EP3947558A1 - Emulsion inverse pour la fracturation hydraulique - Google Patents

Emulsion inverse pour la fracturation hydraulique

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Publication number
EP3947558A1
EP3947558A1 EP20713647.4A EP20713647A EP3947558A1 EP 3947558 A1 EP3947558 A1 EP 3947558A1 EP 20713647 A EP20713647 A EP 20713647A EP 3947558 A1 EP3947558 A1 EP 3947558A1
Authority
EP
European Patent Office
Prior art keywords
water
salts
weight
oil
agent
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
EP20713647.4A
Other languages
German (de)
English (en)
French (fr)
Inventor
Cédrick FAVERO
Olivier Braun
Bruno Tavernier
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 EP3947558A1 publication Critical patent/EP3947558A1/fr
Pending legal-status Critical Current

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Classifications

    • 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
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/64—Oil-based compositions
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/32—Polymerisation in water-in-oil emulsions
    • 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
    • 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
    • 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
    • C09K8/80—Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
    • 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
    • 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
    • E21B43/267—Methods for stimulating production by forming crevices or fractures reinforcing fractures by propping
    • 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
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/28—Friction or drag reducing additives

Definitions

  • the present invention relates to the technical field of polymers in the form of a water-in-oil emulsion, otherwise known as an inverse emulsion. More specifically, the subject of the invention is an inverse emulsion containing a cationic polymer which is stable under conditions of very high salinity.
  • aspects of the invention relate to a process for preparing a fracturing fluid and to a process for hydraulic fracturing of unconventional underground oil and gas reservoirs using said inverse emulsion and finally the last aspect of the invention relates to a method of reducing friction of a fracturing fluid in a hydraulic fracturing operation.
  • unconventional underground reservoirs denotes deposits requiring particular extraction technologies because they do not exist in the form of an accumulation in a rock. porous and permeable (see Source rock hydrocarbons in France Provisional report - CGI ET n ° 2011-04-G - Ministry of ecology, sustainable development, transport and housing - April 2011).
  • shale gas or shale gas in English
  • coal bed methane or gas from compact reservoirs or tight gas in English
  • heavy oils or heavy oil in English
  • shale oil or shale oil in English
  • compact reservoir oils or tight oil in English
  • Production techniques have in fact evolved from vertical wells to horizontal wells, reducing the number of production wells required and their footprint on the ground and making it possible to better cover the volume of the reservoir in order to recover the gas as much as possible.
  • the permeabilities are insufficient for the gas to migrate from the source rock to the well easily, and thus to make it possible to produce the gas or oil economically and in quantity. It is therefore necessary to increase the permeability and the production surfaces by stimulation operations and in particular by hydraulic fracturing of the rock in contact with the well.
  • hydraulic fracturing The purpose of hydraulic fracturing is to create additional permeability and generate larger gas or oil production areas. Indeed, the low permeability, the natural barriers of compact layers and waterproofing by drilling operations severely limit production. The gas or oil in the unconventional reservoir cannot easily migrate from the rock to the well without stimulation.
  • Stimulation of the reservoir by hydraulic fracturing consist in injecting water at high pressure and at a very high flow rate so as to create fractures distributed perpendicularly to the production wells. This is usually done in several stages in order to create fractures along the entire length of the horizontal well, which allows the maximum volume of the reservoir to be covered.
  • a propping agent eg sand, plastics or calibrated ceramics
  • sand e.g. sand, plastics or calibrated ceramics
  • friction reducers In order to reduce the hydraulic power required to quickly inject water or brine into the underground formation polymers known as friction reducers are used. The use of such polymers reduces pressure losses due to internal friction in the fluid by up to 70%.
  • Polymers in reverse emulsion form are commonly used for their ease of processing. Their use is based on dissolving the polymer in water or in brine. To do this, the reverse emulsion is reversed, so as to release the polymer contained in the water phase of the reverse emulsion. After release, the polymer is in water or brine to which the reverse emulsion has been added.
  • Fracturing fluids are increasingly based on waters containing significant amounts of dissolved salts.
  • the industry requires friction reducers that work effectively in high brines (brine with a high concentration of dissolved salts), some of which may contain more than 30,000 mg.L -1 of dissolved salts, or even more than 100 000 mg.L -1 with in particular high contents of divalent salts.
  • the invention also relates to a process for preparing a fracturing fluid using the emulsion of the invention.
  • a third aspect of the invention relates to a hydraulic fracturing process, the injection fluid of which has been prepared according to the method of the preceding invention.
  • a last aspect of the invention relates to a method of reducing friction of a fracturing fluid in a hydraulic fracturing operation using the emulsion of the invention.
  • the invention relates first of all to an inverse water-in-oil emulsion comprising:
  • the mass ratio R of the total amount of inversion agent to the total amount of emulsifying agent being greater than 1.8
  • the inversion agent being chosen from an ethoxylated nonylphenol, preferably having between 4 and 10 ethoxylations; an ethoxylated / propoxylated alcohol, preferably having ethoxylations / propoxylations so as to have a total number of carbon between C12 and C25, an ethoxylated tridecyl alcohol and an ethoxylated / propoxylated fatty alcohol.
  • the emulsifying agent being chosen from sorbitan monooleate, polyethoxylated sorbitan esters or diethanolamide of tall oil fatty acids.
  • the oil used to prepare the water-in-oil emulsion of the invention can be a mineral oil, a vegetable oil, a synthetic oil or a mixture of several of these oils.
  • mineral oil are mineral oils containing saturated hydrocarbons of the aliphatic, naphthenic, paraffinic, isoparaffinic, cycloparaffinic or naphthyl type.
  • synthetic oil are hydrogenated polydecene or hydrogenated polyisobutene, an ester such as octyl stearate or butyl oleate.
  • Exxsol ® line of products from Exxon is ideal.
  • the weight ratio of the aqueous phase to the oily phase in the reverse emulsion is preferably from 50/50 to 90/10, and preferably from 70/30 to 80/20.
  • the water-in-oil emulsion preferably comprises 12 to 24% by weight of oil, more preferably 15 to 22% by weight.
  • the water in oil emulsion advantageously comprises 30 to 55% by weight of water, more preferably 35 to 48% by weight.
  • water soluble polymer refers to a polymer which gives an aqueous solution without insoluble particles when dissolved with stirring for 4 hours at 25 ° C and with a concentration of 20 gL-1 in water. .
  • the term "emulsifying agent” denotes an agent capable of emulsifying water in an oil and an “inverting agent” is an agent capable of emulsifying an oil in water. More specifically, it is considered that an inverting agent is a surfactant having an HLB greater than or equal to 10, and an emulsifying agent is a surfactant having an HLB strictly less than 10.
  • the hydrophilic-lipophilic balance (HLB) of a chemical compound is a measure of its degree of hydrophilicity or lipophilicity, determined by calculating the values of different regions 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, 1949, 1, pages 31 1 - 326).
  • Griffin's method based on calculating a value based on the chemical groups of the molecule.
  • Griffin assigned a dimensionless number between 0 and 20 to provide information on water and oil solubility.
  • Substances with an HLB value of 10 are distributed between the two phases, so that the hydrophilic group (molecular mass Mh) is fully projected into the water while the hydrophobic hydrocarbon group (molecular mass Mp) is adsorbed in the non-phase. watery.
  • HLB 20 (Mh / M)
  • the water-in-oil emulsion according to the invention can be prepared according to any method known to those skilled in the art. Generally, an aqueous solution comprising the monomer (s) and the emulsifying agent (s) is emulsified in an oily phase. Then, the polymerization is carried out by adding a free radical initiator.
  • a free radical initiator Reference may be made to redox couples, with cumene hydroperoxide, tertiary butylhydroxyperoxide or persulphates from among the oxidizing agents, sodium sulphite, sodium metabisulphite and Mohr's salt from among the reducing agents.
  • Azo compounds such as 2,2'-azobis (isobutyronitrile) and 2,2'-azobis (2-amidinopropane) hydrochloride can also be used.
  • the polymerization is generally carried out isothermally, adiabatically or at controlled temperature. That is, the temperature is kept constant, usually between 10 and 60 ° C (isothermal), or the temperature is allowed to rise naturally (adiabatic) and in this case the reaction is usually started at a lower temperature. at 10 ° C and the final temperature is generally higher than 50 ° C or, finally, the increase in temperature is controlled so as to have a temperature curve between the isothermal curve and the adiabatic curve.
  • the inverting agent (s) are added at the end of the polymerization reaction, preferably at a temperature below 50 ° C.
  • the emulsion of the invention contains between 12 and 50% by weight of water-soluble polymer (by dry weight), preferably between 12 to 40% by weight and even more preferably between 12 and 30% by weight.
  • the mass ratio R of the total amount of inversion agent to the total amount of emulsifying agent is greater than 1.8, preferably greater than 2, again more preferably greater than 2.5, even more preferably greater than 3, still more preferably greater than 3.5, even more preferably greater than 4.
  • the water-soluble cationic polymer contained in the emulsion of the invention is a copolymer of nonionic and cationic monomers.
  • the nonionic monomers are preferably chosen from acrylamide, methacrylamide, N-alkylacrylamides, N-alkylmethacrylamides, N, N dialkylacrylamides, N, N dialkylmethacrylamides, acrylic esters; methacrylic esters.
  • the preferred nonionic monomer is acrylamide.
  • the cationic monomers are preferably chosen from dimethylaminoethyl acrylate (ADAME) or its quaternized ammonium salts, dimethylaminoethyl methacrylate (MADAME) or its quaternized ammonium salts, dimethyldiallylammonium chloride (DADMAC), chloride d ' acrylamido propyltrimethyl ammonium (APTAC), and methacrylamido propyltrimethyl ammonium chloride (MAPTAC).
  • the quaternized ammonium salts of the ADAME or MADAME monomers are obtained by quaternization with alkyl chlorides, preferably methyl chloride.
  • the preferred cationic monomer is dimethylaminoethyl acrylate quaternized with methyl chloride.
  • the water-soluble cationic polymer is a copolymer of acrylamide and dimethylaminoethyl acrylate quaternized with methyl chloride.
  • the water soluble cationic polymer has an average molecular weight greater than 3 million daltons. Preferably, this average molecular mass is between 3 and 30 million daltons and even more preferably between 8 and 18 million daltons.
  • the "average molecular weight" according to the present invention is determined by the intrinsic viscosity.
  • the intrinsic viscosity can be measured by methods known to those skilled in the art and can in particular be calculated from the values of reduced viscosity for different concentrations by a graphic method consisting in plotting the values of reduced viscosity (on the y-axis ) as a function of the concentrations (on the abscissa axis) and by extrapolating the curve to zero concentration.
  • the intrinsic viscosity value is read on the y-axis or using the least squares method. Then the weight average molecular weight can be determined by the famous Mark-Houwink equation:
  • M represents the molecular weight of the polymer
  • a and K depend on the particular polymer-solvent system.
  • the emulsion of the invention preferably contains between 0.5 and 10% by weight of inversion agent and between 0.5 and 16% by weight of emulsifying agent.
  • the water-in-oil emulsion advantageously comprises from 0.8 to 2% by weight of at least one emulsifying agent.
  • the water-in-oil emulsion preferably comprises from 3 to 6% by weight of at least one inverting agent.
  • the water-in-oil emulsion comprises from 1 to 40% by weight of salts, preferably from 3 to 30% by weight, even more preferably from 5 to 25% by weight and even more preferably from 7 to 17% by weight of salts .
  • the salts present in the water-in-oil emulsion can be, for example, sodium salts, lithium salts, potassium salts, magnesium salts, aluminum salts, ammonium salts, phosphate salts. , sulfate salts, chloride salts, citrate salts, acetate salts, hydrogen phosphate tartrate salts, water soluble inorganic salts or other inorganic salts and mixtures thereof.
  • salts include sodium chloride, sodium sulfate, sodium bromide, calcium chloride, ammonium sulfate, ammonium chloride, lithium chloride, lithium bromide, potassium chloride, potassium bromide, magnesium sulfate, aluminum sulfate, sodium hydrogen phosphate, potassium hydrogen phosphate, and mixtures thereof.
  • Sodium chloride, calcium chloride, ammonium chloride, ammonium sulfate are preferred, and mixtures thereof are more preferred.
  • Another aspect of the invention relates to a process for preparing a fracturing fluid comprising:
  • total salts is meant the total amount of salt in the brine.
  • the brine can contain monovalent and / or polyvalent salts or combinations thereof.
  • salts include, without limitation, sodium, lithium, potassium, aluminum, ammonium, phosphate, sulfate, magnesium, barium, nitrate and other inorganic salts and mixtures thereof.
  • the brine preferably contains at least one of the following: sodium chloride, calcium chloride, sodium bromide, calcium bromide, barium chloride, magnesium chloride, zinc bromide, sodium formate and potassium formate.
  • the brine used for the preparation of the fracturing fluid contains more than 70,000 ppm of salts and preferentially more than 100,000 ppm of salts, preferably the brine contains from 70,000 to 350,000 ppm of salts, preferably 100,000 at 350,000 ppm.
  • the ratio R of the emulsion (step a) is preferably greater than 1.8,
  • the ratio R of the emulsion is preferably greater than 2
  • the ratio R of the emulsion is preferably greater than 2.5,
  • the ratio R of the emulsion is preferably greater than 3,
  • the ratio R of the emulsion is preferably greater than 3.5
  • the ratio R of the emulsion is preferably greater than 4.
  • the divalent ratio R + mass ratio: divalent salts / total salts is greater than or equal to 0.20 and even more preferably R + > 0.25.
  • the inversion of the emulsion of the invention in the brine can advantageously be carried out with the device and the method of document US Pat. No. 8,383,560 where the emulsion is dissolved continuously with a multiple static mixer arrangement.
  • the present invention also relates to the fracturing fluid obtained by the method of the invention, in particular a fracturing fluid comprising:
  • the proppant can be selected without limitation from sand, ceramic, bauxite, glass beads, and resin impregnated sand. It preferably represents from 0.5 to 40%, more preferably from 1 to 25% and even more preferably from 1.5 to 20%, by weight of the fracturing fluid.
  • the fracturing fluid according to the invention preferably comprises between 0.01% and 3% by weight of water-soluble cationic (co) polymer of the invention (added in the form of an emulsion), and even more preferably between 0.05% and 1%, by weight.
  • the brine that makes up the fracturing fluid may include other compounds known to those skilled in the art, such as those cited in SPE 152596, for example:
  • Anti-swelling agents for clays such as potassium chloride, or choline chloride, and / or
  • Biocides to prevent the development of bacteria in particular reducing sulphate, which can form viscous masses reducing the passage surfaces. Mention may be made, for example, of glutaraldehyde, which is the most widely used, or else formaldehyde or isothiazolinones, and / or
  • Oxygen reducers such as ammonium bisulfite to prevent the destruction of other components by oxidation and corrosion of the injection tubes, and / or Anticorrosion additives to protect the tubes against oxidation by residual amounts of oxygen, N, N dimethylformamide being preferred, and / or
  • Lubricants such as oil distillates, and / or
  • Chelating agents for iron such as citric acid, EDTA (ethylenediaminetetraacetic acid), phosphonates, and / or
  • Anti-scale products such as phosphates, phosphonates, polyacrylates or ethylene glycol.
  • the process for preparing a fracturing fluid comprises:
  • an inverse emulsion according to the invention containing at least between 12 and 30% by mass of a water-soluble cationic copolymer containing between 18 and 32 mol% of dimethylaminoethyl acrylate quaternized with methyl chloride and 68 and 82 mol% acrylamide; at least one inversion agent and at least one emulsifying agent, the mass ratio R of the total amount of inversion agent to the total amount of emulsifying agent being greater than 2.5,
  • a third aspect of the invention relates to a method of hydraulic fracturing of an unconventional underground oil or gas reservoir comprising the preparation of a fracturing fluid as described above, and the injection of said fracturing fluid into an underground formation. .
  • the invention relates to a method of fracturing an underground formation comprising:
  • the introduction of the injection fluid into a part of the underground formation bb) the introduction of the injection fluid into a part of the underground formation, cc) the fracturing of the underground formation with the injection fluid, dd) the recovery of a mixture of gas, oil and fluid aqueous.
  • the injection is carried out under pressure so as to create fractures distributed all along the production well.
  • At least one oxidizing compound and / or at least one surfactant compound is injected into the reservoir.
  • bleach aqueous solution of a hypochlorite salt
  • hydrogen peroxide aqueous solution of a hypochlorite salt
  • ozone aqueous solution of a hypochlorite salt
  • chloramines aqueous solution of a hypochlorite salt
  • persulphates permanganates or perchlorates.
  • the chemical nature of the surfactant compound (s) is not critical. They can be anionic, nonionic, amphoteric, zwitterionic and / or cationic.
  • the surface-active compound (s) of the invention carry (s) anionic charges.
  • the surfactant compounds used are chosen from anionic surfactants and their zwitterions chosen from the group comprising derivatives of alkylsulphates, of alkylethersulphates, of arylalkylsulphates, of arylalkylethersulphates, of alkylsulphonates, of alkylethersulphonates, d arylalkylsulfonates, of arylalkylethersulfonates, of alkylphosphates, of alkyletherphosphates, of arylalkylphosphates, of arylalkyletherphosphates, of alkylphosphonates, of alkyletherphosphonates, of arylalkylphosphonates, of alkyletherphosphonates, of arylalkylcarboxylates, of arylalkylcarboxylcarboxylcarboxylates, of arylalkylcarboxylcarboxylcarboxylates, of arylalky
  • a fourth and last aspect of the invention relates to a method of reducing the friction of a fracturing fluid in a hydraulic fracturing operation of an underground reservoir of unconventional oil or gas, comprising the preparation of a fluid fracturing process as described above, and injecting said fracturing fluid into a subterranean formation.
  • the friction reduction makes it possible to reduce or eliminate the losses linked to friction during the injection of the fracturing fluid.
  • the reduction of friction implies that the polymer of the fracturing fluid brings shear thinning properties to the solution in order to have a relatively low viscosity during injection (at high shear) and a high viscosity in order to maintain l proppant suspended at the fracture as the shear decreases.
  • Example 1 Emulsion containing 20% by weight of a polymer comprising 15 mol% of cationic monomers
  • An aqueous phase is prepared with 27.00% by weight of an acrylamide solution (50% by weight in water), 8.12% by weight of solution of ADAME-MC (dimethylaminoethyl quaternized with chloride of methyl, 80% by weight in water), 39.87% by weight of deionized water and 0.02% by weight of Versenex 80.
  • An oily phase is prepared from 23.45% by weight of oil (Exxsol® D100 S) and the following emulsifying agents: 1.16% by weight of Witcamide®51 1 (diethanolamine of tall oil fatty acids ), 0.16% by weight of Span® 80 (sorbitan monooleate) and 0.23% by weight of Tween® 81 (5EO sorbitan monooleate).
  • the water phase is added to the oil phase while mixing to form an emulsion.
  • the resulting dispersion is bubbled with nitrogen for 30 minutes while the temperature is stabilized at 25 ° C, at which time 0.002% by weight of peroxide is added to the emulsion and a 0.075% by weight solution of sodium metabisulfite. (MBS) is introduced into the dispersion at a rate of 0.1 milliliter per minute.
  • the polymerization temperature is controlled between 38 ° C and 42 ° C for about 90 minutes.
  • the residual monomers are trapped by introducing a 0.03% by weight solution of sodium metabisulphite (MBS) at a flow rate of 1.0 milliliter per minute.
  • a water-in-oil polymer emulsion is obtained containing 20% of active copolymer of acrylamide and ADC. 1.75% by weight of an inverting agent (Marlophen® NP 8, nonylphenol and polyethylene glycol 8 EO ethers) is added to the water-in-oil polymer emulsion to facilitate focusing during the process. 'use.
  • the mass ratio R is equal to 1.5.
  • An aqueous phase is prepared with 23.78% by weight of an acrylamide solution (50% by weight in water), 10.14% by weight of solution of ADAME-MC (dimethylaminoethyl quaternized with chloride of methyl, 80% by weight in water), 41.08% by weight of deionized water and 0.02% by weight of Versenex 80.
  • An oily phase is prepared from 23.45% by weight of oil (Exxsol® D100 S) and the following emulsifying agents; 1.16% by weight of Witcamide®51 1 (diethanolamine of tall oil fatty acids), 0.16% by weight of Span® 80 (sorbitan monooleate) and 0.23% by weight of Tween® 81 (monooleate sorbitan 5EO).
  • the water phase is added to the oil phase while mixing to form an emulsion.
  • the resulting dispersion is bubbled with nitrogen for 30 minutes while the temperature is stabilized at 25 ° C, at which time 0.002% by weight of peroxide is added to the emulsion and a 0.075% by weight solution of sodium metabisulphite. (SMBS) is introduced into the dispersion at a rate of 0.1 milliliters per minute.
  • the polymerization temperature is controlled between 38 ° C and 42 ° C for about 90 minutes.
  • the residual monomers are trapped by introducing a 0.03% by weight solution of sodium metabisulfite (SMBS) at a flow rate of 1.0 milliliter per minute.
  • SMBS sodium metabisulfite
  • an inverting agent (Marlophen® NP 8, ethers of nonylphenol and polyethylene glycol 8 EO) is added to the water-in-oil polymer emulsion to facilitate focusing during the process. 'use.
  • the mass ratio R is equal to 1.5.
  • An aqueous phase is prepared with 16.20% by weight of an acrylamide solution (50% by weight in water), 14.87% by weight of solution of ADAME-MC (dimethylaminoethyl quaternized with chloride of methyl, 80% by weight in water), 43.92% by weight of deionized water and 0.02% by weight of Versenex 80.
  • An oily phase is prepared from 23.45% by weight of oil (Exxsol® D100 S) and the following emulsifying agents: 1.16% by weight of Witcamide®51 1 (diethanolamine of tall oil fatty acids) , 0.16% by weight of Span® 80 (sorbitan monooleate) and 0.23% by weight of Tween® 81 (5EO sorbitan monooleate).
  • the water phase is added to the oil phase while mixing to form an emulsion.
  • the resulting dispersion is bubbled with nitrogen for 30 minutes while the temperature is stabilized at 25 ° C, at which time 0.002% by weight of peroxide is added to the emulsion and a 0.075% by weight solution of sodium metabisulfite. (SMBS) is introduced into the dispersion at a rate of 0.1 milliliters per minute.
  • the polymerization temperature is controlled between 38 ° C and 42 ° C for about 90 minutes.
  • the residual monomers are trapped by introducing a 0.03% by weight solution of sodium metabisulfite (SMBS) at a flow rate of 1.0 milliliter per minute. This gives a water-in-oil polymer emulsion containing 20% of active acrylamide / ADC copolymer.
  • an inverting agent (Marlophen® NP 8, nonylphenol and polyethylene glycol 8 EO ethers) is added to the water-in-oil polymer emulsion to facilitate focusing during the process. 'use.
  • the mass ratio R is equal to 1.5.
  • Examples 4 and 7, then 5 and 8 and finally 6 and 9 are produced respectively according to the same process as Examples 1, 2 and 3 but with higher amounts of Marlophen® NP 8 (inverting agent).
  • Table 1 describes the mass ratio R for each example.
  • Friction flow loop test A friction flow loop was constructed from stainless steel tubing with a 1/4 "outside diameter and a total length of 20 feet. The test solutions are pumped to the bottom of the pipe. a 5 liter conical reservoir The solution passes through the tubing and is returned to the reservoir The flow is obtained using a triplex pump fitted with a variable speed drive.
  • 9% CaCh brine corresponds to 9 g of CaCh in 100 ml of water, its R + is equal to 1.00.
  • API brine is defined as being 8.5 g of NaCl + 2.5 g of CaCh in 100 ml of water, its R + being equal to 0.20.
  • the 2 x API brine corresponds to 17 g of NaCl + 5 g of CaCl2 in 100 ml of water, its R + is equal to 0.20.
  • the saline solution is recirculated until the temperature equilibrates to 25 ° C and a stabilized pressure differential is reached. This pressure is recorded as the "initial pressure" of the 9% CaCl2 or API or 2x API brine.
  • the test amount of pure water-in-oil emulsion polymer is quickly injected with a syringe into the sample reservoir containing the 9% CaCh or API or 2xAPI brine and a timer is started.
  • the dose is recorded in gallons of water-in-oil emulsion per thousand gallons of 9% CaCh or API brine or 2 x API (gpt).
  • the pressure is recorded every second for 5 minutes.
  • the percentage of friction reduction (% FRt) at a given time ⁇ is calculated from the initial pressure drop DR ⁇ and the pressure drop at time t, APt, using the equation:
  • the friction reduction performance is improved when the cationicity of the polymer is 20 mol%. Lower cationicity (15%) and higher cationicity (35%) provide lower performance.

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