CN116063616A - Swelling shrinking agent and preparation method and application thereof - Google Patents

Swelling shrinking agent and preparation method and application thereof Download PDF

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CN116063616A
CN116063616A CN202111278556.3A CN202111278556A CN116063616A CN 116063616 A CN116063616 A CN 116063616A CN 202111278556 A CN202111278556 A CN 202111278556A CN 116063616 A CN116063616 A CN 116063616A
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chloride
swelling agent
salt
potassium
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CN116063616B (en
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赵凯强
吴琼
杨超
王晨
孙振峰
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • 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
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    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • C09K8/504—Compositions based on water or polar solvents
    • C09K8/506—Compositions based on water or polar solvents containing organic compounds
    • C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
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    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • C09K8/504—Compositions based on water or polar solvents
    • C09K8/506—Compositions based on water or polar solvents containing organic compounds
    • C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/512—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
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    • 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
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    • 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
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    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/12—Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/18—Bridging agents, i.e. particles for temporarily filling the pores of a formation; Graded salts

Abstract

The invention discloses a swelling agent and a preparation method and application thereof, wherein the swelling agent comprises monomer, acrylamide, amine-containing monomer, initiator, cross-linking agent, short-chain quaternary ammonium salt, inorganic salt, water and optional diallyl amino methyl phosphonate. The preparation method comprises the steps of mixing a monomer, acrylamide, an amine-containing monomer, an initiator, water and optional diallyl amino methyl phosphonate, uniformly mixing, and performing reaction polymerization to obtain a material flow A; then introducing a cross-linking agent to carry out a cross-linking reaction to obtain a material flow B; and uniformly mixing the material flow B, the short-chain quaternary ammonium salt, the inorganic salt and the initiator to obtain the swelling agent. Also provides an application of the swelling agent in the water injection process of the oil field reservoir. The swelling agent can overcome the influence of high-temperature environment on the use effect, has good swelling effect under high-temperature condition, and solves the problem of low swelling rate of the current swelling agent under high-temperature use condition.

Description

Swelling shrinking agent and preparation method and application thereof
Technical Field
The invention belongs to the field of oilfield chemical products, and particularly relates to a swelling agent and a preparation method thereof.
Background
Water injection is one of the important means for improving the recovery ratio of an oil field, however, long-term water injection can cause hydration expansion, dispersion and migration of clay minerals, block oil and gas circulation channels, reduce permeability, increase water injection pressure and reduce petroleum recovery ratio. At present, in the actual production process of oil fields, a method of adding clay stabilizers at the initial stage of water injection is mostly adopted to slow down the damage of clay minerals to reservoirs. However, clay stabilizers have very limited effect on clays that have already been hydrated and swelled. As a clay treating agent, the swelling agent has certain swelling preventing capability, and can recover the hydrated and swelled clay to a certain extent after dehydrating, compressing volume and storing permeability.
In the research report on the swelling agent disclosed at present, the swelling agent is proved to be capable of realizing the application of the swelling agent in a water-sensitive block and obtaining good effects, sun Huahui ' the application of the clay swelling prevention swelling agent in water injection, depressurization and injection increase ', and the average recovery rate of the HD-1 clay swelling prevention agent to two rock cores is 87.06 percent in 25-27 of 2019 of inner Mongolian petrochemical engineering ', and the technology adopts three slugs of depressurization and injection increase liquid: namely a cleaning slug, a deep unblocking and shrinking and swelling slug, and a water unblocking and shrinking and swelling slug of a near wellbore zone. The oil pressure of the well is 19.0MPa, and after the well is opened and filled with water, the well is filled with water for 20m 3 Actual injection of 20m 3 And/d, the oil pressure is 19.0MPa, the injection pressure is reduced by 4MPa, and the injection allocation can be completed. The effective period reaches 15 months, and 5480 parties are added up, so that a good construction effect is achieved.
CN105623636a discloses an anti-swelling and shrinking agent, a preparation method and application thereof, and the provided anti-swelling and shrinking agent comprises the following raw materials in parts by weight in every 50 parts by weight of water: 4-12 parts of quaternary ammonium cationic polymer; 8-22 parts of sulfamic acid; 8-22 parts of inorganic salt. On the basis of the existing complex formulation of inorganic salt and quaternary ammonium cationic polymer, by further complex formulation with sulfamic acid with specific weight parts, the anti-swelling and shrinking expansion rate of a single component to clay is improved by utilizing the synergistic interaction of the components, so that the anti-swelling and shrinking expansion agent has stronger anti-swelling and shrinking expansion effect, and can compress an electric double layer of clay, release partial lattice water of the clay and adsorb water, thereby preventing the damage of water lock to a reservoir.
CN105154034a discloses an anti-swelling and shrinking agent which is an ethylenediamine diacetate solution. The ethylenediamine diacetate solution not only avoids the adverse factors of the traditional large cation capture bridge plug, but also overcomes the adverse factors of small cation charge density and short effective period, has good clay stabilization effect, and simultaneously has good convergence effect on the swelled clay. The anti-swelling and shrinking agent added with magnesium chloride and/or amino trimethylene phosphonic acid has better anti-swelling and shrinking effect after being compounded. The anti-swelling and shrinkage-swelling agent liquid is clear and transparent, has an anti-swelling rate of more than 95 percent and a shrinkage-swelling rate of more than 35 percent, and is suitable for preventing and solving the problem of clay swelling caused by oil field development.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a swelling agent, a preparation method and application thereof, wherein the swelling agent can overcome the influence of a high-temperature environment on the use effect of the swelling agent when in use, has good swelling effect under the high-temperature condition, and solves the problem of low swelling rate of the current swelling agent under the high-temperature use condition.
In order to achieve the aim of the invention, the first aspect of the invention provides a swelling agent, which comprises, by weight, 1-5 parts of monomer, 5-20 parts of acrylamide, 0.1-2 parts of amine-containing monomer, 0.1-1 part of initiator, 0.1-2 parts of cross-linking agent, 1-15 parts of short-chain quaternary ammonium salt, 0.1-15 parts of inorganic salt and 50-400 parts of water; preferably 3 to 5 parts of monomer, 10 to 15 parts of acrylamide, 0.5 to 1 part of amine-containing monomer, 0.2 to 0.6 part of initiator, 0.5 to 1 part of cross-linking agent, 5 to 10 parts of short-chain quaternary ammonium salt, 1 to 5 parts of inorganic salt and 50 to 200 parts of water.
Further, in the swelling agent, the monomer may be one or more of a cationic monomer and/or a zwitterionic monomer. The cationic monomer can be one or more of dimethyl diallyl ammonium chloride, methacryloxyethyl trimethyl ammonium chloride, acryloxyethyl trimethyl ammonium chloride, allyl trimethyl ammonium chloride and N-methyl-N, N, N-tripropenyl ammonium chloride, and is preferably dimethyl diallyl ammonium chloride and/or allyl trimethyl ammonium chloride. The zwitterionic monomer can be one or more of N-methyldiallyl amine propane sulfonate, N-dimethylallyl amine propane sulfonate, 4-vinyl pyridine propane sulfonate, N-methyldiallyl butane sulfonate, methacryloxyethyl-N, N-dimethyl propane sulfonate, and preferably one or more of N-methyldiallyl amine propane sulfonate and N, N-dimethylallyl amine propane sulfonate.
Further, in the swelling agent, the amine-containing monomer is one or more selected from diallyl amine, N-dimethylallyl amine, triallyl amine, N-diethylallyl amine, dimethylallyl amine, methylethyl allyl amine, N-methylallyl amine, 2-methylallyl amine, allyl hydrazine, crotonyl amine, 3-methyl-2-butene-1-amine, preferably one or more selected from diallyl amine, N-dimethylallyl amine and triallyl amine.
Further, in the swelling shrinking agent, the initiator is one or more of cumene hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, di-tert-butyl peroxide, dibenzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile, potassium persulfate, sodium persulfate, potassium persulfate-potassium hydrogen sulfite and ammonium persulfate, preferably one or more of potassium persulfate, sodium persulfate, potassium persulfate-potassium hydrogen sulfite and ammonium persulfate.
Further, in the swelling agent, the crosslinking agent may be one or more selected from epichlorohydrin, epibromohydrin, epichlorohydrin, and epibromohydrin, and preferably one or more selected from epichlorohydrin and epibromohydrin.
Further, in the swelling agent, the short-chain quaternary ammonium salt is a quaternary ammonium salt of C2-C18, has at least one carbon-carbon double bond (preferably contains one or two carbon-carbon double bonds), and can also optionally have a heteroatom, wherein the heteroatom is O and/or P; the anion of the quaternary ammonium salt can be one or more of Cl, br, I, F, OH. Still further, the short-chain quaternary ammonium salt may be specifically selected from one or more of allyltrimethylammonium, allyltrimethylammonium bromide, dimethyldiallylammonium chloride, methacryloxyethyltrimethylammonium chloride, (3-acrylamidopropyl) trimethylammonium chloride, trimethylvinylammonium bromide, 3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate, 2-methacryloxyethyl phosphorylcholine, trimethylvinylammonium hydroxide, dimethylbenzyl-2-methamidoethyl acrylate chloride, preferably one or more of allyltrimethylammonium, allyltrimethylammonium bromide, dimethyldiallylammonium chloride.
Further, in the above swelling reducing agent, the inorganic salt may be one or more of sodium salt, potassium salt, ammonium salt, magnesium salt, and the inorganic salt may be one or more of sodium sulfate, sodium carbonate, sodium chloride, sodium nitrate, potassium chloride, potassium nitrate, potassium carbonate, potassium sulfate, ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, ammonium iodide, magnesium chloride, magnesium sulfate, and magnesium nitrate; preferably one or more of sodium sulfate, sodium chloride, potassium chloride, magnesium sulfate and ammonium chloride.
Further, the swelling agent also comprises 0.5 to 2 parts of diallyl amino methyl phosphonate with a molecular formula of C 7 H 12 NO 3 PM 2 、C 7 H 12 NO 3 PL、(C 7 H 12 NO 3 P) 3 X 2 、(C 7 H 12 NO 3 P) 2 Y is one or more of monovalent metals, specifically IAOne or more of the group metals may preferably be sodium and/or potassium, more preferably sodium; l is one or more of divalent metals, and can be selected from one or more of magnesium, calcium, copper and ferrous iron; x is one or more of trivalent metals, and can be selected from one or more of iron and aluminum; y is one or more of tetravalent metals, and can be specifically selected from one or more of titanium and zirconium; the molecular structural formula is at least one of the following formulas:
Figure BDA0003330451310000041
In another aspect, the present invention provides a method for preparing a swelling agent, comprising the steps of:
(1) Under the contact condition, mixing a monomer, acrylamide, an amine-containing monomer, an initiator, water and optional diallyl amino methyl phosphonate uniformly, and performing reaction polymerization to obtain a material flow A;
(2) Introducing a cross-linking agent into the solution A obtained in the step (1), and obtaining a material flow B after a cross-linking reaction;
(3) And (3) under the contact condition, uniformly mixing the material flow B obtained in the step (2), the short-chain quaternary ammonium salt, the inorganic salt and the initiator to obtain the swelling agent.
Further, in the preparation method of the swelling agent, the reaction conditions in the step (1) are as follows: the reaction temperature is 40-90 ℃, preferably 55-75 ℃; the reaction time is 1 to 6 hours, preferably 2 to 4 hours.
Further, in the preparation method of the swelling agent, the dosage of the monomer, the acrylamide, the amine-containing monomer, the initiator, the cross-linking agent, the short-chain quaternary ammonium salt, the inorganic salt, the water and the diallyl amino methyl phosphonate is 1 to 5 parts of the monomer, 5 to 20 parts of the acrylamide, 0.1 to 2 parts of the amine-containing monomer, 0.1 to 1 part of the initiator, 0.1 to 2 parts of the cross-linking agent, 1 to 15 parts of the short-chain quaternary ammonium salt, 0.1 to 15 parts of the inorganic salt, 50 to 400 parts of the water and 0.5 to 2 parts of the diallyl amino methyl phosphonate (when the diallyl amino methyl phosphonate is contained, the content is at least 0.2 parts); preferably 3 to 5 parts of monomer, 10 to 15 parts of acrylamide, 0.5 to 1 part of amine-containing monomer, 0.2 to 0.6 part of initiator, 0.5 to 1 part of cross-linking agent, 5 to 10 parts of short-chain quaternary ammonium salt, 1 to 5 parts of inorganic salt, 50 to 200 parts of water and 0.5 to 1 part of diallyl amino methyl phosphonate.
Further, in the preparation method of the swelling agent, the crosslinking reaction conditions in the step (2) are as follows: the reaction temperature is 40-90 ℃, preferably 50-70 ℃; the reaction time is 1 to 6 hours, preferably 2 to 5 hours.
In the preparation method of the swelling agent, the initiator in the step (1) and the initiator in the step (3) can be the same or different, and the dosage ratio of the initiator in the step (1) to the initiator in the step (3) is 1:1 to 1:9.
further, in the above-mentioned method for producing a swelling agent, the mixing in the step (3) may be carried out at room temperature, and the temperature may be usually 10 to 40 ℃, preferably 20 to 30 ℃.
Further, in the preparation method of the swelling agent, the monomer may be one or more of a cationic monomer and/or a zwitterionic monomer. The cationic monomer can be one or more of dimethyl diallyl ammonium chloride, methacryloxyethyl trimethyl ammonium chloride, acryloxyethyl trimethyl ammonium chloride, allyl trimethyl ammonium chloride and N-methyl-N, N, N-tripropenyl ammonium chloride, and preferably one or more of dimethyl diallyl ammonium chloride and allyl trimethyl ammonium chloride. The zwitterionic monomer is one or more of N-methyldiallylamine propane sulfonate, N-dimethylallylamine propane sulfonate, 4-vinylpyridine propane sulfonate, N-methyldiallyl butane sulfonate, methacryloxyethyl-N, N-dimethylpropane sulfonate, preferably one or more of N-methyldiallylamine propane sulfonate and N, N-dimethylallylamine propane sulfonate.
Further, in the preparation method of the swelling agent, the amine-containing monomer is selected from one or more of diallyl amine, N-dimethyl allyl amine, triallyl amine, N-diethyl allyl amine, dimethyl allyl amine, methylethyl allyl amine, N-methyl allyl amine, 2-methyl allyl amine, allyl hydrazine, crotonamine, 3-methyl-2-butene-1-amine, preferably one or more of diallyl amine, N-dimethyl allyl amine and triallyl amine.
Further, in the preparation method of the swelling agent, the initiator is one or more of cumene hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, di-tert-butyl peroxide, dibenzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile, potassium persulfate, sodium persulfate, potassium persulfate-potassium hydrogen sulfite and ammonium persulfate, preferably one or more of potassium persulfate, sodium persulfate, potassium persulfate-potassium hydrogen sulfite and ammonium persulfate.
Further, in the preparation method of the swelling agent, the crosslinking agent may be one or more selected from epichlorohydrin, epibromohydrin, epichlorohydrin, and epibromohydrin, and preferably one or more selected from epichlorohydrin and epibromohydrin.
Further, in the preparation method of the swelling agent, the short-chain quaternary ammonium salt is a quaternary ammonium salt of C2-C18, has at least one carbon-carbon double bond, preferably contains one or two carbon-carbon double bonds, can also optionally have a heteroatom, the heteroatom is O and/or P, and the anion of the quaternary ammonium salt can be one or more than one of Cl, br, I, F, OH. Still further, the short-chain quaternary ammonium salt may be specifically selected from one or more of allyltrimethylammonium, allyltrimethylammonium bromide, dimethyldiallylammonium chloride, methacryloxyethyltrimethylammonium chloride, (3-acrylamidopropyl) trimethylammonium chloride, trimethylvinylammonium bromide, 3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate, 2-methacryloxyethyl phosphorylcholine, trimethylvinylammonium hydroxide, dimethylbenzyl-2-methamidoethyl acrylate chloride, preferably one or more of allyltrimethylammonium, allyltrimethylammonium bromide, dimethyldiallylammonium chloride.
Further, in the preparation method of the swelling agent, the inorganic salt may be one or more of sodium salt, potassium salt, ammonium salt and magnesium salt, preferably one or more of sodium salt, potassium salt, ammonium salt and magnesium salt, and the inorganic salt may be one or more of sodium sulfate, sodium carbonate, sodium chloride, sodium nitrate, potassium chloride, potassium nitrate, potassium carbonate, potassium sulfate, ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, ammonium iodide, magnesium chloride, magnesium sulfate and magnesium nitrate; preferably one or more of sodium sulfate, sodium chloride, potassium chloride, magnesium sulfate and ammonium chloride.
Further, in the preparation method of the swelling agent, the molecular formula of the diallylaminomethyl phosphonate is C 7 H 12 NO 3 PM 2 、C 7 H 12 NO 3 PL、(C 7 H 12 NO 3 P) 3 X 2 、(C 7 H 12 NO 3 P) 2 Any one of Y, wherein M is one or more of monovalent metals, particularly one or more of group IA metals, preferably sodium and/or potassium, more preferably sodium; l is one or more of divalent metals, and can be selected from one or more of magnesium, calcium, copper and ferrous iron; x is one or more of trivalent metals, and can be selected from one or more of iron and aluminum; y is one or more of tetravalent metals, and can be specifically selected from one or more of titanium and zirconium; the molecular structural formula is at least one of the following formulas:
Figure BDA0003330451310000071
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further, the preparation method of the diallyl amino methyl phosphonate comprises the following steps:
(1) Mixing an organic solvent and phosphorous acid, and then adjusting the pH value of a reaction system to be not more than 7;
(2) Slowly adding diallylamine into the reaction system in the step (1) for reaction;
(3) Slowly adding aldehyde into the system after the reaction in the step (2) to react;
(4) And (3) regulating the pH value of the system after the reaction in the step (3) to 6-8, continuing the reaction, further separating the reaction product, and drying the separated solid phase to obtain the product.
Further, in the above preparation method, the organic solvent in the step (1) may be one or more of alcohol, ester, ether and ketone; further, the carbon number of the alcohol, the ester, the ether and the ketone can be 1-12, and specifically can be one or more selected from methanol, ethanol, butanol, ethyl acetate, butyl acetate, isoamyl acetate, diethyl ether, butyl ether, acetone and methyl ethyl ketone.
Further, in the above preparation method, the volume ratio of the organic solvent to the phosphorous acid in the step (1) is 1 to 1:1 to 15, preferably 1 to 2:1 to 8.
In the above production method, the pH of the reaction system in the step (1) is adjusted to 1 to 6.8, preferably to 1 to 4, more preferably to 1 to 3. Further, the pH value of the reaction system can be adjusted by adding acidic substances, and the acidic substances can be inorganic acid and/or organic acid, and can be one or more of hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, glacial acetic acid, carbonic acid, hydrofluoric acid, citric acid, malic acid, tartaric acid, succinic acid and the like.
Further, in the above preparation method, the reaction temperature in the step (2) is-20 to 10 ℃, preferably-10 to 5 ℃.
Further, in the above preparation method, the slowly adding diallylamine in the step (2) may be performed by dropwise addition, and it is further preferable to perform the dropwise addition at a rate of 10mL/h to 200 mL/h.
Further, in the above preparation method, the aldehyde in the step (3) may be one or more of formaldehyde, dimeric formaldehyde, trimeric formaldehyde and paraformaldehyde, preferably formaldehyde is used. The aldehyde is preferably added in liquid form, as when formaldehyde is used, it can be added directly in liquid form; when dimeric formaldehyde, trioxymethylene and paraformaldehyde are adopted, the dimeric formaldehyde and the paraformaldehyde can be firstly dissolved in an organic solvent and then added in a liquid form, and the organic solvent can be one or more of alcohol, ester, ether and ketone; further, the carbon number of the alcohol, the ester, the ether and the ketone can be 1-12, and specifically can be one or more selected from methanol, ethanol, butanol, ethyl acetate, butyl acetate, isoamyl acetate, diethyl ether, butyl ether, acetone and methyl ethyl ketone.
Further, in the above preparation method, the slowly adding aldehyde in the step (3) may be performed by dropwise addition, and more preferably by dropwise addition at a dropping rate of 10mL/h to 200 mL/h.
Further, in the above preparation method, the reaction temperature in the step (3) is-20 to 10 ℃, preferably-10 to 5 ℃.
Further, in the preparation method, in the step (4), the pH value of the system is adjusted to 6-8 by adding an alkaline substance, wherein the alkaline substance may be an inorganic base and/or an alkaline inorganic salt, and the metal in the inorganic base and/or the alkaline inorganic salt is one or more selected from monovalent, divalent, trivalent and tetravalent metal elements, more specifically one or more selected from sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, magnesium hydroxide, magnesium carbonate, calcium hydroxide, iron hydroxide, copper hydroxide, titanium hydroxide, zirconium hydroxide and the like, and preferably one or more selected from sodium hydroxide and potassium hydroxide.
Further, in the above preparation method, the reaction temperature in the step (4) is 0 to 90 ℃, preferably 20 to 40 ℃; the reaction time is 0.5 to 6 hours, preferably 1 to 3 hours.
In the preparation method, the separation in the step (4) is solid-liquid separation, and the solid-liquid separation can be any means capable of realizing solid-liquid two-phase separation, and the selection of the solid-liquid separation means belongs to the requisite basic skills of the person skilled in the art, so that the solid-liquid separation can be reasonably selected according to practical situations, and particularly, one or more modes of filtration separation, centrifugal separation and the like can be adopted.
In the preparation method, the liquid phase separated in the step (4) can be recycled to the step (1) for continuous use, and the reaction is continued after other raw materials are supplemented.
In the preparation method, the drying temperature in the step (4) is 60-120 ℃ and the drying time is 6-12 h.
Further, in the preparation method, the molar ratio of the diallylamine to the phosphorous acid to the aldehyde is that the diallylamine: phosphorous acid: aldehyde=1: (1-2): (1-2), preferably 1:1 to 1.5:1 to 1.5.
The invention also provides a swelling shrinking agent obtained by adopting the preparation method.
The invention also provides an application of the swelling reducer or the swelling reducer obtained by the preparation method in the water injection process of the oilfield reservoir. Further, the addition amount of the swelling agent is generally 0.5 to 5wt% of the water amount when specifically used, and the swelling agent can be used at 20 to 100 ℃.
The swelling agent, the preparation method and the application thereof have the following advantages:
1. in the research process, the applicant finds that under the high temperature condition, the thermal movement of the clay mineral flaky particles can be obviously enhanced, the capability of water molecules penetrating into the clay crystal layer is enhanced, meanwhile, the cation diffusion capability of the clay surface and the crystal layer is enhanced, and the small molecular swelling reducer is easy to diffuse out of the crystal layer due to the influence of the Brownian movement, so that the swelling rate is reduced. The short-chain quaternary ammonium salt contained in the swelling agent provided by the invention is initiated by the initiator after entering the crystal layers, so that the short-chain quaternary ammonium salt is polymerized under the high temperature condition, long-chain quaternary ammonium salt is not easy to separate from the crystal layers, and water is extruded, so that the swelling rate under the high temperature condition is improved, and the technical problem that the current swelling agent is low in swelling rate when being used under the high temperature condition is solved.
2. The swelling shrinkage agent provided by the invention has good anti-swelling performance, and the macromolecular material obtained through crosslinking can prevent hydration of water to clay when being adsorbed on particle surfaces, and has a certain bridging effect when being compounded with inorganic salt, so that a plurality of clay particles can be adsorbed and wrapped at the same time, clay migration in the water injection process is reduced, and pore channels are prevented from being blocked due to migration.
3. The water quality in the water injection well has high mineralization degree, and scaling is easy to form to block a seepage channel, so that the permeability is reduced. The diallyl amino methyl phosphonate has strong coordination capability and chelating capability, and can generate stable chelate with cations such as calcium and the like, thereby preventing the diallyl amino methyl phosphonate from contacting with scale forming anions such as carbonic acid anions and the like, greatly reducing the scale forming probability, and preventing the reduction of permeability caused by scale formation.
4. The swelling agent provided by the invention has the advantages of no generation of waste liquid and waste solid in the preparation process, simple preparation method, green and environment-friendly characteristics, and the product can be directly added into a reservoir for use.
Drawings
FIG. 1 is a chart showing the external appearance of a swelling agent-like magenta spectrum obtained in example 4 of the present invention.
FIG. 2 is a chart showing the hydrogen nuclear magnetic resonance spectrum of a sample of the swelling agent obtained in example 4 of the present invention.
Detailed Description
The operation and effects of the method of the present invention will be further described with reference to specific examples and comparative examples, but the following examples do not limit the method of the present invention.
Throughout the specification and claims, unless explicitly stated otherwise, the term "comprise" or variations thereof such as "comprises" or "comprising", etc. will be understood to include the stated element or component without excluding other elements or other components.
In this document, all numerical values of a parameter (e.g., quantity or condition) are to be understood as being modified in all instances by the term "about," whether or not "about" actually occurs before the numerical value.
Example 1
Preparation of sodium diallylaminomethyl phosphonate
Adding 5.7g of phosphorous acid and 7mL of absolute ethyl alcohol into a reaction vessel, adding 2mL of concentrated sulfuric acid (with the concentration of 98 wt%) to adjust the pH value of the system to 1, then placing the reaction vessel into an ice-water bath, dropwise adding 8.6mL of diallylamine through a constant dropping funnel, controlling the dropwise adding within 45min, continuing to reflux for 2h after the dropwise adding is finished, adding a mixed material of 12.6g of paraformaldehyde and 7mL of absolute ethyl alcohol through a constant dropping funnel, dropwise adding and controlling the dropwise adding to 20min, continuing to reflux for 3h after the dropwise adding is finished, adding 5.6g of NaOH into the system, adjusting the pH value of the system to 7, reacting at 20 ℃ for 1h, further centrifugally separating through a centrifugal machine, and drying the obtained solid phase material at 80 ℃ for 10h to obtain a target product with the yield of 91.1%, wherein the product purity is 98.5%.
Example 2
Preparation of diallylaminomethyl potassium phosphonate
11.4g of phosphorous acid and 7mL of absolute ethyl alcohol are sequentially added into a reaction container, then 3mL of concentrated nitric acid (with the concentration of 70 wt%) is added to adjust the pH value of the system to 1, then the reaction container is placed into an ice water bath, 8.6mL of diallylamine is dropwise added through a constant dropping funnel, the dropwise addition is controlled to be completed within 45min, and the reflux reaction is continued for 2.5h after the dropwise addition is completed. Then, a mixture of 6.3g of paraformaldehyde and 7mL of absolute ethyl alcohol is added into a constant dropping funnel, the mixture is dropwise added and controlled to be added for 10min, and the reflux reaction is continued for 1.5h after the addition is completed. Then adding 5.6g of KOH into the system to adjust the pH value of the system to 7, reacting for 2.5 hours at 20 ℃, further centrifugally separating by a centrifugal machine, and further drying the obtained solid phase material at 80 ℃ for 10 hours to obtain the target product, wherein the yield is 90.0% and the purity is 98.2%.
Example 3
Preparation of magnesium diallylaminomethyl phosphonate
11.4g of phosphorous acid and 7mL of butanol are sequentially added into a reaction container, 5mL of oxalic acid is added to adjust the pH value of the system to 3, then the reaction container is placed into an ice-water bath, 8.6mL of diallylamine is dropwise added through a constant dropping funnel, the adding is controlled to be completed within 45min, and reflux reaction is continued for 2.5h after the adding is completed. Subsequently, a mixture of 10.6g of paraformaldehyde and 7mL of butanol was added via a constant dropping funnel, and the addition was gradually dropped and controlled to be completed at 10 min. After the completion of the dropwise addition, the reflux reaction was continued for 1.5 hours, and then Mg (OH) was added to the system 2 8.8g, regulating the pH value of the system to 7.5, reacting for 2.5 hours at 20 ℃, further centrifugally separating by a centrifugal machine, and further drying the obtained solid phase material at 80 ℃ for 10 hours to obtain the target product, wherein the yield is 92.0% and the purity is 98.3%.
Example 4
20g of acrylamide, 5g of dimethyl diallyl ammonium chloride, 1g of diallyl amine, 1g of diallyl amino methyl phosphonate and 0.2g of potassium persulfate are respectively added into 350g of water to obtain a mixed solution, the temperature is raised to 65 ℃ for reaction for 4 hours, then 1.2g of epichlorohydrin is added, the stirring is continued for 2 hours, and the solution A is obtained after cooling to normal temperature. Then 10g of allyl trimethyl ammonium chloride, 3g of ammonium chloride and 0.3g of potassium persulfate are added into the solution A to obtain a final product, an infrared spectrum of a sample is shown in figure 1, and a hydrogen nuclear magnetic resonance spectrum of the sample is shown in figure 2.
Example 5
10g of acrylamide, 2.0g of allyl trimethyl ammonium chloride, 0.4g of N, N-dimethyl allylamine, 0.5g of diallyl amino methyl phosphonic acid potassium and 0.1g of potassium persulfate are respectively added into 200g of water to obtain mixed solutions, the mixed solutions are heated to 55 ℃ for reaction for 6 hours, then 1.0g of epichlorohydrin is added, the temperature is raised to 70 ℃, stirring is continued for 2 hours, and the solution A is obtained after cooling to normal temperature. Subsequently, 5g of allyl trimethylammonium bromide, 2g of ammonium chloride, and 0.3g of potassium persulfate were added to the solution A to obtain the final product.
Example 6
20g of acrylamide, 3g of methacryloyloxyethyl trimethyl ammonium chloride, 1.5g of triallylamine, 0.5g of diallyl amino methyl phosphonate and 0.2g of ammonium persulfate are respectively added into 300g of water to obtain mixed solutions, the temperature is raised to 75 ℃, the reaction is carried out for 3 hours, then 1.5g of epichlorohydrin is added, the temperature is raised to 85 ℃, stirring is continued for 1 hour, and the solution A is obtained after cooling to normal temperature. 10g of allyl trimethylammonium chloride, 3g of ammonium chloride, and 0.4g of ammonium persulfate were then added to the solution A to obtain the final product.
Example 7
10g of acrylamide, 3g of acryloyloxyethyl trimethyl ammonium chloride, 0.6g of N, N-diethyl allylamine, 0.5g of diallyl amino methyl phosphonic acid potassium and 0.1g of ammonium persulfate are respectively added into 200g of water to obtain mixed solutions, the temperature is raised to 80 ℃ for reaction for 2 hours, then 1.0g of epoxy bromopropane is added, the temperature is reduced to 60 ℃, stirring is continued for 3 hours, and cooling is carried out to normal temperature to obtain a solution A. Subsequently, 8g of dimethyldiallylammonium chloride, 5g of magnesium sulfate and 0.4g of ammonium persulfate were added to the solution A to obtain the final product.
Example 8
20g of acrylamide, 5g of N-methyldiallylamine propanesulfonate, 2g of methylethylallylamine, 2g of magnesium diallylaminomethyl phosphonate and 0.3g of sodium persulfate are respectively added into 400g of water to obtain a mixed solution, the temperature is raised to 70 ℃, the reaction is carried out for 4 hours, then 2.0g of epoxy chlorobutane is added, the temperature is reduced to 40 ℃, stirring is continued for 6 hours, and the solution A is obtained after cooling to normal temperature. 15g of dimethyldiallylammonium chloride, 15g of potassium chloride and 0.5g of sodium persulfate were then added to solution A to give the final product.
Example 9
5g of acrylamide, 2g of N, N-dimethylallylamine propanesulfonate, 0.1g of g N-methylallylamine, 0.5g of magnesium diallylaminomethyl phosphonate and 0.05g of sodium persulfate are respectively added into 80g of water to obtain mixed solutions, the temperature is raised to 60 ℃, the reaction is carried out for 5 hours, then 0.3g of epichlorohydrin is added, stirring is continued for 4 hours, and the solution A is obtained after cooling to normal temperature. Subsequently, 3g of methacryloyloxyethyl trimethyl ammonium chloride, 1g of ammonium chloride, and 0.1g of sodium persulfate were added to the solution A to obtain a final product.
Example 10
Respectively adding 18g of acrylamide, 4.5g of dimethyl diallyl ammonium chloride, 0.9g of diallyl amine and 0.2g of potassium persulfate into 240g of water to obtain a mixed solution, heating to 65 ℃, reacting for 4 hours, then adding 1.0g of epichlorohydrin, continuously stirring for 2 hours, and cooling to normal temperature to obtain a solution A. Subsequently, 9g of allyl trimethyl ammonium chloride, 2.5g of ammonium chloride, and 0.25g of potassium persulfate were added to the solution A to obtain the final product.
Example 11
8g of acrylamide, 1.6g of allyl trimethyl ammonium chloride, 0.35g of N, N-dimethyl allyl amine and 0.1g of potassium persulfate are respectively added into 160g of water to obtain a mixed solution, the temperature is raised to 55 ℃, the reaction is carried out for 6 hours, then 0.9g of epichlorohydrin is added, the temperature is raised to 70 ℃, stirring is continued for 2 hours, and the solution A is obtained after cooling to normal temperature. Subsequently, 4.5g of allyl trimethylammonium bromide, 1.6g of ammonium chloride, and 0.25g of potassium persulfate were added to the solution A to obtain a final product.
Example 12
15g of acrylamide, 2.3g of methacryloxyethyl trimethyl ammonium chloride, 1.2g of triallylamine and 0.25g of ammonium persulfate are respectively added into 220g of water to obtain a mixed solution, the temperature is raised to 75 ℃, the reaction is carried out for 3 hours, then 1.2g of epichlorohydrin is added, the temperature is raised to 85 ℃, stirring is continued for 1 hour, and the solution A is obtained after cooling to normal temperature. Subsequently, 8g of allyl trimethyl ammonium chloride, 2.4g of ammonium chloride, and 0.32g of ammonium persulfate were added to the solution A to obtain a final product.
Comparative example 1
20g of acrylamide, 5g of dimethyl diallyl ammonium chloride, 1g of diallyl amine, 1g of diallyl amino methyl phosphonate and 0.2g of potassium persulfate are respectively added into 350g of water to obtain mixed solutions, the temperature is raised to 65 ℃ for reaction for 4 hours, then 1.2g of epichlorohydrin is added for continuous stirring for 2 hours, and the mixture is cooled to normal temperature to obtain a final product.
Comparative example 2
10g of allyl trimethyl ammonium chloride and 3g of ammonium chloride were added to a solution of 350g of water.
Comparative example 3
20g of acrylamide, 5g of dimethyl diallyl ammonium chloride, 1g of diallyl amine, 1g of diallyl amino methyl phosphonate and 0.2g of potassium persulfate are respectively added into 350g of water to obtain a mixed solution, the temperature is raised to 65 ℃ for reaction for 4 hours, then 1.2g of epichlorohydrin is added, the stirring is continued for 2 hours, and the solution A is obtained after cooling to normal temperature. 10g of allyl trimethylammonium chloride, 3g of ammonium chloride are then added to solution A to give the final product. Effect evaluation:
The swelling agents prepared in examples 4 to 12 and comparative examples 1 to 3 were evaluated for their respective swelling preventing and swelling reducing rates at different temperatures, and the specific evaluation methods are shown in tables 1 and 2.
Expansion preventing rate: adding 0.50g of sodium bentonite and 10mL of 5wt% swelling agent aqueous solution into a reaction kettle, mixing uniformly, putting into a baking oven, standing for 4 hours at different temperatures (60 ℃, 70 ℃, 80 ℃ and 90 ℃), cooling to room temperature (25 ℃) and transferring into a centrifuge tube, centrifuging for 15 minutes at a rotating speed of 1500r/min, and determining that the volume of the treated sodium bentonite is V 1 In the same condition, the control experiment is carried out by changing 10mL of swelling shrinking agent aqueous solution into deionized water and centrifuging to obtain sodium swellingThe soil volume is V 0 The method comprises the steps of carrying out a first treatment on the surface of the The calculation formula of the anti-swelling rate is as follows: (V) 0 -V 1 )/V 0 *100％。
Shrinkage and expansion ratio: adding 0.50g of sodium bentonite and 7.5mL of water into a centrifuge tube, uniformly mixing, standing for 4h, adding 2.5mL of swelling shrinking agent with concentration of 20wt% into the centrifuge tube, uniformly mixing, transferring into a reaction kettle, placing into a baking oven, standing for 4h at different temperatures (60 ℃, 70 ℃, 80 ℃ and 90 ℃), cooling to room temperature (25 ℃), transferring into the centrifuge tube, centrifuging for 15min at a rotating speed of 1500r/min, and determining that the volume of the treated sodium bentonite is V 1 In the same condition, in a control test, 2.5mL of swelling agent is changed into water, and the volume of sodium bentonite obtained by centrifugation is V 0 The calculation formula of the shrinkage and expansion ratio is as follows: (V) 0 -V 1 )/V 0 *100％。
Sodium bentonite used in the evaluation of the anti-swelling and swelling shrinkage herein is produced by Shandong Usoxhlet chemical technology Co.
Table 1 results of examples and comparative examples
Anti-swelling rate at 60 ℃/% Expansion resistance at 70 ℃/% Expansion resistance at 80 ℃/% Expansion resistance at 90 ℃/%
Example 4 86 86 85 87
Example 5 88 86 87 86
Example 6 87 85 88 87
Example 7 85 85 86 85
Example 8 87 86 86 86
Example 9 85 86 87 86
Example 10 83 84 84 83
Example 11 82 84 82 83
Example 12 82 81 83 84
Comparative example 1 80 80 78 76
Comparative example 2 556 53 51
Comparative example 3 82 83 82 80
Table 2 results of examples and comparative examples
Expansion rate at 60 ℃/% Expansion rate at 70 ℃/% Expansion rate at 80 ℃/% Expansion rate at 90 ℃/%
Example 4 45 46 48 46
Example 5 46 47 47 47
Example 6 455 48 47 46
Example 7 48 48 47 48
Example 8 46 4555 44 46
Example 9 45 455 47 46
Example 10 43 44 44 43
Example 11 44 44 455 42
Example 12 42 43 43 42
Comparative example 1 18 15 15 10
Comparative example 2 36 35 30 30
Comparative example 3 39 38 38 36

Claims (27)

1. The swelling agent comprises, by weight, 1-5 parts of monomer, 5-20 parts of acrylamide, 0.1-2 parts of amine-containing monomer, 0.1-1 part of initiator, 0.1-2 parts of cross-linking agent, 1-15 parts of short-chain quaternary ammonium salt, 0.1-15 parts of inorganic salt and 50-400 parts of water; preferably 3 to 5 parts of monomer, 10 to 15 parts of acrylamide, 0.5 to 1 part of amine-containing monomer, 0.2 to 0.6 part of initiator, 0.5 to 1 part of cross-linking agent, 5 to 10 parts of short-chain quaternary ammonium salt, 1 to 5 parts of inorganic salt and 50 to 200 parts of water; wherein the monomer is one or more of cationic monomer and/or zwitterionic monomer.
2. The swelling agent comprises, by weight, 1-5 parts of monomer, 5-20 parts of acrylamide, 0.1-2 parts of amine-containing monomer, 0.1-1 part of initiator, 0.1-2 parts of cross-linking agent, 1-15 parts of short-chain quaternary ammonium salt, 0.1-15 parts of inorganic salt, 50-400 parts of water and 0.5-2 parts of diallylaminomethyl phosphonate; preferably 3 to 5 parts of monomer, 10 to 15 parts of acrylamide, 0.5 to 1 part of amine-containing monomer, 0.2 to 0.6 part of initiator, 0.5 to 1 part of cross-linking agent, 5 to 10 parts of short-chain quaternary ammonium salt, 1 to 5 parts of inorganic salt, 50 to 200 parts of water and 0.5 to 1 part of diallyl amino methyl phosphonate; wherein the monomer is one or more of cationic monomer and/or zwitterionic monomer.
3. A swelling agent according to claim 1 or 2, wherein the cationic monomer is one or more of dimethyl diallyl ammonium chloride, methacryloxyethyl trimethyl ammonium chloride, acryloxyethyl trimethyl ammonium chloride, allyl trimethyl ammonium chloride, N-methyl-N, N-tripropenyl ammonium chloride, preferably dimethyl diallyl ammonium chloride and/or allyl trimethyl ammonium chloride.
4. A swelling agent according to claim 1 or 2, wherein the zwitterionic monomer is one or more of N-methyldiallylamine propane sulfonate, N-dimethylallylamine propane sulfonate, 4-vinylpyridine propane sulfonate, N-methyldiallylbutane sulfonate, methacryloxyethyl-N, N-dimethylpropanesulfonate, preferably one or more of N-methyldiallylamine propane sulfonate, N-dimethylallylamine propane sulfonate.
5. The swelling agent according to claim 1 or 2, wherein the amine-containing monomer is selected from one or more of diallylamine, N-dimethylallylamine, triallylamine, N-diethylallylamine, dimethylallylamine, methylethylallylamine, N-methylallylamine, 2-methylallylamine, allylhydrazine, crotonamine, 3-methyl-2-buten-1-amine, preferably one or more of diallylamine, N-dimethylallylamine, triallylamine.
6. The swelling agent according to claim 1 or 2, wherein the initiator is one or more of cumene hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, di-tert-butyl peroxide, dibenzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile, potassium persulfate, sodium persulfate, potassium persulfate-potassium hydrogen sulfite, ammonium persulfate, preferably one or more of potassium persulfate, sodium persulfate, potassium persulfate-potassium hydrogen sulfite, ammonium persulfate.
7. A swelling agent according to claim 1 or 2, wherein the cross-linking agent is selected from one or more of epichlorohydrin, epibromohydrin, epichlorohydrin, and epibromohydrin, preferably one or more of epichlorohydrin and epibromohydrin.
8. A bulking agent as claimed in claim 1 or claim 2, wherein the short chain quaternary ammonium salt is a C2-C18 quaternary ammonium salt having at least one carbon-carbon double bond and the anion of the quaternary ammonium salt is one or more of Cl, br, I, F, OH.
9. The swelling agent according to claim 1 or 2, wherein the short chain quaternary ammonium salt is selected from one or more of allyltrimethylammonium, allyltrimethylammonium bromide, dimethyldiallylammonium chloride, methacryloxyethyltrimethylammonium chloride, (3-acrylamidopropyl) trimethylammonium chloride, trimethylvinylammonium bromide, 3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate, 2-methacryloyloxyethyl choline phosphate, trimethylvinylammonium hydroxide, dimethylbenzyl-2-methamidoethyl methacrylate chloride, preferably one or more of allyltrimethylammonium, allyltrimethylammonium bromide, dimethyldiallylammonium chloride.
10. The swelling agent according to claim 1, wherein the inorganic salt is one or more of sodium salt, potassium salt, ammonium salt, magnesium salt.
11. The swelling agent according to claim 1 or 2, wherein the inorganic salt is selected from one or more of sodium sulfate, sodium carbonate, sodium chloride, sodium nitrate, potassium chloride, potassium nitrate, potassium carbonate, potassium sulfate, ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, ammonium iodide, magnesium chloride, magnesium sulfate, magnesium nitrate; preferably one or more of sodium sulfate, sodium chloride, potassium chloride, magnesium sulfate and ammonium chloride.
12. The bulking agent of claim 2, wherein the diallylaminomethyl phosphonate has the formula C 7 H 12 NO 3 PM 2 、C 7 H 12 NO 3 PL、(C 7 H 12 NO 3 P) 3 X 2 、(C 7 H 12 NO 3 P) 2 Y, wherein M is oneOne or more of the valence metals, in particular one or more of the group IA metals, preferably sodium and/or potassium, more preferably sodium; l is one or more of divalent metals, and is specifically selected from one or more of magnesium, calcium, copper and ferrous iron; x is one or more of trivalent metals, and is specifically selected from one or more of iron and aluminum; y is one or more of tetravalent metals, and is specifically selected from one or more of titanium and zirconium; the molecular structural formula is at least one of the following formulas:
Figure DEST_PATH_IMAGE001
。
13. a method of preparing a bulking agent, the method comprising the steps of:
(a) Under the contact condition, mixing a monomer, acrylamide, an amine-containing monomer, an initiator, water and optional diallyl amino methyl phosphonate uniformly, and performing reaction polymerization to obtain a material flow A;
(b) Introducing a cross-linking agent into the solution A obtained in the step (a), and obtaining a material flow B after a cross-linking reaction;
(c) And (3) under the contact condition, uniformly mixing the material flow B obtained in the step (B), the short-chain quaternary ammonium salt, the inorganic salt and the initiator to obtain the swelling agent.
14. The process for producing a swelling agent according to claim 13, wherein the reaction conditions in the step (a) are as follows: the reaction temperature is 40-90 ℃, preferably 55-75 ℃; the reaction time is 1 to 6 hours, preferably 2 to 4 hours.
15. The method for producing a swelling agent according to claim 13, wherein the amount of the monomer, acrylamide, amine-containing monomer, initiator, crosslinking agent, short-chain quaternary ammonium salt, inorganic salt, water, diallylaminomethyl phosphonate is 1 to 5 parts by weight, 5 to 20 parts by weight of acrylamide, 0.1 to 2 parts by weight of amine-containing monomer, 0.1 to 1 part by weight of initiator, 0.1 to 2 parts by weight of crosslinking agent, 1 to 15 parts by weight of short-chain quaternary ammonium salt, 0.1 to 15 parts by weight of inorganic salt, 50 to 400 parts by weight of water, 0.5 to 2 parts by weight of diallylaminomethyl phosphonate (when diallyl aminomethylphosphonate is contained); preferably 3 to 5 parts of monomer, 10 to 15 parts of acrylamide, 0.5 to 1 part of amine-containing monomer, 0.2 to 0.6 part of initiator, 0.5 to 1 part of cross-linking agent, 5 to 10 parts of short-chain quaternary ammonium salt, 1 to 5 parts of inorganic salt, 50 to 200 parts of water and 0.5 to 1 part of diallyl amino methyl phosphonate.
16. The process for producing a swelling agent according to claim 13, wherein the crosslinking reaction conditions in the step (b) are as follows: the reaction temperature is 40-90 ℃, preferably 50-70 ℃; the reaction time is 1 to 6 hours, preferably 2 to 5 hours.
17. The process for preparing a swelling agent according to claim 13, wherein the initiator in step (a) and step (c) are the same or different, and the ratio of the amounts of the initiator in step (a) and step (c) is 1:1 to 1:9.
18. the method for producing a swelling agent according to claim 12, wherein the monomer is one or more of a cationic monomer and/or a zwitterionic monomer; the cationic monomer is one or more of dimethyl diallyl ammonium chloride, methacryloxyethyl trimethyl ammonium chloride, acryloxyethyl trimethyl ammonium chloride, allyl trimethyl ammonium chloride and N-methyl-N, N, N-tripropenyl ammonium chloride, preferably one or more of dimethyl diallyl ammonium chloride and allyl trimethyl ammonium chloride; the zwitterionic monomer is one or more of N-methyldiallylamine propane sulfonate, N-dimethylallylamine propane sulfonate, 4-vinylpyridine propane sulfonate, N-methyldiallylbutane sulfonate, methacryloxyethyl-N, N-dimethylpropane sulfonate, preferably one or more of N-methyldiallylamine propane sulfonate and N, N-dimethylallylamine propane sulfonate.
19. The process for producing a swelling agent according to claim 13, wherein the amine-containing monomer is one or more selected from the group consisting of diallylamine, N-dimethylallylamine, triallylamine, N-diethylallylamine, dimethylallylamine, methylethylallylamine, N-methylallylamine, 2-methylallylamine, allylhydrazine, crotonamine, 3-methyl-2-butene-1-amine, preferably one or more selected from the group consisting of diallylamine, N-dimethylallylamine and triallylamine.
20. The process for producing a swelling agent according to claim 13, wherein the initiator is one or more of cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, dibenzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile, potassium persulfate, sodium persulfate, potassium persulfate-potassium hydrogen sulfite, ammonium persulfate, preferably one or more of potassium persulfate, sodium persulfate, potassium persulfate-potassium hydrogen sulfite, ammonium persulfate.
21. The process for producing a swelling agent according to claim 13, wherein the crosslinking agent is one or more selected from the group consisting of epichlorohydrin, epibromohydrin, chlorohydrin, and bromopentane, preferably one or more selected from the group consisting of epichlorohydrin and epibromohydrin.
22. The process for producing a swelling agent according to claim 13, wherein the short-chain quaternary ammonium salt is a quaternary ammonium salt of C2-C18 having at least one carbon-carbon double bond, and the anion of the quaternary ammonium salt is one or more of Cl, br, I, F, OH.
23. The process for producing a swelling agent according to claim 13, wherein the short-chain quaternary ammonium salt is selected from one or more of allyltrimethylammonium bromide, dimethyldiallylammonium chloride, methacryloxyethyl trimethylammonium chloride, (3-acrylamidopropyl) trimethylammonium chloride, trimethylvinylammonium bromide, 3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate, 2-methacryloxyethyl choline phosphate, trimethylvinylammonium hydroxide, dimethylbenzyl-2-methamidoethyl chloride, preferably one or more of allyltrimethylammonium bromide, dimethyldiallylammonium chloride.
24. The process for producing a swelling agent according to claim 13, wherein the inorganic salt is one or more of sodium salt, potassium salt, ammonium salt and magnesium salt, preferably one or more of sodium salt, potassium salt, ammonium salt and magnesium salt, and specifically one or more of sodium sulfate, sodium carbonate, sodium chloride, sodium nitrate, potassium chloride, potassium nitrate, potassium carbonate, potassium sulfate, ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, ammonium iodide, magnesium chloride, magnesium sulfate and magnesium nitrate; preferably one or more of sodium sulfate, sodium chloride, potassium chloride, magnesium sulfate and ammonium chloride.
25. The process for preparing a swelling agent according to claim 13, wherein the diallylaminomethyl phosphonate has the formula C 7 H 12 NO 3 PM 2 、C 7 H 12 NO 3 PL、(C 7 H 12 NO 3 P) 3 X 2 、(C 7 H 12 NO 3 P) 2 Any one of Y, wherein M is one or more of monovalent metals, particularly one or more of group IA metals, preferably sodium and/or potassium, more preferably sodium; l is one or more of divalent metals, and is specifically selected from one or more of magnesium, calcium, copper and iron; x is one or more of trivalent metals, and is specifically selected from one or more of iron and aluminum; y is one or more of tetravalent metals, and is specifically selected from one or more of titanium and zirconium; the molecular structural formula is at least one of the following formulas:
Figure 134742DEST_PATH_IMAGE002
。
26. A swelling agent obtainable by the process of any one of claims 13 to 25.
27. Use of a swelling agent according to any one of claims 1 to 12 or obtainable by a method according to any one of claims 13 to 25 in the flooding of an oilfield reservoir.
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CN104861110A (en) * 2015-05-22 2015-08-26 中国石油集团渤海钻探工程有限公司 Anti-swelling and sand-inhibiting agent for high-permeability heavy oil reservoir and preparation method of anti-swelling and sand-inhibiting agent
CN112457838A (en) * 2020-11-25 2021-03-09 陕西科技大学 Novel acid-resistant and salt-resistant shrinking and swelling agent and preparation method thereof
CN113150765A (en) * 2021-04-25 2021-07-23 陕西科技大学 Expansion shrinkage agent for acidizing and fracturing and preparation method thereof

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