CN117551437A - High-temperature high-salt oil reservoir deep profile control gel water shutoff agent and preparation method thereof - Google Patents
High-temperature high-salt oil reservoir deep profile control gel water shutoff agent and preparation method thereof Download PDFInfo
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- CN117551437A CN117551437A CN202311533928.1A CN202311533928A CN117551437A CN 117551437 A CN117551437 A CN 117551437A CN 202311533928 A CN202311533928 A CN 202311533928A CN 117551437 A CN117551437 A CN 117551437A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 72
- 239000011258 core-shell material Substances 0.000 claims abstract description 40
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 35
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 30
- 239000011734 sodium Substances 0.000 claims abstract description 30
- 229920001577 copolymer Polymers 0.000 claims abstract description 25
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000033558 biomineral tissue development Effects 0.000 claims abstract description 19
- 238000004132 cross linking Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 74
- 238000003756 stirring Methods 0.000 claims description 70
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 48
- 239000000843 powder Substances 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 29
- 239000000839 emulsion Substances 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- ZGUQGPFMMTZGBQ-UHFFFAOYSA-N [Al].[Al].[Zr] Chemical compound [Al].[Al].[Zr] ZGUQGPFMMTZGBQ-UHFFFAOYSA-N 0.000 claims description 20
- 239000010410 layer Substances 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 19
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000012071 phase Substances 0.000 claims description 16
- 230000000630 rising effect Effects 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 13
- 239000011780 sodium chloride Substances 0.000 claims description 13
- 239000002736 nonionic surfactant Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 8
- 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 8
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 8
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 8
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 8
- 239000004280 Sodium formate Substances 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- 239000008346 aqueous phase Substances 0.000 claims description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- 238000007664 blowing Methods 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000012792 core layer Substances 0.000 claims description 8
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 8
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 8
- 230000000977 initiatory effect Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 230000006911 nucleation Effects 0.000 claims description 8
- 238000010899 nucleation Methods 0.000 claims description 8
- 238000010298 pulverizing process Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 8
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 8
- 235000019254 sodium formate Nutrition 0.000 claims description 8
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 8
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 8
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 8
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 8
- 238000001694 spray drying Methods 0.000 claims description 8
- -1 azo diisobutyl amidine Chemical class 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012267 brine Substances 0.000 claims description 6
- 229940071160 cocoate Drugs 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 6
- 150000003754 zirconium Chemical class 0.000 claims description 6
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 5
- BTMZHHCFEOXAAN-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;2-dodecylbenzenesulfonic acid Chemical compound OCCN(CCO)CCO.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O BTMZHHCFEOXAAN-UHFFFAOYSA-N 0.000 claims description 5
- 229940105956 tea-dodecylbenzenesulfonate Drugs 0.000 claims description 5
- 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 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 4
- FWFUWXVFYKCSQA-UHFFFAOYSA-M sodium;2-methyl-2-(prop-2-enoylamino)propane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(C)(C)NC(=O)C=C FWFUWXVFYKCSQA-UHFFFAOYSA-M 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- HLCFGWHYROZGBI-JJKGCWMISA-M Potassium gluconate Chemical compound [K+].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O HLCFGWHYROZGBI-JJKGCWMISA-M 0.000 claims description 3
- 238000010668 complexation reaction Methods 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000004224 potassium gluconate Substances 0.000 claims description 3
- 235000013926 potassium gluconate Nutrition 0.000 claims description 3
- 229960003189 potassium gluconate Drugs 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 claims description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 2
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 claims description 2
- IJCWFDPJFXGQBN-RYNSOKOISA-N [(2R)-2-[(2R,3R,4S)-4-hydroxy-3-octadecanoyloxyoxolan-2-yl]-2-octadecanoyloxyethyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCCCCCCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCCCCCCCCCCCC IJCWFDPJFXGQBN-RYNSOKOISA-N 0.000 claims description 2
- FUQCJMSCGSVFNQ-UHFFFAOYSA-N bis(2-hydroxyethyl)azanium;tetradecanoate Chemical compound OCCNCCO.CCCCCCCCCCCCCC(O)=O FUQCJMSCGSVFNQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000071 diazene Inorganic materials 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 229940050410 gluconate Drugs 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- UWNADWZGEHDQAB-UHFFFAOYSA-N i-Pr2C2H4i-Pr2 Natural products CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000013110 organic ligand Substances 0.000 claims description 2
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 229940083575 sodium dodecyl sulfate Drugs 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 235000012207 sodium gluconate Nutrition 0.000 claims description 2
- 239000000176 sodium gluconate Substances 0.000 claims description 2
- 229940005574 sodium gluconate Drugs 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 235000011078 sorbitan tristearate Nutrition 0.000 claims description 2
- 239000001384 succinic acid Substances 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- GBSRRQISIWGCNC-UHFFFAOYSA-N methyl propane-1-sulfonate Chemical compound CCCS(=O)(=O)OC GBSRRQISIWGCNC-UHFFFAOYSA-N 0.000 claims 2
- 230000036571 hydration Effects 0.000 abstract description 17
- 238000006703 hydration reaction Methods 0.000 abstract description 17
- 230000002035 prolonged effect Effects 0.000 abstract description 5
- 238000010008 shearing Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 2
- 239000000499 gel Substances 0.000 description 61
- 230000001276 controlling effect Effects 0.000 description 21
- 239000003708 ampul Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 229940043237 diethanolamine Drugs 0.000 description 7
- 235000015110 jellies Nutrition 0.000 description 6
- 239000008274 jelly Substances 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 238000005253 cladding Methods 0.000 description 5
- OPRIWFSSXKQMPB-UHFFFAOYSA-N 2-methyl-2-(prop-2-enoylamino)propane-1-sulfonic acid;sodium Chemical compound [Na].OS(=O)(=O)CC(C)(C)NC(=O)C=C OPRIWFSSXKQMPB-UHFFFAOYSA-N 0.000 description 4
- 235000013162 Cocos nucifera Nutrition 0.000 description 4
- 244000060011 Cocos nucifera Species 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003129 oil well Substances 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- 230000005465 channeling Effects 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 125000002370 organoaluminium group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 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
- 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
- C09K8/512—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
Abstract
The invention discloses a high-temperature high-salt oil reservoir deep profile control gel water shutoff agent and a preparation method thereof. The preparation method comprises the steps of carrying out compatibility crosslinking with a high-temperature-resistant organic crosslinking agent by taking an acrylamide/2-acrylamide-2-methylpropanesulfonic acid sodium copolymer and a core-shell polymer based on the acrylamide/2-acrylamide-2-methylpropanesulfonic acid sodium copolymer as a core as a gel main agent. The invention adopts acrylamide/2-acrylamide-2-methylpropanesulfonic acid sodium copolymer to crosslink with high temperature resistant organic crosslinking agent to form gel, when gel is degraded or hydrated gradually, the high temperature resistant/shearing resistant core-shell structure polymer dispersoid dispersed in gel is exposed gradually, and the gel is degraded hydration liquid after shell breaking releases core polymer to dissolve and absorb, and the gel is crosslinked with high temperature resistant organic crosslinking agent for a second time, and the mineralization degree of 41938.8mg/L is prolonged to more than 60 days at 120 ℃.
Description
Technical Field
The invention relates to a high-temperature high-salt oil reservoir deep profile control gel water shutoff agent and a preparation method thereof, and belongs to the technical field of petroleum development.
Background
With the deep and stiff advance of oil field development, the problems of complexity of an oil storage space structure and reservoir heterogeneity are increasingly outstanding, the range of water flooding is very limited, a large amount of water flows into a high-permeability area, and finally, the water forms ineffective channeling detours, so that the recovery ratio is obviously reduced, and the oil field development cost is greatly increased. The water discharged from the oil well can damage the structure of a reservoir, so that a large amount of sand in the oil well is entrained; meanwhile, the water discharged from the oil well can accelerate corrosion of underground equipment, and the underground equipment becomes a hidden trouble of sudden accidents. Therefore, profile control and water shutoff are increasingly widely used as a reasonable and effective important measure. The profile control and water shutoff effects can be shown in: the high permeable layer in the oil well is plugged, the low permeable layer is activated to play a role, the water content is reduced, and the yield is improved. The method for changing the water flooding route to avoid invalid channeling is a means capable of effectively blocking the high permeable layer, improving the water flooding efficiency value and expanding the swept volume.
In the 90 s of the last century, mack et al developed polyacrylamide profile control and water shutoff technologies first by utilizing the principle of adsorption and trapping of chemical agents in pore-throat media. Later, as many expert scholars have conducted intensive research on this basis, deep profile control and water shutoff technologies are proposed. Since 21 st century, centralized deep profile control and deep profile control of microorganisms, sediments, gels and colloidal dispersion gels respectively have been reported abroad and domestically, and good effects are obtained.
The polymer gel plugging agent is often used for plugging a crossflow channel, and the recovery ratio is improved. The polymer loses fluidity under the action of a cross-linking agent, and the polymer is formed into a substance with a net structure. Polymer gels are widely used, can resist high temperature and high salt, and are relatively simple in preparation process, so that the polymer gels are focused by most scientific researchers as a hot subject. The most common polymer at present is a polyacrylamide.
In recent years, research results have been disclosed on gels formed by crosslinking polyacrylamide with an organic crosslinking agent as a gel-forming main agent. For example, CN113897189B uses nonionic polyacrylamide and heat-resistant and salt-tolerant acrylamide/sodium 2-acrylamido-2-methylpropanesulfonate as a gel-forming main agent of the gel system, so that the starting time of gel-forming is shortened. However, the existing gel water shutoff agent has the phenomena of gel breaking and hydration in no more than 30 days under the conditions of high salt and high mineralization.
In order to prolong the gel forming time of a gel system under the condition of 120 ℃ by deep profile control water shutoff, keep the gel strength from decreasing for a longer time, and reduce the risk of opening a channeling channel to discharge water caused by premature failure of the profile control water shutoff, the invention is provided.
Disclosure of Invention
The invention aims to solve the defects of the existing jelly type profile control water shutoff agent in the process technology, and provides a jelly system for deep profile control water shutoff of a high-temperature high-salt oil reservoir and a preparation method thereof, wherein the jelly system can be prolonged to 60 days without breaking gel and hydrating on the premise that the jelly system with the mineralization of 41938.8mg/L at the temperature of 120 ℃ ensures the gel strength and stability, the gel stability of the jelly system is greatly prolonged, and the effect of deep profile control water shutoff is achieved.
The technical scheme adopted by the invention is as follows: the high-temperature high-salt oil reservoir deep profile control gel water shutoff agent is characterized by comprising the following components in percentage by mass: 0.8-1.2% of gelling main agent, 0.3-0.6% of high-temperature-resistant organic cross-linking agent and the balance of simulated saline solvent.
Further, the gel-forming main agent comprises an acrylamide/2-acrylamido-2-methylpropanesulfonic acid sodium copolymer and a core-shell polymer.
Further, the acrylamide/2-acrylamide-2-sodium methylpropanesulfonate copolymer accounts for 65-80% of the weight of the gel-forming main agent; the core-shell polymer accounts for 20-35% of the weight of the gel-forming main agent.
Further, the molecular weight of the acrylamide/2-acrylamide-2-methylpropanesulfonic acid sodium copolymer is 1000 ten thousand to 1500 ten thousand, and the mole percentage of the 2-acrylamide-2-methylpropanesulfonic acid sodium in the acrylamide/2-acrylamide-2-methylpropanesulfonic acid sodium copolymer is 45 percent.
Further, the core-shell polymer comprises a shell layer and an inner core, wherein the inner core is synthesized by adopting acrylamide and 2-acrylamide-2-methylpropanesulfonic acid sodium, and the mole percentage of 2-acrylamide-2-methylpropanesulfonic acid sodium monomer is 45% -55%; the shell layer is composed of one of vinyl polyethylene glycol ether-1000 (VPEG-1000) or ethylene glycol monovinyl polyoxyethylene ether (EPEG-1000), and the shell layer accounts for 4-8% of the weight of the core-shell polymer;
the preparation method of the core-shell polymer comprises the following steps:
s1, nucleation reaction:
core layer emulsion: adding 300-400 parts of water, 2-8 parts of nonionic surfactant A, 2-8 parts of nonionic surfactant B, 4-10 parts of anionic surfactant C, 60-120 parts of acrylamide, 240-300 parts of 2-acrylamido-2-methylpropanesulfonic acid sodium salt, 0.01-0.05 part of sodium formate and 0.05-0.1 part of disodium ethylenediamine tetraacetate into A2L reactor, regulating the pH to 6.3-6.5, and stirring and mixing fully to uniformly emulsify;
introducing nitrogen to replace for 40 minutes, adding 0.005-0.02 part of benzoyl peroxide, stirring uniformly, then initiating the reaction by using 1g/L sodium bisulphite solution, controlling the dropping speed to ensure that the rising speed of the reaction temperature is 30-40s/0.5 ℃, controlling the whole reaction temperature to be 48-50 ℃ and the polymerization reaction to be 4.5 hours, and cooling to 25 ℃ after the completion of the reaction to obtain nuclear emulsion, and keeping nitrogen blowing;
s2, coating reaction:
shell aqueous phase: adding 15-20 parts of one of VPEG-1000 or EPEG-1000 into 200-300 parts of deionized water according to parts by weight, adding 1-5 parts of nonionic surfactant D, and fully and uniformly stirring to obtain a shell water phase;
maintaining the nuclear layer emulsion at 25 ℃ under the nitrogen filling condition, adding 0.01-0.02 part of ammonium persulfate and 0.2 part of azo diisobutyl amidine dihydrochloride (V50), slowly adding a shell water phase, and fully and uniformly stirring; continuously dropwise adding 1g/L sodium metabisulfite solution to perform an envelope reaction, controlling the reaction at a temperature rising speed of 30-40s/0.5 ℃, starting to keep the temperature for 3 hours when the temperature reaches 80 ℃, and cooling after the reaction is finished to obtain a polymer;
s3, pulverizing:
the polymer is subjected to spray drying to obtain 50-100 μm polymer powder, namely the fine powder core-shell polymer.
Further, the nonionic surfactant A is one or more of SPAN40, SPAN65 and SPAN 80; the nonionic surfactant B is one or more of AEO-3, AEO-7 and AEO-9; the anionic surfactant C is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and triethanolamine dodecyl benzene sulfonate; the nonionic surfactant D is one or more of monoethanolamine cocoate, diethanolamine cocoate and diethanolamine myristate.
Further, the high-temperature-resistant organic cross-linking agent is an organic aluminum zirconium cross-linking agent.
Further, the preparation method of the high-temperature-resistant organic aluminum zirconium cross-linking agent comprises the following steps:
adding 150-250 parts of deionized water into a three-neck flask according to parts by weight, heating to 60 ℃, slowly adding 50-150 parts of polyol while stirring, and stirring for 20 minutes;
in the stirring process, adding 10-20 parts of aluminum salt and 15-25 parts of zirconium salt into the solution in the step 1) according to parts by weight, and fully stirring to dissolve the aluminum salt and the zirconium salt;
adjusting the temperature of the reactor to 80 ℃, adding 15-25 parts of organic acid and 5-15 parts of gluconate according to parts by weight, adding 1-5 parts of crosslinking auxiliary agent, stirring to dissolve completely, keeping reflux at 80 ℃ for carrying out complexation reaction for 4 hours, and slowly cooling to room temperature to obtain the high-temperature-resistant organic aluminum zirconium crosslinking agent.
Further, the zirconium salt is one or two of zirconium oxychloride and zirconium chloride; the aluminum salt is one or two of aluminum chloride and aluminum sulfate; the polyalcohol is one or more of ethylene glycol, propylene glycol and glycerol; the organic ligand is one or more of potassium gluconate and sodium gluconate; the organic acid is one or two of lactic acid and succinic acid; the cross-linking auxiliary agent is one or two of dimethyl diimine ester or N, N' -methylene bisacrylamide.
Further, the simulated brine mineralization was 41938.8Mg/L, with a Ca2+ concentration of 9693.7Mg/L and a Mg2+ concentration of 1123.1Mg/L.
A preparation method of a high-temperature high-salt oil reservoir deep profile control gel water shutoff agent is characterized by comprising the following steps: adding 0.65-0.80% of acrylamide/2-acrylamido-2-methylpropanesulfonic acid sodium copolymer powder and 0.20-0.35% of core-shell polymer fine powder into simulated saline with mineralization degree of 41938.8Mg/L, ca < 2+ > concentration of 9693.7Mg/L and Mg < 2+ > concentration of 1123.1Mg/L, fully stirring and dispersing for 60 minutes, adding 0.3-0.6% of organic aluminum zirconium cross-linking agent, and continuously stirring for 60 minutes.
Compared with the prior art, the high-temperature high-salt oil reservoir deep profile control gel water shutoff agent has the following beneficial effects: the high-temperature-resistant and salt-resistant acrylamide/2-acrylamide-2-methylpropanesulfonic acid sodium copolymer and the core-shell polymer are compounded, so that the gel forming time can be obviously prolonged, and the gel strength and stability are longer and lasting. The shell layer of the core-shell polymer adopts vinyl polyethylene glycol ether-1000 (VPEG-1000) or ethylene glycol monovinyl polyoxyethylene ether-1000 (EPEG-1000) macromonomer, unsaturated double bonds in the molecular structure of the core-shell polymer are directly connected with one oxygen atom to form a group of C-O bond molecular structure, so that the electron cloud distribution of C=C double bonds shifts, the charge environment is improved, the reactivity of double bonds in the macromonomer is high, and the polymerization reaction is easier to carry out.
Firstly, the acrylamide/2-acrylamide-2-sodium methylpropanesulfonate copolymer is crosslinked with a high-temperature-resistant organic aluminum zirconium crosslinking agent to form jelly; the core-shell polymer is completely maintained due to the characteristics of temperature resistance, salt resistance and mechanical shearing resistance, the hydrophilic groups with polar surfaces on the surface of the shell layer do not participate in the crosslinking reaction in the early stage, and the hydrophilic groups are quickly expanded to form a dispersion after being absorbed by water. After the action of the on-site simulated brine with the mineralization degree of 41938.8mg/L at the high temperature and high salt of 120 ℃ for a period of time, the gel gradually undergoes partial degradation and hydration, the high temperature resistant/shearing resistant core-shell structure polymer dispersoid dispersed in the gel is gradually exposed, the hydrophilic shell layer is broken under the action of the high temperature and high salt, and the released core polymer is dissolved and absorbs the early-stage gel hydration liquid and then is subjected to secondary crosslinking with the high temperature resistant organic crosslinking agent in the gel system. Thus, the gel strength and long-acting stability are ensured, and the effective time of gel profile control and water shutoff at the stratum depth is prolonged to more than 60 days.
Drawings
FIG. 1 is a gel strength rating (gel strength increasing from A-L).
Detailed Description
The following example simulates brine with brine mineralization of 41938.8mg/L, and simulates the water quality analysis result of the Xinjiang Ji Muxal block flowback fluid:
the preparation method of the high-temperature-resistant organic aluminum zirconium cross-linking agent comprises the following steps:
1) 160 parts of deionized water is added into a three-neck flask according to parts by weight, 75 parts of propylene glycol is slowly added while stirring after the temperature is raised to 60 ℃, and stirring is carried out for 20 minutes;
2) During stirring, 15 parts of aluminum sulfate and 18 parts of zirconium oxychloride are added to the solution in step 1), and the mixture is sufficiently stirred to dissolve the aluminum sulfate and the zirconium oxychloride,
3) Regulating the temperature of the reactor to 80 ℃, adding 21 parts of lactic acid, 12 parts of potassium gluconate, adding 3 parts of dimethyl diimidate, stirring to dissolve completely, keeping the mixture at 80 ℃ for reflux to carry out complexation reaction for 4 hours, and slowly cooling to room temperature to obtain the high-temperature-resistant organic aluminum zirconium cross-linking agent;
in the following examples and comparative examples, the acrylamide/sodium 2-acrylamido-2-methylpropanesulfonate copolymer powder was obtained from commercial sources, in which sodium 2-acrylamido-2-methylpropanesulfonate was 45 mol%.
Example 1: preparation of core-shell polymer:
example 1 preparation of core-shell Polymer: s1, nucleation reaction:
core layer emulsion: adding 350 parts of water, 80 parts of SPAN (SPAN), 5 parts of AEO-7 4 parts of triethanolamine dodecylbenzenesulfonate, 7 parts of triethanolamine dodecylbenzenesulfonate, 96 parts of acrylamide, 254 parts of 2-acrylamido-2-methylpropanesulfonate, 0.03 part of sodium formate and 0.08 part of disodium ethylenediamine tetraacetate into a 2L reactor, adjusting the pH to 6.3-6.5, and stirring and mixing fully to uniformly emulsify;
introducing nitrogen to replace for 40 minutes, adding 0.01 part of benzoyl peroxide, stirring uniformly, then initiating the reaction by using 1g/L sodium bisulphite solution, controlling the dropping speed to ensure that the rising speed of the reaction temperature is 30-40s/0.5 ℃, controlling the whole reaction temperature to be 48-50 ℃ and the polymerization reaction to be 4.5 hours, and cooling to 25 ℃ after the completion of the reaction to obtain nuclear emulsion, and keeping nitrogen blowing;
s2, coating reaction:
shell aqueous phase: adding VPEG-1000 19 parts into 250 parts of deionized water, adding 2.5 parts of coconut diethanol amine, and fully and uniformly stirring to obtain a shell water phase;
maintaining the nuclear layer emulsion at 25 ℃ under the nitrogen filling condition, adding 0.015 part of ammonium persulfate and 0.2 part of azo V50, slowly adding a shell water phase, and fully and uniformly stirring; continuously dropwise adding 1g/L sodium metabisulfite solution to perform an envelope reaction, controlling the reaction at a temperature rising speed of 30-40s/0.5 ℃, starting to keep the temperature for 3 hours when the temperature reaches 80 ℃, and cooling after the reaction is finished to obtain a polymer;
s3, pulverizing:
the polymer is subjected to spray drying to obtain 50-100 mu m polymer powder, namely core-shell polymer fine powder;
a preparation method of a high-temperature high-salt oil reservoir deep profile control gel water shutoff agent comprises the following steps: adding 0.65% of acrylamide/2-acrylamide-2-methylpropanesulfonic acid sodium copolymer powder and 0.35% of core-shell polymer fine powder into simulated saline with the mineralization degree of 41938.8mg/L, fully stirring, dispersing and dissolving for 60 minutes, adding 0.5% of organic aluminum zirconium cross-linking agent, and continuously stirring for 60 minutes; the system solution was then poured into an ampoule, placed in a 120 ℃ oven, and observed to track 60 days of gel strength and hydration status.
Example 2:
s1, nucleation reaction:
core layer emulsion: adding 350 parts of water, 80 parts of SPAN (SPAN), 80 parts of AEO-7 3 parts of triethanolamine dodecylbenzenesulfonate, 7 parts of triethanolamine salt, 83 parts of acrylamide, 268 parts of 2-acrylamido-2-methylpropanesulfonate, 0.03 part of sodium formate and 0.08 part of disodium ethylenediamine tetraacetate into a 2L reactor, adjusting the pH to 6.3-6.5, and stirring and mixing fully to uniformly emulsify;
introducing nitrogen to replace for 40 minutes, adding 0.01 part of benzoyl peroxide, stirring uniformly, then initiating the reaction by using 1g/L sodium bisulphite solution, controlling the dropping speed to ensure that the rising speed of the reaction temperature is 30-40s/0.5 ℃, controlling the whole reaction temperature to be 48-50 ℃ and the polymerization reaction to be 4.5 hours, and cooling to 25 ℃ after the completion of the reaction to obtain nuclear emulsion, and keeping nitrogen blowing;
s2, coating reaction:
shell aqueous phase: adding VPEG-1000 18 parts into 250 parts of deionized water, adding 2.5 parts of coconut diethanol amine, and fully and uniformly stirring to obtain a shell water phase;
maintaining the nuclear layer emulsion at 25 ℃ under the nitrogen filling condition, adding 0.015 part of ammonium persulfate and 0.2 part of azo V50, slowly adding a shell water phase, and fully and uniformly stirring; continuously dropwise adding 1g/L sodium metabisulfite solution to perform a cladding reaction, controlling the reaction at a temperature rising speed of 30-40s/0.5 ℃, starting to keep the temperature for 3 hours when the temperature reaches 80 ℃, and cooling after the reaction is finished to obtain a polymer;
s3, pulverizing:
the polymer is subjected to spray drying to obtain 50-100 mu m polymer powder, namely core-shell polymer fine powder;
a preparation method of a high-temperature high-salt oil reservoir deep profile control gel water shutoff agent comprises the following steps: adding 0.72% of acrylamide/2-acrylamide-2-methylpropanesulfonic acid sodium copolymer powder and 0.28% of core-shell polymer fine powder into simulated saline with the mineralization degree of 41938.8mg/L, fully stirring, dispersing and dissolving for 60 minutes, adding 0.5% of organic aluminum zirconium cross-linking agent, and continuously stirring for 60 minutes; the system solution was then poured into an ampoule, placed in a 120 ℃ oven, and observed to track 60 days of gel strength and hydration status.
Example 3:
s1, nucleation reaction:
core layer emulsion: adding 350 parts of water, 80 parts of SPAN (SPAN), 7 4 parts of AEO (AEO-5), 7 parts of sodium dodecyl sulfate, 71 parts of acrylamide, 281 parts of 2-acrylamido-2-methylpropanesulfonic acid sodium, 0.03 part of sodium formate and 0.08 part of disodium ethylenediamine tetraacetate into a 2L reactor, regulating the pH to 6.3-6.5, and stirring and mixing fully to uniformly emulsify;
introducing nitrogen to replace for 40 minutes, adding 0.01 part of benzoyl peroxide, stirring uniformly, then initiating the reaction by using 1g/L sodium bisulphite solution, controlling the dropping speed to ensure that the rising speed of the reaction temperature is 30-40s/0.5 ℃, controlling the whole reaction temperature to be 48-50 ℃ and the polymerization reaction to be 4.5 hours, and cooling to 25 ℃ after the completion of the reaction to obtain nuclear emulsion, and keeping nitrogen blowing;
s2, coating reaction:
shell aqueous phase: adding VPEG-1000 17 parts into 250 parts of deionized water, adding 2.5 parts of coconut diethanol amine, and fully and uniformly stirring to obtain a shell water phase;
maintaining the nuclear layer emulsion at 25 ℃ under the nitrogen filling condition, adding 0.015 part of ammonium persulfate and 0.2 part of azo V50, slowly adding a shell water phase, and fully and uniformly stirring; continuously dropwise adding 1g/L sodium metabisulfite solution to perform a cladding reaction, controlling the reaction at a temperature rising speed of 25-30 s/0.5 ℃, starting to keep the temperature for 3 hours when the temperature reaches 80 ℃, and cooling after the reaction is finished to obtain a polymer;
s3, pulverizing:
the polymer is subjected to spray drying to obtain 50-100 mu m polymer powder, namely core-shell polymer fine powder;
a preparation method of a high-temperature high-salt oil reservoir deep profile control gel water shutoff agent comprises the following steps: adding 0.80% of acrylamide/2-acrylamide-2-methylpropanesulfonic acid sodium copolymer powder and 0.20% of core-shell polymer fine powder into simulated saline with the mineralization degree of 41938.8mg/L, fully stirring, dispersing and dissolving for 60 minutes, adding 0.5% of organic aluminum zirconium cross-linking agent, and continuously stirring for 60 minutes; the system solution was then poured into an ampoule, placed in a 120 ℃ oven, and observed to track 60 days of gel strength and hydration status.
Example 4:
s1, nucleation reaction:
core layer emulsion: adding 350 parts of water, 80 parts of SPAN, 7 4 parts of AEO-7 4 parts of sodium dodecyl sulfate and 7 parts of acrylamide, 95 parts of 2-acrylamido-2-methylpropanesulfonic acid sodium 252 parts, 0.03 part of sodium formate and 0.08 part of disodium ethylenediamine tetraacetate into a 2L reactor, regulating the pH to 6.3-6.5, and stirring and mixing fully to uniformly emulsify;
introducing nitrogen to replace for 40 minutes, adding 0.01 part of benzoyl peroxide, stirring uniformly, then initiating the reaction by using 1g/L sodium bisulphite solution, controlling the dropping speed to ensure that the rising speed of the reaction temperature is 30-40s/0.5 ℃, controlling the whole reaction temperature to be 48-50 ℃ and the polymerization reaction to be 4.5 hours, and cooling to 25 ℃ after the completion of the reaction to obtain nuclear emulsion, and keeping nitrogen blowing;
s2, coating reaction:
shell aqueous phase: adding EPEG-1000 22 parts by weight into 250 parts by weight of deionized water, adding 2.5 parts by weight of coconut diethanol amine, and fully and uniformly stirring to obtain a shell water phase;
maintaining the nuclear layer emulsion at 25 ℃ under the nitrogen filling condition, adding 0.015 part of ammonium persulfate and 0.2 part of azo V50, slowly adding a shell water phase, and fully and uniformly stirring; continuously dropwise adding 1g/L sodium metabisulfite solution to perform a cladding reaction, controlling the reaction at a temperature rising speed of 30-40s/0.5 ℃, starting to keep the temperature for 3 hours when the temperature reaches 80 ℃, and cooling after the reaction is finished to obtain a polymer;
s3, pulverizing:
the polymer is subjected to spray drying to obtain 50-100 mu m polymer powder, namely core-shell polymer fine powder;
a preparation method of a high-temperature high-salt oil reservoir deep profile control gel water shutoff agent comprises the following steps: adding 0.65% of acrylamide/2-acrylamide-2-methylpropanesulfonic acid sodium copolymer powder and 0.35% of core-shell polymer fine powder into simulated saline with the mineralization degree of 41938.8mg/L, fully stirring, dispersing and dissolving for 60 minutes, adding 0.5% of organic aluminum zirconium cross-linking agent, and continuously stirring for 60 minutes; the system solution was then poured into an ampoule, placed in a 120 ℃ oven, and observed to track 60 days of gel strength and hydration status.
Example 5:
s1, nucleation reaction:
core layer emulsion: adding 350 parts of water, 80 parts of SPAN (SPAN), 7 4 parts of AEO (AEO-5), 7 parts of sodium dodecyl sulfate, 82 parts of acrylamide, 266 parts of 2-acrylamido-2-methylpropanesulfonic acid sodium, 0.03 part of sodium formate and 0.08 part of disodium ethylenediamine tetraacetate into a 2L reactor, regulating the pH to 6.3-6.5, and stirring and mixing fully to uniformly emulsify;
introducing nitrogen to replace for 40 minutes, adding 0.01 part of benzoyl peroxide, stirring uniformly, then initiating the reaction by using 1g/L sodium bisulphite solution, controlling the dropping speed to ensure that the rising speed of the reaction temperature is 30-40s/0.5 ℃, controlling the whole reaction temperature to be 48-50 ℃ and the polymerization reaction to be 4.5 hours, and cooling to 25 ℃ after the completion of the reaction to obtain nuclear emulsion, and keeping nitrogen blowing;
s2, coating reaction:
shell aqueous phase: adding EPEG-1000 21 parts into 250 parts of deionized water, adding 2.5 parts of diethanolamine cocoate, and fully and uniformly stirring to obtain a shell water phase;
maintaining the nuclear layer emulsion at 25 ℃ under the nitrogen filling condition, adding 0.015 part of ammonium persulfate and 0.2 part of azo V50, slowly adding a shell water phase, and fully and uniformly stirring; continuously dropwise adding 1g/L sodium metabisulfite solution to perform a cladding reaction, controlling the reaction at a temperature rising speed of 30-40s/0.5 ℃, starting to keep the temperature for 3 hours when the temperature reaches 80 ℃, and cooling after the reaction is finished to obtain a polymer;
s3, pulverizing:
the polymer is subjected to spray drying to obtain 50-100 mu m polymer powder, namely core-shell polymer fine powder;
a preparation method of a high-temperature high-salt oil reservoir deep profile control gel water shutoff agent comprises the following steps: adding 0.72% of acrylamide/2-acrylamide-2-methylpropanesulfonic acid sodium copolymer powder and 0.28% of core-shell polymer fine powder into simulated saline with the mineralization degree of 41938.8mg/L, fully stirring, dispersing and dissolving for 60 minutes, adding 0.5% of organic aluminum zirconium cross-linking agent, and continuously stirring for 60 minutes; the system solution was then poured into an ampoule, placed in a 120 ℃ oven, and observed to track 60 days of gel strength and hydration status.
Example 6:
s1, nucleation reaction:
core layer emulsion: adding 350 parts of water, 80 parts of SPAN (SPAN), 7 4 parts of AEO (AEO-5), 7 parts of sodium dodecyl sulfate, 71 parts of acrylamide, 279 parts of 2-acrylamido-2-methylpropanesulfonic acid sodium, 0.03 part of sodium formate and 0.08 part of disodium ethylenediamine tetraacetate into a 2L reactor, regulating the pH to 6.3-6.5, and stirring and mixing fully to uniformly emulsify;
introducing nitrogen to replace for 40 minutes, adding 0.01 part of benzoyl peroxide, stirring uniformly, then initiating the reaction by using 1g/L sodium bisulphite solution, controlling the dropping speed to ensure that the rising speed of the reaction temperature is 30-40s/0.5 ℃, controlling the whole reaction temperature to be 48-50 ℃ and the polymerization reaction to be 4.5 hours, and cooling to 25 ℃ after the completion of the reaction to obtain nuclear emulsion, and keeping nitrogen blowing;
s2, coating reaction:
shell aqueous phase: adding EPEG-1000 20 parts into 250 parts of deionized water, adding 2.5 parts of diethanolamine cocoate, and fully and uniformly stirring to obtain a shell water phase;
maintaining the nuclear layer emulsion at 25 ℃ under the nitrogen filling condition, adding 0.015 part of ammonium persulfate and 0.2 part of azo V50, slowly adding a shell water phase, and fully and uniformly stirring; continuously dropwise adding 1g/L sodium metabisulfite solution to perform a cladding reaction, controlling the reaction at a temperature rising speed of 30-40s/0.5 ℃, starting to keep the temperature for 3 hours when the temperature reaches 80 ℃, and cooling after the reaction is finished to obtain a polymer;
s3, pulverizing:
the polymer is subjected to spray drying to obtain 50-100 mu m polymer powder, namely core-shell polymer fine powder;
a preparation method of a high-temperature high-salt oil reservoir deep profile control gel water shutoff agent comprises the following steps: adding 0.80% of acrylamide/2-acrylamide-2-methylpropanesulfonic acid sodium copolymer powder and 0.20% of core-shell polymer fine powder into simulated saline with the mineralization degree of 41938.8mg/L, fully stirring, dispersing and dissolving for 60 minutes, adding 0.5% of organic aluminum zirconium cross-linking agent, and continuously stirring for 60 minutes; the system solution was then poured into an ampoule, placed in a 120 ℃ oven, and observed to track 60 days of gel strength and hydration status.
Adding 1.0% of acrylamide/2-acrylamide-2-methylpropanesulfonic acid sodium copolymer powder into simulated saline with the mineralization degree of 41938.8mg/L, fully stirring, dispersing and dissolving for 60 minutes, adding 0.5% of organic aluminum zirconium cross-linking agent, and continuously stirring for 60 minutes; the system solution was then poured into an ampoule, placed in a 120 ℃ oven, and the tracking gel was observed for 60 days of freeze strength and hydration.
Comparative example 2: the core-shell polymer was prepared as in example 1.
Adding 1.0% of core-shell polymer fine powder into simulated brine with the mineralization degree of 41938.8mg/L, fully stirring, dispersing and dissolving for 60 minutes, adding 0.5% of organic aluminum zirconium cross-linking agent, and continuously stirring for 60 minutes; the system solution was then poured into an ampoule, placed in a 120 ℃ oven, and observed to track 60 days of gel strength and hydration status.
Adding 0.65% of acrylamide/2-acrylamide-2-methylpropanesulfonic acid sodium copolymer powder and 0.35% of core-shell polymer fine powder into simulated saline with the mineralization degree of 41938.8mg/L, fully stirring, dispersing and dissolving for 60 minutes, adding 0.5% of high-temperature-resistant organic zirconium (commercially available) and continuously stirring for 60 minutes; the system solution was then poured into an ampoule, placed in a 120 ℃ oven, and observed to track 60 days of gel strength and hydration status.
Comparative example 4: the core-shell polymer was prepared as in example 4.
Adding 0.80% of acrylamide/2-acrylamide-2-methylpropanesulfonic acid sodium copolymer powder and 0.20% of core-shell polymer fine powder into simulated saline with the mineralization degree of 41938.8mg/L, fully stirring, dispersing and dissolving for 60 minutes, and adding 0.5% of phenolic resin to continuously stir for 60 minutes; the system solution was then poured into an ampoule, placed in a 120 ℃ oven, and observed to track 60 days of gel strength and hydration status.
The following is a comparative table of the properties of the example and comparative gel systems:
as can be seen from the above table, in comparative example 1, the gel forming time was fast and the initial gel forming crosslinking strength was high, but the gel forming strength was only D at 30 days (the gel forming strength results A to D were weak and not ideal), and gel breaking and hydration occurred at 45 to 60 days, as compared with the long-acting gel forming strength of 60 days or more and high water blocking rate of example 1 to example 6;
the initial gel forming time of comparative example 2 is too long, and the gel forming strength is not high in 2 days;
in comparative example 3, the composition of the gel is similar to that of example 2, but the difference is that a single high temperature resistant organozirconium cross-linking agent is adopted as the cross-linking agent, and in the examples, a composite high temperature resistant organoaluminium zirconium cross-linking agent is adopted, and because aluminium ions and zirconium ions respectively carry out double cross-linking reaction with amide groups and carboxyl groups in polymer molecules, the gel strength of a cross-linked acid system is greatly improved compared with that of a cross-linked system formed by a single zirconium ion cross-linking agent; it decreased in gel strength to E at 45 days and showed hydration at 60 days (23.6%);
comparative example 4, similar to comparative example 3, but using a phenolic resin as the crosslinking agent; the gel strength at 45 days is D, the hydration rate at 60 days is 26.3%, and the application effect is greatly different from that of the high-temperature-resistant organic aluminum zirconium cross-linking agent used in the examples.
The test result shows that the gel profile control water shutoff agent provided by the invention can provide longer and continuous gel strength and stability under the conditions of high temperature and high salt, and meets the requirements of profile control water shutoff on a construction site.
Claims (11)
1. The high-temperature high-salt oil reservoir deep profile control gel water shutoff agent is characterized by comprising the following components in percentage by mass: 0.8-1.2% of gelling main agent, 0.3-0.6% of high-temperature-resistant organic cross-linking agent and the balance of simulated saline solvent.
2. The high-temperature high-salt oil reservoir deep profile control gel water shutoff agent according to claim 1, which is characterized in that: the gel forming main agent comprises an acrylamide/2-acrylamide-2-methylpropanesulfonic acid sodium copolymer and a core-shell polymer.
3. The high-temperature high-salt oil reservoir deep profile control gel water shutoff agent according to claim 2, which is characterized in that: the acrylamide/2-acrylamide-2-sodium methylpropanesulfonate copolymer accounts for 65-80% of the total weight of the gel-forming main agent; the core-shell polymer accounts for 20-35% of the weight of the gel-forming main agent.
4. The high-temperature high-salt oil reservoir deep profile control gel water shutoff agent according to claim 2 or 3, wherein the high-temperature high-salt oil reservoir deep profile control gel water shutoff agent is characterized by: the molecular weight of the acrylamide/2-acrylamide-2-methylpropanesulfonic acid sodium copolymer is 1000-1500 ten thousand, and the mole percentage of the 2-acrylamide-2-methylpropanesulfonic acid sodium in the acrylamide/2-acrylamide-2-methylpropanesulfonic acid sodium copolymer is 45%.
5. The high-temperature high-salt oil reservoir deep profile control gel water shutoff agent according to claim 2 or 3, wherein the high-temperature high-salt oil reservoir deep profile control gel water shutoff agent is characterized by: the core-shell polymer comprises a shell layer and an inner core, wherein the inner core is synthesized by adopting acrylamide and 2-acrylamide-2-sodium methylpropanesulfonate, and the mole percentage of 2-acrylamide-2-sodium methylpropanesulfonate monomer is 45% -55%; the shell layer is one of vinyl polyethylene glycol ether-1000 (VPEG-1000) or ethylene glycol monovinyl polyoxyethylene ether (EPEG-1000), and the shell layer accounts for 4-8% of the weight of the core-shell polymer;
the preparation method of the core-shell polymer comprises the following steps:
s1, nucleation reaction:
core layer emulsion: adding 300-400 parts of water, 2-8 parts of nonionic surfactant A, 2-8 parts of nonionic surfactant B, 4-10 parts of anionic surfactant C, 60-120 parts of acrylamide, 240-300 parts of 2-acrylamido-2-methylpropanesulfonic acid sodium salt, 0.01-0.05 part of sodium formate and 0.05-0.1 part of disodium ethylenediamine tetraacetate into a reactor, adjusting the pH to 6.3-6.5, and stirring and mixing to be uniformly emulsified; introducing nitrogen to replace for 40 minutes, adding 0.005-0.02 part of benzoyl peroxide, stirring uniformly, then initiating the reaction by using 1g/L sodium bisulphite solution, controlling the dropping speed to ensure that the rising speed of the reaction temperature is 30-40s/0.5 ℃, controlling the whole reaction temperature to be 48-50 ℃ and the polymerization reaction to be 4.5 hours, and cooling to 25 ℃ after the completion of the reaction to obtain nuclear emulsion, and keeping nitrogen blowing;
s2, coating reaction:
shell aqueous phase: adding VPEG-1000 or EPEG-100015-20 parts by weight into 200-300 parts by weight of deionized water, adding 1-5 parts by weight of nonionic surfactant D, and fully and uniformly stirring to obtain a shell water phase;
maintaining the nuclear layer emulsion at 25 ℃ under the nitrogen filling condition, adding 0.01-0.02 part of ammonium persulfate and 0.2 part of azo diisobutyl amidine dihydrochloride (V50), slowly adding a shell water phase, and fully and uniformly stirring; continuously dropwise adding 1g/L sodium metabisulfite solution to perform an envelope reaction, controlling the reaction at a temperature rising speed of 30-40s/0.5 ℃, starting to keep the temperature for 3 hours when the temperature reaches 80 ℃, and cooling after the reaction is finished to obtain a polymer;
s3, pulverizing:
the polymer is subjected to spray drying to obtain 50-100 μm polymer powder, namely the fine powder core-shell polymer.
6. The high-temperature high-salt oil reservoir deep profile control gel water shutoff agent according to claim 5, which is characterized in that: the nonionic surfactant A is one or more of SPAN40, SPAN65 and SPAN 80; the nonionic surfactant B is one or more of AEO-3, AEO-7 and AEO-9; the anionic surfactant C is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and triethanolamine dodecyl benzene sulfonate; the nonionic surfactant D is one or more of monoethanolamine cocoate, diethanolamine cocoate and diethanolamine myristate.
7. The high-temperature high-salt oil reservoir deep profile control gel water shutoff agent according to claim 1, which is characterized in that: the high-temperature-resistant organic cross-linking agent is an organic aluminum zirconium cross-linking agent.
8. The high-temperature high-salt oil reservoir deep profile control gel water shutoff agent according to claim 7, wherein the water shutoff agent is characterized by: the preparation method of the high-temperature-resistant organic aluminum zirconium cross-linking agent comprises the following steps:
adding 150-250 parts of deionized water into a three-neck flask according to parts by weight, heating to 60 ℃, slowly adding 50-150 parts of polyol while stirring, and stirring for 20 minutes;
in the stirring process, adding 10-20 parts of aluminum salt and 15-25 parts of zirconium salt into the solution in the step 1) according to parts by weight, and fully stirring to dissolve the aluminum salt and the zirconium salt;
adjusting the temperature of the reactor to 80 ℃, adding 15-25 parts of organic acid and 5-15 parts of gluconate according to parts by weight, adding 1-5 parts of crosslinking auxiliary agent, stirring to dissolve completely, keeping reflux at 80 ℃ for carrying out complexation reaction for 4 hours, and slowly cooling to room temperature to obtain the high-temperature-resistant organic aluminum zirconium crosslinking agent.
9. The high-temperature high-salt oil reservoir deep profile control gel water shutoff agent according to claim 8, which is characterized in that: the zirconium salt is one or two of zirconium oxychloride and zirconium chloride; the aluminum salt is one or two of aluminum chloride and aluminum sulfate; the polyalcohol is one or more of ethylene glycol, propylene glycol and glycerol; the organic ligand is one or more of potassium gluconate and sodium gluconate; the organic acid is one or two of lactic acid and succinic acid; the cross-linking auxiliary agent is one or two of dimethyl diimine ester or N, N' -methylene bisacrylamide.
10. The high temperature high salt reservoir depth profile control gel water plugging agent of claim 1, wherein the simulated brine mineralization is 41938.8Mg/L, wherein the ca2+ concentration is 9693.7Mg/L and the mg2+ concentration is 1123.1Mg/L.
11. A preparation method of a high-temperature high-salt oil reservoir deep profile control gel water shutoff agent is characterized by comprising the following steps: adding 0.65-0.80% of acrylamide/2-acrylamido-2-methylpropanesulfonic acid sodium copolymer powder and 0.20-0.35% of core-shell polymer fine powder into simulated saline with mineralization degree of 41938.8Mg/L, ca < 2+ > concentration of 9693.7Mg/L and Mg < 2+ > concentration of 1123.1Mg/L, fully stirring and dispersing for 60 minutes, adding 0.3-0.6% of organic aluminum zirconium cross-linking agent, and continuously stirring for 60 minutes.
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