CN118360037A - Blocking well wall stabilizing treatment agent, preparation method thereof and drilling fluid - Google Patents
Blocking well wall stabilizing treatment agent, preparation method thereof and drilling fluid Download PDFInfo
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- CN118360037A CN118360037A CN202310083168.2A CN202310083168A CN118360037A CN 118360037 A CN118360037 A CN 118360037A CN 202310083168 A CN202310083168 A CN 202310083168A CN 118360037 A CN118360037 A CN 118360037A
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- 238000011282 treatment Methods 0.000 title claims abstract description 37
- 238000005553 drilling Methods 0.000 title claims abstract description 32
- 239000012530 fluid Substances 0.000 title claims abstract description 29
- 230000000087 stabilizing effect Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000000903 blocking effect Effects 0.000 title description 3
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 59
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229920001577 copolymer Polymers 0.000 claims abstract description 40
- 229920000098 polyolefin Polymers 0.000 claims abstract description 38
- 239000002105 nanoparticle Substances 0.000 claims abstract description 35
- 238000004132 cross linking Methods 0.000 claims abstract description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 229910052796 boron Inorganic materials 0.000 claims abstract description 4
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 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
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 5
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 4
- WDFKEEALECCKTJ-UHFFFAOYSA-N n-propylprop-2-enamide Chemical compound CCCNC(=O)C=C WDFKEEALECCKTJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 239000012188 paraffin wax Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- -1 polypropylene Polymers 0.000 claims description 4
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-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
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 2
- 229910021538 borax Inorganic materials 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 2
- YRVUCYWJQFRCOB-UHFFFAOYSA-N n-butylprop-2-enamide Chemical compound CCCCNC(=O)C=C YRVUCYWJQFRCOB-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-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
- 239000004328 sodium tetraborate Substances 0.000 claims description 2
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 230000004044 response Effects 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 11
- 230000009977 dual effect Effects 0.000 abstract description 4
- 239000000706 filtrate Substances 0.000 abstract description 2
- 230000009545 invasion Effects 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 15
- 239000011259 mixed solution Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 238000011161 development Methods 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 239000011435 rock Substances 0.000 description 6
- 239000010426 asphalt Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 239000005543 nano-size silicon particle Substances 0.000 description 4
- 239000002954 polymerization reaction product Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- AVSXGQJYEFAQNK-UHFFFAOYSA-N prop-2-enamide;hydrate Chemical compound O.NC(=O)C=C AVSXGQJYEFAQNK-UHFFFAOYSA-N 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 102100034769 Thioredoxin-dependent peroxide reductase, mitochondrial Human genes 0.000 description 2
- 101710150060 Thioredoxin-dependent peroxide reductase, mitochondrial Proteins 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 238000002156 mixing Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
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- 239000007790 solid phase Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920006372 Soltex Polymers 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 229940092782 bentonite Drugs 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
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 229940080314 sodium bentonite Drugs 0.000 description 1
- 229910000280 sodium bentonite Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000012498 ultrapure water Substances 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
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
-
- 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
- C09K8/02—Well-drilling compositions
- C09K8/04—Aqueous well-drilling compositions
- C09K8/14—Clay-containing compositions
- C09K8/18—Clay-containing compositions characterised by the organic compounds
- C09K8/22—Synthetic organic compounds
- C09K8/24—Polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/10—Nanoparticle-containing well treatment fluids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/12—Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the field of well wall stabilizing materials of drilling fluid, and discloses a plugging well wall stabilizing treatment agent, a preparation method and the drilling fluid, wherein the treatment agent comprises a plurality of nano particles, polyolefin chains and a cross-linked copolymer; wherein the crosslinked copolymer comprises a copolymer and a crosslinking point M for connecting different molecular chains in the copolymer, the copolymer comprises a structural unit a from an acrylic monomer, a structural unit b from acrylamide and a structural unit c from an N-alkyl substituted acrylamide monomer, wherein M is selected from Zn, zr, B, S or Cr. The material can respond to 40-100 ℃, so that the quick response to the dual factors of the stratum environment temperature and [ H + ] is realized, the quick matching of the micro-crack size is realized, the invasion of drilling fluid filtrate to the stratum is reduced, and the stability of the well wall of the hard and brittle stratum is improved.
Description
Technical Field
The invention relates to the technical field of well wall stabilizing materials of drilling fluid, in particular to a plugging well wall stabilizing treatment agent, a preparation method thereof and the drilling fluid.
Background
Along with the acceleration of shale oil and gas exploration and development and the development of petroleum exploration and development to deep stratum and offshore, drilling and encountering stratum conditions are more and more complex, complex wells, deep wells, ultra-deep wells and the increase of the number of special wells, well leakage, collapse, shrinkage, serious slurry production and other well wall instability problems are easy to occur in complex stratum drilling. Local broken stratum has many weak points, strong heterogeneity, crack development and high block dropping hardness, and is easy to cause accidents such as drill sticking. The drilling operation has higher requirements on the anti-collapse performance of the drilling fluid and the capability of reinforcing the well wall, and the anti-collapse treatment agent of the drilling fluid is a key for improving the anti-collapse performance of the drilling fluid and the stability of the well wall.
The addition of the high-efficiency borehole wall stabilizing treatment agent into the drilling fluid is one of the main methods for improving and solving the borehole wall instability problem, and the adoption of inert filling plugging is one of the main technical ideas aiming at the borehole wall instability problem of hard and brittle complex stratum at present. Asphalt treating agents such as emulsified asphalt, sulfonated asphalt, oxidized asphalt and the like, such as Soltex series products of the Chevron company and PRO-TEX products of the Progress company, mainly utilize asphalt particles in the treating agents to soften and deform at a temperature near a softening point, and squeeze into cracks and pore throats of stratum layer by layer under the action of pressure difference to seal cracks and pores of a well wall. The silicate treating agent can form nanometer level particles of ions, colloids and polymers with different sizes in water, and forms a layer of protecting film on the surface of stratum rock through the actions of adsorption, diffusion, chemical precipitation and the like, so that stratum microcracks are plugged, stratum minerals are bonded, the overall cementing capacity of stratum is improved, and a well wall is sealed. However, the silicate treating agent has higher pH requirement on drilling fluid, often more than 11, and the rheological property of the drilling fluid is difficult to regulate and control due to less compatible treating agent, so that the application of the silicate treating agent is limited to a certain extent. The effective action temperature range of the polymeric alcohol treating agent is limited, and the cloud point temperature of the polymeric alcohol treating agent is required to be equal to the bottom hole circulation temperature, so that microcracks of the stratum can be effectively plugged.
The existing well wall stabilization technology mainly adopts a passive treatment mode for underground complex treatment to treat hysteresis. The material is often added in a large amount, and the addition amount is more than 10-20%, so that the material is difficult to actively adapt to stratum conditions, difficult to accurately and efficiently match stratum microcracks, and cannot completely meet the exploration and development requirements, and becomes a technical bottleneck for restricting economic and efficient exploration and development. The technology of high-efficiency high-performance well wall stabilizing materials has become a main demand and development direction in the future.
In recent years, some aluminum-based treatments for formation [ H + ] have been developed, such as CN106947439A, which discloses a pH-responsive drilling fluid aluminum-based collapse preventing agent and a preparation method thereof, wherein the pH-responsive drilling fluid aluminum-based collapse preventing agent prepared by reacting polyether polyol, lactone monomer, initiator, aluminum compound and pH regulator has pH responsiveness, stably exists in a dissolved state in drilling fluid (pH > 8), can rapidly respond to form aluminum hydroxide precipitate in a pH response range (pH is less than or equal to 5 and less than or equal to 7.5), and seals pore throats and microcracks of the formation by physical and chemical actions.
The multifunctional aluminum anti-collapse agent AOP-1 is reported in indoor evaluation and field application of the multifunctional aluminum anti-collapse agent AOP-1 (drilling fluid and completion fluid, 9 2005), and the aluminum-based treating agent is a chemical reaction type plugging anti-collapse agent and has the functions of inhibiting gypsum dissolution, cleaning solid phase and the like. The anti-collapse agent is suitable for plugging anti-collapse of microcrack shale stratum, anti-balling of shale with strong slurrying property and solid phase cleaning.
However, in the prior art, only aiming at a single factor of stratum environment, in actual drilling engineering, the underground environment is intricate and complex, and 2 factors are required to be responded simultaneously under the restriction of a plurality of factors so as to accurately judge and treat stratum microcracks and realize the first-time quick plugging and wall fixing of the hard and brittle shale microcracks.
Disclosure of Invention
The invention aims to solve the problem that the current drilling fluid material is difficult to accurately judge and treat stratum microcracks under the restriction of various factors in the prior art, and provides a plugging well wall stabilizing treatment agent, a preparation method thereof and drilling fluid.
In order to achieve the above object, the first aspect of the present invention provides a plugged borehole wall stabilizing treatment agent, wherein the treatment agent comprises a plurality of nanoparticles, polyolefin chains and a crosslinked copolymer; wherein the crosslinked copolymer comprises a copolymer and a crosslinking point M for connecting different molecular chains in the copolymer, the copolymer comprises a structural unit a from an acrylic monomer, a structural unit b from acrylamide and a structural unit c from an N-alkyl substituted acrylamide monomer, wherein M is selected from Zn, zr, B, S or Cr.
The second aspect of the invention provides a preparation method of a plugging well wall stabilizing treatment agent, wherein the method comprises the following steps:
(1) Mixing acrylic acid monomer, acrylamide, N-alkyl substituted acrylamide monomer and water, and regulating the pH value of the obtained mixed solution to be 1-9;
(2) Carrying out polymerization reaction on the mixture obtained in the step (1), the nano particles and the initiator;
(3) Crosslinking modification is carried out on the product obtained in the step (2), a crosslinking agent and chlorinated polyolefin;
(4) And (3) regulating the pH value of the modified product obtained in the step (3) to 8-10 to obtain the treating agent.
The third aspect of the invention provides a drilling fluid, wherein the drilling fluid contains the plugging well wall stabilizing treatment agent.
Through the technical scheme, the plugging well wall stabilizing treatment agent provided by the invention not only contains the polyacrylic acid fragment responding to the stratum [ H + ] but also contains the N-alkyl substituted acrylamide and the polyolefin fragment responding to the stratum temperature, so that the directional response to the stratum temperature can be realized, and the plugging effect of the treatment agent is further improved by adopting the nano particles and the cross-linking agent. The material can respond to 40-100 ℃ by adjusting the dosage of the N-alkyl substituted acrylamide and the cross-linking agent, so that the dual factor rapid response to the stratum environment temperature and the [ H + ] is realized, the form change of the material can be excited and regulated by the stratum environment [ H + ] and the temperature dual factor, the rapid matching of the sizes of microcracks is realized, the microcracks are rapidly aggregated and grown mutually, the rapid repair of the microcracks is realized, the hydration channel is blocked, the invasion of drilling fluid filtrate to the stratum is reduced, and the stability of the well wall of a hard and brittle stratum is improved.
Drawings
FIG. 1 is a schematic illustration of a structural formula of a plugged borehole wall stabilizing treatment;
FIG. 2 is a diagram showing nuclear magnetic resonance characterization of the product of example 1.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides a plugged borehole wall stabilizing treatment agent, the treatment agent comprising a plurality of nanoparticles, polyolefin chains, and a crosslinked copolymer; wherein the crosslinked copolymer comprises a copolymer and a crosslinking point M for connecting different molecular chains in the copolymer, the copolymer comprises a structural unit a from an acrylic monomer, a structural unit b from acrylamide and a structural unit c from an N-alkyl substituted acrylamide monomer, wherein M is selected from Zn, zr, B, S or Cr.
In the present invention, the structural units a, b and c contained in the crosslinked copolymer are repeating units formed in the crosslinked copolymer by addition polymerization of olefin carbon-carbon double bonds contained in the corresponding acrylic monomer, acrylamide and N-alkyl-substituted acrylamide monomer, respectively. In the crosslinked copolymer, the structural unit a, the structural unit b, or the structural unit c may be bonded to the surface of the nanoparticle. In the bonding relationship between the crosslinked copolymer and the nanoparticle, the plurality of nanoparticles may be a structure unit a derived from an acrylic monomer, a structure unit b derived from an acrylamide, a structure unit c derived from an N-alkyl substituted acrylamide monomer, or may be a structure unit c derived from an N-alkyl substituted acrylamide monomer, a structure unit b derived from an acrylamide, a structure unit a derived from an acrylic monomer, which are sequentially connected.
In some embodiments of the invention, the nanoparticle is attached to a carbon atom at one end of the crosslinked copolymer through a hydroxyl group at the surface.
In some embodiments of the present invention, the nanoparticle is selected from one or more of nano calcium carbonate, nano silicon dioxide, nano aluminum oxide, nano titanium oxide, and nano zinc oxide. Preferably, the nanoparticles have an average particle diameter of 1 to 1000nm, preferably 20 to 500nm.
In some embodiments of the invention, the weight average molecular weight of the copolymer is from 1 ten thousand to 100 ten thousand g/mol.
In some embodiments of the present invention, the acrylic monomer is selected from one or more of acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobornyl acrylate, and isobornyl methacrylate.
In some embodiments of the present invention, the N-alkyl substituted acrylamide monomer is selected from one or more of N-isopropyl acrylamide, N-dimethyl acrylamide, N-diethyl acrylamide, N-dimethyl bisacrylamide, N-butyl acrylamide, N-propyl acrylamide, and N-hydroxymethyl acrylamide.
In some embodiments of the invention, the weight ratio of structural unit a, structural unit b, structural unit c, structural unit d, polyolefin chain is: 10 (5-40): 1-10): 0.1-2): 5-20, preferably 10 (10-20): 2-8): 0.5-2: (10-20); preferably, the weight ratio of the nanoparticle to the structural unit d is: (0.1-10): (1-20), preferably (1-10): (5-20).
In some embodiments of the invention, in the copolymer, the structural unit a, structural unit b or structural unit c is bonded to the surface of the nanoparticle.
In some embodiments of the present invention, preferably, each of the crosslinking points M is bonded to an oxygen atom contained in the structural unit a, structural unit b or structural unit c; the oxygen atoms are derived from different building blocks bonded to different ones of the nanoparticles. For example, two nanoparticles shown in the pellets in fig. 1, the oxygen atoms contained in the structural units in the different crosslinked copolymers to which the two nanoparticles are each attached are connected by a crosslinking point M.
In some embodiments of the invention, a portion of the polyolefin chains are bonded to the surface of the nanoparticle and another portion of the polyolefin chains are connected to the crosslinking point M. For example, as shown in FIG. 1, the polyolefin chain may be bonded to the surface of the nanoparticle, and the polyolefin chain may be bonded to the crosslinking point M.
In some embodiments of the invention, the chlorinated polyolefin has a weight average molecular weight of 1000 to 100000g/mol.
In the preferred embodiment of the invention, the structure of the blocking well wall stabilizing treatment agent can be shown as a figure 1, wherein the weight average molecular weight of the copolymer is 1 ten thousand to 100 ten thousand g/mol, the weight average molecular weight of the polyolefin is 1000 to 100000g/mol, m, n and p represent the number of different repeating units, and a side chain group R' is an alkyl group or H which is substituted differently.
In a preferred embodiment of the present invention, the structural unit a may be of the structure shown below,
The structural unit b may have a structure as shown below,
The structural unit c may have a structure as shown below,
The crosslinked copolymer may have the structure shown below,
The polyolefin chain may have a structure as shown below,
The assay and characterization methods that can be used to determine the composition and structure of the treatment agents of the present invention include: determination of the molecular weight of the Polymer can be determined by gel permeation chromatography (Gel Permeation Chromatography, GPC), by nuclear magnetic measurement of-COOH, -NH 2 saturated-CH 2 -, -C-O-C, etc.
In the invention, the composition and structure of the plugging borehole wall stabilizing treatment agent can be determined by determination of nuclear magnetism, infrared, GPC, elemental analysis and the like, or by preparation and feeding.
The second aspect of the invention provides a preparation method of a plugging well wall stabilizing treatment agent, wherein the method comprises the following steps:
(1) Mixing acrylic acid monomer, acrylamide, N-alkyl substituted acrylamide monomer and water, and regulating the pH value of the obtained mixed solution to be 1-9;
(2) Carrying out polymerization reaction on the mixture obtained in the step (1), the nano particles and the initiator;
(3) Crosslinking modification is carried out on the product obtained in the step (2), a crosslinking agent and chlorinated polyolefin;
(4) And (3) regulating the pH value of the modified product obtained in the step (3) to 8-10 to obtain the treating agent.
In some embodiments of the present invention, the initiator is selected from one or more of benzoyl peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, azobisisobutyronitrile, azobisisoheptonitrile, lauroyl peroxide, and dimethyl azobisisobutyrate.
In some embodiments of the present invention, the cross-linking agent is selected from one or more of zinc oxide, zirconium tetrachloride, sulfur, boric acid, borax, and chromium nitrate.
In some embodiments of the present invention, the chlorinated polyolefin is selected from one or more of chlorinated polyethylene, chlorinated paraffin, and chlorinated polypropylene, and the weight average molecular weight of the chlorinated polyolefin is 1000-100000g/mol.
In some embodiments of the invention, the polymerization temperature in step (2) is 10 to 100 ℃, preferably 30 to 80 ℃.
In some embodiments of the invention, the acrylic monomer is 100 parts by weight, the acrylamide is 50-400 parts by weight, the nanoparticle is 0.1-10 parts by weight, the N-alkyl substituted acrylamide monomer is 10-100 parts by weight, the initiator is 0.01-10 parts by weight, the crosslinking agent is 1-20 parts by weight, and the chlorinated polyolefin is 50-200 parts by weight;
In some embodiments of the present invention, preferably, the acrylic monomer is 100 parts by weight, the acrylamide is 100-200 parts by weight, the nanoparticle is 1-10 parts by weight, the N-alkyl substituted acrylamide monomer is 20-80 parts by weight, the initiator is 0.5-5 parts by weight, the crosslinking agent is 5-20 parts by weight, and the chlorinated polyolefin is 100-200 parts by weight.
In some embodiments of the invention, in step (2), the product comprises a copolymer polymerized from the acrylic monomer, acrylamide, and N-alkyl substituted acrylamide monomer; the weight average molecular weight of the copolymer is 1 ten thousand to 100 ten thousand g/mol.
According to a particularly preferred embodiment of the invention, a method for preparing a plugging well wall stabilizing treatment agent comprises the following steps:
(1) Sequentially adding an acrylic monomer, acrylamide, an N-alkyl substituted acrylamide monomer and water into a reaction kettle, uniformly stirring to uniformly disperse all components in the water, and adding alkali to adjust the pH value of the obtained mixed solution to be 1-9;
(2) Carrying out polymerization reaction on the mixture obtained in the step (1), the nano particles and the initiator for 1-24 h, wherein the polymerization reaction temperature is 30-80 ℃;
(3) Crosslinking and modifying the product obtained in the step (2), a crosslinking agent and chlorinated polyolefin for 1-10 h;
(4) Regulating the pH value of the modified product obtained in the step (3) to 8-10 to obtain the treating agent;
Preferably, the acrylic monomer is 100 parts by weight, the acrylamide is 100-200 parts by weight, the nanoparticle is 1-10 parts by weight, the N-alkyl substituted acrylamide monomer is 20-80 parts by weight, the initiator is 0.5-5 parts by weight, the crosslinking agent is 5-20 parts by weight, and the chlorinated polyolefin is 100-200 parts by weight.
The third aspect of the invention provides a drilling fluid, which contains the plugging well wall stabilizing treatment agent.
In some embodiments of the invention, the drilling fluid comprises: 4wt% of pre-hydrated bentonite slurry, (0.4 wt% -0.5 wt%) PAC-LV high viscosity polyanionic cellulose, 2wt% of SMC sulfonated lignite, 2wt% of SMP sulfonated phenolic resin, 0.1wt% of NaOH and (1 wt% -3 wt%) of plugging well wall stabilizing treatment agent.
The present invention will be described in detail by examples.
The following examples and comparative examples were conducted under conventional conditions or conditions recommended by the manufacturer, where specific conditions were not noted. The reagents or apparatus used were conventional products available commercially without the manufacturer's knowledge.
Example 1
After three times of air extraction in a 2000mL three-necked flask, 150g of methacrylic acid, 50g of lauryl acrylate, 400g of acrylamide, 30g of N-N-propyl acrylamide, 10g of N-methylol acrylamide and 500mL of distilled water are added to form a mixed solution, sodium methoxide is added to adjust the pH of the mixed solution to 6, and the mixed solution is stirred until all components are fully dispersed to obtain a mixture;
Controlling the temperature of the mixture to be 30 ℃, adding 2g of nano silicon dioxide and 1g of azobisisobutyronitrile, and carrying out polymerization reaction for 3h;
Adding 10g of chromium nitrate and 200g of chlorinated polypropylene into the polymerization reaction product to carry out crosslinking modification for 3h;
Adding sodium hydroxide into the obtained modified product to adjust the pH value of the solution to 10, and finally obtaining 657.9g of brown yellow solid through drying and crushing to obtain the plugging well wall stabilizing treatment agent (response temperature 100 ℃);
Wherein, in the treating agent, the weight ratio of the structural unit a, the structural unit b, the structural unit c, the crosslinking point M (Cr) and the polyolefin chain is as follows: 10:20:2:0.5:10; the weight ratio of the nano silicon dioxide to the crosslinking point M (Cr) is as follows: the weight average molecular weight of the copolymer was 100 ten thousand g/mol, and the weight average molecular weight of the chlorinated polyolefin was 100000g/mol.
Example 2
After three times of air extraction in a 2000mL three-port bottle, adding 100g of N-butyl methacrylate, 100g of acrylic acid, 200g of acrylamide, 30g of N-N-propyl acrylamide, 10g of N-methylol acrylamide and 500mL of distilled water to form a mixed solution, adding sodium methoxide to adjust the pH of the mixed solution to 8, and stirring until all components are fully dispersed to obtain a mixture;
controlling the temperature of the mixture to 80 ℃, adding 20g of nano alumina and 10g of azo-diisoheptonitrile, and carrying out polymerization reaction for 12h;
adding 40g of zirconium tetrachloride, 300g of chlorinated polyethylene and 100g of chlorinated paraffin into the polymerization reaction product to carry out crosslinking modification for 8 hours;
adding sodium hydroxide into the obtained modified product to adjust the pH of the solution to 8-9, and finally obtaining 913.2g of brown yellow solid after drying and crushing to obtain the plugging well wall stabilizing treatment agent (response temperature 80 ℃);
Wherein, in the treating agent, the weight ratio of the structural unit a, the structural unit b, the structural unit c, the crosslinking point M (Zr) and the polyolefin chain is as follows: 10:10:2:2:15; the weight ratio of the nanoparticle to the crosslinking point M (Zr) is as follows: the weight average molecular weight of the copolymer was 1 ten thousand g/mol, and the weight average molecular weight of the chlorinated polyolefin was 1000g/mol.
Example 3
After three times of air extraction in a 2000mL three-port bottle, 50g of methyl acrylate, 50g of N-butyl methacrylate, 400g of acrylamide, 80g of N-isopropyl acrylamide, 20g of N, N-diethyl acrylamide and 500mL of high-purity water are added to form a mixed solution, potassium hydroxide is added to adjust the pH value of the mixed solution to 9, and the mixed solution is stirred until all components are fully dispersed to obtain a mixture;
controlling the temperature of the mixture to be 100 ℃, adding 10g of nano silicon dioxide and 10g of ammonium persulfate, and carrying out polymerization reaction for 1h;
Adding 20g of sulfur and 200g of chlorinated paraffin into the polymerization reaction product to carry out crosslinking modification for 1h;
Adding sodium hydroxide into the obtained modified product to adjust the pH of the solution to 8-9, and finally obtaining 835.3g of brown yellow solid after drying and crushing to obtain the plugging well wall stabilizing treatment agent (response temperature 60 ℃);
Wherein, in the treating agent, the weight ratio of the structural unit a, the structural unit b, the structural unit c, the crosslinking point M (S) and the polyolefin chain is as follows: 10:40:10:2:20; the weight ratio of the nano particles to the crosslinking point M (S) is as follows: 1:2, the weight average molecular weight of the copolymer was 50 ten thousand g/mol, and the weight average molecular weight of the chlorinated polyolefin was 10000g/mol.
Example 4
After three times of air extraction in a 500mL three-necked flask, 25g of acrylic acid, 25g of methacrylic acid, 25g of acrylamide, 5g of N-isopropyl acrylamide and 150mL of distilled water are added to form a mixed solution, sodium hydroxide is added to adjust the pH of the mixed solution to 1, and the mixed solution is stirred until all components are fully dispersed to obtain a mixture;
Controlling the temperature of the mixture to be 10 ℃, adding 0.05g of nano calcium carbonate and 0.005g of benzoyl peroxide, and carrying out polymerization reaction for 24 hours;
Adding 1.0g boric acid and 25g chlorinated polyethylene into the polymerization reaction product to carry out crosslinking modification for 10 hours;
Adding sodium hydroxide into the obtained modified product to adjust the pH of the solution to 8-9, and finally obtaining 113.7g of pale yellow solid after drying and crushing to obtain the plugging well wall stabilizing treatment agent (response temperature 40 ℃);
Wherein, in the treating agent, the weight ratio of the structural unit a, the structural unit B, the structural unit c, the crosslinking point M (B) and the polyolefin chain is as follows: 10:5:1:0.2:5; the weight ratio of the nano particles to the crosslinking point M (B) is as follows: the weight average molecular weight of the copolymer was 10 ten thousand g/mol, and the weight average molecular weight of the chlorinated polyolefin was 80000g/mol, 0.05:1.
Test case
And (3) material structure characterization:
as the nuclear magnetic characterization of the product of the example 1 shows that the test sample contains groups such as-COOH, -NH 2, saturated-CH 2 -, -C-O-C and the like, the molecular structure design is consistent, and the characterization result is shown in figure 2.
1 H NMR of the product of example 1, delta=4.4 ppm being-CH 2 -COOH, delta=3.25 and 3.72ppm being-COOH and-NH 2, delta = 0.87-1.81 ppm-C-O-CH 2 -and saturated-CH 2 -, consistent with molecular structural design.
Response performance characterization:
The sample prepared in example 1 was dissolved in water to a pH of 9, adjusted to pH 10 by adding an appropriate amount of alkali (the pH of the drilling fluid is generally 8 to 10), and then a 3% hydrochloric acid standard solution was prepared, and further dropped into the above mixture, while the pH of the mixture was measured by a pH meter. The pH value is 9, the state change of the solution is small, hydrochloric acid is further dripped, the pH value is reduced to 9, 8 and 7.5 in sequence, but when the pH value is 7.5, the solution becomes turbid obviously when the temperature is heated to 100 ℃. And the heating is removed and the solution returns to the original state after readjusting the pH, indicating that the material has a pronounced pH and temperature responsiveness.
And (3) plugging performance evaluation:
evaluation of plugging performance of hard and brittle shale core: the pressure penetration capacity is measured by adopting an RSA-6000 rock seepage device of university of Talssa in the United states, and the plugging performance evaluation is carried out by using a Xinjiang shale rock sample standardized processing system. The formula of the base slurry comprises the following steps: 4wt% sodium bentonite slurry +2wt% hand piece. Compared with a blank rock sample and a comparison sample (wherein the blank rock sample has original permeability of 1.24 multiplied by 10 -2 mD, the comparison sample uses a blocking agent of a Max-Plex blocking agent product sold by Bekkes company), the small samples 1-4 greatly block pressure penetration, the permeability of the rock sample is reduced from 1.24 multiplied by 10 -2 mD to 0.5 multiplied by 10 -4-1.3×10-4 mD, the permeability of the shale is respectively reduced by 99% through dual response, and the results are shown in table 1.
TABLE 1
From the above table, the borehole wall stabilizing agents with response temperatures of 100 ℃,80 ℃, 60 ℃ and 40 ℃ are obtained in examples 1-4 respectively, and the plugging rate of the borehole wall stabilizing agent with response temperature of the formation environment [ H + ] in the drilling fluid under the corresponding temperature conditions is higher than 99%, which indicates that the borehole wall stabilizing agent has good plugging capability on the nano-micro pore stratum.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (15)
1. A plugged borehole wall stabilizing treatment agent, which is characterized by comprising a plurality of nano particles, polyolefin chains and cross-linked copolymers; wherein the crosslinked copolymer comprises a copolymer and a crosslinking point M for connecting different molecular chains in the copolymer, the copolymer comprises a structural unit a from an acrylic monomer, a structural unit b from acrylamide and a structural unit c from an N-alkyl substituted acrylamide monomer, wherein M is selected from Zn, zr, B, S or Cr.
2. The treating agent according to claim 1, wherein the nanoparticle is one or more selected from the group consisting of nano calcium carbonate, nano silica, nano alumina, nano titania and nano zinc oxide;
Preferably, the nanoparticles have an average particle diameter of 1 to 1000nm, preferably 20 to 500nm.
3. A treatment agent according to claim 1 or 2, characterized in that the weight average molecular weight of the copolymer is 1-100 ten thousand g/mol.
4. A treatment agent according to any one of claims 1 to 3, wherein the acrylic monomer is selected from one or more of acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobornyl acrylate, isobornyl methacrylate.
5. The treating agent according to any one of claims 1 to 4, wherein the N-alkyl substituted acrylamide monomer is one or more selected from the group consisting of N-isopropylacrylamide, N-dimethylacrylamide, N-diethylacrylamide, N-dimethylbisacrylamide, N-N-butylacrylamide, N-N-propylacrylamide and N-methylolacrylamide.
6. The treating agent according to any one of claims 1 to 5, wherein the weight ratio of the structural unit a, the structural unit b, the structural unit c, the crosslinking point M, the polyolefin chain is: 10 (5-40): 1-10): 0.1-2): 5-20, preferably 10 (10-20): 2-8): 0.5-2: (10-20);
Preferably, the weight ratio of the nanoparticle to the crosslinking point M is: (0.1-10): (1-20), preferably (1-10): (5-20).
7. The treatment agent according to any one of claims 1 to 6, wherein in the copolymer, the structural unit a, structural unit b or structural unit c is bonded to the surface of the nanoparticle;
Preferably, each of the crosslinking points M is bonded to an oxygen atom contained in the structural unit a, structural unit b or structural unit c.
8. The treating agent according to any one of claims 1 to 7, wherein a part of the polyolefin chains are bonded to the surface of the nanoparticle and another part of the polyolefin chains are bonded to the crosslinking point M;
Preferably, the weight average molecular weight of the polyolefin chain is 1000 to 100000g/mol.
9. A preparation method of a plugging well wall stabilizing treatment agent is characterized by comprising the following steps:
(1) In the presence of an initiator, carrying out polymerization reaction on an acrylic monomer, acrylamide, an N-alkyl substituted acrylamide monomer and nano particles;
(2) Crosslinking modification is carried out on the product obtained in the step (1), a crosslinking agent and chlorinated polyolefin;
(3) And (3) regulating the pH value of the modified product obtained in the step (2) to 8-10 to obtain the treating agent.
10. The preparation method according to claim 9, wherein the initiator is one or more selected from benzoyl peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, azobisisobutyronitrile, azobisisoheptonitrile, lauroyl peroxide, and dimethyl azobisisobutyrate;
preferably, the cross-linking agent is selected from one or more of zinc oxide, zirconium tetrachloride, sulfur, boric acid, borax and chromium nitrate.
11. The preparation method according to claim 9 or 10, wherein the chlorinated polyolefin is selected from one or more of chlorinated polyethylene, chlorinated paraffin, and chlorinated polypropylene;
Preferably, the chlorinated polyolefin has a weight average molecular weight of from 1000 to 100000g/mol.
12. The process according to any one of claims 9 to 11, wherein in step (1) the polymerization temperature is 10 to 100 ℃, preferably 30 to 80 ℃.
13. The production method according to any one of claims 9 to 12, wherein 100 parts by weight of the acrylic monomer, 50 to 400 parts by weight of the acrylamide, 0.1 to 10 parts by weight of the nanoparticle, 10 to 100 parts by weight of the N-alkyl substituted acrylamide monomer, 0.01 to 10 parts by weight of the initiator, 1 to 20 parts by weight of the crosslinking agent, and 50 to 200 parts by weight of the chlorinated polyolefin;
Preferably, the acrylic monomer is 100 parts by weight, the acrylamide is 100-200 parts by weight, the nanoparticle is 1-10 parts by weight, the N-alkyl substituted acrylamide monomer is 20-80 parts by weight, the initiator is 0.5-5 parts by weight, the crosslinking agent is 5-20 parts by weight, and the chlorinated polyolefin is 100-200 parts by weight.
14. The method according to any one of claims 9 to 13, wherein in the step (2), the product contains a copolymer obtained by polymerizing the acrylic monomer, acrylamide and N-alkyl substituted acrylamide monomer;
preferably, the weight average molecular weight of the copolymer is from 1 to 100 thousand g/mol.
15. A drilling fluid, characterized in that the drilling fluid contains the plugging well wall stabilizing treatment agent prepared by the preparation method of any one of claims 1-8 or any one of claims 9-14.
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