WO1992011441A1 - GELS D'HETEROPOLYSACCHARIDE A TOLERANCE DE pH UTILISES POUR LA REGULATION DE PROFIL - Google Patents

GELS D'HETEROPOLYSACCHARIDE A TOLERANCE DE pH UTILISES POUR LA REGULATION DE PROFIL Download PDF

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Publication number
WO1992011441A1
WO1992011441A1 PCT/US1991/009451 US9109451W WO9211441A1 WO 1992011441 A1 WO1992011441 A1 WO 1992011441A1 US 9109451 W US9109451 W US 9109451W WO 9211441 A1 WO9211441 A1 WO 9211441A1
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Prior art keywords
gel
composition
heteropolysaccharide
crosslinking agent
stage
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PCT/US1991/009451
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English (en)
Inventor
Dennis Harold Hoskin
Thomas Raymond Sifferman
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Mobil Oil Corporation
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Priority claimed from US07/628,042 external-priority patent/US5156214A/en
Application filed by Mobil Oil Corporation filed Critical Mobil Oil Corporation
Publication of WO1992011441A1 publication Critical patent/WO1992011441A1/fr

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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
    • C09K8/84—Compositions based on water or polar solvents
    • C09K8/86—Compositions based on water or polar solvents containing organic compounds
    • C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/887—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
    • 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
    • C09K8/84—Compositions based on water or polar solvents
    • C09K8/86—Compositions based on water or polar solvents containing organic compounds
    • C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/90—Compositions based on water or polar solvents containing organic compounds macromolecular compounds of natural origin, e.g. polysaccharides, cellulose
    • C09K8/905—Biopolymers
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/25—Methods for stimulating production
    • E21B43/26—Methods for stimulating production by forming crevices or fractures
    • E21B43/261—Separate steps of (1) cementing, plugging or consolidating and (2) fracturing or attacking the formation

Definitions

  • This invention relates to the use of polymeric gels for profile control to enable increased amounts of reservoir fluids to be recovered from a subterranean formation.
  • formation oil can usually be recovered through the use of primary recovery methods.
  • a primary recovery method is one which utilizes only the natural forces present in the
  • a fluid is introduced into the oil-bearing formation in order to displace oil to a production system comprising one or more production wells.
  • the displacing or "drive" fluid may be an aqueous liquid such as brine or fresh water, a gas such as carbon dioxide, steam or
  • polyacrylamides polysaccharides, celluloses, furfural-alcohol and acrylic/epoxy resins, silicates and polyisocyanurates.
  • a major part of this work has been conducted with the polyacrylamides, both in their normal, non-crosslinked form, as well as in the form of metal complexes, as described, for example, in US-A-4,009,755, US-A-4,069,869 and US-A-4,413,680.
  • the beneficial effects derived from these polyacrylamides seem to dissipate rapidly due to shear degradation during injection and sensitivity to reservoir brines, low pH and high temperature.
  • dilute solutions of these polymers have sometimes been injected first and then complexed in-situ.
  • polysaccharides particularly those produced by the action of bacteria of the genus
  • Xanthomonas on carbohydrates For example,
  • US-A-3,757,863 and US-A-3,383,307 disclose a process for mobility control by the use of polysaccharides.
  • US-A-3,741,307, US-A-4,009,755 and US-A-4,069,869 disclose the use of polysaccharides in the control of reservoir permeability.
  • US-A-4,413,680 describes the use of crosslinked polysaccharides for selective permeability control in oil reservoirs.
  • US-A-3,908,760 describes a polymer waterflooding process in which a gelled, water-soluble Xanthomonas campestris polysaccharide is injected into a stratified reservoir to form a slug, band or front of gel
  • S-130 is a member of a group of welan gums and is produced by fermentation with a microorganism of the genus
  • heteropolysaccharide S-194 Another welan gum heteropolysaccharide, known as S-194, is also produced by fermentation with a microorganism of the genus Alcaligenes.
  • S-130 A notable characteristic of the heteropolysaccharide S-130 is that it develops a high viscosity in saline waters.
  • divalent cations such as Ca 2+ and Mg 2+ or monovalent cations such as Na + and K + .
  • US-A-4,658,898 discloses the use of welan gum S-130 in saline waters.
  • Crosslinking with trivalent cations such as chromium, aluminum, zirconium and iron is also disclosed.
  • crosslinking with organic compounds containing at least two positively charged nitrogen atoms is disclosed in US-A-4, 658,898; while U.S. Serial Number 283,399, filed on December 12, 1988, discloses welan gums crosslinked with phenolic resins or mixtures of phenols and aldehydes.
  • US-A-4,653,585 discloses the use of block copolymers, which may be crosslinked with polyvalent metal ions. for use as permeability control agents in enhanced oil recovery applications.
  • compositions discussed While a number of the different compositions discussed have been proposed for permeability control, some of these compositions may be unsuitable for use as permeability control agents under certain
  • US-A-4, 653,585 may not be effectively crosslinked with polyvalent metal ions under all conditions encountered in the enhanced oil recovery applications, e.g., in acidic conditions commonly found in carbon dioxide (CO 2 ) flooding operations.
  • Polyacrylamides display instability in the presence of high brine concentration at temperatures over 70oC.
  • Xanthan gums are very brine tolerant but display thermal instability, even at temperatures below 60°C.
  • other polymers are unsuitable as permeability control agents when used in conjunction with steam flooding operations. This is due to the fact that they lose their structural
  • Basic to the problem of diverting displacing fluid with polymeric gels is the necessity of placing the polymer where it is needed, i.e. selective penetration into the high permeability zone.
  • the first method is to inject gelled polymer into the formation. This is the so-called surface gelation method.
  • the advantage of this method is that the polymer will enter the loose, more highly permeable zone in preference to the tighter, low permeability zone, due to the high viscosity of the gelled polymer.
  • Another advantage is that gelation is ensured since the gel is prepared at the surface.
  • the polymer gel will not penetrate far enough to block a high pore volume of the designated zone at low pumping pressures and low pumping rates. This is particularly so when a high pressure drop is experienced within a small radius of the injection wellbore. While increasing pumping pressure and/or flow rate could serve to diminish this problem, there are increased risks of fracturing the reservoir and degrading the gel structure by high shear forces, as those skilled in the art will readily understand.
  • the second method is the so-called in-situ
  • an activator reducing agents such as thiourea and bisulfite
  • non-crosslinked polymer slug can also enter the tight zone and cause its blockage, defeating the purpose of the profile control treatment.
  • a further disadvantage of this method is that there is no guarantee that the two slugs of treatment will be placed in the same area and mix well enough to form a strong gel.
  • in-situ gelation involves the injection of polyacrylamide containing chromium in the form of chromate.
  • a reducing agent such as thiourea or sodium thiosulfate is also injected to reduce the chromate in-situ to Cr +3 , a species capable of crosslinking hydrolyzed polyacrylamide.
  • the polyacrylamide solution has a viscosity greater than water, it is not capable of the
  • polyacrylamides crosslinked with chromium in-situ can also go into low permeability zones. It is not useful to crosslink polyacrylamides above ground and inject them as gels, because polyacrylamide gels undergo shear degradation.
  • US-A-4,606,407 discloses a method in which polymers are gelled in a controlled manner through the use of rapid and delayed polyvalent metal gelling agents.
  • the gelling agents disclosed are capable of forming two or more coordinate bonds with donor atoms in the polymers.
  • Polymers disclosed within US-A-4,606,407 as having the requisite donor atoms for forming coordinate linkages include polyacrylamides, other acrylic polymers and polysaccharides.
  • a solution or dispersion of the polymer is first lightly gelled on the surface through the use of the rapid polyvalent metal crosslinking agent.
  • the delayed polyvalent metal crosslinking agent is also added to the solution or dispersion so as to effect complete gelation at a later period of time when the desired depth of penetration has been achieved.
  • a first gel is placed into an aqueous solution in an amount sufficient to enter the pores of a formation's more permeable zones.
  • a gel forms ex-situ and is shear thinning.
  • a second, in-situ-forming gel is combined with the first gel, the second gel substantially more resistant to formation conditions than the first gel.
  • the composition containing ungelled in-situ gel components is directed into the formation's more permeable zones by the selective penetration of the ex-situ gel, where it reheals.
  • a selective ex-situ gel composition capable of gelling over a broad range of pH conditions can be combined with an in-situ gel composition so as to obtain greater selectivity in closing a zone of greater permeability in a formation while forming a gel having substantially better qualities to withstand formation conditions.
  • a pH tolerant aqueous gel-forming composition for placement within a subterranean formation
  • heteropolysaccharide prepared by growing Xanthomonas campestris NCIB 11854 in an aqueous nutrient medium by aerobic fermentation and recovering said
  • heteropolysaccharide in an amount sufficient to cause gelation of said aqueous solution of said Xanthomonas campestris NCIB 11854 heteropolysaccharide.
  • a method for imparting selectivity to an in-situ gel-forming composition for placement within a subterranean oil-bearing formation having relatively high permeability zones and relatively low permeability zones comprising the steps of:
  • a first stage gel-forming composition in an amount effective to selectively enter the relatively high permeability zones of the formation, the first stage composition including a heteropolysaccharide prepared by growing
  • Xanthomonas campestris NCIB 11854 in an aqueous nutrient medium by aerobic fermentation and recovering the heteropolysaccharide and a crosslinking agent for the heteropolysaccharide;
  • composition ex-situ by reacting the Xanthomonas campestris NCIB 11854 heteropolysaccharide with the crosslinking agent for the hetero- polysaccharide;
  • a first stage gel-forming composition in an amount effective to selectively enter the relatively high permeability zones of the formation, the first stage composition including a heteropolysaccharide prepared by growing
  • Xanthomonas campestris NCIB 11854 in an aqueous nutrient medium by aerobic fermentation and recovering the heteropolysaccharide and a crosslinking agent for the heteropolysaccharide;
  • gel-forming composition comprising a water-dispersible polymer and a
  • composition ex- situ by reacting the Xanthomonas campestris NCIB 11854 heteropolysaccharide with the crosslinking agent for the hetero- polysaccharide;
  • step (b) injecting the aqueous-based mixture of step (b) into the relatively high permeability zones within the formation;
  • the present invention provides a two-stage gel system comprised of a pH tolerant first-stage
  • gel-forming composition for selectively entering a high permeability zone of a subterranean formation and transporting a substantially thinner second-stage nonselective gel-forming composition into the high permeability zone.
  • the gel system which does not require the utilization of mechanical isolation for placement within a formation's zone of greater
  • the composition is capable of gelling over a broad range of pH conditions.
  • the present invention is predicated on the
  • heteropolysaccharide prepared from Xanthomonas
  • the ability of this Xanthomonas heteropolysaccharide to gel over a broad pH range is particularly advantageous in the practice of the present invention wherein a two-stage gel system including an ex-situ-forming first stage gel comprising the crosslinked Xanthomonas campestris heteropolysaccharide and an in-situ-forming second stage gel are combined in one system for the purpose of
  • the in-situ gel system can be selected to have a
  • the period of time required for the in-situ gel system to form a gel can be selected by adjusting the initial pH of the overall composition at the time of its formation.
  • a nonselective in-situ gel can be selectively delivered into a target zone of an oil-bearing subterranean formation for subsequent gelation.
  • the ex-situ-forming first stage gel comprising the aforementioned crosslinked Xanthomonas campestris heteropolysaccharide is utilized to obtain selectivity so that the combined gel system can enter zones of greater permeability in a formation.
  • Another gel the in-situ-forming second stage gel, is used to obtain increased rigidity and better temperature stability. Utilization of the combined system permits, in one sequence, to enter a more permeable zone of the formation. In another sequence, the combined system propagates a desired distance into a formation.
  • the two-stage gel system of the present invention is injected into the formation, in the usual case, through an injection well which extends from the surface of the earth into the formation.
  • a production well is situated on a horizontal distance or offset from the injection well so that, once the gel system has been placed in the formation to control the
  • the flooding fluid such as water, carbon dioxide, etc.
  • recovery of the oil displaced by the flooding fluid can be made through the production well.
  • a profile control treatment using the two-stage gel system of the present invention can also be performed by injection of the system through a production well, when desired.
  • the polymer which is used to produce the desired gel may be of natural or synthetic origin. Suitable polymers include acrylic polymers, e.g. polyacrylic acid, polyacrylic acid esters, polyacrylamide, polymethacrylic acid,
  • polymethacrylic acid esters copolymers of unsaturated carboxylic acids, such as acrylic acid or methacrylic acid with olefins such as ethylene, propylene, and butylene, vinyl polymers such as polyvinyl acetate and polyvinyl alcohol, polymers of unsaturated dibasic acids and anhydrides such as maleic anhydride, and their copolymers with other monomers such as ethylene, propylene, styrene and methylstyrene.
  • Other exemplary polymers are described in US-A-3,208,518.
  • Preferred polymers for use in the second stage gel-forming system include the various polyacrylamides and related polymers which are either water-soluble or water- dispersible and which can be used in an aqueous medium with the gelling agents described herein to yield an aqueous gel.
  • These can include the various substantially linear homopolymers and copolymers of acrylamide and methacrylamide.
  • substantially linear is meant that the polymers are substantially free of crosslinking between the polymer chains.
  • the polymers can have up to about 50 percent of the carboxamide groups hydrolyzed to carboxyl groups. However, as the degree of hydrolysis increases, the polymers often become more difficult to disperse in brines, especially hard brines.
  • the degree of hydrolysis increases, the polymers often become more difficult to disperse in brines, especially hard brines.
  • hydrolyzed includes modified polymers wherein the carboxyl groups are in the acid form and also such polymers wherein the carboxyl groups are in the salt form, provided such salts are
  • Such salts include the ammonium salts, the alkali metal salts, and others which are water-dispersible.
  • Hydrolysis can be carried out in any suitable fashion, for example, by heating an aqueous solution of the polymer with a suitable amount of sodium hydroxide.
  • copolymers which can be used for the in-situ-forming second stage gel of the present
  • acrylamide or methacrylamide resulting from the polymerization of acrylamide or methacrylamide with an ethylenically unsaturated monomer. It is desirable that sufficient acrylamide or methacrylamide be present in the monomer mixture to impart to the resulting copolymer water-dispersible properties. Any suitable ratio of monomers meeting this condition can be used. Under proper conditions of use, examples of suitable ethylenically unsaturated monomers include acrylic acid, methacrylic acid, vinylsulfonic acid, vinylbenzylsulfonic acid,
  • a group of copolymers useful in forming the second stage gel system of the present invention are the copolymers of acrylamide or methacrylamide and a monomer such as the well known 2-acrylamido-2-methyl- propanesulfonic acid (AMPS) monomer.
  • AMPS is the registered trademark of the Lubrizol Corporation of Cleveland, OH.
  • Useful monomers, such as the AMPS monomer, and methods for their preparation are
  • alkali metal salts such as sodium 2-acrylamido-2-methylpropane sulfonate are also useful in the practice of this invention. These are also readily available.
  • Copolymers of acrylamide and the AMPS monomer, and/or its sodium salt are known and useful in the practice of this invention.
  • a copolymer see the above-mentioned US-A-3,768,565.
  • a number of these copolymers are available from Hercules Incorporated, Wilmington, Delaware; for example,
  • Hercules SPX-5024 a 90:10 acrylamide/ AMPS sodium salt copolymer; Hercules SPX-5022, an 80:20 acrylamide/AMPS sodium salt copolymer; Hercules SPX-5023, a 50:50 acrylamide/AMPS sodium salt copolymer; and Hercules SPX-5025, a 30:70 acrylamide/AMPS sodium salt
  • copolymers useful in the practice of the invention are the copolymers of acrylamide or methacrylamide with a monomer such as those which are the subject of US-A-3,573,263.
  • These useful monomers include the well known commercially available material (acryloyloxyethyl) diethylmethyl ammonium methyl sulfate, commonly referred to as DEMMS and the commercially available material (methacryloyloxyethyl) trimethylammonium methylsulfate also known as MTMMS.
  • Copolymers of acrylamide with the DEMMS monomer are commercially available, for example, an 80:20 acrylamide/DEMMS copolymer.
  • Copolymers of acrylamide with the MTMMS monomer are also commercially available, for example, Hercules Reten 210, a 90:10
  • a particularly preferred polymeric material for use in the second stage gel system of this invention is the class of high molecular weight vinyl lactum
  • a polymer suitable for use in the second stage nonselective gel system of the present invention is Halliburton's K-Trol polymer, discussed in SPE/DOE paper 14958, entitled “In-Situ Polymerization Controls CO 2 /Water Channeling at Lick Creek", presented at the Fifth SPE/DOE EOR Symposium at Tulsa, Oklahoma on April 20-23, 1988.
  • Hoechst V-2825 and V-3140 polymers are also useful polyacrylamides in which functional groups are incorporated during synthesis. These functional groups can be crosslinked with organic or transitional metal crosslinkers. The composition of the Hoechst polymers is discussed in US-A-4,309,523.
  • a pre-formed phenolic resin can be used; such a resin is generally obtained by the condensation of phenol or substituted phenols with an aldehyde such as formaldehyde, acetaldehyde and furfural.
  • phenol and aldehyde constituents can be added separately to produce the compositions of this invention, rather than being added as a pre-formed phenolic resin.
  • Phenolic compounds suitable for use in the present invention include phenol, resorcinol, catechol, 4,4'-diphenol,
  • Resorcinol and phenol are the preferred phenolics for most water and carbon dioxide drive applications, with phenol being
  • a broad range of water-dispersible aldehydes are useful as a constituent of the phenolic crosslinking agent in the practice of the present invention. It is known that both aliphatic and aromatic monoaldehydes and dialdehydes can be used.
  • the useful aliphatic monoaldehydes include those containing from one to ten carbon atoms per molecule, such as formaldehyde, paraformaldehyda, acetaldehyde, proprionaldehyde, butylaldehyde, isobutylaldehyde, heptaldehyde and others.
  • the useful dialdehydes are glyoxal, glutaraldehyde and terephthaldehyde. Mixtures of the various, aforementioned aldehydes are also useful in the practice of the present invention.
  • formaldehyde is
  • advantageous gels will be in the range of 0.02 to 5.0 weight percent.
  • the amount of the phenol compound used will be in the range of 0.01 to about 2.0 weight percent, with
  • concentrations of 0.05 to 1.0 weight percent preferred concentrations of 0.05 to 1.0 weight percent preferred.
  • concentration of aldehyde used will be in the range of 0.01 to 3.0 weight percent, with concentrations of 0.1 to 1.0 weight percent preferred.
  • aminoplast resins form a class of thermosetting resins produced by the reaction of an amine with an aldehyde.
  • Preferred aminoplast resins include melamine
  • formaldehyde resins which are formed as a reaction product of melamine and formaldehyde.
  • aminoplast resin is employed as the crosslinking agent for the nonselective polymer
  • the preferred polymer for utilization is one having at least one functional group selected from a member of the group consisting of an amine, an amide, a hydroxyl, or a thiol.
  • An aminoplast resin utilized should contain a methylol group and its alkylated varieties which are reactive to such a polymer.
  • Aminoplast resins can be reacted with a crosslinkable polymer in an aqueous medium under substantially all pH conditions, needing no catalyst. This reaction can be carried out at ambient conditions. and also under conditions occurring in a subterranean hydrocarbonaceous formation.
  • Methylated melamine formaldehyde resins derived as a reaction product of melamine and formaldehyde may also be used to crosslink the polymers preferred for use in the gel system of the present invention.
  • Such resins have a molar ratio of between 1-6. A ratio of 3-6 is commonly found in commercial resins.
  • the methylol group, -CH 2 OH and its methylated varieties are reactive to various functional groups such as NH 2 , -CONH 2 , -OH, -SH and can also self-condense to form cured resins. The preparation of these resins is convenient and well documented in preparative polymer manuals.
  • the melamine resin that is utilized in this invention can be a commercial product such as American Cyanamid's Parez resins. Included among these melamine formaldehyde resins which are useful in this invention are the partially methylated resins and the
  • the resin has to be one that is soluble or dispersible in an aqueous medium.
  • Other amino resins can also be used. Examples are urea-formaldehyde, ethylene and propylene urea formaldehyde, triazone, uron, and glyoxal resins.
  • concentrations are from about 0.2 to about 5.0 wt.
  • Amino resins are useful crosslinkers because they (1) are economical to use; (2) can be applied to a wide variety of polymers; (3) form thermally stable, brine tolerant gels; and (4) do not need an acid or base catalyst.
  • a typical formulation for the preferred selective ex-situ-forming crosslinked heteropolysaccharide gel consists of about 2000 ppm of the Xanthomonas
  • campestris NCIB 11854-based heteropolysaccharide and about 100 ppm Cr +3 . As indicated above, such a
  • heteropolysaccharide is prepared by growing Xanthomonas campestris NCIB 11854 in an aqueous nutrient medium by aerobic fermentation and recovering the heteropolysaccharide.
  • the heteropolysaccharide is marketed by the Shell International Chemical Company of London,
  • the selective first-stage gel is capable of being injected into a formation because it is shear thinning and rehealing. Were the gel not preformed prior to injection, the solution could block the low permeability regions which have not been fully swept by a drive fluid. Should this occur, decreased fluid drive injectivity would occur which would reduce oil recovery.
  • the Xanthomonas campestris NCIB 11854-based heteropolysaccharide-Cr gel is reasonably firm with a consistency like that of a gelatin. Due to gel
  • temperature limit for these first-stage gels is about 140-150oF (60-66oC).
  • nonselective gel system may be selected so that they are reasonably unaffected by high saline
  • Nonselective gels can be formed under all pH conditions and are particularly useful in pH conditions of 10 or less.
  • Polymerization retarders can be added to delay gelation so that the nonselective polymer can penetrate the formation to the desired distance.
  • the second stage gel, when formed, can be formulated to be
  • Polymers mentioned in US-A-4,157,322 may also be utilized in the formulation of the second stage gel system. Polymer concentrations will generally range from about 0.1 to about 5.0 wt. percent depending upon the molecular weight of polymer used. Lower molecular weight polymers require a higher polymer concentration to gel. A polymer concentration of about 0.2-5.0 wt. percent is preferred. Use of the method of the present invention produces high integrity polymer gels able to withstand high temperatures and high salinity conditions often found in subterranean hydrocarbonaceous formations.
  • the gelation rate of a system will depend on the amount of the components and the temperature at which the reaction is conducted.
  • the aqueous solution can comprise fresh water, brackish water, sea water, produced formation waters and mixtures thereof.
  • a brine solution comprising sodium chloride in about 1 wt.% to 20 wt.%, preferably about 7.0 wt.% can be utilized.
  • Xanthomonas campestris NCIB 11854-based heteropolysaccharide can be used in an amount of from about 1000 to about 5000 ppm.
  • Chromic ions utilized should be from about 30 to about 300 ppm.
  • Other polyvalent metal ions which can be utilized include aluminum, boron and iron. Alkali metal
  • hydroxides which can be utilized include sodium and potassium hydroxide. Sodium hydroxide is preferred.
  • the amount of alkali or alkaline earth metal hydroxide utilized should be from about 10 to about 1000 ppm, preferably about 100 ppm.
  • a method for making a xanthan gel crosslinked with transitional metal ions, and an alkali or alkaline earth metal hydroxide is disclosed in US-A-4,782,901.
  • the nonselective gel can be comprised of polymer concentrations of from about 0.2 to about 5.0 wt. percent of the above mentioned crosslinkable polymer having the designated functional group.
  • the organic crosslinking agent which crosslinks with the nonselective polymer should be in an amount of from about 0.02 to about 50.0 wt. percent.
  • the stage one gel disappears upon shearing and the stage two gel forms over a period of time of less than a day to several weeks, depending upon pH and temperature.
  • the stage one gel is formed using a Xanthomonas campestris-based heteropolysaccharide and a crosslinking agent for the heteropolysaccharide.
  • this gel sheared to a fluid which easily poured. Ampules of these thin fluids were then aged in ovens at 210, 230 and 250oF (99, 110 and 120oC).
  • Flocon 4800 was used in the examples which follow.
  • Xanthan/Cr gels The gel was sheared in a Waring blender for 30 seconds to a non-viscous foam. This system was sealed in ampules and aged at 210°F and at
  • stage two gels can be pH and temperature dependent.
  • Samples were prepared as described in Example 1, with the exception that aqueous HCl was added to adjust them to various pH values over the range of from 3-5.
  • heteropolysaccharide unexpectedly, form stage one gels over a broader range of pH values.
  • samples were made in accordance with the formulations of Example 2, with the exception of the substitution of the Xanthomonas canpestris NCIB 11854-based hetercpolysaccharide, Shellflo XA, rather than the Xanthomonas campestris NRRL B-1459-based heteropolysaccharide, Flocon 4800, and the samples were adjusted to various values of pH over the range of from 6.6 to 10.53, all formed stage one gels, although the stage one gels having a pH of 7.11 and 7.45 were observed to be looser and less homogeneous than the others. All samples formed good stage two gels in a period of one day to about one week at all temperatures between 210oF to 250oF (99oC to 121oC).
  • heteropolysaccharide can also be pH and temperature dependent.
  • a sample was prepared as described in Example 5, with the exception that the pH was adjusted to a value of 6.58.
  • the stage two gel formed after a period of about two weeks.
  • the stage two gel formed after a period of about one month.
  • This example illustrates a variety of second stage gel systems useful in the formulation of the gel systems of the present invention.
  • the nonselective gel systems shown below may be substituted for the phenol-formaldehyde-crosslinked gel system, above, which employed the Phillips HE-B polymer.
  • Nonselective gels were formed in a 30 wt. % brine solution cmtaining about 1500 ppm Ca(II) and about 500 ppm Mg(II). The gels so formed were stable as determiner, by sustained gel integrity and low gel shrinkage at a temperature of at least about 195oF (91oC) for at least three months. Examples of preferred nonselective gel compositions are set forth below. TABLE VI
  • a Xanthomonas campestris NCIB 11854 heteropolysaccharide-based/Cr gel can be used to selectively deliver a brine tolerant polyacrylamide (such as
  • gels of this invention can be used to plug a previously swept portion of a formation.
  • the gels can be directed to areas of increased permeability by utilization in any of the below methods.
  • One method where gels of this invention can be utilized is during a waterflooding process for the recovery of oil from a subterranean formation. After plugging the more permeable zones of a reservoir with the novel gels of this invention, a waterflooding process can be commenced. US-A-4,479,894 describes one such waterflooding process.
  • Cyclic carbon dioxide steam stimulation can be
  • Increased sweep efficiency can be obtained when the subject gels are used in combination with a carbon dioxide process by lowering the carbon dioxide minimum miscibility pressure ("MMP") and recovering oil. Prior to commencement of the carbon dioxide process, the more permeable zones are plugged with these novel gels.
  • MMP carbon dioxide minimum miscibility pressure

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Composition aqueuse formant un gel et à tolérance de pH, devant être introduite dans une formation souterraine. La composition comprend de l'eau, une quantité d'un hétéropolysaccharide produisant la viscosité et que l'on obtient en faisant pousser du Xanthomonas campestris NCIB 11854 dans un bouillon de culture aqueux par fermentation aérobie et en récupérant l'hétéropolysaccharide, ainsi qu'un agent de réticulation destiné à l'hétéropolysaccharide en une quantité suffisante pour gélifier la solution aqueuse de l'hétéropolysaccharide de Xanthomonas campestris NCIB 11854. On décrit aussi une composition formant un gel en deux étapes et utilisée pour réguler le profil d'une formation souterraine. La composition formant un gel peut être utilisée dans un procédé consistant à conférer la sélectivité à une composition formant un gel in situ et devant être introduite dans une formation pétrolifère souterraine présentant des zones de perméabilité relativement élevée et des zones de perméabilité relativement faible.
PCT/US1991/009451 1990-12-17 1991-12-16 GELS D'HETEROPOLYSACCHARIDE A TOLERANCE DE pH UTILISES POUR LA REGULATION DE PROFIL WO1992011441A1 (fr)

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US628,042 1984-07-05
US62804390A 1990-12-17 1990-12-17
US628,043 1990-12-17
US07/628,042 US5156214A (en) 1990-12-17 1990-12-17 Method for imparting selectivity to polymeric gel systems

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WO1992011441A1 true WO1992011441A1 (fr) 1992-07-09

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CN105733536A (zh) * 2016-02-02 2016-07-06 天津亿利科能源科技发展股份有限公司 生物自修复深度调剖段塞组合及其使用方法
CN115059440A (zh) * 2022-07-08 2022-09-16 中海石油(中国)有限公司 一种油田注水井大尺度多维度剖面调整方法

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CN103821474A (zh) * 2012-11-16 2014-05-28 中国石油天然气股份有限公司 一种超低渗透油藏深部调剖方法
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CN105733536B (zh) * 2016-02-02 2021-06-15 高立红 生物自修复深度调剖段塞组合及其使用方法
CN115059440A (zh) * 2022-07-08 2022-09-16 中海石油(中国)有限公司 一种油田注水井大尺度多维度剖面调整方法
CN115059440B (zh) * 2022-07-08 2024-03-26 中海石油(中国)有限公司 一种油田注水井大尺度多维度剖面调整方法

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