SPE 113845

Selection and Screening of Polymers for Enhanced-Oil Recovery

David B. Levitt, SPE, and Gary A. Pope, SPE, The University of Texas at Austin
Copyright 2008, Society of Petroleum Engineers

This paper was prepared for presentation at the 2008 SPE/DOE Improved Oil Recovery Symposium held in Tulsa, Oklahoma, U.S.A., 1923April2008.

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 of the paper have not been
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect 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 not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.


Abstract
A number of commercially available polymers have been tested for enhanced oil recovery based upon viscosity, filterability,
and surfactant compatibility, and chemical and thermal stability testing has been carried out with some of these as well.
Several high molecular weight polymers exhibited high viscosities at salinities up to 170,000 ppm NaCl and with greater than
17,000 ppm CaCl
2
present. Polyacrylamide polymers hydrolyze at high temperatures and beyond a certain point are subject to
precipitation by calcium. If calcium concentrations can be kept below about 200 ppm, the use of polyacrylamide polymers is
feasible up to reservoir temperatures of at least 100 C. For higher concentrations of calcium, copolymers including AMPS
moieties should be considered. Calcium tolerance can be improved with sodium metaborate or by using copolymers of
acrylamide and sodium 2-acrylamido-2-methylpropane sulfonate (AMPS). The stability problems at elevated temperatures
in the presence of iron can be mitigated by the use of chemicals such as sodium dithionite and sodium carbonate. The
polymers tested did not lose viscosity after 220 days of aging at 100 C with dithionite present.

Introduction
Following Mullers (1981) terminology, we will use chemical degradation when referring to the hydrolysis of polymer
functional groups and thermal degradation when describing the free radical induced breakdown of the acrylic backbone,
resulting in molecular weight reduction. Chemical degradation leads to a higher degree of hydrolysis and can only be
prevented by the inclusion of more chemically stable monomers, but does not necessarily limit application, and in fact, often
results in higher viscosity. Thermal degradation results in a reduction of molecular weight and a loss in viscosity, but this
degradation can be prevented in most situations.

Chemical Degradation; Hydrolysis and Precipitation of Polymers. Solutions of non-hydrolyzed polyacrylamide (PAM)
are nonionic, and hence the viscosity is essentially insensitive to salinity. At elevated temperature and/or pH, the amide
moiety undergoes hydrolysis, resulting in a acrylate moiety and the evolution of ammonium ion, as illustrated in Figure 1.
The anionic charges of the acrylate moieties results in intramolecular repulsions that increase the hydrodynamic radius of the
polymer molecules and hence the solution viscosity. Because of this benefit, commercial polyacrylamide for EOR is usually
either post-hydrolyzed by addition of alkali or produced as a copolymer of acrylamide (AM) and acrylic acid or its salt (AA).
In either case, the molar fraction of the acrylate moiety is referred to as the degree of hydrolysis (), and is typically between
0.15 and 0.40 for commercial hydrolyzed polyacrylamide (HPAM) polymers used for enhanced oil recovery. During its
residence in the reservoir at elevated temperature and/or pH, of polyacrylamide polymers increases.
At high salinity, the acrylate moieties on HPAM are strongly associated with cations, and the viscosity approaches that of
non-hydrolyzed polyacrylamide. Multivalent cations have a much stronger effect than monovalent cations. If exceeds
approximately 0.33 (Zatouin and Potie, 1983), then precipitation is possible if excessive amounts of multivalent cations are
present. The critical amount of calcium necessary to precipitate hydrolyzed polyacrylamide decreases with temperature, ,
and decreasing monovalent cation concentration. At a high degree of hydrolysis, this has been described as a site fixation
phenomenon, and occurs at close to the stochiometric equivalence point between acrylate moieties and cations (around 200
ppm of calcium for a 1000 ppm polymer solution). At lower , the precipitation phenomenon is due to poor solvation (theta-
type precipitation) (Ikagami, 1962).
The kinetics of hydrolysis are a strong function of pH, and can be understood as a combination of acid and basic
hydrolysis mechanisms and neighbor effects, as well as the buffering effect of evolved ammonium, as explained by
Kheradmand (1987). In small molecules, amide hydrolysis proceeds through an acid or basic mechanism. The rate is lowest
at neutral pH and increases linearly as pH rises or falls. In a macromolecule, the neighboring units can catalyze or retard
2 SPE 113845
hydrolysis. At low pH protonated neighboring acrylate moieties catalyze further hydrolysis, while at high pH ionized acrylate
moieties repel hydroxide molecules resulting in autoretard kinetics, which makes it difficult to achieve > 2/3 (Kulicke and
Horl, 1985). Due to the evolution of ammonium (pK
a
= 9.7) the pH is driven towards around 8.2 as hydrolysis proceeds,
complicating the interpretation of results in unbuffered solutions.
At near neutral pH, hydrolysis proceeds slowly but will result in complete hydrolysis of amide moieties after several
months at temperatures of 100 C and higher. At high pH, hydrolysis is more rapid and occurs within the first weeks, but may
be limited due to the autoretard kinetics mentioned above.
Several researchers (Moradi et al., 1987b; Doe et al., 1987; Taylor and El Din, 1985; Martin et al. 1983) have examined
the effects of including co-monomers to improve chemical stability or viscosity in the presence of salt. This may be achieved
either by reducing the extent of hydrolysis or by finding other ways to increase the viscosity to negate the reduction of
hydrodynamic radius due to shielding by cations. These include:
Substituting some of the acrylamide moieties within the molecule with other nonionic monomers more resistant
to chemical alteration, and whose presence may also stabilize neighboring acrylamide moieties. Examples are N-
vinyl pyrrolidone (NVP) and diacetone acrylamide (DAAM).
Substituting some of the acrylate moieties with another anionic monomer more resistant to cation shielding
and/or precipitation itself, and which may also stabilize neighboring acrylamide moieties. An example is sodium
2-acrylamid-2-methylpropane sulfonate (AMPS).
Sterically hindering the polymer chain so that the hydrodynamic radius does not fully collapse to a random coil
configuration at high salinity. These have been called "comb" polymers.
Adding a small amount of hydrophobe so that intermolecular associations increase solution viscosity, but still
allow for flow through porous media.
These mechanisms are not mutually exclusive.
The difficulty in using some of these improved polymers is that their flow properties and long term chemical stability
have not been tested to nearly the extent of HPAM. Available data on copolymers of PAM including AMPS and NVP
(Moradi et al., 1987b; Parker and Lezzi 1993) indicate that both moieties are more chemically stable than acrylamide. Also a
lower ultimate degree of hydrolysis may result after extended aging when AMPS or NVP is substituted for some of the AM
moieties in HPAM (e.g. poly(AM-co-AMPS)), indicating neighbor effects are significant (Figure 2). For the case of AMPS,
it has yet to be determined what properties the aged polymer will have, particularly in terms of calcium tolerance. As
poly(AM-co-AMPS) ages at high temperature, the some of AM moieties will hydrolyze, leaving AA. Although sulfonate
groups are typically regarded as more resistant to precipitation, it is unclear how the resulting terpolymer of AMPS, AA, and
AM will behave in the presence of divalent cations. Additionally, Parker and Lezzi (1993) report that the AMPS moiety is
susceptible to hydrolysis at temperatures above roughly 100 C. They report a sudden and rapid hydrolysis of AMPS
moieties after 50 days at 120 C and after only 4 days at 150 C. Using the rule of thumb that rate constants double every 10
C, it could be expected that at 100 C hydrolysis of AMPS moieties may occur after approximately 200 days, however this
was not reported by Moradi et al. (1987b). In this paper, we use the symbol to represent the mol fraction of AMPS moieties
on a polymer, analogous to the use of to represent mol fraction of AA moiety.

Thermal Degradation; Breakdown of the Acrylic Backbone. Viscosity loss during aging experiments is typically
attributed to a reduction of molecular weight as a result of free-radical induced scission of the acrylic backbone (Grollman,
1982; Wellington, 1983). Sorbie (1991) presents an excellent review on thermal as well as chemical degradation.
Certain radicals are capable of abstracting hydrogen from acrylic polymers, the most favorable location being from the
carbon on the acrylic backbone which attaches to the pendant group (Grollman, 1982). This results in a carbon-centered
radical on the polymer backbone and can result in the cleavage of the backbone through the steps outlined by Grollman
(1982) and others.
Previous research (Muller, 1981a and 1981b; Kheradmand, 1987; Ramsden and McKay, 1986) as well as our current
work suggests that depolymerization reactions can occur when any two of the following three are present: (1) oxygen, (2)
iron, and (3) residual initiators from polymerization. Antioxidants or easily oxidizable sacrificial species are typically added
to prevent this. Notable exceptions to these depolymerization conditions are:
When iron is not present, the degradation is only observed at elevated temperatures (Muller, 1981b).
At high pH (>pH 8) and if residual initiators are removed through purification, Ramsden and McKay (1986)
demonstrated that degradation was not observed, despite the visual evidence of rapid conversion of Fe(II) to
Fe(III).
Degradation occurs at room temperature when sulfite or dithionite is added to polymer solutions containing
oxygen. However if only the residual 8 ppm or so of oxygen in solution is allowed to react, the degradation is
limited. This assumes that no other source of oxygen (e.g., headspace) is present.
The types of radicals that may be present in dilute polymer solutions in the lab and the oil reservoir are carbon-centered
(residual initiators), sulfur-centered (sulfite, dithionite), or oxygen centered (from decomposition of peroxide initiators or
oxygen-mediated oxidation of iron (II)). While only oxygen-centered radicals are believed to be efficient hydrogen
abstractors, both carbon-centered and sulfur-centered radicals react with oxygen rapidly (near diffusion controlled limits)
SPE 113845 3
producing oxygen-centered radicals (Fossey et al., 1995). Autoxidation of polymers and/or the presence of alkyl peroxide
groups on the polymers, as theorized by some researchers (Wellington, 1983), is unlikely because of the reported stability of
purified commercial polymers with oxygen at elevated temperatures (Muller, 1981b; Kheradmand, 1987). While the iron
encountered in the region far from the wellbore is assumed to be largely in the reduced state, Kheradmand et al. (1988) have
demonstrated that degradation occurs when either ferrous or ferric iron and residual impurities are present, even in the
absence of oxygen.
Radical-induced oxidation is often attributed to oxygen-centered radicals, particularly the powerful hydroxyl radical.
Hydroxyl radicals are formed by the reduction of a peroxide by iron as first observed by Fenton (1894). Peroxides may be
present as residual initiators (Kheradmand, 1987), formed by the autoxidation of iron (Ramsden and McKay, 1986), or
formed from peroxyl radicals generated by the reaction with carbon- or sulfur-centered radicals as discussed below. Hydroxyl
radicals are the strongest known oxidants, and will abstract hydrogen almost indiscriminately from the nearest organic
molecule. As such, true antioxidants are ineffective, however easily oxidized compounds such as alcohols or glycols may be
used as sacrificial substrates (Anbar et al., 1966; Wellington, 1983; Shupe 1981). However, peroxide-decomposing
antioxidants may be effective at preventing the formation of hydroxyl radicals.
Carbon-centered radicals are formed by the thermal decomposition of residual initiators at elevated temperature, or they
may be present on a polymer backbone following the abstraction of hydrogen. These radicals are relatively weak, and are
only able to abstract allyl hydrogen, hence their efficiency for radical polymerization of vinyl-backbone polymers such as
HPAM. Though unable to abstract hydrogen from a saturated carbon backbone, these radicals will react with oxygen to form
alkyl peroxyl radicals. The resulting radicals are described by different authors as "slightly reactive"(Fossey et al., 1995) and
capable of abstracting hydrogen from a polymer backbone (Moad and Solomon, 2006), at least at high temperatures (Alfassi,
1997). In this case, the depolymerization reaction proceeds until the oxygen is consumed. Carbon-centered as well as peroxyl
radicals may be trapped by certain antioxidants, as discussed below.
The dithionite ion rapidly decomposes to bisulfate and thiosulfate. The sulfur dioxide radical is a transient reaction
product. Commercial samples of sodium dithionite frequently contain greater amounts of these radicals that decrease to an
equilibrium amount of around 0.01 mole % in aqueous solution. The sulfur dioxide radical is also a reaction intermediate in
the oxidation of sulfite to sulfate (Janzen, 1972). Sulfur dioxide radicals are strong reductants and will not abstract hydrogen
directly, however they will rapidly react with oxygen to form superoxide radicals (Alfassi, 1999). While superoxide is not
considered a strongly oxidizing radical, it is known to abstract hydrogen (Affanas'ev, 1989), and this may explain the loss of
viscosity observed when scavengers are added to solutions with dissolved oxygen or when further oxygen is allowed to enter
polymer solutions containing scavengers. In the absence of further oxygen, this depolymerization reaction will cease.

Antioxidants, Reducing Agents, and Sacrificial Substrates. Alcohols and other low molecular weight substrates with
easily abstractable hydrogen can play a sacrificial role and prevent oxidation of the polymer backbone, as previously noted by
Shupe (1981), Wellington (1983), Ryles (1983), and Yang and Treiber (1985). Primary alcohols are most easily oxidized.
Anbar (1966) showed that the apparent rate constant for oxidation of various solvents by the hydroxyl radical increases with
carbon length and decreases with additional OH groups. Shupe (1981) found better stabilization of viscosity using IBA than
with IPA, which is in agreement with the difference in rate constants found by Anbar. Glycols and surfactants, particularly
those of higher molecular weight, should also act as sacrificial agents that may be oxidized in lieu of the polymer backbone.
It should be noted that rate constants for reactions between the hydroxyl radical and most of these compounds are near
diffusion controlled limits, so the differences in rate may be less important than the ratio of substrate to polymer. Table 1
summarizes some of the factors that should be taken into account when choosing a cosolvent for use in a chemical flood.

Chloride, Bicarbonate, and Carbonate. Chloride, bicarbonate, and carbonate anions can all act as antioxidants, as
observed by Wellington (1983), Liao et al. (2000), and Rice and Wilkes (1994). Rice and Wilkes report an order of
magnitude increase in the OH radical scavenging rate of CO
3
2-
over HCO
3
-
.

Effect of pH. Transition metals such as iron play a catalytic role in many free radical reactions. Fenton (1894) first
observed that the combination of hydrogen peroxide with iron resulted in the breakdown of organic molecules, as generalized
by the following:

2 2
Fe H O Fe OH OH
++ +++
+ + +
At high pH, the oxidation of iron is extremely rapid and the solubility of iron is very low, particularly in the presence of
carbonate (Hem, 1961). Shupe (1981) reported a significant reduction in polymer degradation in the presence of iron at
pH=10. Ramsden and McKay (1986) noted that despite the rapid and visible change in oxidation state of iron, no change in
viscosity was observed at pH=8 and above with a purified polymer. Others have noted that peroxides may break down at high
pH through non-radical as well as radical pathways (Beylerian and Asaturyan, 2004). Any of these reasons or a combination
of these reasons may explain the improved stability of polymers to radical degradation observed in this work and others.
Figure 3 summarizes the importance of pH for polymer stability.

4 SPE 113845
Antioxidants. Antioxidants are capable of donating a proton or electron and trapping the radical species by forming a
stable radical. Hindered phenol compounds are common antioxidants which form resonance stabilized radicals. The five-
membered ring of NVP may trap radicals the same way. Strong radicals such as hydroxyl radicals react almost
indiscriminately, and are therefore not effectively combated by such antioxidants. Peroxide decomposing or "secondary"
antioxidants, such as phosphite and thiol compounds, prevent the formation of radical species.

Reducing Agents. Salts of dithionite, sulfite or bisulfite can be used to remove oxygen from polymer solutions.
Sodium dithionite is a powerful reducing agent and exists in equilibrium with the SO
2
radical, as mentioned above. Each
dithionite ion is capable of forming two radicals, which can each reduce Fe(III) to Fe(II). Dithionite is capable of reducing
water and is thus quite unstable in solution (Carvalho and Schwedt, 2001) particularly at high temperature (Rinker et al.,
1965), however the SO
2
radical appears to persist sufficiently to propagate low E
h
fronts in situ (Amonette et al., 1994; Istok,
1999). With transition metals such as iron kept in the reduced state, Fenton-type reactions are prevented.
Sodium sulfite is another reducing agent that can be used to scavenger oxygen, but is not powerful enough to reduce iron.
Sodium bisulfate and ammonium bisulfate are closely related compounds which are often preferred in the field due to their
higher solubility and lower molecular weight. The pK
a
of the disassociation of bisulfite to sulfite is 6.4 and it has been shown
that sulfite is the species which reacts with oxygen, hence the rate of oxygen scavenging increases with pH, at least up to pH
10 (Miron, 1981). The difficulty in using sulfite or bisulfate is that the scavenging of oxygen can be quite slow unless
catalyzed by a transition metal, which may itself cause degradation. There are reports that the use of sulfite may cause greater
degradation to polymer than dithionite (Dunlop, 1973), however this may be due to the use of transition metals as a catalyst.
If oxygen can be mostly or completely scavenged using sulfite, then dithionite could be added with minimal degradation.

Experimental Methods
Polymers. Polymer samples were provided by SNF Floerger and Hengju and used as provided except as noted. Table 2
describes the commercial polymer samples tested.

Polymer Hydration. Proper hydration of powdered polymers can repeatedly be obtained in the lab by mixing a low salinity
brine solution on a stir plate at 400-600 rpm using a cross shaped magnetic stir bar and slowly sprinkling the powder onto the
shoulder of the vortex. A solid addition burette capable of slowly adding powdered polymer was designed and has made the
process quicker and easier. As the polymer hydrates, the solution becomes more viscous and the stir bar must often be slowed
to 100-200 rpm. After 1-2 hours the solution begins to appear homogenous. The solution is allowed to stir slowly for a
minimum of 16 hours before use.
Polymer hydrated in the field was sprayed with water as it was slowly fed into a stirring tank. The tank was baffled to
ensure polymer was allowed a minimum residence time of 1-2 hours.
Polymer powders were stored in a vacuum desiccator. Moisture content was routinely measured and found to be around
10%. The test weights given in the results section do not correct for this moisture.

Filtration. Filtration tests have been used here to rapidly gauge the potential for new polymers to be propagated through
porous media in the same way that they have been used for years to ensure proper hydration of polymers. Approximately 250
mL of a 1500 ppm solution of polymer in 1000 ppm NaCl is placed in a 90 mm filter press bell with a 1.2 micron Millipore
cellulose filter (part # RAWP09025) and filtered under 15 psi Argon. The time is recorded when 60, 80, 180, and 200 mL of
cumulative fluid have been filtered. The filtration ratio is calculated as
FR = (t
200 ml
t
180 ml
)/(t
80 ml
t
60ml
)
Following the test, the filter is inspected qualitatively to see if any polymer has been filtered out due to fish eyes or other
problems.

Polymer and Surfactant Compatibility. Surfactants and polymers used for surfactant-polymer flooding or alkaline-
surfactant-polymer (ASP) flooding must be compatible in both the aqueous solution injected as a slug and in the
microemulsions that form when the slug mixes with the oil. The first requirement is simply that the aqueous solution remains
clear and stable when the polymer is added to the surfactant solution. Co-solvents are sometimes needed to meet this
requirement. Dilute surfactant typically has very little effect on the viscosity of the HPAM polymer solutions when the
mixtures are clear and stable. However, this is not true in general, so another compatibility condition is that the surfactant
does not have a large effect on the polymer solution. In some cases, a polymer will cause a three phase microemulsion to
form a separate, polymer-rich aqueous phase, so this is another type of incompatibility.

Viscosity Measurement. Viscosity is measured using a Contraves LS-30 couette viscometer. Viscosities are recorded over a
range of shear rates from 0.02 to 129 s
-1
. Shear rates of 1 to 20 s
-1
are expected in most of the reservoir except very close to
wells, so this is typically the shear rate range of focus. Viscosities reported in the results section were measured at 23 C and
correspond to a shear rate of 11 s
-1
unless otherwise stated.

SPE 113845 5
Chemical Stability and Degree of Hydrolysis. Chemical stability refers to the hydrolysis of the amine from the acrylamide
moiety and/or , dimethyl taurine (Audibert and Argillier, 1995) from the AMPS moiety. In either case this results in the
formation of an additional acrylate (AA) moiety in the hydrolyzed polymer molecule. This was observed qualitatively by the
increase in viscosity observed at most salinities as well as measured quantitatively by peak integration of
13
C NMR spectra.
Initial degree of hydrolysis was determined by dissolving 4 wt% polymer in 10 wt% D2O with 3% NaCl.
Dilute polymer samples were heated in 15 mL glass ampules that were flame sealed. Early experiments with off-the-shelf
ampules resulted in thermal fractures when ampules were sealed under vacuum. These fractured samples then were potted in
epoxy to prevent air leakage of oxygen. Additional samples were blanketed with argon and then quickly sealed while open to
atmosphere. In all of these initial samples, 1 ppm of resazurin was included in order to visually detect leaks. Resazurin is
initially blue in solution. It is reduced irreversibly to a pink color and then reversibly to clear, after which it serves as a redox
indicator, changing from clear to pink as the redox potential increases from about -100 mV to 0 mV using a Ag/AgCl
combination electrode (E
h
= -300 mV to -100 mV). Some samples turned pink when left overnight before heating or when
placed in the oven, indicating a leak, and these samples were discarded. After heating, some samples did not turn pink when
opened for measurement. This corresponded with low viscosity, indicating that extensive degradation occurred to the
polymer as well as the resazurin. These samples were discarded.
Thicker, custom ampules and a manifold where then fabricated by the glass shop in the UT Department of Chemistry and
Biochemistry so that the headspace of the ampules could be reliably cycled with purified argon and vacuum and sealed under
vacuum. Experiments showed that cycling three times with argon and vacuum does not change the amount of dissolved
oxygen in solution.
Samples of polymer heated as described above were analyzed viscometrically and 10% D
2
O was added to the samples
prior to concentration to around 4 wt% using an ultrafiltration cell with a 100,000 MW filter.
NMR work was performed by UT Analytical Services Laboratory in the Department of Chemistry and Biochemistry
using a Varion Inova 500. A delay time of 2 s was determined to be necessary from preliminary experiments, and
approximately 1800 cycles were acquired (1 hour acquisition time). In some cases where insufficient amounts of polymer
were recovered, acquisition time was increased to 16 or 64 hours. Peaks were assigned to the carbonyl carbon of acrylamide
(180 ppm), acrylate (183 ppm), and AMPS (176 ppm) moieties (Lezzi and Parker, 1993). The mol % of each moiety was
calculated as the fraction of the integration of the peak corresponding to the carbonyl carbon of that moiety divided by the
sum of the integration of all carbonyl peaks.

Calcium Tolerance. Calcium tolerance of 8 million Dalton HPAM with degrees of hydrolysis varying from 0 to 100 were
measured by preparing samples of 1500 ppm polymer and various amounts of sodium with incrementally more CaCl
2
until
cloudiness was observed. This was reported as a function of Na
+
concentration with Na
+
added as either NaCl or sodium
metaborate (Na
2
B
2
O
4
8H
2
O). Sodium metaborate supplies Na
+
and also can sequester calcium. In some cases samples were
placed in a 55 C or 85 C oven and observed quickly to determine the change in calcium tolerance with temperature. A
sample of poly(AM-co-AMPS) copolymer (AN-125) was hydrolyzed at room temperature by the addition of NaOH and then
neutralized with HCl. The sample was concentrated in an ultrafiltration cell and analyzed by NMR as described above. The
salt was then removed by repeated dilution and concentration in the ultrafiltration cell, after which calcium tolerance was
measured as above.

Thermal Stability. Stability of the acrylic backbone to radical degradation, as discussed above, can be observed
viscometrically. At room temperature, any change in viscosity can be attributed to change in molecular weight distribution of
the polymer. At elevated temperature, hydrolysis may also cause a change in solution viscosity and so observation of
degradation is more complicated. Performing experiments in 3% NaCl or above will limit the change in viscosity due to
hydrolysis. Some experiments were also performed using poly(ammonium acrylate) (PAA), a salt of poly(acrylic acid) which
is similar to what is obtained if polyacrylamide is totally hydrolyzed. Because no further hydrolysis can occur viscometric
interpretations are more readily made. In some cases iron was added as FeCl
2
, or FeCl
3
. When FeCl
2
was used the solution
was first bubbled with hydrogen gas to ensure iron was in the reduced state. Sodium dithionite and sodium sulfite were also
added to some experiments. When either of these scavengers was used, care was taken to maintain an argon blanket over the
polymer solution to ensure further oxygen did not enter the solution after the chemicals were added. All of these chemicals
were obtained from Fisher Scientific.

Core Flooding. Core flooding was performed with some polymers, using methods described by Levitt (2006).

Results
Preliminary Screening of Polymers. Filtration and surfactant compatibility data obtained with polymers are summarized in
Table 3. Aside from hydrophobically modified associative polymers, all polymers were filtered through 1.2 micron filters
with filtration ratios below 1.5. Higher MW polymers and poly(AM-co-AMPS) (AN-125) required longer hydration times
before a low filtration ratio was obtained. It is unknown how the time required for proper hydration will scale up when field
hydration equipment is used, or for what permeability range this filter test is appropriate. In the case of Flopaam 3330S good
hydration, obtained after 1-2 days in lab conditions, was achieved after only 90 minutes using field hydration equipment.
6 SPE 113845
Associative polymers present filtration and surfactant compatibility issues and therefore require additional work before ready
for application as mobility control agents. Levitt (2006), Jackson (2006) and Flaaten (2007) performed core floods in both
outcrop and reservoir cores using Flopaam 3330S, 3630S and AN-125 with excellent transport (no plugging problems). We
have observed excellent polymer behavior in core floods when the filtration ratio is less than 1.2. However, this may stricter
than necessary in some cases and will certainly depend on the pore size and structure of the rock.
Viscosity of 1500 ppm solutions of several polymers as a function of NaCl concentration is summarized in Figure 4. For
all except for Kypaam 5, the viscosity is nearly constant for salinities above 3% NaCl. This data is not presented for the
purposes of comparing these products, as the viscosity is merely a reflection of the molecular weight, but to illustrate that
high molecular weight HPAM polymers have sufficient viscosity for use in enhanced oil recovery even if the brine has a very
high salinity. The same is true in the presence of calcium containing brines; Figure 5 presents data comparing viscosity of a
HPAM in hard and soft brine. Even in the presence of 17,000 ppm CaCl
2
viscosity is high.
Surfactant compatibility was also an issue for hydrophobically modified associative polymers. A large drop in viscosity
was observed when surfactant was added to these polymer solutions. This is likely due to shielding of intermolecular
associations of the polymer hydrophobes by the surfactant hydrophobe.
Flopaam 3330S, Flopaam 3630S, and AN-125 were compatible with the particular surfactants tested by Levitt (2006),
Jackson (2006) and Flaaten (2007). Hengfloc 63020, Hengfloc 63026, and Kypaam 5 were not tested for surfactant
compatibility.
The viscosities of samples of 8 million molecular weight HPAM with different degrees of hydrolysis are presented in
Figure 6. These data show that the viscosity is nearly independent of the degree of hydrolysis at high salinities. However, as
discussed elsewhere in this paper, the calcium tolerance is a strong function of the degree of hydrolysis.

Calcium Tolerance of Partially Hydrolyzed Polyacrylamides. Calcium tolerance of various acrylamide-co-sodium
acrylate copolymers as a function of sodium concentration at room temperature is presented in Figure 7. At low salinity PAA,
which is comparable to fully hydrolyzed polyacrylamide, is capable of tolerating about 200 ppm of Ca
++
before precipitation
is observed at 23 C. Although precipitation of PAA with Ca++ occurred at close to stochiometric equivalence point with
around 1500 ppm polymer, the precise proportionality to polymer concentration expected if this is purely a site fixation
phenomenon was not observed. As Na
++
concentration increases or decreases, calcium tolerance is quickly increased to at
least 400 ppm. At 85 C, the calcium tolerance is lowered by about 50 %. The addition of 1wt% IBA does not increase
calcium tolerance of PAA.
In some cases, calcium tolerance is higher when sodium metaborate is used rather than sodium chloride, indicating
sequestration of Ca
++
. However, when greater than about 1000 ppm Na
+
(about 0.6 wt % sodium metaborate) was added, no
improvement was noted. This amount corresponds closely to the apparent solubility of calcium metaborate (Nikolaev and
Chelischeva, 1940). This is illustrated in Figure 8 for a copolymer of = 0.7.

Chemical Stability of HPAM and Poly(AM-co-AMPS). Samples of HPAM and poly(AM-co-AMPS) (AN-125)heated for
220 days at 85 C were determined to be composed of approximately 68 mol% and 63 mol% anionic groups ( and + ,
respectively). The amount of AMPS present remained unchanged in the aged poly(AM-co-AMPS). The viscosity data for
these experiments are presented in Figure 9. Because the initial pH was set to about 8.5 by the addition of 1000 ppm
NaHCO
3
, the hydrolysis occurs very rapidly and then stops within about 2 weeks. By comparison, data presented by Moradi
(1987a) exhibit much slower hydrolysis kinetics, consistent with the fact that the solutions were unbuffered and hence
probably between pH 6 and 7. The ultimate degree of hydrolysis obtained agrees very well with that obtained by Moradi for
PAM, as illustrated in Figure 2. It is interesting to note that, although the a lower proportion of the amide groups were
hydrolyzed on the poly(AM-co-AMPS) sample, the total anionicity resulting was the same. Figure 10 compares the results of
this paper and Moradi (1987a, 1987b) presented as total anionicity (+ ).
In order to determine if the presence of some AMPS moieties instead of only AA moieties yields improved tolerance to
divalent cations, a sample of poly(AM-co-AMPS) (AN-125) was hydrolyzed under basic conditions as described above.
Total anionicity (+ ) of the post hydrolyzed poly(AM-co-AMPS) sample was determined to be 67% by NMR. Calcium
tolerance of this terpolymer is presented in Figure 11 along with a HPAM of similar total anionicity. Although precipitation
can still occur, calcium tolerance is greatly increased by the presence of AMPS moieties. The transition to cloudiness as
calcium is added is more gradual and thus slightly difficult to determine with these polymers. In order to more quantitatively
observe the precipitation phenomena, the viscosity of both clear and cloudy solutions were measured before and after the
point at which precipitation was observed. As illustrated in Figure 12, the viscosity decline experienced at the point where
cloudiness is observed is similar with HPAM and hydrolyzed poly(AM-co-AMPS) polymer. It has been reported (Zaitoun
and Potie, 1983) that observed turbidity is closely related to plugging behavior. Transport studies are necessary to determine
if the same holds true for hydrolyzed poly(AM-co-AMPS), but based upon the above results it is the belief of the authors that
the findings of Zaitoun and Potie (1983) would be true for these polymers as well.
As discussed above, calcium tolerance of HPAM polymers decreases with increasing temperature. Upon heating from 23
C to 55 C, calcium tolerance of hydrolyzed poly(AM-co-AMPS) samples decreased approximately 25%. Upon heating to
85 C, calcium tolerance is reduced to approximately 50% of the amount observed at 23 C. At 85 C and with 20,000 ppm
SPE 113845 7
NaCl present, the calcium tolerance of extensively hydrolyzed poly(AM-co-AMPS) (hydrolyzed AN-125) is around 800
ppm. This is about a four fold increase in the calcium tolerance of HPAM after aging at the same temperature.

Thermal Stability of HPAM and Poly(AM-co-AMPS). Figure 13 presents viscosity data collected with the same polymers
at 100 C, as well as a with SAV301, a terpolymer including thermally stable moieties such as those discussed above. As
indicated by viscosity data in Figures 9 and 13, no further degradation was observed after a small initial drop in viscosity
when sodium dithionite was added to polymer solutions containing dissolved oxygen. An initial increase in viscosity due to
amide hydrolysis is followed by no further change in viscosity. For Flopaam 3630S at 100 C, the viscosity first increased
due to hydrolysis and then decreased, but is still at its original viscosity after 200 days. This may be due to the complete
hydrolysis of this sample. As indicated in Figure 6, complete hydrolysis results in a quicker decline to the viscosity of the
unexpanded coil for a given molecular weight, and this is consistent with the return to the original viscosity. These data
indicate that in the presence of sodium dithionite these polymer solutions maintain their original viscosity for long periods of
time up to at least 100 C.

Stability of Acrylic Backbone. Adding either ferrous or ferric iron as iron chloride to polymer solutions had markedly
different effects depending on the presence of Na
2
CO
3
. Viscosity of PAA in NaCl or Na
2
CO
3
solutions after either oxidized
or reduced iron is added is presented in Figure 14.
Viscosity reduction at high temperature due to the presence of residual impurities and oxygen was also strongly effected
by the presence of Na
2
CO
3
. In the presence of residual impurities and with 8 ppm of oxygen originally in solution, polymer
solutions aged at 100 C containing sodium carbonate experienced much less degradation than similar solutions containing
sodium metaborate or sodium chloride, even when the sodium chloride solution was adjusted to above pH 9 using NaOH, as
illustrated in Figure 15.
The addition of sodium sulfite or sodium dithionite to polymer solutions containing dissolved oxygen results in a decrease
in viscosity, as discussed above. Figure 16 compares the viscosity loss caused by each chemical as a function of initial
dissolved oxygen present. Because viscosity is a complex function of salinity, pH, polymer molecular weight and
concentration, these data are intended to provide an indication of the relative amounts and overall severity of degradation,
and will not apply quantitatively if conditions are substantially changed. Degradation experienced when 400ppm sodium
dithionite was added to polymer solutions from a 80,000 ppm stock solution containing 6-8 ppm oxygen ranged from 10% to
25%
An attempt was made to determine the optimal strategy for formulating polymer solutions with sodium dithionite. Less
than 2% viscosity loss was experienced when uncatalyzed sodium sulfite was added to a brine solution prior to polymer
hydration. After 20 hours of hydration under an argon atmosphere, sodium dithionite was added to the solution. The
scavenging of oxygen when sodium sulfite was added prior to polymer was quicker and more extensive and resulted in
higher viscosity than that observed when it was added after the polymer.
Additional experiments in Na
2
CO
3
revealed that the viscosity loss encountered when dithionite is added to polymer
solutions is also lower in the presence of Na
2
CO
3
(8.5%) than in the presence of NaCl alone (14.7%).
Solutions of polymer to which only sodium sulfite was added experienced significant degradation upon the addition of
iron(III) chloride.

Conclusions
We have tested a number of commercially available polymers using filtration and viscosity testing as a preliminary screening
step for enhanced oil recovery applications, followed by surfactant compatibility, and chemical and thermal stability testing.
All of the commercially available polymers tested aside from a hydrophobically modified HPAM passed filtration testing
through a 1.2 micron filter. Several high molecular weight polymers exhibited high viscosities at salinities up to 170,000 ppm
NaCl and with greater than 17,000 ppm CaCl
2
present.
Polyacrylamide polymers hydrolyze at high temperatures and beyond a certain point are subject to precipitation by
calcium. If calcium concentrations can be kept below about 200 ppm, the use of polyacrylamide polymers is feasible up to
reservoir temperatures of at least 100 C. For higher concentrations of calcium, copolymers including AMPS moieties
should be considered.
After extended aging at 85 C, the calcium tolerance of poly(AM-co-AMPS) (AN-125) is about four times as high as a
comparable HPAM polymer. Although amide hydrolysis is limited by inclusion of AMPS moieties, total anionicity (AMPS
plus AA) resulting from aging at 85 C for 200 days was approximately the same. Precipitation of hydrolyzed poly(AM-co-
AMPS) with divalent cations is still possible, although the amount of calcium tolerated is much greater for a 20-30% AMPS
copolymer. Thus poly(AM-co-AMPS) may be desirable in situations where 200 ppm or more of divalent ions will be present
and moderate or extensive hydrolysis is expected. However, screening studies should first be performed to determine the
amount of AM and AMPS moieties that will be hydrolyzed during aging for a given temperature, pH and initial composition,
and tolerance to divalent cations should be determined for this resulting copolymer.
Calcium tolerance of hydrolyzed polyacrylamide polymers can be increased by adding sodium metaborate
(Na
2
B
2
O
4
8H
2
O), but if more than about 0.6 wt% is included the benefit becomes negligible.
8 SPE 113845
Sodium carbonate improves the thermal stability of polymer solutions, resulting in less viscosity loss from radical attacks.
The mechanism of this improved stability has not yet been fully elucidated. Polymer solutions with sodium dithionite added
are thermally stable at temperatures up to at least 100 C over long periods of time provided no further oxygen is added to the
solution. An initial viscosity loss of 10-25% is observed and this is proportional to the amount of dissolved oxygen in
solution. This can be minimized by adding sodium carbonate or by using uncatalyzed sodium sulfite to scavenge some of the
oxygen prior to polymer addition.

Acknowledgements
The authors wish to thank the industrial affiliates of the chemical enhanced oil recovery project at the University of Texas for
funding of this research. We would also like to thank Larry Britton, Stephane Jouenne, Michel Duc, Jacques Kieffer, Nicolas
Gaillard, Ludwig Gil, and R. Ravikiran for very helpful dialog. We are grateful for samples provided by Hengju, SNF
Floerger, and Stepan Chemical Co. We are equally thankful for NMR services provided by Dr. Ben Shoulders and Steve
Sorey in the UT Chemistry and Biology Analytical Service Laboratory as well as Mike Ronalter in the glass shop of the same
department. We would like to thank the support staff of the Center for Petroleum and Geosystems Engineering and in
particular Joanna Castillo. Finally, we thank Adam Jackson, Seun Magbagbeola, Mike Weatherl, Ryan Taylor, Josh Whitney,
Ghazal Dashti, and Will Slaughter for work performed in the laboratory in conjunction with these experiments.

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10 SPE 113845

Table 1Suitability of Different Solvents for EOR
Solvent Flash point
(C)
K
OH

(X 10
-8
LM
-1
s
-1
(Anbar 1966))
Cost
($/lb)
IPA 12 12.5 0.50
IBA 28 21 0.65
EGBE 65 - 0.65
DGBE 110 - 0.90


Table 2Commercial Polymers Tested
Polymer Vendor MW X 10
-6
Description
Flopaam 3630S SNF Floerger 20 HPAM
Flopaam 3330S SNF Floerger 8 HPAM
AN-125 SNF Floerger 8 Poly(AM-co-AMPS), 20-30% AMPS
SuperPusher SAV301 SNF Floerger 5 Confidential; PAM modified for enhanced thermal stability
SuperPusher B192 SNF Floerger Unknown Hydrophobically modified PAM
Hengfloc 63020 Hengju 20 Post hydrolyzed PAM
Hengfloc 63026 Hengju 26 Post hydrolyzed PAM
Kypam 5 Hengju Unknown Confidential; "comb" polymer
Note: Molecular weights are approximate, as stated by suppliers, and have not been verified.
Flopaam 3330S and 3630S contain a confidential low-molecular weight antioxidant.
An additional series of copolymers were supplied by SNF Floerger with degrees of hydrolysis ranging from 0 to
100 for testing their calcium and salinity tolerance.


Table 3Preliminary Screening Results of Commercial Polymers
Polymer Mixing Time Filter Ratio Surfactant Compatibility
2 days (Lab) <1.2 Flopaam 3330S
90 min (Field) <1.1
Pass
Flopaam 3630S 4-5 days 1.2-1.4 Pass
AN-125 4-5 days 1.2-1.4 Pass
SuperPusher B192 N.A. Plugs Filter Causes viscosity loss
SuperPusher SAV301 2 days <1.2 Untested
KKYPAM 5 4-5 days 1.49 Untested
Hengfloc 63026 11 days 1.31 Untested
Hengfloc 63020 5 days 1.26 Untested



SPE 113845 11
At elevated
temperatures and/or
high pH...
Hydrolysis of amide
proceeds;
HPAM-> PAA
Creating less calcium
tolerant polymers
+ Ca
++
1
H
2
C CH
C
NH
2
O
H
2
C CH
C
O

O
x y
H
2
O
NH
3
H
+
H
2
C CH
C
O

O
y
H
+
H
2
C CH
C
O

O
x
H
+

Fig. 1Hydrolysis of HPAM lowers calcium tolerance.
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
0 20 40 60 80 100 120 140 160
Temperature, C
D
e
g
r
e
e

o
f

H
y
d
r
o
l
y
s
i
s
PAM (Moradi 1987a, 100
Days)
PAM-co-AMPS; 65/35 mol%
(Moradi 1987b, 100 Days)
HPAM (Authors, 220 Days)
PAM-co-AMPS (Authors,
220 Days)

Fig. 2Degree of hydrolysis after extended aging.
12 SPE 113845
Reservoir
Improved stability with iron
Protonation of
carboxylate
Na
2
CO
3
NaOH
NaBO
2
7 8 9 10 11 6 5 12 7 8 9 10 11 6 5 12
Increasing rate, extent of hydrolysis
Basic hydrolysis
M
++
(OH)
2
precipitation
pH
Relevant
pK
a
s:
RCOOH/RCOO
- HCO
3
-
/CO
3
2-
NH
4
+
/NH
3

Fig. 3pH is a critical factor affecting polymer stability.
0
10
20
30
40
50
60
70
80
0 60,000 120,000 180,000
NaCl Concentration, ppm
V
i
s
c
o
s
i
t
y
,

c
P
20M Dalton HPAM (Flopaam 3630S)
8M Dalton HPAM (Flopaam 3330S)
20M Dalton HPAM (Hengfloc 63020)
26M Dalton HPAM (Hengfloc 63026)
'Comb' Polymer (Kypaam 5)

Fig. 4Salinity tolerance of some commercially available polymers.
SPE 113845 13
0
5
10
15
20
25
30
35
40
45
50
0 60,000 120,000 180,000
Total Dissolved Solids, ppm
V
i
s
c
o
s
i
t
y
,

c
P
NaCl only
9:1 NaCl/CaCl2

Fig. 5Effect of brine hardness on salinity tolerance of 20M Dalton HPAM (Flopaam 3630S).
1
10
100
0 60,000 120,000 180,000
NaCl Concentration
V
i
s
c
o
s
i
t
y
,

c
P
30% hydrolyzed HPAM (Flopaam 3330S)
0% Hydrolyzed (PAM; FA920SH)
70% hydrolyzed HPAM
100% hydrolyzed (PAA)

Fig. 6Relationship between degree of hydrolysis and salinity tolerance for 8M Dalton HPAM.
14 SPE 113845
0
200
400
600
800
0 1,000 2,000 3,000 4,000 5,000 6,000 7,000 8,000 9,000
Na+ Concentration, ppm
C
a
+
+

C
o
n
c
e
n
t
r
a
t
i
o
n
,

p
p
m
= 0.66
= 1
= 0.45

Fig. 7Effect of degree of hydrolysis on calcium tolerance.
0
200
400
600
800
1000
1200
0 1,000 2,000 3,000 4,000 5,000 6,000 7,000 8,000 9,000
Na+ Concentration, ppm
C
a
+
+

C
o
n
c
e
n
t
r
a
t
i
o
n
,

p
p
m
NaCl
Na2B2O4

Fig. 8Effect of sodium metaborate on calcium tolerance of hydrolyzed PAM.
SPE 113845 15
0
5
10
15
20
25
30
0 50 100 150 200 250
Time, days
V
i
s
c
o
s
i
t
y
,

c
P
20M Dalton HPAM (Flopaam 3630S)
8M Dalton PAM-co-AMPS (AN-125)
+ = 0.63
= 0.68
1500 ppm polymer, 30,000 ppm NaCl

Fig. 9Stability of commerical polymers at 85 C with sodium dithionite.
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
0 20 40 60 80 100 120 140 160
Temperature, C
D
e
g
r
e
e

o
f

A
n
i
o
n
i
c
i
t
y

(

)
PAM (Moradi '87(a))
PAM-co-AMPS, 65/35 mol%
(Moradi 1987b, 100 Days)
HPAM (Authors, 220 Days)
PAM-co-AMPS (Authors, 220
Days)

Fig. 10Total anionicity after extended aging.
16 SPE 113845
0
500
1000
1500
2000
2500
0 1,000 2,000 3,000 4,000 5,000 6,000 7,000 8,000 9,000
Na+ Concentration, ppm
C
a
+
+

C
o
n
c
e
n
t
r
a
t
i
o
n
,

p
p
m
HPAM
Hydrolyzed PAM-co-AMPS
+ = 0.67
= 0.66

Fig. 11Effect of the presence of 20-30% AMPS moieties on the calcium tolerance of extensively hydrolyzed polymers, 23 C.
0
2
4
6
8
10
12
0 1,000 2,000 3,000 4,000 5,000 6,000
Calcium Concentration, ppm
V
i
s
c
o
s
i
t
y
,

c
P
Extensively Hydrolyzed PAM-co-AMPS
(Hydrolyzed AN-125, )
Extensively Hydrolyzed HPAM
1500 ppm polymer, 20,000 ppm NaCl, 23 C
Cloudy
+ = 0.67
( = 0.66)

Fig. 12Viscometric comparison of precipitation phenomena of extensively hydrolyzed PAM-co-AMPS and HPAM.
SPE 113845 17
0
5
10
15
20
25
0 50 100 150 200 250
Time, days
V
i
s
c
o
s
i
t
y
,

c
P
20M Dalton HPAM (Flopaam 3630S)
8M Dalton PAM-co-AMPS(AN-125)
5M Dalton Modified PAM* (SAV 301)
= 1
1500 ppm polymer, 30,000 ppm NaCl
1500 ppm polymer, 30,000 ppm NaCl
2000 ppm polymer, 30,000 ppm NaCl
*Composition Confidential

Fig. 13Stability of polymers at 100 C with dithionite.
0
5
10
15
20
25
30
35
0 10 20 30 40 50
Time, days
V
i
s
c
o
s
i
t
y
,

c
P
NaCl Fe++
Na2CO3 Fe++
NaCl Fe+++
Na2CO3 Fe+++
1500 ppm PAA, 23 C

Fig. 14Thermal stability acrylic backbone to radical attack in the presence of 8ppm O
2
, 20 ppm Fe(II) or Fe(III) and 1% NaCl or
Na
2
CO
3
.
18 SPE 113845
0
5
10
15
20
25
30
35
40
45
0 5 10 15 20 25 30
Time, days
V
i
s
c
o
s
i
t
y
,

c
P
0.1M Na2CO3, pH-10
0.1M Na2B2O4, pH-9.9
0.1M NaCl, pH-6.5
0.1M NaOH/0.1M NaCl, pH-9.1
1500 ppm PAA

Fig. 15Thermal stability acrylic backbone to radical attack in the presence of various salts at 100 C with 8ppm O
2
present.
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
0 1 2 3 4 5 6 7
Original Dissolved Oxygen, ppm
%

V
i
s
c
o
s
i
t
y

R
e
t
a
i
n
e
d
1500 ppm PAM (FA920SH), 23 C

Fig 16Effect of original amount of dissolved oxygen on PAM degradation upon addition of 400 ppm sodium dithionite.