EP3918027A1 - Verfahren zur modifizierung der wasserdurchlässigkeit einer unterirdischen formation - Google Patents

Verfahren zur modifizierung der wasserdurchlässigkeit einer unterirdischen formation

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Publication number
EP3918027A1
EP3918027A1 EP20707499.8A EP20707499A EP3918027A1 EP 3918027 A1 EP3918027 A1 EP 3918027A1 EP 20707499 A EP20707499 A EP 20707499A EP 3918027 A1 EP3918027 A1 EP 3918027A1
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EP
European Patent Office
Prior art keywords
polymer
monomer
formula
group
linear
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20707499.8A
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English (en)
French (fr)
Inventor
Cédrick FAVERO
Olivier Braun
Lionel LAUBER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SNF Group
Original Assignee
SPCM SA
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Filing date
Publication date
Application filed by SPCM SA filed Critical SPCM SA
Publication of EP3918027A1 publication Critical patent/EP3918027A1/de
Pending legal-status Critical Current

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Classifications

    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof

Definitions

  • This invention is in the field of oil and gas recovery from an underground formation. More particularly, the invention relates to a method for modifying the water permeability of a subterranean formation, comprising injecting, into the subterranean formation, an injection fluid comprising at least one encapsulated (co) polymer. in an envelope.
  • the formations sometimes have interesting areas containing hydrocarbons but with strong contrasts in permeabilities or different volume fractions of water.
  • the injected water finds the path with the least resistance to its propagation, that is to say the most relative permeability. favorable to water, to reach production wells quickly, i.e. it passes through areas with a high water volume fraction and / or with a high permeability, thus flowing avoiding d other areas rich in hydrocarbons less favorable to its propagation without pushing them towards production wells.
  • Polymeric solutions are injected into such high permeability and / or high water content areas to replace existing fluids and reduce their water permeability due to their high viscosity. These polymeric solutions, once in their gelled form, are used to divert the flow of water or gas towards the less permeable zones by permanently blocking the zones of high permeability. The blocking of certain areas may indeed prove to be necessary given that they may be the source of water inflows which seriously disturb the recovery of the hydrocarbons.
  • the gel-based processes do not make it possible to easily control either the gelation kinetics or the consistency of the gel; they generate a high risk of damage to the well, they cause the retention and adsorption of the crosslinking agent on the reservoir rock, and they only allow the placement of the gel in areas of high permeability with difficulty while avoiding the invasion of the oil or gas zones by, among other things, the viscosity which they impart to the injected fluid.
  • the problem which the Applicant proposes to solve is the protection against chemical and mechanical degradation of the polymers used during a process for modifying the permeability to water of an underground formation without using crosslinking agents.
  • the invention relates to a method of modifying the permeability to water of a subterranean formation using a (co) polymer capable of viscosifying the injection fluid in the presence of water.
  • the injection fluid comprises at least one linear (co) polymer.
  • the (co) polymer is injected into the subterranean formation in order to modify the permeability of the latter.
  • the invention relates to a process for modifying the water permeability of a subterranean formation comprising petroleum, the process comprising at least the following steps:
  • hydrophilic phase comprising at least one linear (co) polymer E
  • RI, R2, R3 are independently selected from the group consisting of a hydrogen atom, a methyl group and Z-X,
  • ⁇ X is a group selected from alkanolamides, sorbitan esters, ethoxylated sorbitan esters, glyceryl esters, and polyglycosides; and comprising a hydrocarbon chain, saturated or unsaturated, linear, branched or cyclic, optionally aromatic,
  • the fluid comprising a concentration of linear (co) polymer E such that once released and in contact with water, the viscosity of the injection fluid is greater than the viscosity of petroleum present in the training.
  • polymer composed of at least one monomer is meant a polymer obtained from several molecules of at least one monomer.
  • a polymer of a monomer corresponds to a polymer obtained from several repeating units of molecules of a monomer.
  • the dispersion and the injection fluid are devoid of a crosslinking agent.
  • the modification of the underground formation results from the increase in the viscosity of the fluid injected during the release of the polymer E.
  • the polymer E being linear and not crosslinking during its release into the injected fluid, the modification of the formation underground is not due to the gelation of the fluid.
  • the viscosity of the injected fluid is advantageously between 1 and 300 cps, more advantageously between 1 and 250 cps
  • the viscosity of the injected fluid is advantageously between 1 and 15,000 cps, more advantageously between 1 and 13,000 cps.
  • the viscosity of the injected fluid increases with the release of the linear (co) polymer E.
  • the injected fluid in which the (co) linear polymer E is released has a higher viscosity than this same injected fluid in which the linear (co) polymer E is still enveloped by the interfacial polymer.
  • the viscosity of the injected fluid in which the linear (co) polymer E is free (released form) is higher than the viscosity of the petroleum contained in the formation.
  • the dispersion of hydrophilic phase in lipophilic phase is a dispersion of a hydrophilic phase in a lipophilic phase.
  • the lipophilic phase is the continuous phase and the hydrophilic phase is the dispersed phase.
  • the interfacial polymer is placed at the interface between the hydrophilic phase and the lipophilic phase.
  • the hydrophilic phase is an aqueous phase and the lipophilic phase is an oily phase.
  • the composition according to the invention is advantageously a water-in-oil dispersion, more advantageously a water-in-oil emulsion.
  • the interfacial polymer obtained by polymerization of at least one monomer of formula (I) forms an envelope at the interface of the hydrophilic phase and the lipophilic phase.
  • the envelope is resistant to mechanical stresses such as shear and more particularly shear during the dissolution of the polymer, during its injection through valves, nozzles and other restrictions with passage speeds greater than 3 meters per second, or when scanning a subterranean formation near the layer-hole link.
  • the casing is also resistant to chemical stresses which may be due to the presence of oxygen, ESA or metals during the injection phase.
  • the envelope is semi-permeable.
  • the dispersion is preferably in the form of an inverse emulsion.
  • the hydrophilic phase is in the form of dispersed micrometric droplets, advantageously emulsified, in the lipophilic phase.
  • the average size of these droplets is advantageously between 0.01 and 30 mhi, more advantageously between 0.05 and 3 mhi.
  • the interfacial polymer therefore comes to be placed at the interface between the hydrophilic phase and the lipophilic phase at the level of each droplet.
  • the average size of the droplets is advantageously measured with a laser measuring device using conventional techniques which form part of the general knowledge of those skilled in the art. A Mastersizer type device from Malvem can be used for this purpose.
  • the dispersion according to the invention contains between 10 and 65% by mass of (co) polymer, more advantageously between 30 and 60% by mass.
  • the dispersion according to the invention has a hydrophilic phase / lipophilic phase mass ratio advantageously between 0.1 and 100, more advantageously between 1 and 80, and even more advantageously between 10 and 60.
  • the process for preparing the dispersion is described in patent application FR 3,075,219 by the Applicant, cited by reference.
  • the (co) polymer E present in the hydrophilic phase may be a natural (co) polymer, such as, for example xanthan gums, guar gums, schyzophillan, scleroglucan or other compounds of the polysaccharide family, or a ( co) synthetic or semi-synthetic polymer.
  • the (co) polymer is a synthetic (co) polymer.
  • the (co) polymer is a synthetic (co) polymer
  • it is preferably a (co) polymer obtained from at least one nonionic monomer and / or at least one anionic monomer and / or at least a cationic monomer and / or a zwitterionic monomer.
  • the nonionic monomer (s) which can be used within the framework of the invention can be chosen, in particular, from the group comprising vinyl monomers soluble in water.
  • the nonionic monomer does not include the monomers of formula (I).
  • Preferred monomers belonging to this class are, for example, acrylamide, methacrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide and N-methylolacrylamide.
  • N-vinylformamide N-vinyl acetamide, N-vinylpyridine and N-vinylpyrrolidone
  • acryloyl morpholine ACMO
  • glycidyl methacrylate glyceryl methacrylate
  • diacetone acrylamide A preferred nonionic monomer is acrylamide.
  • the anionic monomer (s) are preferably chosen from acrylic acid, methacrylic acid, itaconic acid, maleic acid, acrylamido tertio butyl sulfonic acid (also called ATBS or 2-acrylamido-2-methylpropane sulfonic acid ), vinylsulphonic acid, vinylphosphonic acid, said anionic monomer being unsalted, partially or totally salified, and salts of 3-sulfopropyl methacrylate.
  • the salified form advantageously corresponds to the salts of alkali metals (Li, Na, K ...), of alkaline earth metals (Ca, Mg ...) or of ammonium, in particular quaternary ammoniums.
  • the cationic monomers and the anionic monomers include the unsalted, partially or totally salified forms.
  • the cationic monomer (s) which can be used in the context of the invention can be chosen, in particular from monomers of the acrylamide, acrylic, vinyl, allylic or maleic type having a quaternary ammonium function by salification or quaternization. Mention may be made, in particular and in a non-limiting manner, of quaternized dimethylaminoethyl acrylate (AD AME), quaternized dimethylaminoethyl methacrylate (MADAME), dimethyldiallylammonium chloride (DADMAC), acrylamido propyltrimethyl ammonium chloride (APTAC) , and methacrylamido propyltrimethyl ammonium chloride (MAPTAC).
  • AD AME quaternized dimethylaminoethyl acrylate
  • MADAME quaternized dimethylaminoethyl methacrylate
  • DDADMAC dimethyldiallylammonium chloride
  • ATAC acrylamido
  • the cationic monomer (s) can also be chosen from associative cationic monomers as described in patent FR 2 868 783.
  • the monomer can optionally be a zwitterionic monomer of acrylamide, acrylic, vinyl, allylic or maleic type having an amine or quaternary ammonium function and an acid function of carboxylic, sulphonic or phosphoric type.
  • dimethylammonio dimethylamino propylacrylamide
  • dimethylamino propylacrylamide derivatives of dimethylamino propylacrylamide such as 2 - ((3-acrylamidopropyl) dimethylammonio) ethane-l-sulfonate, 3 - ((3- acrylamidopropyl) dimethylammonio) propane-1-sulfonate, 4- ( (3-acrylamidopropyl) dimethylammonio) butane-1-sulfonate, [3- (acryloyloxy) propyl] (dimethylammonio) acetate, dimethylamino propyl methyl acrylamide derivatives such as 2 - ((3-methacrylamidopropyl) dimethylammonio) ethane-l -sulfonate, 3 - ((3- methacrylamidopropyl) dimethylammonio) propane- 1-sulfonate, 4 - ((3
  • the (co) polymer is composed only of ATBS.
  • the (co) polymer is preferably an anionic (co) polymer based on acrylamide, preferentially a (co) polymer of acrylamide and acrylamido tertio butyl sulfonic acid (ATBS) optionally partially post-hydrolyzed, more preferably a ter ( co) polymer of acrylamide, acrylic acid and acrylamido tertio butyl sulfonic acid (ATBS).
  • ATBS acrylamido tertio butyl sulfonic acid
  • the (co) polymer preferably contains between 10% and 50 mol% of anionic monomer (s), more preferably between 20% and 45 mol%.
  • the (co) polymer preferably contains between 50% and 90 mol% of nonionic monomer (s), more preferably between 60% and 75 mol%.
  • the (co) polymer contains only anionic and nonionic monomeric units. In other words, it is preferably obtained from at least one anionic monomer and at least one nonionic monomer.
  • the (co) polymer can be obtained by any polymerization technique such as conventional radical polymerization, controlled radical polymerization known as RAFT (reversible chain transfer by addition-fragmentation, from the English “reversible-addition fragmentation chain transfer "), NMP (polymerization in the presence of nitroxides, standing for" Nitroxide Mediated Polymerization ”) or ATRP (radical polymerization by atom transfer, standing for" Atom Transfert Radical Polymerization ").
  • RAFT controlled radical polymerization
  • NMP polymerization in the presence of nitroxides, standing for" Nitroxide Mediated Polymerization
  • ATRP radioactive radical polymerization by atom transfer, standing for" Atom Transfert Radical Polymerization
  • the (co) polymer of the hydrophilic phase comprises at least one associative cationic monomer and / or at least one LC ST group.
  • the (co) polymer can comprise at least one LCST group.
  • an LCST group corresponds to a group whose solubility in water for a determined concentration is modified beyond a certain temperature and as a function of the salinity.
  • This is a group exhibiting a transition temperature by heating defining its lack of affinity with the solvent medium.
  • the lack of affinity with the solvent results in an opacification or a loss of transparency which can be due to a precipitation, an aggregation, a gelation or a viscosification of the medium.
  • the minimum transition temperature is called “LCST” (lower critical solubility temperature, from the acronym “Lower Critical Solution Temperature”). For each group concentration at LCST, a heating transition temperature is observed.
  • the (co) polymer can comprise at least one UCST group.
  • a UCST group corresponds to a group whose solubility in water for a determined concentration is modified below a certain temperature and according to the salinity.
  • This is a group exhibiting a cooling transition temperature defining its lack of affinity with the solvent medium.
  • the lack of affinity with the solvent results in opacification or loss of transparency which may be due to precipitation, aggregation, gelation or viscosification of the medium.
  • the maximum transition temperature is called "UCST” (upper critical solubility temperature, from the acronym “Upper Critical Solution Temperature”).
  • UCST upper critical solubility temperature
  • the (co) polymer has an advantageously high molecular weight.
  • high molecular weight denotes molecular weights of at least 1 million g / mol, preferably between 2 and 40 million g / mol, more preferably between 5 and 30 million g / mol. Molecular weight is referred to as weight average molecular weight.
  • the interfacial polymer is obtained from at least one monomer of formula (I):
  • o RI, R2, R3 are independently selected from the group comprising a hydrogen atom, a methyl group and ZX,
  • o X is a group selected from alkanolamides, sorbitan esters, ethoxylated sorbitan esters, glyceryl esters, and polyglycosides; and comprising a hydrocarbon chain, saturated or unsaturated, linear, branched or cyclic, optionally aromatic.
  • X comprises a hydrocarbon chain and a group selected from alkanolamides, sorbitan esters, ethoxylated sorbitan esters, glyceryl esters, and polyglycosides.
  • this hydrocarbon chain comprises C2 to C30 carbon atoms. According to a preferred embodiment, it forms an integral part of the group chosen from alkanolamides, sorbitan esters, ethoxylated sorbitan esters, glyceryl esters, and polyglycosides.
  • X may in particular be one of the following groups: an alkanolamide, preferably of formula diethanolamide monooleate (Witcamide 511), stearoyl ethanolamide (Witcamide 70), oleic acid monoisopropanolamide (Witcamide 61), isostearic acid monoisopropanolamide (Witcamide SPA), coconut monoisopropanolamide (Empilan CLS), coconut monoethanolamide, oleic acid diethanolamide (Mexanyl), or oleyl monoisopropanolamide (Simaline IE 101), a sorbitan ester, for example and not exhaustively a monolaurate sorbitan (Span 20), sorbitan monopalmitate (Span 40), sorbitan monostearate (Span 60), sorbitan monoisostearate (Span 70), sorbitan tristearate (Span 65), sorbitan monooleate (Span 80), sorbitan sesquioleate (
  • the monomer of formula (I) has an HLB value advantageously less than 4.5, and advantageously at least 1.
  • the HLB value (“hydrophilic - lipophilic balance” or hydrophilic / lipophilic balance) makes it possible to quantify the balance existing between the hydrophilic part and the lipophilic part of a molecule. This value is determined by calculating the values of the different parts of the molecule, as described by Griffin in 1949 (Griffin WC, Classification of Surface-Active Agents by HLB, Journal of the Society of Cosmetic Chemists 1 (1949): 311).
  • Mh the molecular mass of the hydrophilic part.
  • the monomer of formula (I) has the following formula: [Chem. l]
  • o RI, R2, R3 are independently a hydrogen atom or a methyl group
  • o X is a group chosen from alkanolamide and sorbitan esters, and comprising a hydrocarbon chain, saturated or unsaturated, linear, branched or cyclic, optionally aromatic.
  • the monomer of formula (1) is chosen from (meth) acrylate of sorbitan monooleate, 2-hydroxypropyl (meth) acrylate of diethanolamide monooleate and glyceryl (meth) acrylate of monooleate of sorbitan.
  • the monomer of formula (I) is the following: [Chem.2]
  • the interfacial polymer according to the invention is obtained by polymerization of at least one monomer of formula (I).
  • the interfacial polymer according to the invention is obtained by polymerization of at least one monomer of formula (I) and of at least one nonionic monomer and / or at least one anionic monomer and / or minus one cationic monomer.
  • the interfacial polymer comprises between 0.0001 and 10%, more advantageously between 0.0001 and 5% even more advantageously from 0.0001 to 1% of monomer of formula (I), by weight relative to the total weight of monomers.
  • the interfacial polymer comprises between 50 and 99.9999%, more advantageously between 60 and 99.9999% of nonionic monomer (different from the monomer of formula (I)) by weight relative to the total weight of monomers.
  • the interfacial polymer comprises between 10 and 99.9999%, more advantageously between 20 and 99.9999% of anionic monomer, by weight relative to the total weight of monomers.
  • the interfacial polymer comprises between 1 and 99.9999%, more advantageously between 10 and 99.9999% of cationic monomer, by weight relative to the total weight of monomers.
  • the interfacial polymer is neither crosslinked nor branched. It is advantageously linear.
  • the interfacial polymer forms an envelope around droplets forming the hydrophilic phase.
  • the interfacial polymer can comprise at least one structural agent.
  • the structural agent is advantageously chosen from diacrylamides or methacrylamides of diamines; acrylic esters of di, tri, or tetrahydroxy compounds; methacrylic esters of di, tri, or tetrahydroxy compounds; divinyl compounds preferably separated by an azo group; diallyl compounds preferably separated by an azo group; vinyl esters of di or trifunctional acids; allylic esters of di or trifunctional acids; methylenebisacrylamide; diallylamine; triallylamine; tetraallylammonium chloride; divinylsulfone; polyethylene glycol dimethacrylate and diethylene glycol diallyl ether.
  • the injection fluid used in the method according to the invention has the functionality of blocking areas of high permeability and / or with a high water content in order to reduce or eliminate the permeability of these areas.
  • the method of modifying the water permeability of a subterranean formation according to the invention comprises the following steps:
  • Operations to modify the water permeability of a reservoir are distinct from enhanced oil recovery techniques.
  • the modification operations are characterized by injections limited in volume of polymer solution in order to create a phenomenon localized in the reservoir, namely, for conformity, a blocking of areas of high permeability and, for stopping the water, a blockage of area where water enters the formation.
  • the injections are generally carried out either via an injection well or via a production well over fairly short durations of a few days and generally less than a month, and with volumes representing less than 5% of the volume of the pores of the reservoir.
  • the pore volume corresponds to the volume not occupied by rock in the reservoir, which allows a correlation with the permeable zone.
  • a person skilled in the art will know how to adapt the minimum volume of fluid injected allowing the water permeability of a reservoir to be modified according to the characteristics of said reservoir.
  • enhanced oil recovery techniques using polymers involve a continuous and prolonged injection of polymer solution in order to sweep the reservoir from an injection well to a production well.
  • the objective is not to treat one area of the reservoir but the reservoir as a whole, in order to recover as much oil as possible. For this, it is necessary to inject a much larger volume of aqueous solution generally representing at least 30% to 500%, or even more, of the pore volume. An oily and sometimes gaseous aqueous mixture is then recovered from the producing wells.
  • the dispersion as described above not only makes it possible to protect the linear (co) polymers E from chemical and mechanical degradation during the stages of preparation and injection of the injection fluid, but also to delay the injection. viscosification of the fluid. These properties are obtained thanks to the envelope formed by the interfacial polymer which, by degrading by hydrolysis, causes the release of the linear (co) polymer E.
  • the injection fluid advantageously comprises between 30 ppm and 50,000 ppm (by weight) of the dispersion or of the concentrated dispersion or of the solid form obtained from the dispersion, more advantageously between 100 and 30,000 ppm, and even more advantageously between 300 and 15,000 ppm.
  • the injection fluid advantageously comprises between 200 ppm and 50,000 ppm (by weight) of (co) polymer E, more advantageously between 250 and 25,000 ppm, and even more advantageously between 500 and 20,000 ppm.
  • the (co) polymer is released, following the degradation of the shell formed by the interfacial polymer under the temperature and / or pH conditions of the underground formation.
  • the (co) polymer included in the hydrophilic phase is protected by the shell formed of at least one interfacial polymer obtained by polymerization of at least one monomer of formula (I), the shell being capable of being degraded in the temperature and / or pH conditions of the subterranean formation.
  • the process according to the invention makes it possible to preserve the polymer from mechanical and chemical degradation (oxygen, metals, LES) linked to the preparation of the composition injected with the polymer, and to its injection, while maintaining good injectivity and good faculty. sealing the permeable areas of the underground formation.
  • the envelope makes it possible to delay the release of (co) polymers.
  • the formation of the injection fluid by introducing the dispersion according to the invention does not make it possible to release the (co) polymer from its envelope, even in the presence of an inverter (surfactant oil in water).
  • the pH and / or the temperature of the subterranean formation allows the hydrolysis of the interfacial polymer and therefore the delayed release of the (co) polymer.
  • the injection fluid can comprise up to 2000 ppm (by weight) of non-enveloped linear (co) polymer (NE).
  • the linear (co) polymer NE may be the same or different from the linear (co) polymer E of the dispersion.
  • the linear (co) polymer NE is obtained from monomers chosen from the respective lists cited previously in the description. linear (co) polymer E of the hydrophilic phase, in the same proportions.
  • the injection fluid comprising the linear (co) polymer E can be injected before, during or after a step of enhanced oil and / or gas recovery.
  • This enhanced oil and / or gas recovery step can optionally be implemented with a fluid of lower viscosity than that of the conformance fluid.
  • the injection fluid is injected into an injection well.
  • the injection fluid is injected into a producing well.
  • Figure 1 is a schematic illustration of linear (co) polymers in a shell formed by an interfacial polymer.
  • Figure 2 illustrates the release of linear (co) polymers from the dispersion of Example 1, measured by the increase in viscosity.
  • Figure 3 illustrates the viscosity, as a function of shear, of the dispersion of Example 2 with the shell formed by the interfacial polymer, without shell and after release of the water-soluble (co) polymer.
  • Part A Preparation of a composition C1 comprising an XI monomer corresponding to formula (I)
  • glycidyl methacrylate 97% by weight aqueous solution
  • oleyl diethanolamide diethanolamide monooleate, Witcamide 511 - Akzo nobel
  • Part B Preparation of a dispersion according to the invention
  • a hydrophilic phase is prepared containing 365.8g of acrylamide (50% aqueous solution by weight), 24.6g of acrylic acid (100%), 234.6g of sodium salt of 2-acrylamido 2-tertio butyl acid. sulfonic acid (50% by weight aqueous solution), 29.0g of deionized water, 25.9g of soda (50% by weight aqueous solution), 1.6g of an aqueous solution of sodium hypophosphite (5g / L), 0.94g of tert-butyl hydroperoxide (0.7% by weight aqueous solution), 0.40g of pentasodium salt of diethylene triamine penta acetic acid (Versenex 80) dispersed in a mixture of 280g of aliphatic hydrocarbon DI 00s (Exxsol DI 00) and 20 g of composition C1 comprising a monomer XI. The pH is adjusted to 6.50.
  • the polymerization is initiated by adding a solution of sodium bisulfite.
  • Part A Preparation of a C2 composition comprising a monomer X2 corresponding to formula (I)
  • glycidyl methacrylate 97% by weight aqueous solution
  • oleyl diethanolamide diethanolamide monooleate, Witcamide 511 - Akzo nobel
  • Part B Preparation of a dispersion without interfacial polymer (counterexample)
  • aqueous phase containing 363.8g of acrylamide (50% aqueous solution by weight), 24.6g of acrylic acid (100%), 234.6g of sodium salt of 2-acrylamido 2-tertio butyl sulfonic acid ( 50% by weight aqueous solution), 29.0g of deionized water, 25.9g of soda (50% by weight aqueous solution), 1.6g of an aqueous solution of sodium hypophosphite (5g / L) , 0.94g of tert-butyl hydroperoxide (0.7% by weight aqueous solution), 0.40g of pentasodium salt of diethylene triamine penta acetic acid (Versenex 80) dispersed in a mixture of 280g of hydrocarbon aliphatic DI 00s (Exxsol D100) and 20g of Witcamide 511. The pH is adjusted to 6.50.
  • the polymerization is initiated by adding a solution of sodium bisulfite.
  • Part C Preparation of a dispersion according to the invention 36 g of acrylamide (50% by weight), 1.6 g of tert-butyl hydroperoxide (0.7% by weight) and 0.6 g of composition C2 comprising a monomer X2 are added to the dispersion obtained in part B.
  • the formation of the interfacial polymer, by polymerization of the monomers of composition C2, is initiated by adding a solution of sodium bisulphite (radical initiator).
  • Example 3 Resistance to mechanical degradation as a function of the polymer concentration
  • Aqueous solutions of linear polymer are produced by adding a dispersion, described in Example 1, at variable polymer concentration, with vigorous stirring in synthetic seawater.
  • Table 1 Viscosity (cp) of aqueous polymer solutions with polymer shell after degradation of the shell as a function of the polymer concentration measured at 10 s 1 and T: 25 ° C.
  • the viscosity of the aqueous polymer solution with a shell remains low and allows injection into the well and propagation to the target area. After degradation of the shell, viscosity can develop and block the high permeability zone.
  • Example 5 Resistance to mechanical degradation as a function of the shear gradient
  • the solutions were sheared by passing them through a small section pipe at different pressures.
  • the shear gradient is determined by measuring the flow at the outlet of a 0.5 mm capillary.
  • the samples are then collected at the outlet of the pipe and the viscosity is measured at 7.3 s 1 and at 25 ° C. on a Kinexus Pro + from Malvem Instruments.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP20707499.8A 2019-02-01 2020-01-29 Verfahren zur modifizierung der wasserdurchlässigkeit einer unterirdischen formation Pending EP3918027A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1901019A FR3092328B1 (fr) 2019-02-01 2019-02-01 Procédé de modification de la perméabilité à l’eau d’une formation souterraine
PCT/FR2020/050135 WO2020157430A1 (fr) 2019-02-01 2020-01-29 Procede de modification de la permeabilite a l'eau d'une formation souterraine

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EP3918027A1 true EP3918027A1 (de) 2021-12-08

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US4683949A (en) 1985-12-10 1987-08-04 Marathon Oil Company Conformance improvement in a subterranean hydrocarbon-bearing formation using a polymer gel
US4745154A (en) * 1986-04-14 1988-05-17 Alco Chemical Corporation Water soluble polymers, their preparation and their uses
CA2015832C (en) * 1989-05-15 2002-05-28 Eric K. Eisenhart Multi-stage polymer particles having a hydrophobically-modified, ionically-soluble stage
FR2868783B1 (fr) 2004-04-07 2006-06-16 Snf Sas Soc Par Actions Simpli Nouveaux polymeres amphoteres associatifs de haut poids moleculaire et leurs applications
AU2009239586B2 (en) * 2008-04-21 2013-10-03 Championx Llc Composition and method for recovering hydrocarbon fluids from a subterranean reservoir
EP2547747A1 (de) * 2010-03-15 2013-01-23 S.P.C.M. Sa Verbessertes ölgewinnungsverfahren mit wasserlöslichen polymeren mit erhöhtem scherwiderstand
RU2017105522A (ru) * 2014-07-24 2018-08-29 Арланксео Сингапур Пте. Лтд. Ультрачистые сополимеры
FR3075219B1 (fr) * 2017-12-14 2019-11-22 S.P.C.M. Sa Composition comprenant un (co)polymere hydrosoluble encapsule dans une enveloppe et son utilisation dans la recuperation assistee du petrole et du gaz

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CO2021010140A2 (es) 2021-08-09
FR3092328A1 (fr) 2020-08-07
US12098325B2 (en) 2024-09-24
AR117967A1 (es) 2021-09-08
CA3127292A1 (en) 2020-08-06
BR112021014261A2 (pt) 2021-09-28
WO2020157430A1 (fr) 2020-08-06
CN113939574A (zh) 2022-01-14
EA202191836A1 (ru) 2021-12-07
US20220145166A1 (en) 2022-05-12
CN113939574B (zh) 2023-08-25
FR3092328B1 (fr) 2021-08-06

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