CN117304429A - Composite high-temperature-resistant and salt-resistant water shutoff agent and preparation method thereof - Google Patents
Composite high-temperature-resistant and salt-resistant water shutoff agent and preparation method thereof Download PDFInfo
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- CN117304429A CN117304429A CN202311604721.9A CN202311604721A CN117304429A CN 117304429 A CN117304429 A CN 117304429A CN 202311604721 A CN202311604721 A CN 202311604721A CN 117304429 A CN117304429 A CN 117304429A
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- Prior art keywords
- resistant
- salt
- diisocyanate
- water shutoff
- shutoff agent
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 49
- 150000003839 salts Chemical class 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 24
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims abstract description 34
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims abstract description 34
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 29
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims abstract description 24
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 16
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 16
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 12
- 239000001116 FEMA 4028 Substances 0.000 claims abstract description 12
- 229960004853 betadex Drugs 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 12
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001412 amines Chemical class 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 230000009471 action Effects 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- ASVKKRLMJCWVQF-UHFFFAOYSA-N 3-buten-1-amine Chemical compound NCCC=C ASVKKRLMJCWVQF-UHFFFAOYSA-N 0.000 claims description 7
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 2
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 claims description 2
- LPLKJLLIRPEGHK-UHFFFAOYSA-N 2,2-dihydroxyethyl-methyl-octadecylazanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[NH+](C)CC(O)O LPLKJLLIRPEGHK-UHFFFAOYSA-N 0.000 claims description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000005341 cation exchange Methods 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 2
- UVBBCQLPTZEDHT-UHFFFAOYSA-N pent-4-en-1-amine Chemical compound NCCCC=C UVBBCQLPTZEDHT-UHFFFAOYSA-N 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 230000001502 supplementing effect Effects 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 2
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 2
- 239000000499 gel Substances 0.000 description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000011049 filling Methods 0.000 description 7
- 229920002401 polyacrylamide Polymers 0.000 description 7
- 239000004576 sand Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 239000002981 blocking agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000033558 biomineral tissue development Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 208000023445 Congenital pulmonary airway malformation Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—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
- C09K8/5083—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- 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
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Sealing Material Composition (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention provides a composite high-temperature-resistant and salt-resistant water shutoff agent and a preparation method thereof, wherein the water shutoff agent comprises the following raw materials in parts by weight: 2.5 to 3.5 weight percent of acrylamide, 0.5 to 0.8 weight percent of 6-acrylamide-beta-cyclodextrin, 0.5 to 1 weight percent of unsaturated amine, 0.03 to 0.05 weight percent of initiator, 0.1 to 0.3 weight percent of N, N' -methylene bisacrylamide, 0.7 to 1 weight percent of sodium bisulfite blocked diisocyanate and 0.5 to 0.9 weight percent of quaternary ammonium salt intercalated montmorillonite, wherein the water is added to 100 percent, and the sodium bisulfite blocked diisocyanate is prepared by the reaction of sodium bisulfite and diisocyanate under the action of a phase transfer catalyst; the molar ratio of sodium bisulphite to isocyanate groups is 1.1-1.2:1. The water shutoff agent can form double crosslinked gel, and has obvious high temperature resistance and salt resistance.
Description
Technical Field
The invention belongs to the technical field of chemical plugging agents, and particularly relates to a composite high-temperature-resistant and salt-resistant plugging agent and a preparation method thereof.
Background
The basic principle of chemical plugging of oil well is to inject chemical plugging agent into high-permeability water outlet interval to reduce water phase permeability in near-wellbore zone, control the output of injected water, bottom water and side water and increase crude oil output. The chemical plugging agent adopted in the chemical plugging technology can be classified into gel type, precipitation type and colloid dispersion type according to the form, and has the characteristics of rapid development and remarkable effect due to various available chemical reagents. The proprozen blocking agent is one of gel type blocking agents, and is various types of polyacrylamide, including NPAM (nonionic polyacrylamide), APAM (anionic polyacrylamide), CPAM (cationic polyacrylamide), and amphoteric polyacrylamide, polyacrylamide latex, instant polyacrylamide, copolymers of AM and other types of monomers, and the like, and forms various types of water-insoluble gels together with various corresponding types of crosslinking agents to block formation pores, and has: swelling in water to generate a gel water shutoff agent with high viscosity; the adhesive is good, and various solid propping agents can be carried to increase the strength of the plugging agent; the water is not required, the equipment and the pipeline are not corroded, and the adaptability to stratum is good; the gel time is adjustable, the gel viscosity is high, the strength is high, the plugging agent does not spit back under the pressure of 10Mpa, the plugging agent can be plugged and removed, the stratum is not polluted after plugging, and the like, so that the application is the most widely.
The water shutoff agent disclosed in patent CN103923629B comprises the following raw materials in percentage by weight: 6-15% of acrylamide monomer, 0-10% of acrylic acid, 0.005-0.03% of N, N' -methylene bisacrylamide, 0-0.01% of azo initiator, 0-0.1% of ammonium persulfate, 0-2% of sodium hydroxide and the balance of salt water; stirring the raw materials at room temperature, fully dissolving in saline water, slowly heating to 80 ℃, keeping the temperature at 80 ℃ for 4-6 hours, and reacting to generate gel. The patent CN109942739B discloses a water glass-acrylate composite gel water shutoff agent and a preparation method thereof, wherein an acrylate grouting material and water glass are fused together and are compounded to form the multiple composite gel water shutoff agent. Finally prepared composite gel plugThe water aqua has higher advantages in the aspect of strength, good water retention, difficult shrinkage and leakage, and stronger plugging capability. However, the water shutoff agent is easy to hydrolyze and degrade in high temperature and high mineralization degree, and is compatible with Ca 2+ 、Mg 2+ The coordination complex causes coagulation, and the pre-crosslinking body is easy to crush by extrusion of the bentonite particles, and is thoroughly degraded in a few days at high temperature (120 ℃), so that the polypropylene blocking agent is not suitable for water blocking operation of high-temperature high-salt oil reservoirs, and has great significance for improving high-temperature resistance and salt resistance of the polypropylene blocking agent.
Disclosure of Invention
Aiming at the problems, the invention provides a composite high-temperature-resistant and salt-resistant water shutoff agent and a preparation method thereof, wherein the composite high-temperature-resistant and salt-resistant water shutoff agent comprises an acrylamide, 6-acrylamide-beta-cyclodextrin, unsaturated amine and N, N' -methylene bisacrylamide polymerization monomer system, and is polymerized to generate water-insoluble gel to block stratum gaps under the initiation action of an initiator, and along with the progress of polymerization reaction, heat is accumulated, sodium bisulphite and isocyanate groups are gradually unsealed, active isocyanate reacts with amino groups and hydroxyl groups on gel molecules to form a double-crosslinked gel shutoff agent, and the double-crosslinked structure has remarkable high-temperature resistance and salt resistance.
In order to achieve the above purpose, the following specific technical scheme is adopted:
the composite high temperature resistant and salt resistant water shutoff agent comprises the following raw materials in parts by weight: 4.5-7wt% of acrylamide, 0.5-0.8wt% of 6-acrylamide-beta-cyclodextrin, 0.5-1wt% of unsaturated amine, 0.03-0.05wt% of initiator, 0.1-0.3wt% of N, N' -methylene bisacrylamide, 0.7-1wt% of sodium bisulphite blocked diisocyanate and 0.5-0.9wt% of quaternary ammonium salt intercalated montmorillonite, wherein water is used for supplementing 100%, and the sodium bisulphite blocked diisocyanate is prepared by reacting sodium bisulphite with isocyanate groups under the action of a phase transfer catalyst; the molar ratio of the sodium bisulphite to the isocyanate groups is 1.1-1.2:1.
Sodium bisulphite blocks diisocyanate to make active isocyanate group not reactive below 80 ℃.
The diisocyanate is selected from one or two of 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and trimethylhexamethylene diisocyanate.
The sodium bisulfite blocked diisocyanate is prepared by a process comprising the steps of:
under inert atmosphere, diisocyanate is dissolved in an organic solvent, a phase transfer catalyst is added and mixed uniformly to obtain a mixture, the mixture is dripped into a sodium bisulphite solution by controlling the temperature, the reaction is carried out under the conditions of controlling the temperature and stirring, the di-n-butylamine dripping method is used for detecting the-NCO content in the mixed system, and the reaction is stopped after the-NCO content reaches the minimum point, so that the sodium bisulphite closed diisocyanate is obtained.
The temperature control is controlled at 10-20 ℃, the stirring rotating speed is 200-500r/min, the organic solvent is selected from one or two of chlorobenzene, o-dichlorobenzene, toluene, acetone, dioxane, ethanol and isopropanol, the mass ratio of the organic solvent to the sum of sodium bisulphite and diisocyanate serving as reaction raw materials is 1-1.2:1, the phase transfer catalyst is selected from one or two of benzyl triethyl ammonium chloride (TEBA), tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bisulfate (TBAB), trioctyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride and tetradecyl trimethyl ammonium chloride, the dosage of the catalyst is 1-3% of the sum of the molar weight of diisocyanate and sodium bisulphite, the dripping time of the mixture is 0.5-1h, the concentration of sodium bisulphite solution is 30-40wt%, the solvent of the sodium bisulphite solution is water, and the reaction time is 1-3h.
The initiator is selected from one or two of ammonium persulfate, potassium persulfate and sodium persulfate.
The unsaturated amine is selected from one or a combination of two or more of 3-butene-1-amine, pent-4-ene-1-amine and oleylamine.
The quaternary ammonium salt intercalated montmorillonite is prepared by using quaternary ammonium salt intercalated montmorillonite, the preparation method is not particularly limited, and the quaternary ammonium salt intercalated montmorillonite is commonly used in the field.
The montmorillonite cation exchange capacity is 100-130eq/100g, and the average grain diameter is 40-70 mu m.
The quaternary ammonium salt is not particularly limited and is commonly used in the art, and includes, but is not limited to, one or a combination of two or more of cetyltrimethylammonium chloride and octadecyl dihydroxyethyl methyl ammonium bromide.
The method specifically comprises the following steps: adding montmorillonite into water, heating, stirring at high speed to form suspension, dropwise adding quaternary ammonium salt solution under stirring, naturally cooling, centrifuging, washing, drying, and grinding to obtain organic modified montmorillonite.
The temperature is raised to 60-100 ℃, the high-speed stirring speed is 500-800r/min, the stirring time is 5-8h, the solid content of the suspension is 1-3wt%, the concentration of the quaternary ammonium salt solution is 3-5wt%, the dripping time is 0.5-1h, the continuous stirring speed is 100-300r/min, the time is 1-3h, the grinding is carried out until the particle size is 30-50 mu m, and the use amount of the quaternary ammonium salt is 60-100wt% of montmorillonite.
The invention also provides a preparation method of the composite high-temperature-resistant salt-resistant water shutoff agent, which comprises the following steps:
the quaternary ammonium salt intercalated montmorillonite is dispersed into water by ultrasonic, acrylamide, 6-acrylamide-beta-cyclodextrin, unsaturated amine and initiator are added and mixed uniformly, then N, N' -methylene bisacrylamide and sodium bisulphite blocked diisocyanate are added and mixed uniformly, and the composite high-temperature-resistant and salt-resistant plugging agent is obtained.
The application condition of the composite high temperature resistant and salt resistant water shutoff agent is 80-90 ℃ and gel is formed after 10-15 hours.
Compared with the prior art, the invention has the beneficial effects that:
the water shutoff agent comprises an acrylamide, 6-acrylamide-beta-cyclodextrin, unsaturated amine and N, N' -methylene bisacrylamide polymerization monomer system, and is polymerized to generate water-insoluble gel to block stratum gaps under the initiation of an initiator, and as the polymerization reaction is carried out, heat is accumulated, sodium bisulfite and isocyanate groups are gradually unsealed, and active isocyanate reacts with amino groups and hydroxyl groups on gel molecules to form a double-crosslinked gel shutoff agent.
Detailed Description
The invention is further illustrated below in connection with specific examples, but is not limited to the disclosure. If no special description exists, the parts are parts by weight in the embodiment of the invention. All reagents used are those commercially available in the art.
Sodium-based montmorillonite was purchased from Zhejiang Feng iridite New Material Co., ltd, ion exchange capacity was 100mmol/100g, and average particle size was 60. Mu.m.
Preparation of organically modified montmorillonite
Preparation example a1
Adding 15 parts of sodium montmorillonite into 500 parts of water, heating to 80 ℃, stirring at a high speed of 500r/min for 6 hours to form a suspension, dropwise adding 300 parts of cetyltrimethylammonium chloride solution with the concentration of 5wt% under the stirring condition of 500r/min, continuously stirring at the rotating speed of 200r/min after 30min, naturally cooling, centrifuging, washing, drying, and grinding to 50 mu m to obtain the organic modified montmorillonite.
Preparation example a2
The remainder was the same as in preparation example a1 except that the amount of the cetyltrimethylammonium chloride solution of 5wt% was 180 parts.
Preparation of sodium bisulfite blocked diisocyanate
Preparation example 1
Under nitrogen atmosphere, 0.5mol of 2, 4-toluene diisocyanate is dissolved in 203g of dioxane, 48mmol of benzyl triethyl ammonium chloride is added to be uniformly mixed to obtain a mixture, the mixture is dripped into a sodium bisulphate solution containing 1.1mol (with the concentration of 33 wt%) at the temperature of 15 ℃ and is reacted under the stirring condition of 200r/min at the temperature of 15 ℃ after 45min, the di-n-butylamine dripping method is used for detecting the-NCO content in the mixed system, the-NCO content is the lowest when the reaction is carried out for 1.5h, and the reaction is stopped to obtain the sodium bisulphate closed diisocyanate.
Preparation example 2
The rest was the same as in preparation example 1 except that the amount of sodium hydrogensulfite was 1.2mol.
Preparation example 3
The remainder was the same as in preparation example 1 except that diphenylmethane diisocyanate was used in place of 2, 4-toluene diisocyanate in an equimolar amount.
Preparing composite high-temperature-resistant salt-resistant water shutoff agent
Example 1
Dispersing 0.9 part of the organic modified montmorillonite of the preparation example a1 into water by ultrasonic, adding 7 parts of acrylamide, 0.8 part of 6-acrylamide-beta-cyclodextrin, 1 part of 3-butene-1-amine, 0.05 part of initiator and water, uniformly mixing, adding 0.3 part of N, N' -methylene bisacrylamide and 1 part of sodium bisulphite blocked diisocyanate of the preparation example 1, and uniformly mixing to obtain the composite high-temperature-resistant and salt-resistant water shutoff agent, wherein the water is used in an amount that all components are integrated into 100 parts.
The composite high-temperature-resistant and salt-resistant water shutoff agent is placed in an environment of reaction for 10 hours at 80 ℃ to form gel.
Examples 2 to 3
The remainder was the same as in example 1, except that sodium hydrogensulfite blocked diisocyanate was prepared in preparation examples 2 to 3, respectively.
Example 4
The remainder was the same as in example 1, except that the organically modified montmorillonite was prepared in preparation example a 2.
Example 5
The remainder was the same as in example 1 except that the amount of the sodium hydrogensulfite blocked diisocyanate was 0.7 part, and the corresponding water was 100 parts.
Example 6
The remainder was the same as in example 1 except that 3-butene-1-amine was used in an amount of 0.5 parts, and the corresponding water was used in an amount of 100 parts.
Example 7
The remainder was the same as in example 1 except that the amount of 6-acrylamido- β -cyclodextrin was 0.5 part, and the corresponding water was 100 parts.
Example 8
Dispersing 0.5 part of the organic modified montmorillonite of the preparation example a1 into water by ultrasonic, adding 4.5 parts of acrylamide, 0.8 part of 6-acrylamide-beta-cyclodextrin, 1 part of 3-butene-1-amine, 92.07 parts of water and 0.03 part of initiator, uniformly mixing, adding 0.1 part of N, N' -methylene bisacrylamide and 1 part of sodium bisulphite blocked diisocyanate of the preparation example 1, and uniformly mixing to obtain the composite high-temperature-resistant and salt-resistant water shutoff agent.
The composite high temperature resistant and salt resistant water shutoff agent is placed in an environment of 80 ℃ and reacted for 10 hours to form gel.
Comparative example 1
The remainder was the same as in example 1, except that sodium hydrogensulfite blocked diisocyanate was not added.
Comparative example 2
The rest is the same as in example 1, except that 6-acrylamido-beta-cyclodextrin is not added, and that 6-acrylamido-beta-cyclodextrin is replaced with acrylamide of equal mass.
Comparative example 3
The remainder was the same as in example 1 except that 3-butene-1-amine was not added and that 3-butene-1-amine was replaced with acrylamide of equal mass.
The plugging agents prepared in the above examples and comparative examples were subjected to the following performance tests:
plugging rate: filling a sand filling pipe with the length of 30cm and the inner diameter of 2.54cm by using 80-mesh quartz sand, vacuumizing the sand filling pipe, saturating the sand filling pipe with clear water for 3 hours, then measuring the initial permeability of the water phase of the sand filling pipe by using clear water, performing a sand filling pipe plugging test under the condition that the injection amount of plugging agent is 1.0PV, heating the system to 80 ℃, waiting for 10 hours, performing reverse displacement by using clear water, and measuring the permeability of the sand filling pipe after plugging. Referring to the standard SSY/T5345-2007 and SSY/T5590-2004, the plugging rate calculation formula is as follows:
temperature resistance: after the 5 sample gels of each example were sufficiently dried to constant weight, they were charged to a mineralization degree of 5.0X10 4 mg/L simulated formation water-CaCl 2 Placing the water solution in a 120 ℃ incubator, taking out samples at 0d and 180d respectively, rapidly sucking surface water with filter paper, and recording the mass as m 0d 、m 180d The water loss rate (T) is calculated by the following formula:
T=(m 180d -m 0d )/m 0d ×100%。
the water loss (T) was averaged over 5 samples.
Salt resistance: with an equivalent degree of mineralization of 6X 10 4 mg/L simulated formation water-CaCl 2 The aqueous solution is used for replacing water in the examples to measure gel strength (5 samples in each example), a bottle test method is adopted, and the specific implementation mode is that a water shutoff agent is poured into a wide-mouth bottle, the wide-mouth bottle is sealed and then put into an oven at 80 ℃, timing is started, the solution is taken out according to a specified time interval to be observed in an inverted mode, corresponding records are made according to the following table, and then the solution is put into the oven for continuous observation:
TABLE 1 gel strength code Standard
Table 2 Water shutoff agent Performance test
As can be seen from the test results in Table 2, the water shutoff agent prepared by the invention has good temperature resistance and salt resistance, high water shutoff efficiency and the shutoff rate is more than 97%.
The foregoing detailed description is directed to one of the possible embodiments of the present invention, which is not intended to limit the scope of the invention, but is to be accorded the full scope of all such equivalents and modifications so as not to depart from the scope of the invention.
Claims (10)
1. The composite high-temperature-resistant and salt-resistant water shutoff agent is characterized by comprising the following raw materials in parts by weight: 4.5-7wt% of acrylamide, 0.5-0.8wt% of 6-acrylamide-beta-cyclodextrin, 0.5-1wt% of unsaturated amine, 0.03-0.05wt% of initiator, 0.1-0.3wt% of N, N' -methylene bisacrylamide, 0.7-1wt% of sodium bisulphite blocked diisocyanate and 0.5-0.9wt% of quaternary ammonium salt intercalated montmorillonite, wherein water is used for supplementing 100%, and the sodium bisulphite blocked diisocyanate is prepared by reacting sodium bisulphite with diisocyanate under the action of a phase transfer catalyst; the molar ratio of the sodium bisulphite to the isocyanate groups of the diisocyanate is 1.1-1.2:1.
2. The composite high temperature resistant and salt resistant water shutoff agent according to claim 1, wherein the diisocyanate is selected from one or two of 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and trimethylhexamethylene diisocyanate.
3. The composite high temperature resistant and salt resistant water shutoff agent of claim 1, wherein the sodium bisulphite blocked diisocyanate is prepared by a method comprising the following steps:
under inert atmosphere, diisocyanate is dissolved in an organic solvent, a phase transfer catalyst is added and mixed uniformly to obtain a mixture, the mixture is dripped into a sodium bisulphite solution by controlling the temperature, the reaction is carried out under the conditions of controlling the temperature and stirring, and the reaction is stopped after the-NCO content reaches the minimum point, thus obtaining the sodium bisulphite closed diisocyanate.
4. The composite high temperature resistant and salt resistant water shutoff agent according to claim 3, wherein the organic solvent is selected from one or two of acetone, dioxane, ethanol and isopropanol, and the phase transfer catalyst is selected from one or two of benzyl triethyl ammonium chloride, tetrabutyl ammonium bromide, tetrabutyl ammonium chloride, tetrabutyl ammonium bisulfate, trioctyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride and tetradecyl trimethyl ammonium chloride.
5. The composite high temperature resistant and salt resistant water shutoff agent according to claim 1, wherein the unsaturated amine is selected from one or a combination of two or more of 3-butene-1-amine, pent-4-en-1-amine, and oleylamine; the initiator is selected from one or two of ammonium persulfate, potassium persulfate and sodium persulfate.
6. The composite high temperature resistant and salt resistant water shutoff agent according to claim 1, wherein the quaternary ammonium salt intercalated montmorillonite is prepared by a method comprising the following steps: adding montmorillonite into water, heating, stirring at high speed to form suspension, dropwise adding quaternary ammonium salt solution under stirring, naturally cooling, centrifuging, washing, drying, and grinding to obtain organic modified montmorillonite.
7. The composite high temperature resistant and salt resistant water shutoff agent of claim 6, wherein the montmorillonite cation exchange capacity is 100-130eq/100g, and the average grain diameter is 40-70 μm; the quaternary ammonium salt is selected from one or a combination of two or more of cetyl trimethyl ammonium chloride and stearyl dihydroxyethyl methyl ammonium bromide.
8. The composite high temperature resistant and salt resistant water shutoff agent of claim 6, wherein the quaternary ammonium salt is 60-100wt% of montmorillonite.
9. The method for preparing the composite high-temperature-resistant salt-resistant water shutoff agent as claimed in any one of claims 1 to 8, which is characterized by comprising the following steps:
the quaternary ammonium salt intercalated montmorillonite is dispersed into water by ultrasonic, acrylamide, 6-acrylamide-beta-cyclodextrin, unsaturated amine and initiator are added and mixed uniformly, then N, N' -methylene bisacrylamide and sodium bisulphite blocked diisocyanate are added and mixed uniformly, and the composite high-temperature-resistant and salt-resistant plugging agent is obtained.
10. The method for preparing the composite high-temperature-resistant and salt-resistant water shutoff agent according to claim 9, which is characterized in that the application condition of the composite high-temperature-resistant and salt-resistant water shutoff agent is 80-90 ℃ and gel is formed after 10-15 hours.
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