding in offshore Bohai Bay, China (Kang et
al., 2011). Several polymer pilots have been conducted in Canada to recover viscous oil (Wassmuth et al.
2009; Delamaide et al, 2013; Renouf, 2014). Similarly onshore polymer pilots to recover viscous oil in
Suriname (Manichand et al, 2010), India (Prasad et al. 2014) and light oil in Argentina (Hryc et al., 2013)
have confirmed the ability of polymer flooding to successfully improve oil recovery. All these recent
2 SPE-179657-MS

floods used the powder version of partially hydrolyzed polyacrylamide polymers (HPAM). Powder
polymer applications are typically popular for onshore application due to the availability of space to store,
mix and hydrate polymer into viscous solutions for injection.
Powder polymers typically require two-stage hydration. The first stage involves mixing a one percent
by weight mother solution, followed by dilution to the desired concentration in the second stage. In
addition, the ability to handle and meter powder accurately into the initial polymer-mother-solution
mixing unit is critical the success of injecting high quality polymer. Liquid HPAM polymers are typically
prepared by inverse water-in-oil emulsion polymerization with subsequent removal of water to achieve
high activity (Ryles and Cicchiello, 1986). Inversion of liquid polymers requires the presence of an
inversion surfactant that emulsifies the oil and allows for hydration of the HPAM. Liquid polymers can
potentially be hydrated in a single step if an appropriate chemical inversion package is developed and
added to the emulsion. Liquid polymers do not require complex powder handling and dispensing
equipment.
For offshore applications, with space constraints or the inability to retrofit platforms with polymer
mixing and hydration equipment, the use of liquid polymers may be attractive. Liquid polymers show
similar rheology/viscosity yields and low retention (during corefloods) when compared against powder
polymers with similar molecular weights (Osterloh et al., 1998). In terms of usage and handling, liquid
polymers can be easily shipped to remote and off-shore locations with no need for handling powders.
Furthermore the potential for using simplified mixing schemes such as single stage dilutions greatly
minimize the complexity and improve reliability of field operations. The polymer pilot at Marmul (Teeuw
et al., 1983; Koning et al., 1988) used a 30% by weight liquid HPAM and demonstrated the applicability
of using liquid polymers for polymer EOR.
Successful implementation of polymer flooding requires high polymer injectivity with minimal
plugging near wellbore to maintain required injection rates. If appropriately treated water is used to mix
powder polymers and the mixture is allowed to hydrate sufficiently, there are minimal issues with regard
to long term polymer injectivity. Despite several apparent advantages in terms of rapid deployment and
better reliability, liquid polymers are potentially prone to plugging near wellbor regions. The injection of
liquid polymers also includes injection of low concentrations of suspended oil, which has a propensity to
reduce permeability due to either straining or interception (Schmidt et al., 1984). Straining is pore
plugging induced by the emulsion oil trapped in the pore throats. Interception is the adhesion of oil to
mineral surfaces, which reduces the area available for liquid flow and hence is manifested in the form of
lower injectivity. Figure 1 illustrates both straining and interception during stable emulsion flow in porous
media. In addition, liquid polymers are more expensive due to the large fraction of inactive material in the
form of the carrier oil and require carefully tailored inversion packages which may induce other challenges
in terms of interferences with above ground facilities.
SPE-179657-MS 3

Figure 1—Plugging phenomena: interception or straining of oil in porous media

Polymer selection techniques outlined in literature focus on polymer rheology and oil recovery. This
is because plugging mechanisms such as interception and straining are not observed during use of powder
polymers. Our goal is to determine the applicability limits of liquid polymers for reservoir applications in
terms of long-term injectivity. We first establish baseline injectivity with powder and emulsion polymers
in clean (no oil) surrogate core with 25 PV of polymer injection. We follow polymer injection with several
pore volumes of water to determine residual resistance factors. Given that the plugging is hypothesized
to be caused by either straining or interception, we test the ability of tailored surfactant packages to
improve injectivity. Based upon our work we identify the boundaries of applicability of liquid polymers
and provide a mechanism to improve injectivity if permeability loss due to liquid polymer injection is
observed.
Materials and Methods

Four commercial liquid polymers (LP#1 through LP#4) and one commercial powder polymer (HPAM)
were evaluated in this study. All the polymers had a molecular weight of approximately 18-21MM
Daltons. Products LP#1 and LP#4 are considered to be first generation products and LP#2 and LP#3 are
improved products developed after review of coreflood results that illustrated injectivity constraints.
Bentheimer rock and F-95 Ottawa sand packs were used as surrogate core. Some experiments were also
conducted with unconsolidated field sand. An 80 cP crude oil was used in oil recovery experiments and
all the corefloods were conducted at 31°C. The polymer mixing procedures for both powder and liquid
polymers are presented in Appendix A. All the polymers were mixed in synthetic reservoir brine whose
composition is summarized in Table. 1.

Table 1—Brine composition

Ion Concentration (ppm)

Naⴙ 5,048
Ca2ⴙ 569
Mg2ⴙ 210
Cl- 9403
TDS 15,230
4 SPE-179657-MS

For all the polymers the basic rheology in terms of viscosity versus concentration, viscosity versus shear
rate, neat polymer viscosity and filtration ratios of 2000 ppm polymer solutions through 5 2m and 1.2 mm
polycarbonate filters was measured. For coreflood evaluations, epoxy-coated Bentheimer sandstone or
F-95 Ottawa sandpacks without oil were used to measure long-term polymer injectivity. The packing
procedures to prepare the Ottawa sand packs are given in Dwarakanath et al.(1999). Epoxy coating
procedures for sandstone cores as well as core preparation techniques are summarized in Jackson (2006).
The description of filtration ratio is given as follows:

Filtration ratio tests

The filter ratio (FR) can be determined using a 1.2 micron filter at 15 psi at ambient temperature (e.g.,
25°C). The 1.2 micron filter can have a diameter of 47 mm or 90 mm, and the filter ratio can be calculated
as the ratio of the time for 180 to 200 ml of the inverted polymer solution to filter divided by the time for
60 to 80 ml of the inverted polymer solution to filter (see Levitt, 2009; Koh, 2015).

Long term injectivity experiments

The long term injectivity of the liquid polymers was established for both Bentheimer and Ottawa sand
packs. The cores were setup vertically with water being injected from the bottom. The initial permeability
was measured with synthetic brine, followed by tracer tests to ensure that cores were acceptably
homogeneous. On completion of the tracer tests, 2000ppm polymer solution was injected at a rate of
approximately 5 ft/day for more than 25 PV to establish plugging tendencies. Pressure drops were
measured across the whole core and for some Bentheimer coreflood experiments, pressure taps near the
inlet measured face plugging. No intermediate pressure taps were used in the Ottawa sand experiments.

Surfactant remediation experiments

Once the permeability of the cores was measurably reduced by the liquid polymers, 3-4 PV of the
surfactant-polymer formulation was injected to solubilize the carrier oil trapped due to interception and
straining. Two-component and three-component surfactant packages were developed for cleanup, and
evaluated in the corefloods. Tables 2 and 3 summarize details of various corefloods conducted for
evaluating both plugging and surfactant remediation.

Table 2—Summary of injectivity tests in Bentheimer rock

krw Approximate
EXP # Rock Injected Perm (D) PV (cc) after PF@ 25PV Q (ft/day)

#1 Bentheimer LP#1 2.1 104 0.6 6.5

#2 Bentheimer LP#2 1.3 114 0.9 10
#3 Bentheimer LP#3 2 105 0.88 6.5
#4 Bentheimer LP#4 2 105 0.2 6.5
SPE-179657-MS 5

Table 3—Summary of core floods: permeability reduction and remediation formulation

Results and Discussion

The challenges of liquid polymer application are illustrated in Figure 2, where a clear solution is observed
for 1% HPAM solutions in contrast to milky suspensions for 1% solutions prepared from liquid polymers.
The opaque milky solutions illustrate the presence of large particles that do not allow for transmission of
light. Additional discussion of particle sizes is provided later in the paper. Figure 3 shows the viscosity
of the neat liquid polymers and a comparison of the four liquid polymers with the HPAM as a 2000ppm
solution in synthetic brine. The liquid polymers show shear thinning behavior. The viscosities of the
HPAM and the different liquid polymers at 2000 ppm are very similar, essentially within experimental
error. Figure 4 shows the filtration ratios (FR’s) for four liquid polymers and one HPAM. All the polymers
show excellent FR’s through 5 sm filters. Two of the four liquid polymers did not provide a measurable
FR through the 1.2 mm filter. LP#2, LP#3 and HPAM successfully passed through the 1.2 mm filter with
the HPAM and the LP#2 meeting a FR specification of 1.2. These results confirm that particles larger than
1.2 lm are formed during liquid polymer inversion and can potentially inhibit long-term injectivity.
6 SPE-179657-MS

Figure 2—Photos of 1% polymer solution made from powder (left) and liquid polymer (right)

Figure 3—Viscosity plot of neat liquid polymer (a) and 2000 ppm polymer in synthetic brine (b)
SPE-179657-MS 7

Figure 4 —Filtration test result for 2000 ppm polymer solutions prepared from liquid polymer and powder polymer; (a) FR through 5 ␮m
filter (b) FR through 1.2 ␮m filter

The ability of the liquid polymer to mobilize oil compared to the powder HPAM is shown in Figure
5. Both the liquid polymer and HPAM successfully mobilize oil and achieve low final oil saturation of
18⫾2%. The corresponding pressure drops for the experiments are shown in Figure 6. The pressure drop
8 SPE-179657-MS

across the core increases as an oil bank forms, but then declines for the powder HPAM experiment due
to increase in relative permeability. In contrast, the pressure drop across the core continuously increases
for the liquid polymer thereby illustrating plugging.

Figure 5—Oil recovery plot in 6-Darcy unconsolidated sand using (a) liquid polymer solution (b) HPAM powder solution
SPE-179657-MS 9

Figure 6 —Pressure drop during the oil recovery core flood shown in Figure 5: (a) liquid polymer and (b) powder HPAM solution

We further evaluated the long-term injectivity of all four liquid polymers in Bentheimer sandstone. The
results are presented in Figure 7. For LP#1 and LP#4, increases in pressure drop are observed with a
decrease in relative permeability. These results illustrate that the particle sizes in LP#1 and LP#4 are large
enough to plug the Bentheimer sandstone. In order to prevent plugging due to straining the particle sizes
should be less than the pore throat diameter (See Figure 1). To prevent plugging due to straining, the
10 SPE-179657-MS

particle sizes should be ⬍ 10% of the pore throat diameter. Based upon the plugging observed for LP#1
and LP#4, we can infer that the particle sizes for these liquid polymers do not meet the requirements to
prevent plugging. Unsurprisingly LP#2 and LP#3 do not plug the Bentheimer sand as they were tailored
to have smaller particle sizes that would prevent straining and interception.

Figure 7—Pressure drop and relative permeability for injectivity test in Bentheimer sandstone cores. Some liquid polymers show the
indication of plugging such as increase of pressure drop and decrease of relative permeability while the others don’t show any
plugging at all. (a) LP#1, (b) LP#2, (c) LP#3, (d) LP#4

In order to confirm our hypothesis of plugging due to straining and interception we developed and
tested two surfactant mixtures that could successfully solubilize the oil in the liquid polymers. Adding
surfactant to the liquid polymers would reduce the number of particles in suspension as some of the oil
would be incorporated into the surfactant micelles. Secondly, the polymer-oil trapped due to straining and
interception would also be solubilized and increase relative permeability. Figure 8 shows the reduction in
relative permeability due to injection of LP#1 into Ottawa sand containing oil at residual saturation. As
observed in Figure 7, LP#1 reduces the permeability due to potential straining and interception. In order
to further gain insights into the plugging, we measured particle sizes for different solutions. The particle
densities in 2000 ppm liquid-polymer solution, 2000 ppm powder polymer solution and the two and
three-component surfactant solutions are summarized in Table 4. All particles ⬎ 1 ␮m are counted for
these measurements. The liquid polymer solution contains 6.7 million particles compared to 113,000 for
the polymer solution prepared from powder. The two and three-component surfactant formulations
containing the polymer have particle densities of 689,000 and 232,000 respectively. Based upon these
SPE-179657-MS 11

measurements it may be inferred that the addition of the surfactant would have potential to solubilize the
liquid polymer oils and mitigate the effects of straining and interception.

Figure 8 —Permeability reduction in Ottawa sand (LP#1-S1)

Table 4 —Particle size analysis in liquid polymer

Particle size analysis Particle density

(count/ml)

Liquid Polymer 6.7 million

Liquid polymer (Filtered) 11.7 million
Emulsion w/o polymer 8.9 million
Powder Polymer (Filtered) 113 thousand
Liquid Polymer ⫹ 2 component surfactant 689 thousand
Liquid Polymer ⫹ 3 component surfactant 232 thousand

Surfactant flooding of the plugged Ottawa sand column was used to validate our hypotheses. The
relative permeability to the polymer is approximately 0.2 after 20 PV of the LP#1 polymer injection. In
contrast, the relative permeability to water at residual oil saturation is 0.4 and the addition of the LP#1
solution has reduced the relative permeability by 50%, confirming plugging of the core. Based upon
particle density measurements we hypothesized that the three-component surfactant formulation should
achieve a better final relative permeability. As seen in Figure 9, the addition of the two component
surfactant formulation increases the relative permeability rapidly to 0.7 after 2 PV of surfactant injection.
A slow increase to a relative permeability of 0.78 after 6 PV of surfactant injection is then observed. At
6 PV of surfactant injection, the three-component surfactant formulation was injected, and the relative
permeability increased rapidly to 0.84. These results confirm that the surfactant formulations behaved as
expected and that the three-component formulation was superior due to lower particle densities observed
when mixed with LP#1 solution. As a side benefit the surfactant also successfully recovered the trapped
12 SPE-179657-MS

oil from the core (Figure 10). These results indicate that a liquid polymer can be successfully used with
an appropriately tailored surfactant formulation to simultaneously remediate injectivity reduction and
recover oil.

Figure 9 —Permeability enhancement due to the remediation process by injection of 2 surfactant formulation (red) followed by 3
surfactant formulation (green). Coreflood LP#1-S2

Figure 10 —Photos of cleanout process in the presence of residual oil in the core. This shows the surfactant front solubilizing the oil
in the core during the cleanout phase. Time is passing going from left to right
SPE-179657-MS 13

Interception and straining are potentially near-wellbore effects. The larger particles will tend to
aggregate near the wellbore with smaller particles propagating through the reservoir. Once critical
accumulation is reached, some of the larger particles may squeeze through the pore throats and start
damaging the subsequent portions of the reservoir. Figure 11 illustrates the behavior in coreflood results
from brine-saturated Bentheimer sandstone with pressure taps across the core. As expected, the first three
inches show maximum damage as the relative permeability is reduced to 0.2 after 25 PV of total injection
across the core. In the subsequent section of the core, the final relative permeability is approximately 0.7
after 25 PV. Figure 12 shows the relative damage when we normalize the results for each section with total
pore volumes injected. These results indicate the damage rate is faster near the injection face compared
to subsequent sections of the core as expected.

Figure 11—Permeability reduction in Bentheimer sandstone with a pressure tap showing face plugging at the inlet
14 SPE-179657-MS

Figure 12—Normailized permeability reduction in Bentheimer sandstone with a pressure tap showing face plugging at the inlet

Finally we evaluated the effect of iron on plugging tendencies of the liquid polymer. The effect of iron
on polymer is discussed by Seright and Skjevrak (2014). Figure 13 shows liquid polymers before and after
exposure to iron. The yellowish tinge observed after exposure to iron is in line with previously presented
results (Seright and Skjevrak, 2014). Figure 14a shows the enhanced plugging tendencies in the presence
of iron, where a rapid loss in relative permeability is observed. In order to evaluate the effect of iron, a
separate coreflood was conducted in which Ethylenediaminetetraacetic acid (EDTA) was used to chelate
and sequester the iron. The results in Figure 14b indicate stable pressure drops after multiple pore
volumes. From Figure 14b, it appears that the EDTA has successfully chelated the iron and the
permeability reduction is due to the liquid polymer alone.

Figure 13—Photos of liquid polymer without (left) and with (right) iron
SPE-179657-MS 15

Figure 14 —Permeability enhancement using chelant: (a) 5000 ppm liquid polymer plugged the core (b) 5000 ppm liquid polymer with
2000 ppm EDTA maintains injectivity

Conclusion
We present the applicability and limitations of liquid polymer use for EOR. The first generation liquid
polymer samples were prone to plugging porous media due to interception and straining of the carrier oils.
The use of a surfactant was shown to significantly reduce plugging by (a) solubilizing some of the liquid
polymer oil into the surfactant micelles and (b) solubilization of the oil entrapped by straining and
interception. The surfactant was also shown to mobilize trapped residual reservoir oil. An excellent
correlation between FR’s through 1.2 ␮m filters and core plugging was established. For powder HPAM
16 SPE-179657-MS

and second generation liquid polymers, excellent FR’s were observed through 1.2 ␮m filters and
consequentially minimal plugging was observed during corefloods. The plugging by the liquid polymers
did not affect oil displacement and recovery.
Data from pressure taps indicated that plugging rates were higher near the injection face compare to
subsequent portions of the core. This is arguably to most important finding of this work as uniform
plugging across the core would necessitate the continuous use of the surfactant formulation in order to
prevent this thus deeming liquid polymer prohibitively expensive. Because the damage is near-wellborm,
periodic treatments alleviate the problem and allow for liquid polymers to remain financially competitive.
Finally the presence of iron increased plugging rates and the addition of chelant successfully eliminated
the adverse effects due to iron cross-linking in the polymer. The second generation liquid polymers
successfully passed long-term injectivity tests and are attractive options for rapid polymer deployments.

Acknowledgements
The authors would like to thank Chevron Energy Technology Company for granting permission to publish
this paper. We also appreciate the vendors to provide the polymer samples. We would like to especially
thank several members of Chevron ETC, including Harry Linnemeyer, Pete Ricci, Marlon Solano and
Dinnara Dussanova (Intern) for help with experiments.

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Appendix A
Liquid polymer hydration and stock solution preparation procedure
The standard procedure is to prepare 10,000 ppm liquid polymer solutions, i.e., LP#1 at 30% active in
desired salinity brine. The brine composition used in this study is shown in Table 1. Subsequently, this
stock solution can be filtered and diluted to desired concentrations.
1. Prepare the make-up water according to the brine composition, and filter through 0.45␮m
Millipore® nitrocellulose membrane filter.
2. Weigh exactly 350.0 g of brine into 1000 mL glass jar.
3. Place the mixing jar under an overhead mixer equipped with a long multiblade paddle and create
a water vortex at 500 rpm while maintaining an Argon blanket.
4. Weigh exactly 12.18 g of liquid polymer (for a 30% active sample) into a syringe.
5. Inject the polymer emulsion uniformly just below the upper curve or shoulder of the water vortex,
ensuring that no agglomerates are formed.
6. Mix at full vortex for 120 minutes until the polymer is well-dispersed. The stirrer speed to
maintain full vortex depends on the fluid viscosity.
Diluting polymer stock solution
The polymer stock solution can be further diluted in appropriate brines to prepare polymer solutions
with target concentration and salinity. Concentrations range from 1000 ppm to 3000 ppm.
1. Weigh correct amount of above prepared stock solution into 1000 mL jar.
2. Equip with a long paddle in an overhead mixer.
3. Stir at an rpm of 500.
4. Add correct weight of the make-up brine.
5. Stir for a minimum of two hours at 500 rpm and under Argon blanket before filtration.
6. Separate 10 mL of the un-filtered polymer solution and measure the viscosity.
7. Filter the polymer solution according to the procedure given above using 1.2 ␮m filter. Discard
and repeat if the filter ratio is not between 1-1.2.
8. Take 10 mL of the filtered polymer solution and measure the viscosity; compare the value with
that of the unfiltered polymer solution to determine if there is any viscosity loss.