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(2008) Selection and Screening of Polymers For Enhanced-Oil Recovery
(2008) Selection and Screening of Polymers For Enhanced-Oil Recovery
(2008) Selection and Screening of Polymers For Enhanced-Oil Recovery
This paper was prepared for presentation at the 2008 SPE/DOE Improved Oil Recovery Symposium held in Tulsa, Oklahoma, U.S.A., 19–23 April 2008.
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 CaCl2 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 Muller’s (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 (τ), 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, τ 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 τ 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, τ,
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 τ, 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 τ > 2/3 (Kulicke and
Horl, 1985). Due to the evolution of ammonium (pKa= 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
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
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 CO32- over HCO3-.
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:
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 SO2 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
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 = (t200 ml – t180 ml)/(t80 ml – t60ml)
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 β,β 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 13C 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
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 CaCl2 until
cloudiness was observed. This was reported as a function of Na+ concentration with Na+ added as either NaCl or sodium
metaborate (Na2B2O4·8H2O). 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 FeCl2, or FeCl3. When FeCl2 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
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 (τ and τ+ σ,
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
NaHCO3, 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 (τ+ σ).
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 (τ+ σ) 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
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 Na2CO3. Viscosity of PAA in NaCl or Na2CO3 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 Na2CO3. 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 Na2CO3 revealed that the viscosity loss encountered when dithionite is added to polymer
solutions is also lower in the presence of Na2CO3 (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 CaCl2 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
(Na2B2O4·8H2O), 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
References
Afanas'ev, I.B. 1989. Superoxide Ion: Chemistry and Biological Implications Volume I Boca Raton: CRC Press, Inc.
Alfassi, Z. ed. 1997. Peroxyl Radicals West Sussex, England: John Wiley & Sons Ltd.
Alfassi, Z. ed. 1999. S-centered Radicals West Sussex, England: John Wiley & Sons Ltd.
Amonette, J.E., Szecsody, J.E., Schaef, H.T., Templeton, J.C., Gorby, Y.A., and Fruchter, J.S. 1994. Abiotic Reduction of Aquifer
Materials by Dithionite: A Promising In-situ Remediation Technology. Presented at the Thirty-Third Symposium on Health & the
Environmental In Situ Remediation: Scientific Base for Current & Future Technologies, Richland, WA 7-11 November, Contract No.
DE-AC06-76RLO 1830, US DOE.
Anbar, M., Meyerstein, D., and Neta, P. 1966. Reactivity of Aliphatic Compounds towards Hydroxyl Radicals. J. Chemical Society B:
Physical Organic 742-747.
Audibert, A. and Lecourtier, J. 1992. Compatibility of Hydrosoluble Polymers With Corrodible Materials. SPEPE 7 (2): 193-198. SPE
21026.
Beylerian, N.M. and Asaturyan, M.Z. 2004. On the Mechanism of Hydrogen Peroxide Decomposition in Alkaline Medium. Oxidation
Communications 27 (2): 263-273.
Carvalho, L.M. and Schwedt, G. 2001. Polarographic determination of dithionite and its decomposition products: kinetic aspects,
stabilizers, and analytical application. Analytica Chimica Acta 436: 293-300.
Doe, P.H, Moradi-Araghi, A., Shaw, J.E., and Stahl, G.A. 1987. Development and Evaluation of EOR Polymers Suitable for Hostile
Environments-Part 1: Copolymers of Vinylpyrrolidone and Acrylamide. SPERE 461-467.
Dunlop, A.K. 1973. Corrosion Inhibition in Secondary Recovery. In Corrosion Inhibitors, ed. C.C. Nathan, 76-88. Houston: NACE.
Fenton, H.J.H. 1894. Oxidation of tartaric acid in presence of iron. J. Chem. Soc. 65: 899-910.
Flataan, A. 2007. Experimental Study of Microemulsion Characterization and Optimization in Enhanced Oil Recovery: A Design
Approach for Reservoirs with High Salinity and Hardness. Master’s Thesis, University of Texas, Austin, Texas.
Fossey, J., Lefort, D. and Sorba J. 1995. Free Radicals in Organic Chemistry Paris: Masson.
Grollmann, U. and Schnabel, W. 1982. Free Radical-Induced Oxidative Degradation of Polyacrylamide in Aqueous Solution. Polymer
Degradation and Stability 4: 203-212.
Hem, J.D. 1961. Stability Field Diagrams as Aids in Iron Chemistry Studies. J. AWWA 53 (2): 211-232.
Ikegami, A. and Imai, N. 1962. Precipitation of Polyelectrolytes by Salts. J. Polymer Science 56: 133-152.
Istok, J.D., Amonette, J.E., Cole, C.R., et. al. 1999. In Situ Manipulation by Dithionite Injection: Intermediate-Scale Laboratory
Experiments. Ground Water 37 (6): 884-889.
Jackson, A. 2006. Experimental Study of the Benefits of Sodium Carbonate on Surfactants for Enhanced Oil Recovery. Master’s Thesis,
University of Texas, Austin, Texas.
Janzen, E.G. 1972. Electron Spin Resonance Study of the SO2.- Formation in the Thermal Decomposition of Sodium Dithionite, Sodium
and Potassium Metabisulfite, and Sodium Hydrogen Sulfite. J. Physical Chemistry 76 (2): 157-162.
Kheradmand, H. 1987. Contribution A L'Etude De La Degradation Et La Stabilisation De Polyacrylamides En Solution Aqueuse. These
Pour Obtenir Le Grade De Docteur D'Etat Es Sciences Physiques, Universite Louis Pasteur De Strasbourg, Strasbourg, France.
Kheradmand, H., Francois, J., and Plazanet, V. 1988. Degradation of Acrylamide-Sodium Acrylate Copolymer in Aqueous Solution. J.
Applied Polymer Science 36: 1583-1600.
Kulicke, W.M. and Horl, H.H. 1985. Preparation and characterization of a series of poly(acrylamide-co-acrylates), with a copolymer
composition between 0-96.3 mol-% acrylate units with the same degree and distribution of polymerization. Colloid & Polymer
Science 263: 530-540.
Levitt, D. B. 2006. Experimental Evaluation of High Performance EOR Surfactantsfor a Dolomite Oil Reservoir. Master’s Thesis,
University of Texas, Austin, Texas.
Liao, C.H., Kang, S.F., and Wu, F.A. 2001. Hydroxyl radical scavenging role of chloride and bicarbonate ions in the H2O2/UV process.
Chemosphere 44: 1193-1200.
Martin, F.D., Hatch, M.J., Shepitka, J.S., and Ward, J.S. 1983. Improved Water-Soluble Polymers for Enhanced Recovery of Oil. Paper
SPE 11786 presented at the International Symposium on Oilfield and Geothermal Chemistry, Denver, CO 1-3 June.
Miron, R.L. 1981. Removal of Aqueous Oxygen by Chemical Means in Oil Production Operations. Materials Performance 45-50.
SPE 113845 9
Moad, G. and Solomon D.H. 2006. The Chemistry of Radical Polymerization second fully revised edition Oxford, England: Elsevier.
Moradi-Araghi, A. and Doe, P.H. 1987. Hydrolysis and Precipitation of Polyacrylamides in Hard Brines at Elevated Temperatures. SPERE
189-198.
Moradi-Araghi, A., Cleveland, D.H., Jones, W.W., and Westerman, I.J. 1987. Development and Evaluation of EOR Polymers Suitable for
Hostile Environments: II-Copolymers of Acrylamide and Sodium AMPS. Paper SPE 16273 presented at the International Symposium
on Oilfield Chemistry, San Antonio, TX 4-6 February.
Muller, G. 1981a. Thermal Stability of High-molecular-weight Polyacrylamide Aqueous Solutions. Polymer Bulletin 5: 31-37.
Muller, G. 1981b. Thermal Stability of Polyacrylamide Solutions: Effect of Residual Impurities in the Molecular-weight-degradation
Process upon Heating. Polymer Bulletin 5: 39-45.
Nikolaev, A.V. and Chelischeva, A.G. 1940. The 25° isotherm of the systems: CaO-B2O3-H2O and MgO-B2O3-H2O. Doklady Akademii
H2C CH H2C CH
C O C O At elevated
temperatures and/or
NH2 O– high pH...
x H+ y
H2C CH H2C CH
Hydrolysis of amide
C O C O proceeds;
O– O– HPAM-> PAA
H+ x H+ y
70%
60% PAM -co-AM PS (Authors,
220 Days)
50%
40%
30%
20%
10%
0%
0 20 40 60 80 100 120 140 160
Temperature, °C
Fig. 2—Degree of hydrolysis after extended aging.
12 SPE 113845
M++(OH)2
Protonation of precipitation
carboxylate Improved stability with iron
NaBO2
5 6 7 8 9 10 11 12
pH
Fig. 3—pH is a critical factor affecting polymer stability.
80
20M Dalton HPAM (Flopaam 3630S)
70 8M Dalton HPAM (Flopaam 3330S)
60 20M Dalton HPAM (Hengfloc 63020)
26M Dalton HPAM (Hengfloc 63026)
50
Viscosity, cP
30
20
10
0
0 60,000 120,000 180,000
NaCl Concentration, ppm
Fig. 4—Salinity tolerance of some commercially available polymers.
SPE 113845 13
50
45
NaCl only
40
35 9:1 NaCl/CaCl2
Viscosity, cP
30
25
100
30% hydrolyzed HPAM (Flopaam 3330S)
0% Hydrolyzed (PAM; FA920SH)
70% hydrolyzed HPAM
100% hydrolyzed (PAA)
Viscosity, cP
10
1
0 60,000 120,000 180,000
NaCl Concentration
Fig. 6—Relationship between degree of hydrolysis and salinity tolerance for 8M Dalton HPAM.
14 SPE 113845
800
τ = 0.66
τ=1
τ = 0.45
Ca++ Concentration, ppm
600
400
0
0 1,000 2,000 3,000 4,000 5,000 6,000 7,000 8,000 9,000
Na+ Concentration, ppm
Fig. 7—Effect of degree of hydrolysis on calcium tolerance.
1200
NaCl
1000
Na2B2O4
Ca++ Concentration, ppm
800
600
400
200
0
0 1,000 2,000 3,000 4,000 5,000 6,000 7,000 8,000 9,000
Na+ Concentration, ppm
Fig. 8—Effect of sodium metaborate on calcium tolerance of hydrolyzed PAM.
SPE 113845 15
30
20M Dalton HPAM (Flopaam 3630S)
10 τ + σ = 0.63
5
1500 ppm polymer, 30,000 ppm NaCl
0
0 50 100 150 200 250
Time, days
Fig. 9—Stability of commerical polymers at 85 °C with sodium dithionite.
100%
90%
80%
Degree of Anionicity (σ+τ)
70%
60%
PAM (Moradi '87(a))
50%
40% PAM-co-AMPS, 65/35 mol%
(Moradi 1987b, 100 Days)
30% HPAM (Authors, 220 Days)
20%
PAM-co-AMPS (Authors, 220
10% Days)
0%
0 20 40 60 80 100 120 140 160
Temperature, °C
Fig. 10—Total anionicity after extended aging.
16 SPE 113845
2500
HPAM
2000 Hydrolyzed PAM-co-AMPS
Ca++ Concentration, ppm
τ + σ = 0.67
1500
τ = 0.66
500
0
0 1,000 2,000 3,000 4,000 5,000 6,000 7,000 8,000 9,000
Na+ Concentration, ppm
Fig. 11—Effect of the presence of 20-30% AMPS moieties on the calcium tolerance of extensively hydrolyzed polymers, 23 °C.
12
Extensively Hydrolyzed PAM-co-AMPS
(Hydrolyzed AN-125, τ + σ = 0.67)
10
Extensively Hydrolyzed HPAM
(τ = 0.66)
8
Viscosity, cP
4
Cloudy
2
1500 ppm polymer, 20,000 ppm NaCl, 23 °C
0
0 1,000 2,000 3,000 4,000 5,000 6,000
Calcium Concentration, ppm
Fig. 12—Viscometric comparison of precipitation phenomena of extensively hydrolyzed PAM-co-AMPS and HPAM.
SPE 113845 17
15
0
0 50 100 150 200 250
Time, days
*Composition Confidential
Fig. 13—Stability of polymers at 100 °C with dithionite.
35
1500 ppm PAA, 23 °C
30
25
Viscosity, cP
20
15
NaCl Fe++
10 Na2CO3 Fe++
NaCl Fe+++
5
Na2CO3 Fe+++
0
0 10 20 30 40 50
Time, days
Fig. 14—Thermal stability acrylic backbone to radical attack in the presence of 8ppm O2, 20 ppm Fe(II) or Fe(III) and 1% NaCl or
Na2CO3.
18 SPE 113845
45
40 1500 ppm PAA 0.1M Na2CO3, pH-10
100%
90%
80%
% Viscosity Retained
70%
60%
50%
40%
30%
20%
1500 ppm PAM (FA920SH), 23 °C
10%
0%
0 1 2 3 4 5 6 7
Original Dissolved Oxygen, ppm
Fig 16—Effect of original amount of dissolved oxygen on PAM degradation upon addition of 400 ppm sodium dithionite.