CA1231229A - Gelled aqueous compositions - Google Patents
Gelled aqueous compositionsInfo
- Publication number
- CA1231229A CA1231229A CA000493956A CA493956A CA1231229A CA 1231229 A CA1231229 A CA 1231229A CA 000493956 A CA000493956 A CA 000493956A CA 493956 A CA493956 A CA 493956A CA 1231229 A CA1231229 A CA 1231229A
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- composition
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- polyamide
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/24—Homopolymers or copolymers of amides or imides
- C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S507/00—Earth boring, well treating, and oil field chemistry
- Y10S507/922—Fracture fluid
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S507/00—Earth boring, well treating, and oil field chemistry
- Y10S507/935—Enhanced oil recovery
- Y10S507/936—Flooding the formation
Abstract
GELLED AQUEOUS COMPOSITIONS
Abstract of Disclosure Disclosed are gelled aqueous polymer compositions in brine solutions containing an amount of an anionic partially hydrolyzed polyacrylamide capable of gelling in the presence of a gelling agent characterized in that the gelling agent is a water-soluble cationic polyamide-epihalohydrin resin in an amount sufficient to cause a gel to form and is used, preferably, in brine solutions having a salt concentration from about 1% to about 10% at a pH of about 3 to about 11.
The compositions are useful in the recovery of oil and gas by fracturing and in enhanced oil recovery.
Abstract of Disclosure Disclosed are gelled aqueous polymer compositions in brine solutions containing an amount of an anionic partially hydrolyzed polyacrylamide capable of gelling in the presence of a gelling agent characterized in that the gelling agent is a water-soluble cationic polyamide-epihalohydrin resin in an amount sufficient to cause a gel to form and is used, preferably, in brine solutions having a salt concentration from about 1% to about 10% at a pH of about 3 to about 11.
The compositions are useful in the recovery of oil and gas by fracturing and in enhanced oil recovery.
Description
This invention relates to gelled aqueous polymer com-positions comprising an anionic partially hydrolyzed acryla-mide and a water-soluble cationic polyamide-epihalohydrin resin useful in the recovery of oil and gas by fracturing and in enhanced oil recovery.
Oil and gas are generally found in porous or permeable subterranean formations. Once penetrated, oil and gas contained in the pore spaces are displaced into the wellbore by a variety of known methods. However, the production of the oil and gas may be impaired due to the plugging of the channels through which the oil and gas must flow to the wellbore by drilling Eluids or as a result of insufficient flow channels to carry the oil and gas to the wellbore. Such well formations are said to have low permeability.
An established method used today to stimulate the production of oil from a well having low permeability is fracturing with a hydraulic fracturing fluid, typically, containing propping agents, such as sand, walnut shell fragments and glass beads, to maintain the fracture in a propped condition when the pressure is relieved. This technique comprises the injection of a suitable fracturing fluid into the formation under sufficient pressure to frac-ture the formation. The resulting fracture provides passage-ways to facilitate the flow of the oil and gas into the wellbore.
During the injection of fluid into the well formation, the fracturing fluid must have and must maintain the proper-ties necessary to give fractures of reasonable lengths and widths. This is referred Jo as the fluid efficiency of the fracturing fluid. Such properties are related to the fluid 106s characteristics and the viscosity of the particular fluid used. One way to min;mize the loss of water to the walls of the wellbore and the fracture is to increase the viscosity of the fracturing fluid.
The use of gelled polymer solutions to improve the fracturing fluid efficiency has been taught. In fact, water-insoluble ge's are the state-of-the-art in fracturing fluids. Such gels are also formed by crosslinking the water-soluble polymers with a polyvalent metal, metal salt or complex which forms metal coordinate bonds with the polymer, such as are disclosed in U.S. Patents 4,018~28~ and 4,043,921.
This invention eliminates the need to use polyvalent metals, metal salts and complexes.
Gelled polymer compositions can also be used as plugging agents in enhanced oil recovery. For example, the gelled polymer compositions can be placed in high permeability zones in the formation so that subsequent treatment is forced into the low permeability zones, thereby giving better sweep efficiency by increasing the contact with, and removal of, oil. Gelled polymer compositions can also be used as mobility control or "pusher" materials in post-primary oil recovery operations. For example, in surfactant flooding, gelled polymer compositions can be injected as slugs to push previously injected surfactant slugs to recover oil at a producing well.
None of the known materials provide a gelled polymer composition having the gel strength and thermal stability necessary to withstand the varied conditions encountered in the use of fracturing fluids, plugging agents and mobility control materials.
This invention provides gelled aqueous polymer composi-tions in brine solutions containing an anionic partially hydrolyzed polyacrylamide capable of gelling in the presence of a gelling agent characterized in that the gelling agent is a water-soluble cationic polyamicle-epihalohydrin resin in an amount sufficient to cause a gel to form.
The length of time which a polymer gel can maintain its integrity depends on the depth of the well and on the thermal stability of the gel at that depth. The temperature of the well formation varies as a function of depth. The deeper the well, the higher the temperature at the bottom of the well.
For example, the typical temperature range of the bottom of a well 2,000 feet deep is 89-91F, whereas a well l0,000 feet deep generally has a bottom hole temperature range of 200F, and a well 18,000 feet deep a bottom hole tempera-ture range of 199-385F. At the present time, most wells drilled are under 10,000 feet in dep-th.
The thermal stability of a polymer gel depends on the strength of the polymer-polymer bonds and on the stability o the polymer backbone to degradation. The superior gel strength of the gelled compositions of this invention is believed to result from the electrostatic interaction ox the cationic polyamide-epihalohydrin resin and the anionic partially hydrolyzed polyacrylamide useful in this invention.
Suitable anionic partially hydrolyzed polyacrylamide include any partially hydrolyzed homopolymer of acrylamide, homopolymer of methacrylamide, and copolymer of acrylamide or methacrylamide with other water-soluble vinyl addition monomers containing an anionic charge or capable of generat-ing an anionic charge. Preferably, the anionic partially hydrolyzed polyacrylamide is used in brine solutions having a salt concentration of from about 1% to about 10% at a pH of from about 3 to about 11.
Suitable vinyl addition monomers include maleic anhydride and unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, maleic acid, crotonic acid, itaconic acid, and their alkali metal salts. Other monomers, such as acrylonitrile and alkyl esters of acrylic acid or methacrylic acid, can also be employed provided the resulting copolymerswith acrylamide can be hydrolyzed to form anionic carboxylate groups. The mole ratio of acrylamide to comonomers is from about 99:l to about 0:100, preferably from about 95:5 to about 5:95.
The preferred anionic polyacrylamides are copolymers of acrylamide with sodium acrylate containing about 5 to about 95 mole % sodium acrylate and polyacrylamides treated with an alkali metal hydroxide, preferably sodium hydroxide to hydrolyze about 5 to about 95 mole % amide groups to carboxy-late groups. Molecular weights can range from 100,000 to 10 million or more, preferably 2-10 million or more. The most preferred anionic polyacrylamides are copolymers of acryla-mide with sodium acrylate containing about 10 to about 70 mole % sodium acrylate and polyacrylamides treated with an alkali metal hydroxide, pre-ferably sodium hydroxide to hydrolyze about 10 to about 70 mole % am;de groups to carboxylate groups. The polymers can be prepared by any method practiced in the art. Thus, polymerization can be conducted with chemical initiators, such as redox initiators;
with thermally-active initiators, such as persulfates, peroxides and azo compounds; with ionizing irradiation, such as ultraviolet light, X-ray, gamma ray, or electron beam.
Typical polymerization methods employed include solution polymerization, precipitation polymerization, water-in-oil emulsion polymerization, and water-in-oil suspension polymerization.
Suitable alkali metals include sodium and potassium.
Sodium is the preferred alkali metal.
Suitable copolymers of acrylamide and sodium acrylate include acrylamide-sodium acrylate copolymers and methacrylamide-sodium acrylate copolymers. The acrylamide-sodium acrylate copolymer is preferred. Typically, the molecular weight of such copolymers ranges from about 50, noo to about 30,000,000. The preparation of copolymers of acrylamide and sodium acrylate is well known in the art.
The amount of anionic polyacrylamide used in the practice of this invention can vary depending on the viscosity and purity of the polymer. In general, a water thickening amount, i.e. that amount which will significantly ~3 thicken the water to which it is added, is used. Typically,this amount is from about 0.1% to about 1.07O, preferab].y 0.1%
to about 0.6~.
The polyamide-epichlorohydrin resins are generally prepared by the reaction of a dicarboxylic acid with a polyalkylene polyamine to form a water-soluble, long-chain polyamide containing -N~l(CnH2nNH)X-CORCO-recurring units, where n and x are each 2 or more, preferably
Oil and gas are generally found in porous or permeable subterranean formations. Once penetrated, oil and gas contained in the pore spaces are displaced into the wellbore by a variety of known methods. However, the production of the oil and gas may be impaired due to the plugging of the channels through which the oil and gas must flow to the wellbore by drilling Eluids or as a result of insufficient flow channels to carry the oil and gas to the wellbore. Such well formations are said to have low permeability.
An established method used today to stimulate the production of oil from a well having low permeability is fracturing with a hydraulic fracturing fluid, typically, containing propping agents, such as sand, walnut shell fragments and glass beads, to maintain the fracture in a propped condition when the pressure is relieved. This technique comprises the injection of a suitable fracturing fluid into the formation under sufficient pressure to frac-ture the formation. The resulting fracture provides passage-ways to facilitate the flow of the oil and gas into the wellbore.
During the injection of fluid into the well formation, the fracturing fluid must have and must maintain the proper-ties necessary to give fractures of reasonable lengths and widths. This is referred Jo as the fluid efficiency of the fracturing fluid. Such properties are related to the fluid 106s characteristics and the viscosity of the particular fluid used. One way to min;mize the loss of water to the walls of the wellbore and the fracture is to increase the viscosity of the fracturing fluid.
The use of gelled polymer solutions to improve the fracturing fluid efficiency has been taught. In fact, water-insoluble ge's are the state-of-the-art in fracturing fluids. Such gels are also formed by crosslinking the water-soluble polymers with a polyvalent metal, metal salt or complex which forms metal coordinate bonds with the polymer, such as are disclosed in U.S. Patents 4,018~28~ and 4,043,921.
This invention eliminates the need to use polyvalent metals, metal salts and complexes.
Gelled polymer compositions can also be used as plugging agents in enhanced oil recovery. For example, the gelled polymer compositions can be placed in high permeability zones in the formation so that subsequent treatment is forced into the low permeability zones, thereby giving better sweep efficiency by increasing the contact with, and removal of, oil. Gelled polymer compositions can also be used as mobility control or "pusher" materials in post-primary oil recovery operations. For example, in surfactant flooding, gelled polymer compositions can be injected as slugs to push previously injected surfactant slugs to recover oil at a producing well.
None of the known materials provide a gelled polymer composition having the gel strength and thermal stability necessary to withstand the varied conditions encountered in the use of fracturing fluids, plugging agents and mobility control materials.
This invention provides gelled aqueous polymer composi-tions in brine solutions containing an anionic partially hydrolyzed polyacrylamide capable of gelling in the presence of a gelling agent characterized in that the gelling agent is a water-soluble cationic polyamicle-epihalohydrin resin in an amount sufficient to cause a gel to form.
The length of time which a polymer gel can maintain its integrity depends on the depth of the well and on the thermal stability of the gel at that depth. The temperature of the well formation varies as a function of depth. The deeper the well, the higher the temperature at the bottom of the well.
For example, the typical temperature range of the bottom of a well 2,000 feet deep is 89-91F, whereas a well l0,000 feet deep generally has a bottom hole temperature range of 200F, and a well 18,000 feet deep a bottom hole tempera-ture range of 199-385F. At the present time, most wells drilled are under 10,000 feet in dep-th.
The thermal stability of a polymer gel depends on the strength of the polymer-polymer bonds and on the stability o the polymer backbone to degradation. The superior gel strength of the gelled compositions of this invention is believed to result from the electrostatic interaction ox the cationic polyamide-epihalohydrin resin and the anionic partially hydrolyzed polyacrylamide useful in this invention.
Suitable anionic partially hydrolyzed polyacrylamide include any partially hydrolyzed homopolymer of acrylamide, homopolymer of methacrylamide, and copolymer of acrylamide or methacrylamide with other water-soluble vinyl addition monomers containing an anionic charge or capable of generat-ing an anionic charge. Preferably, the anionic partially hydrolyzed polyacrylamide is used in brine solutions having a salt concentration of from about 1% to about 10% at a pH of from about 3 to about 11.
Suitable vinyl addition monomers include maleic anhydride and unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, maleic acid, crotonic acid, itaconic acid, and their alkali metal salts. Other monomers, such as acrylonitrile and alkyl esters of acrylic acid or methacrylic acid, can also be employed provided the resulting copolymerswith acrylamide can be hydrolyzed to form anionic carboxylate groups. The mole ratio of acrylamide to comonomers is from about 99:l to about 0:100, preferably from about 95:5 to about 5:95.
The preferred anionic polyacrylamides are copolymers of acrylamide with sodium acrylate containing about 5 to about 95 mole % sodium acrylate and polyacrylamides treated with an alkali metal hydroxide, preferably sodium hydroxide to hydrolyze about 5 to about 95 mole % amide groups to carboxy-late groups. Molecular weights can range from 100,000 to 10 million or more, preferably 2-10 million or more. The most preferred anionic polyacrylamides are copolymers of acryla-mide with sodium acrylate containing about 10 to about 70 mole % sodium acrylate and polyacrylamides treated with an alkali metal hydroxide, pre-ferably sodium hydroxide to hydrolyze about 10 to about 70 mole % am;de groups to carboxylate groups. The polymers can be prepared by any method practiced in the art. Thus, polymerization can be conducted with chemical initiators, such as redox initiators;
with thermally-active initiators, such as persulfates, peroxides and azo compounds; with ionizing irradiation, such as ultraviolet light, X-ray, gamma ray, or electron beam.
Typical polymerization methods employed include solution polymerization, precipitation polymerization, water-in-oil emulsion polymerization, and water-in-oil suspension polymerization.
Suitable alkali metals include sodium and potassium.
Sodium is the preferred alkali metal.
Suitable copolymers of acrylamide and sodium acrylate include acrylamide-sodium acrylate copolymers and methacrylamide-sodium acrylate copolymers. The acrylamide-sodium acrylate copolymer is preferred. Typically, the molecular weight of such copolymers ranges from about 50, noo to about 30,000,000. The preparation of copolymers of acrylamide and sodium acrylate is well known in the art.
The amount of anionic polyacrylamide used in the practice of this invention can vary depending on the viscosity and purity of the polymer. In general, a water thickening amount, i.e. that amount which will significantly ~3 thicken the water to which it is added, is used. Typically,this amount is from about 0.1% to about 1.07O, preferab].y 0.1%
to about 0.6~.
The polyamide-epichlorohydrin resins are generally prepared by the reaction of a dicarboxylic acid with a polyalkylene polyamine to form a water-soluble, long-chain polyamide containing -N~l(CnH2nNH)X-CORCO-recurring units, where n and x are each 2 or more, preferably
2 to 4, and R is the divalent organic radical of the dicar-boxylic acid. This long-chain polyamide is then reacted with epichlorohydrin to form a water-soluble cationic thermosetting resin.
Typical dicarboxylic acids include sarurated aliphatic dicarboxylic acids preferably containing 3-8 carbon atoms, such as malonic, succinic, glutaric, adipic, azelaic, and sebacic acid, or blends of 2 or more. Suitable polyalkylene polyamines contain two primary amine groups and at least one secondary amine group and include polyethylene polyamines, polypropylene polyamines, and polybutylene polyamines.
Typical polyamines include diethylenetriamine, triethylene-tetramine, tetraethylenepentamine, propylenediamine, hexamethylenediamine, and piperazine, or mixtures thereof.
The mole ratios of polyalkylene polyamine to dicarboxylic acid are from about 0.9:1 to about 1.2:1. The aqueous polyamide formed above is converted to a cationic thermo-setting resin by reaction with epichlorohydrin at 45-100C
until the viscosity of a 25~ solids solution at 25C has reached at least B, and preferably at least D, on the Gardner-Holt scale. It is preferred that all secondary amine groups be converted to tertiary and/or quaternary ammonium groups. Thus, it is preferred to utilize from about 0.9 mole to about 1.5 mole of epichlorohydrin per mole of secondary amine group.
Polyamide-epihalohydrin resins are prepared in aqueous solution at a pH of from about 7 to about 9.5 and has a tendency to gel on standing. The resin solution is stabilized ox against gelation by adding to the aqueous solution thereof sufficient acid, such as hydrochloric acid, to obtain and maintain the pH at about 2. Such resins are referred to in the art as acid-stabllized resins, and are usually marketed in this form.
In forming the gel, the anionic polyacrylamide is generally used at concentrations of about 500 pp~ to about 10,000 ppm polymer solids, based on the total weight of the composition. Preferably about 1,000 ppm to about 6,000 ppm polymer solids is used. expressed as a percent, this is usually from about 0.05% to about 1.07O polymer solids, by weight of the total composition, preferably 0.1% to about 0.6%.
The polyamide-epichlorohydrin resin is generally used at concentrations of about 100 ppm to about 5,000 ppm resin solids, preferably about 500 ppm to about 2,500 ppm. As a percent, this is from about 0.01% to about 0.5% resin solids, preferably about 0.05% to about 0.25'.
Exact amounts of each will depend on the molecular weight and mole % anionic groups in the anionic polyacryl-amide, ionic strength, temperature, pH, and the strength of gel desired.
Some mineral salts must be present in the aqueous solution, since a precipitate will form between the anionic polyacrylamide and the cationic polyamide-epichlorohydrin resin in the absence of salts or ionic strength. Typically, the salt concentration is from about 1% to about 10%, preferably 1% to about 6%, most preferably 17~ to about 4%.
Any water-soluble salt may be employed, but generally salts of alkali metals are preferred, such as NaCl, KCl, KBr, Na2S04 and NaN03. KCl is preferred. Generally there is an optimum amount of salt that will provide the best gel strength for a given anionic polyacrylamide. For example, for anionic polyacrylamides containing about 7 to about mole % sodium acrylate groups, about 1 wt. % KCl is best for anionic polyacrylamides containing about 24 mole % sodium acrylate groups, about 2 wt. % KCl is best, and for anionic polyacrylamides containing about 50 mole % sodium acrylate groups about 2 to about 4 wt. % KCl is best. As the mole 7 of sodium acrylate or mole carboxylate groups to amide groups increases, the optimum salt concentration increases.
The pH of the solution can be from 3-11, most preferably from 5-9. Often a pH near 7 gives the best gel strength.
Oilfield brines containing mineral salts with greater than 1,000 ppm solids content (0.1%) may be employed, although sea water and hard brines containing 1,000 ppm (0.1%) or more divalent cations, such as Ca+~, and having a total dissolved solids (TDS) above 30,000 ppm (3Ø), are unsatisfactory.
Gels are formed at about 75F (25C) to about 185F
(85C) or higher. The temperature can govern the rate of gel formation, the maximum gel strength, and the rate of gel decay. Thus, it is often necessary to vary the anionic polyacrylamide and cationic polyamide resin concentrations, the type and amount of salt, and the pi to obtain the rate of gel formation and gel strength desired for a particular oil reservoir at a given temperature.
The compositions of this invention can be prepared for use as fracturing fluids at the surface in a suitable tank equipped with a suitable mixing means, and pumped down the wellbore into the formation using conventional equipment for such compositions. The compositions can also be prepared "on the fly", i.e. while being pumped down the well. In this case the anionic polyacrylamide solution containing the proppant is prepared in a tank near the well head and pumping of the solution into the wellbore through a conduit is commenced. The solution of the cationic resin in its active form is prepared in a separate tank and is introduced into the aqueous solution stream of the anionic polyacrylamide containing the proppant by a suitable connection a few feet downstream from the anionic polyacrylamide mixing tank. The rate at which the components are introduced into the conduit will depend on the pumping rate of the particular composition of this invention and will be within the skill of those skilled in the art. Alternative methods for combining such fracturing fluid ingredients will also be known to those skilled in the art.
The compositions of this invention can also be mixed in solution at the surface to form dilute gels which are readily pumpable. The heat of the wellbore, particularly at the bottom of the wellbore, will activate the polymer-polymer bonding reaction. For shallow fracturing, the composition or the separate polymer and resin solutions can be heated before pumping.
The following examples are illustrative of this invention. All parts and percentages used in this specification are by weight unless otherwise specified.
Example 1 15 This example illustrates an emboAiment of the gelled aqueous polymer composition of this invention and how to prepare it.
A mixing vessel equipped with a stirrer is charged with 1.2 g of an acrylamide-sodium acrylate copolymer, having a sodium acrylate content of 24 mole %, in 198.~ g of water.
Stirring is continued until the polymer is completely dissolved to give a 6,000 ppm polymer solids solution.
An acid-stabilized solution of the (diethylenetriamine-adipic acid) polyamide-epichlorohydrin resin is diluted in a separate container to give a 5% active resin solids solution.
Another mixing vessel is charged with 41.66 g of the 6,000 ppm polymer solids solution, 51 g of water and 1.0 g KCl and hand stlrred until the ingredients are dissolved and a homogeneous mixture is obtained. jive (5.0) g of the 5 cationic resin solids solution is added and hand stirred until a homogeneous mixture is obtained. The pH is adjusted to pH 7.0 with 10% NaOH and 10% H2SO4. Additional water is then added to give exactly 100.0 g total solution contain-ing 2500 ppm of the acrylamide-sodium acrylate copolymer and ~3 2500 ppm of t`he (die~hylenetriamine-adipic acid) polyamide-epichlorohydrin resin. The solution is then stored at a temperature of 104F (40C). A medium gel is formed in one day and a medium-heavy gel in 2 days. The gel is still medium-heavy after 3 days.
Examples 2-38 Theses examples illustrate other embodiments of the gelled aqueous polymer compositions of this invention.
The procedure and formulation of Example 1 are used to prepare the compositions except that the formulation is changed as set forth in Table I below.
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_ _ _ us o In O Us Examples 39-44 Theses examples illustrate other embodiments of the gelled aqueous polymer compositions of this invention.
The procedure and formulation of Example 1 are used to prepare the compositions except that the formulation is changed as set forth in Table II below.
The compositions were tested under near optimum conditions, i.e., at pH 7 and at a salt concentration of from about 1% to about 2%.
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o us O
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O CO f _ ~Ln _ c Jo o o or o I, or oo~ Jo ooo~ oo o ox ox ox it d I
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us o n o '~2 Examples 45-53 Theses examples illustrate other embodiments of the gelled aqueous compositions of this invention.
The procedure and formulation of Example 1 are used to prepare the compositions except that the formulation is changed as set forth in Table III below.
The compositions were tested under near optimum conditions at high polyacrylamide concentrations and at varying polyamide-epichlorohydrin resin concentrations.
aft Ln Ln I Ln D7 JO Ln MY Ln or Ln or O
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n Ln Ln Ln Ln Ln O O O Us l S
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Typical dicarboxylic acids include sarurated aliphatic dicarboxylic acids preferably containing 3-8 carbon atoms, such as malonic, succinic, glutaric, adipic, azelaic, and sebacic acid, or blends of 2 or more. Suitable polyalkylene polyamines contain two primary amine groups and at least one secondary amine group and include polyethylene polyamines, polypropylene polyamines, and polybutylene polyamines.
Typical polyamines include diethylenetriamine, triethylene-tetramine, tetraethylenepentamine, propylenediamine, hexamethylenediamine, and piperazine, or mixtures thereof.
The mole ratios of polyalkylene polyamine to dicarboxylic acid are from about 0.9:1 to about 1.2:1. The aqueous polyamide formed above is converted to a cationic thermo-setting resin by reaction with epichlorohydrin at 45-100C
until the viscosity of a 25~ solids solution at 25C has reached at least B, and preferably at least D, on the Gardner-Holt scale. It is preferred that all secondary amine groups be converted to tertiary and/or quaternary ammonium groups. Thus, it is preferred to utilize from about 0.9 mole to about 1.5 mole of epichlorohydrin per mole of secondary amine group.
Polyamide-epihalohydrin resins are prepared in aqueous solution at a pH of from about 7 to about 9.5 and has a tendency to gel on standing. The resin solution is stabilized ox against gelation by adding to the aqueous solution thereof sufficient acid, such as hydrochloric acid, to obtain and maintain the pH at about 2. Such resins are referred to in the art as acid-stabllized resins, and are usually marketed in this form.
In forming the gel, the anionic polyacrylamide is generally used at concentrations of about 500 pp~ to about 10,000 ppm polymer solids, based on the total weight of the composition. Preferably about 1,000 ppm to about 6,000 ppm polymer solids is used. expressed as a percent, this is usually from about 0.05% to about 1.07O polymer solids, by weight of the total composition, preferably 0.1% to about 0.6%.
The polyamide-epichlorohydrin resin is generally used at concentrations of about 100 ppm to about 5,000 ppm resin solids, preferably about 500 ppm to about 2,500 ppm. As a percent, this is from about 0.01% to about 0.5% resin solids, preferably about 0.05% to about 0.25'.
Exact amounts of each will depend on the molecular weight and mole % anionic groups in the anionic polyacryl-amide, ionic strength, temperature, pH, and the strength of gel desired.
Some mineral salts must be present in the aqueous solution, since a precipitate will form between the anionic polyacrylamide and the cationic polyamide-epichlorohydrin resin in the absence of salts or ionic strength. Typically, the salt concentration is from about 1% to about 10%, preferably 1% to about 6%, most preferably 17~ to about 4%.
Any water-soluble salt may be employed, but generally salts of alkali metals are preferred, such as NaCl, KCl, KBr, Na2S04 and NaN03. KCl is preferred. Generally there is an optimum amount of salt that will provide the best gel strength for a given anionic polyacrylamide. For example, for anionic polyacrylamides containing about 7 to about mole % sodium acrylate groups, about 1 wt. % KCl is best for anionic polyacrylamides containing about 24 mole % sodium acrylate groups, about 2 wt. % KCl is best, and for anionic polyacrylamides containing about 50 mole % sodium acrylate groups about 2 to about 4 wt. % KCl is best. As the mole 7 of sodium acrylate or mole carboxylate groups to amide groups increases, the optimum salt concentration increases.
The pH of the solution can be from 3-11, most preferably from 5-9. Often a pH near 7 gives the best gel strength.
Oilfield brines containing mineral salts with greater than 1,000 ppm solids content (0.1%) may be employed, although sea water and hard brines containing 1,000 ppm (0.1%) or more divalent cations, such as Ca+~, and having a total dissolved solids (TDS) above 30,000 ppm (3Ø), are unsatisfactory.
Gels are formed at about 75F (25C) to about 185F
(85C) or higher. The temperature can govern the rate of gel formation, the maximum gel strength, and the rate of gel decay. Thus, it is often necessary to vary the anionic polyacrylamide and cationic polyamide resin concentrations, the type and amount of salt, and the pi to obtain the rate of gel formation and gel strength desired for a particular oil reservoir at a given temperature.
The compositions of this invention can be prepared for use as fracturing fluids at the surface in a suitable tank equipped with a suitable mixing means, and pumped down the wellbore into the formation using conventional equipment for such compositions. The compositions can also be prepared "on the fly", i.e. while being pumped down the well. In this case the anionic polyacrylamide solution containing the proppant is prepared in a tank near the well head and pumping of the solution into the wellbore through a conduit is commenced. The solution of the cationic resin in its active form is prepared in a separate tank and is introduced into the aqueous solution stream of the anionic polyacrylamide containing the proppant by a suitable connection a few feet downstream from the anionic polyacrylamide mixing tank. The rate at which the components are introduced into the conduit will depend on the pumping rate of the particular composition of this invention and will be within the skill of those skilled in the art. Alternative methods for combining such fracturing fluid ingredients will also be known to those skilled in the art.
The compositions of this invention can also be mixed in solution at the surface to form dilute gels which are readily pumpable. The heat of the wellbore, particularly at the bottom of the wellbore, will activate the polymer-polymer bonding reaction. For shallow fracturing, the composition or the separate polymer and resin solutions can be heated before pumping.
The following examples are illustrative of this invention. All parts and percentages used in this specification are by weight unless otherwise specified.
Example 1 15 This example illustrates an emboAiment of the gelled aqueous polymer composition of this invention and how to prepare it.
A mixing vessel equipped with a stirrer is charged with 1.2 g of an acrylamide-sodium acrylate copolymer, having a sodium acrylate content of 24 mole %, in 198.~ g of water.
Stirring is continued until the polymer is completely dissolved to give a 6,000 ppm polymer solids solution.
An acid-stabilized solution of the (diethylenetriamine-adipic acid) polyamide-epichlorohydrin resin is diluted in a separate container to give a 5% active resin solids solution.
Another mixing vessel is charged with 41.66 g of the 6,000 ppm polymer solids solution, 51 g of water and 1.0 g KCl and hand stlrred until the ingredients are dissolved and a homogeneous mixture is obtained. jive (5.0) g of the 5 cationic resin solids solution is added and hand stirred until a homogeneous mixture is obtained. The pH is adjusted to pH 7.0 with 10% NaOH and 10% H2SO4. Additional water is then added to give exactly 100.0 g total solution contain-ing 2500 ppm of the acrylamide-sodium acrylate copolymer and ~3 2500 ppm of t`he (die~hylenetriamine-adipic acid) polyamide-epichlorohydrin resin. The solution is then stored at a temperature of 104F (40C). A medium gel is formed in one day and a medium-heavy gel in 2 days. The gel is still medium-heavy after 3 days.
Examples 2-38 Theses examples illustrate other embodiments of the gelled aqueous polymer compositions of this invention.
The procedure and formulation of Example 1 are used to prepare the compositions except that the formulation is changed as set forth in Table I below.
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_ _ _ us o In O Us Examples 39-44 Theses examples illustrate other embodiments of the gelled aqueous polymer compositions of this invention.
The procedure and formulation of Example 1 are used to prepare the compositions except that the formulation is changed as set forth in Table II below.
The compositions were tested under near optimum conditions, i.e., at pH 7 and at a salt concentration of from about 1% to about 2%.
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us o n o '~2 Examples 45-53 Theses examples illustrate other embodiments of the gelled aqueous compositions of this invention.
The procedure and formulation of Example 1 are used to prepare the compositions except that the formulation is changed as set forth in Table III below.
The compositions were tested under near optimum conditions at high polyacrylamide concentrations and at varying polyamide-epichlorohydrin resin concentrations.
aft Ln Ln I Ln D7 JO Ln MY Ln or Ln or O
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n Ln Ln Ln Ln Ln O O O Us l S
~0 a) o pa a) V 3 o l O C ' 0 O O O O O ~Oq 5 q 30 D Al Ln Lq l o Ln Ln Ln Ln Ln Ln Ln Ln Ln 30 3 3 tq O l Q O I, a I, a a g Q
a~I do Lq l I Lq O g O f O
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3 ~-,~
. I,. Jo a) ~-,~
O ) Us 11 11 11 1' 1' 1' tq l ; O Lo f Ln Ln us o r Ln Ln Ln Ln __~ _ X
Ln o Ln o The test results in Table III show that gels develop at room temperature (77F) at high anionic polyacrylamide concentrations. Further, the test shows the buildup in gel strength that occurs in the presence of cationic polyamide-epichlorohydrin resins.
The aqueous gelled polymer compositions have good thermal stability as indicated by their high thermal breakdown temperatures, TB, and by their storage modulus, I'. G' is a measure of gel strength. A strong gel has a storage modulus of about 100 dynes/cm2. A weak gel has a storage modulus of about 10 dynes/cm2. For example, the TB and G', as measured by a Rheometrics pressure rheometer, for the gel of Example 54 formed with 5600 ppm acrylamide-sodium acrylate (24 mole % sodium acryla~e), 2500 ppm (diethylene triamine-adipic acid) polyamide-epichlorohydrin resin, and 1.5% KCl at pH 7 is 350F (TB~ and 120 dynes/cm2 (G').
Thus, this invention provides aqueous gelled polymer compositions having high temperature stability useful in fracturing fluids for the recovery of oil and gas from well formations. The gels are also useful as plugging agents in enhanced oil recovery and in other gas and oil recovery operations.
Features, advantages and other specific embodiments of this invention will become readily apparent to those exercising ordinary skill in the art after reading the foregoing disclosures. In this regard 9 while specific embodiments of this invention have been described in considerable detail, variations and modifications of these embodiments can be effected without departing from the spirit and scope of the invention as disclosed and claimed.
. I,. Jo a) ~-,~
O ) Us 11 11 11 1' 1' 1' tq l ; O Lo f Ln Ln us o r Ln Ln Ln Ln __~ _ X
Ln o Ln o The test results in Table III show that gels develop at room temperature (77F) at high anionic polyacrylamide concentrations. Further, the test shows the buildup in gel strength that occurs in the presence of cationic polyamide-epichlorohydrin resins.
The aqueous gelled polymer compositions have good thermal stability as indicated by their high thermal breakdown temperatures, TB, and by their storage modulus, I'. G' is a measure of gel strength. A strong gel has a storage modulus of about 100 dynes/cm2. A weak gel has a storage modulus of about 10 dynes/cm2. For example, the TB and G', as measured by a Rheometrics pressure rheometer, for the gel of Example 54 formed with 5600 ppm acrylamide-sodium acrylate (24 mole % sodium acryla~e), 2500 ppm (diethylene triamine-adipic acid) polyamide-epichlorohydrin resin, and 1.5% KCl at pH 7 is 350F (TB~ and 120 dynes/cm2 (G').
Thus, this invention provides aqueous gelled polymer compositions having high temperature stability useful in fracturing fluids for the recovery of oil and gas from well formations. The gels are also useful as plugging agents in enhanced oil recovery and in other gas and oil recovery operations.
Features, advantages and other specific embodiments of this invention will become readily apparent to those exercising ordinary skill in the art after reading the foregoing disclosures. In this regard 9 while specific embodiments of this invention have been described in considerable detail, variations and modifications of these embodiments can be effected without departing from the spirit and scope of the invention as disclosed and claimed.
Claims (8)
1, A gelled aqueous polymer composition in brine solution containing an anionic partially hydrolyzed polyacrylamide capable of gelling in the presence of a gelling agent characterized in that the gelling agent is a water-soluble cationic polyamide-epihalohydrin resin in an amount sufficient to cause a gel to form.
2. The composition of claim 1 wherein the brine solution has a salt concentration of from about 1% to about 10%.
3. The composition of claim 1 wherein the brine solution has a salt concentration of from about 1% to about 6%.
4. The composition of claims 1, 2 or 3 in a brine solution at a pH of from about 3 to about 11.
5. The composition of claims 1, 2 or 3 wherein the anionic partially hydrolyzed polyacrylamide is a copolymer of acrylamide and sodium acrylate having from about 5 to about 95 mole % sodium acrylate.
6. The composition of claims 1, 2 or 3 wherein the water-soluble cationic polyamide-epihalohydrin resin is a (polyalkylene polyamine-dicarboxylic acid) polyamide-epichlorohydrin resin having about 0.9:1 to about 1.2:1 polyalkylene polyamine:dicarboxylic acid and about 0.9 mole to about 1.5 mole epichlorohydrin per mole of secondary amine group.
7. The composition of claims 1, 2 or 3 wherein the water-soluble cationic polyamide-epihalohydrin resin is present in an amount from about 0.01% to about 0.50% resin solids.
8. The composition of claims 1, 2 or 3 wherein the water-soluble cationic polyamide-epihalohydrin resin is a (diethylene triamine-adipic acid) polyamide-epichlorohydrin resin having about 0.9:1 to about 1.2:1 diethylene triamine:adipic acid and about 0.9 mole to about 1.5 mole epichlorohydrin per mole of secondary amine group.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/669,485 US4579667A (en) | 1984-11-07 | 1984-11-07 | Gelled aqueous compositions |
US669,485 | 1984-11-07 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1231229A true CA1231229A (en) | 1988-01-12 |
Family
ID=24686497
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000493956A Expired CA1231229A (en) | 1984-11-07 | 1985-10-28 | Gelled aqueous compositions |
Country Status (8)
Country | Link |
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US (1) | US4579667A (en) |
EP (1) | EP0187451B1 (en) |
AT (1) | ATE71643T1 (en) |
CA (1) | CA1231229A (en) |
DE (1) | DE3585221D1 (en) |
DK (1) | DK512285A (en) |
ES (1) | ES8705006A1 (en) |
FI (1) | FI86737C (en) |
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US4676930A (en) * | 1985-09-25 | 1987-06-30 | Mobile Oil Corporation | Zirconium crosslinked gel compositions, methods of preparation and application in enhanced oil recovery |
US4787451A (en) * | 1986-12-11 | 1988-11-29 | Mobil Oil Corporation | Melamine/formaldehyde cross-linking of polymers for profile control |
US4793416A (en) * | 1987-06-30 | 1988-12-27 | Mobile Oil Corporation | Organic crosslinking of polymers for CO2 flooding profile control |
DE3822490A1 (en) * | 1988-07-02 | 1990-01-04 | Hoechst Ag | WAFER SOLUTIONS OF POLYAMIDOAMINE-EPICHLORHYRIN RESINS, PROCESS FOR THEIR PREPARATION AND THEIR USE |
US5244936A (en) * | 1988-12-12 | 1993-09-14 | Mobil Oil Corporation | Enhanced oil recovery profile control with crosslinked anionic acrylamide copolymer gels |
US5079278A (en) * | 1989-12-13 | 1992-01-07 | Mobil Oil Corporation | Enhanced oil recovery profile control with crosslinked anionic acrylamide copolymer gels |
JPH0678364B2 (en) | 1989-01-31 | 1994-10-05 | ユニオン、カーバイド、ケミカルズ、アンド、プラスチックス、カンパニー、インコーポレイテッド | Polysaccharides having alkyl-aryl hydrophobic groups and latex composition containing them |
US4917186A (en) * | 1989-02-16 | 1990-04-17 | Phillips Petroleum Company | Altering subterranean formation permeability |
US4973410A (en) * | 1989-11-29 | 1990-11-27 | Air Products And Chemicals, Inc. | Crosslinked vinylamine polymer in enhanced oil recovery |
US5085787A (en) * | 1989-11-29 | 1992-02-04 | Air Products And Chemicals, Inc. | Crosslinked vinylamine polymer in enhanced oil recovery |
US5504123A (en) * | 1994-12-20 | 1996-04-02 | Union Carbide Chemicals & Plastics Technology Corporation | Dual functional cellulosic additives for latex compositions |
US5771971A (en) * | 1996-06-03 | 1998-06-30 | Horton; David | Clay stabilizing agent and a method of use in subterranean formations to inhibit clay swelling |
US6186231B1 (en) | 1998-11-20 | 2001-02-13 | Texaco Inc. | Conformance improvement in hydrocarbon bearing underground strata using lignosulfonate-acrylic acid graft copolymer gels |
US6025304A (en) * | 1998-12-15 | 2000-02-15 | Marathon Oil Company | Permeability or fluid mobility reduction treatment for a hydrocarbon-bearing formation using a dual molecular weight polymer gel |
US7205262B2 (en) * | 2001-12-12 | 2007-04-17 | Weatherford/Lamb, Inc. | Friction reducing composition and method |
US7183239B2 (en) * | 2001-12-12 | 2007-02-27 | Clearwater International, Llc | Gel plugs and pigs for pipeline use |
US8273693B2 (en) * | 2001-12-12 | 2012-09-25 | Clearwater International Llc | Polymeric gel system and methods for making and using same in hydrocarbon recovery |
US7405188B2 (en) | 2001-12-12 | 2008-07-29 | Wsp Chemicals & Technology, Llc | Polymeric gel system and compositions for treating keratin substrates containing same |
US20030114315A1 (en) * | 2001-12-12 | 2003-06-19 | Clearwater, Inc. | Polymeric gel system and use in hydrocarbon recovery |
US7067460B2 (en) * | 2002-11-14 | 2006-06-27 | Baker Hughes Incorporated | Organofunctional compounds for shale stabilization of the aqueous dispersed phase of non-aqueous based invert emulsion drilling system fluids |
US6994166B2 (en) * | 2003-06-24 | 2006-02-07 | Baker Hughes Incorporated | Composition and method for diversion agents for acid stimulation of subterranean formations |
US7482310B1 (en) | 2003-11-12 | 2009-01-27 | Kroff Chemical Company, Inc. | Method of fracturing subterranean formations utilizing emulsions comprising acrylamide copolymers |
US7531600B1 (en) | 2003-11-12 | 2009-05-12 | Kroff Chemical Company | Water-in-oil polymer emulsion containing microparticles |
US7528095B2 (en) * | 2005-02-04 | 2009-05-05 | Halliburton Energy Services, Inc. | Methods and compositions for improving the thermal stability of aqueous polymeric wellbore treatment fluids |
US8099997B2 (en) | 2007-06-22 | 2012-01-24 | Weatherford/Lamb, Inc. | Potassium formate gel designed for the prevention of water ingress and dewatering of pipelines or flowlines |
US8065905B2 (en) | 2007-06-22 | 2011-11-29 | Clearwater International, Llc | Composition and method for pipeline conditioning and freezing point suppression |
AU2011281600B2 (en) | 2010-07-21 | 2016-01-14 | Basf Se | A proppant |
MY176334A (en) | 2013-01-18 | 2020-07-29 | Conocophillips Co | Nanogels for delayed gelation |
US9657216B2 (en) * | 2013-10-23 | 2017-05-23 | Shell Oil Company | Process for reducing viscosity of polymer-containing fluid produced in the recovery of oil |
CN107250320A (en) | 2014-11-19 | 2017-10-13 | 科诺科菲利浦公司 | The delay gelatinizing of polymer |
WO2018071669A2 (en) | 2016-10-12 | 2018-04-19 | Schlumberger Canada Limited | Crosslinking of cellulose fibers |
US20180346802A1 (en) * | 2017-06-05 | 2018-12-06 | Noles Intellectual Properties, Llc | Hydraulic Fracturing Fluid |
US11815639B2 (en) * | 2019-10-31 | 2023-11-14 | Halliburton Energy Services, Inc. | Borehole fluid gel strength measurement |
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US3272640A (en) * | 1960-12-22 | 1966-09-13 | Hercules Powder Co Ltd | Water insolubilizing and insensitizing process |
US3224986A (en) * | 1962-04-18 | 1965-12-21 | Hercules Powder Co Ltd | Cationic epichlorohydrin modified polyamide reacted with water-soluble polymers |
US3909423A (en) * | 1972-02-09 | 1975-09-30 | Phillips Petroleum Co | Gelled polymers and methods of preparing same |
US3816556A (en) * | 1972-06-09 | 1974-06-11 | American Cyanamid Co | Composition comprising a polysalt and paper made therewith |
US4043921A (en) * | 1975-09-10 | 1977-08-23 | Phillips Petroleum Company | Cellulose ether-polyacrylamide aqueous gels |
US4055502A (en) * | 1975-12-24 | 1977-10-25 | Phillips Petroleum Company | Method and composition for acidizing subterranean formations |
US4409110A (en) * | 1981-01-06 | 1983-10-11 | Halliburton Company | Enhanced oil displacement processes and compositions |
-
1984
- 1984-11-07 US US06/669,485 patent/US4579667A/en not_active Expired - Lifetime
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1985
- 1985-10-25 FI FI854191A patent/FI86737C/en not_active IP Right Cessation
- 1985-10-28 CA CA000493956A patent/CA1231229A/en not_active Expired
- 1985-11-06 DK DK512285A patent/DK512285A/en not_active Application Discontinuation
- 1985-11-06 EP EP85308077A patent/EP0187451B1/en not_active Expired - Lifetime
- 1985-11-06 ES ES548573A patent/ES8705006A1/en not_active Expired
- 1985-11-06 AT AT85308077T patent/ATE71643T1/en not_active IP Right Cessation
- 1985-11-06 DE DE8585308077T patent/DE3585221D1/en not_active Expired - Fee Related
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ES8705006A1 (en) | 1987-04-16 |
FI854191A0 (en) | 1985-10-25 |
ATE71643T1 (en) | 1992-02-15 |
US4579667A (en) | 1986-04-01 |
DE3585221D1 (en) | 1992-02-27 |
DK512285D0 (en) | 1985-11-06 |
FI86737C (en) | 1992-10-12 |
EP0187451A2 (en) | 1986-07-16 |
FI86737B (en) | 1992-06-30 |
FI854191L (en) | 1986-05-08 |
EP0187451B1 (en) | 1992-01-15 |
ES548573A0 (en) | 1987-04-16 |
DK512285A (en) | 1986-05-08 |
EP0187451A3 (en) | 1988-07-06 |
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