CN111574989A - Polyhydroxy thickening agent, high-temperature-resistant alcohol-based fracturing liquid system and application thereof - Google Patents
Polyhydroxy thickening agent, high-temperature-resistant alcohol-based fracturing liquid system and application thereof Download PDFInfo
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- CN111574989A CN111574989A CN202010467946.4A CN202010467946A CN111574989A CN 111574989 A CN111574989 A CN 111574989A CN 202010467946 A CN202010467946 A CN 202010467946A CN 111574989 A CN111574989 A CN 111574989A
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- alcohol
- polyhydroxy
- fracturing fluid
- based fracturing
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000002562 thickening agent Substances 0.000 title claims abstract description 57
- 239000007788 liquid Substances 0.000 title description 21
- 239000012530 fluid Substances 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000000178 monomer Substances 0.000 claims abstract description 39
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 34
- 239000002131 composite material Substances 0.000 claims abstract description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 30
- YJHSJERLYWNLQL-UHFFFAOYSA-N 2-hydroxyethyl(dimethyl)azanium;chloride Chemical compound Cl.CN(C)CCO YJHSJERLYWNLQL-UHFFFAOYSA-N 0.000 claims abstract description 29
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 21
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000003999 initiator Substances 0.000 claims description 24
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000004132 cross linking Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 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 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 229910021538 borax Inorganic materials 0.000 claims description 11
- 239000004310 lactic acid Substances 0.000 claims description 11
- 235000014655 lactic acid Nutrition 0.000 claims description 11
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 11
- 239000000176 sodium gluconate Substances 0.000 claims description 11
- 235000012207 sodium gluconate Nutrition 0.000 claims description 11
- 229940005574 sodium gluconate Drugs 0.000 claims description 11
- 239000004328 sodium tetraborate Substances 0.000 claims description 11
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 11
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 10
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 10
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 8
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- 238000012216 screening Methods 0.000 claims description 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 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 5
- 229960004063 propylene glycol Drugs 0.000 claims description 5
- 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 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 claims description 4
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 4
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 4
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 4
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- 235000010265 sodium sulphite Nutrition 0.000 claims description 4
- -1 amidine hydrochloride Chemical class 0.000 claims description 3
- 239000000084 colloidal system Substances 0.000 claims description 3
- 230000003750 conditioning effect Effects 0.000 claims description 3
- 229940058015 1,3-butylene glycol Drugs 0.000 claims description 2
- UFQDKRWQSFLPQY-UHFFFAOYSA-N 4,5-dihydro-1h-imidazol-3-ium;chloride Chemical compound Cl.C1CN=CN1 UFQDKRWQSFLPQY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 19
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000010008 shearing Methods 0.000 description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 229920001938 Vegetable gum Polymers 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229920013818 hydroxypropyl guar gum Polymers 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 3
- 101150025129 POP1 gene Proteins 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- DFENKTCEEGOWLB-UHFFFAOYSA-N n,n-bis(methylamino)-2-methylidenepentanamide Chemical compound CCCC(=C)C(=O)N(NC)NC DFENKTCEEGOWLB-UHFFFAOYSA-N 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 238000000974 shear rheometry Methods 0.000 description 3
- 229940083957 1,2-butanediol Drugs 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229960005150 glycerol Drugs 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
- C09K8/685—Compositions based on water or polar solvents containing organic compounds containing cross-linking agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
- C09K8/604—Polymeric surfactants
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/882—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/25—Methods for stimulating production
- E21B43/26—Methods for stimulating production by forming crevices or fractures
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Abstract
The application discloses a polyhydroxy thickening agent and a high-temperature-resistant alcohol-based fracturing fluid system, wherein the polyhydroxy thickening agent is formed by copolymerizing three monomers, namely acrylamide, N-vinylpyrrolidone and N-acrylamidopropyl-N, N, N-dimethylhydroxyethylammonium chloride, in an aqueous solution, and the mass ratio of the three monomers is 40-85% of acrylamide, 5-35% of N-vinylpyrrolidone and 3-25% of N-acrylamidopropyl-N, N, N-dimethylhydroxyethylammonium chloride based on the total mass of the monomers; the raw materials of the high-temperature resistant alcohol-based fracturing fluid system comprise a polyhydroxy thickening agent, a composite cross-linking agent, a regulator, high-flash-point alcohol and water. The alcohol-based fracturing fluid system has high temperature resistance and shear resistance by introducing the polyhydroxy thickening agent, and the temperature resistance can reach over 160 ℃; the high-flash-point alcohol is used to ensure that a fracturing system is safer, the alcohol/water ratio can be improved to more than 60 percent, even can reach an anhydrous system with 100 percent alcohol/water ratio, and the high-flash-point alcohol-water-based fracturing system has the advantages of high flowback rate, small formation damage, safety, environmental protection and the like.
Description
Technical Field
The invention belongs to the oil exploitation technology, and particularly relates to a polyhydroxy thickening agent, a high-temperature-resistant alcohol-based fracturing liquid system and application thereof.
Background
For the development of tight hypotonic hydrocarbon reservoirs, large-scale hydraulic fracturing is one of the conventional stimulation techniques. However, because the pore throat radius of the tight oil reservoir is small, after fracturing transformation, fracturing fluid filtrate and gel breaking liquid enter a seepage channel under the action of capillary force and pressure difference and are difficult to discharge, water lock damage is formed, the relative permeability of oil and gas is reduced, and the yield of the oil and gas is reduced. Meanwhile, for some water-sensitive and alkali-sensitive strata, the problems of stratum cliff instability, large sand output, serious stratum blockage and serious and insufficient flowback are caused by large-scale water flow soaking and the alkalescence of a traditional guanidine gum thickener fracturing system.
Thus, several new non-hydraulic fracturing systems are being studied and used by the skilled artisan in hydrocarbon reservoir development, such as oil-based fracturing systems, alcohol-based fracturing systems, and CO2Supercritical pressure systems, and the like. The alcohol-based fracturing fluid system has good performances in rheological property, residue, filtration loss, sand carrying capacity, fracture conductivity retention rate and the like, can be applied to fracturing development processes of various compact oil and gas layers, and is particularly suitable for reservoirs with serious sensitivity and water lock damage.
In order to solve the above problems of water-based fracturing systems, researchers have conducted constant research and study. For example, an alcohol-based fracturing fluid using hydroxypropyl guar gum molecules (HPG) as a thickening agent is disclosed in a paper of volume 44 and phase 2 of 2015 of Petroleum and Natural gas chemical industry, and the system is prepared by 20% methanol water solution and can resist 120 ℃.
However, most of the existing alcohol-based fracturing liquid systems are developed around vegetable gums such as hydroxypropyl guar gum and the like as thickeners, and the vegetable gums are poor in temperature resistance and difficult to break after crosslinking, so that the existing alcohol-based fracturing liquid systems still cause damage to stratums. Moreover, the existing alcohol-based fracturing liquid system generally adopts a methanol-based system, and the methanol-based system has poor safety due to low flash point and flammability of methanol, so that the methanol-based system cannot be used as a fracturing system with too large alcohol/water ratio (such as more than 60 percent) and cannot be used for a 100 percent anhydrous methanol system, so that the problems of instability and sand production of a water-sensitive stratum are caused, and the above-mentioned water lock problem also exists. Also, the toxicity of methanol can adversely affect the health of the technician in the field.
Disclosure of Invention
In view of the above defects or deficiencies in the prior art, the application is expected to provide a polyhydroxy thickener for an alcohol-based fracturing fluid and a high temperature resistant alcohol-based fracturing fluid system, so as to solve the technical problems of limited application, poor safety and great formation damage of the existing alcohol-based fracturing fluid system under the high temperature condition.
As a first aspect of the present application, there is provided a polyhydroxy thickener.
Preferably, the polyhydroxy thickening agent is formed by copolymerizing three monomers, namely acrylamide, N-vinyl pyrrolidone and N-acrylamidopropyl-N, N, N-dimethylhydroxyethyl ammonium chloride, in an aqueous solution, wherein the ratio of the three monomers is as follows based on the total mass of the monomers during preparation: 40-85% of acrylamide, 5-35% of N-vinylpyrrolidone, and 3-25% of N-acrylamidopropyl-N, N, N-dimethylhydroxyethylammonium chloride; wherein the structural formula of the N-acrylamidopropyl-N, N, N-dimethylhydroxyethylammonium chloride is shown as follows:
preferably, the N-acrylamidopropyl-N, N, N-dimethylhydroxyethylammonium chloride is prepared by the contact reaction of N, N-dimethylaminopropyl acrylamide and 2-chloroethanol in an ethanol solution.
Preferably, the preparation method of the polyhydroxy thickener comprises the following steps:
dissolving acrylamide, N-vinylpyrrolidone and N-acrylamidopropyl-N, N, N-dimethylhydroxyethylammonium chloride in water 2-4 times of the total mass of the monomers, and stirring for dissolving; then adding urea accounting for 3-5% of the total mass of the monomers and EDTA accounting for 0.01-0.05% of the total mass of the monomers, and fully dissolving to obtain a mixed solution;
introducing nitrogen into the mixed solution for 30min at 15-30 ℃, adding an oxidation initiator accounting for 0.001-0.01% of the total mass of the monomers, a reduction initiator accounting for 0.001-0.01% of the total mass of the monomers and an auxiliary initiator accounting for 0.001-0.02% of the total mass of the monomers, carrying out polymerization reaction for 3-6 h, and then granulating, drying, crushing and screening the obtained colloid to obtain the polyhydroxy thickening agent.
Preferably, the oxidation initiator is at least one of potassium persulfate, sodium persulfate, hydrogen peroxide and dibenzoyl peroxide; the reduction initiator is at least one of sodium sulfite, sodium bisulfite, sodium metabisulfite and sodium formaldehyde sulfoxylate; the auxiliary initiator is at least one of azodiisobutyl amidine hydrochloride, azodiisobutyronitrile, azodiisobutyl imidazoline hydrochloride and azodiisoheptanonitrile.
As a second aspect of the present application, a high temperature resistant alcohol-based fracturing fluid system is provided.
Preferably, the components of the high temperature resistant alcohol-based fracturing fluid system include a polyhydroxy thickener as described in the first aspect of the present application.
Preferably, the high-temperature-resistant alcohol-based fracturing fluid system is formed by performing a crosslinking reaction on the following raw materials in percentage by mass: 0.5-1% of polyhydroxy thickening agent, 0.3-0.6% of composite cross-linking agent, 0.05-0.2% of regulator, 20-99% of high-flash-point alcohol and 0-50% of water.
Preferably, the composite cross-linking agent is obtained by contact reaction of borax, zirconium oxychloride, glycerol, triethanolamine, lactic acid, sodium gluconate and water;
the preparation method of the composite cross-linking agent comprises the following steps:
adding 10-25% of glycerol and 10-40% of water into a reaction kettle according to mass percentage, adding 5-20% of zirconium oxychloride, stirring and dissolving, and adjusting the pH value to 7-8;
heating to 50-70 ℃, adding 5-20% of borax, and stirring for dissolving; then adding 10-15% of triethanolamine, 5-10% of lactic acid and 5-10% of sodium gluconate, and stirring for dissolving;
and heating to 70-90 ℃, and continuously stirring for reacting for 2-4 hours to obtain the composite cross-linking agent.
Preferably, the conditioning agent is an aqueous solution of hydrochloric acid, acetic acid or formic acid.
Preferably, the high-flash-point alcohol is one or a mixture of more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, glycerol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, n-amyl alcohol and n-hexyl alcohol.
Preferably, the alcohol/water ratio of the high-temperature-resistant alcohol-based fracturing fluid system is in a range of 20-100%.
As a third aspect of the present application, there is provided the use of the high temperature resistant alcohol-based fracturing fluid system of the second aspect in oil field exploitation.
The beneficial effect of this application:
1) the polyhydroxy thickening agent has excellent temperature resistance and shear resistance, the temperature resistance can reach over 160 ℃, and compared with the traditional vegetable gum, the polyhydroxy thickening agent has the advantages of excellent solubility and small formation damage;
2) on one hand, the alcohol-based fracturing fluid system has high temperature resistance and shear resistance by introducing the polyhydroxy thickening agent, and the temperature resistance can reach over 160 ℃; on the other hand, the high-flash-point alcohol is used, so that the fracturing system is safer, the alcohol/water ratio of the fracturing fluid system can be increased to more than 60 percent, even can reach an anhydrous system with 100 percent of alcohol/water ratio, the anhydrous fracturing system is realized in the true sense, and the method has the advantages of high flowback rate, small formation damage, safety, environmental protection and the like.
Drawings
Other features, objects and advantages of the present application will become more apparent upon reading of the following detailed description of non-limiting embodiments thereof, made with reference to the accompanying drawings in which:
FIG. 1 is an infrared spectrum of N-acrylamidopropyl-N, N, N-dimethylhydroxyethylammonium chloride prepared in example 1 of the present application.
Fig. 2 is a 160 ℃ high temperature shear rheology profile of an alcohol-based fracturing fluid system according to an embodiment of the present application.
Detailed Description
The present application will be described in further detail with reference to the following drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention. It should be noted that, for convenience of description, only the portions related to the present invention are shown in the drawings.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present application will be described in detail below with reference to the embodiments with reference to the attached drawings.
It is noted that the endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and that such ranges or values are understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
According to a first aspect of the application, a polyhydroxy thickener is provided, which is formed by copolymerizing three monomers of acrylamide, N-vinyl pyrrolidone and N-acrylamidopropyl-N, N, N-dimethylhydroxyethyl ammonium chloride in an aqueous solution, wherein the ratio of the three monomers is as follows based on the total mass of the monomers during preparation: 40-85% of acrylamide, 5-35% of N-vinylpyrrolidone and 3-25% of N-acrylamidopropyl-N, N, N-dimethylhydroxyethylammonium chloride.
Wherein the structural formula of the N-acrylamidopropyl-N, N, N-dimethylhydroxyethylammonium chloride is shown as follows:
in some preferred embodiments, the N-acrylamidopropyl-N, N, N-dimethylhydroxyethylammonium chloride is prepared by contacting N, N-dimethylaminopropyl acrylamide with 2-chloroethanol in an ethanol solution.
In this embodiment, the amide group of the Acrylamide (AM) can undergo imidization to form a cross-linked structure, so that the copolymer has good temperature resistance. The N-vinyl pyrrolidone (NVP) has larger molecular volume, and the introduction of the pyrrole ring can increase the rigidity of the molecular weight of the polymer, thereby improving the temperature resistance of the molecular chain of the polymer. The introduction of a large side group in N-acrylamide propyl-N, N, N-dimethylhydroxyethyl ammonium chloride (MPP) enables the copolymer to have stronger alcohol solubility and temperature resistance.
On one hand, the unit volume of the copolymer formed by polymerizing the three monomers is larger, the steric hindrance of molecules is increased, the main chain of the copolymer is protected, and the high-temperature resistance of the copolymer is improved; on the other hand, the three monomer structures contain reasonable proportion of hydrophilic groups (hydroxyl groups) and hydrophobic groups, have good water solubility, accord with the molecular structure characteristics of the surfactant and have higher surface activity, so that the surface tension of a fracturing fluid system comprising the polyhydroxy thickening agent is reduced and the fracturing fluid system is easy to flow back; and after gel breaking, no water insoluble substance and no residue exist, so that the reservoir gap is not easy to block.
In the present application, the polymerization reaction may be initiator-initiated polymerization, thermal-initiated polymerization, photo-initiated polymerization, radiation polymerization, or the like. In some preferred embodiments, the polyhydroxy thickeners are obtained herein using an in situ polymerization process based on redox reactions, the preparation process comprising the steps of:
dissolving acrylamide, N-vinylpyrrolidone and N-acrylamidopropyl-N, N, N-dimethylhydroxyethylammonium chloride in water 2-4 times of the total mass of the monomers, and stirring for dissolving; then adding urea accounting for 3-5% of the total mass of the monomers and EDTA accounting for 0.01-0.05% of the total mass of the monomers, and fully dissolving to obtain a mixed solution;
introducing nitrogen into the mixed solution for 30min at 15-30 ℃, adding an oxidation initiator accounting for 0.001-0.01% of the total mass of the monomers, a reduction initiator accounting for 0.001-0.01% of the total mass of the monomers and an auxiliary initiator accounting for 0.001-0.02% of the total mass of the monomers, carrying out polymerization reaction for 3-6 h, and then granulating, drying, crushing and screening the obtained colloid to obtain the polyhydroxy thickening agent.
In the embodiment, on one hand, the urea is used as a cosolvent to increase the solubility of the three monomers in water and enhance the interaction among the three monomers, so that the long-term stability of the generated polyhydroxy thickener is better; on the other hand, the configuration time can be greatly reduced, and the polymer efficiency can be improved. In this embodiment, EDTA may be used to enhance the stability of the system.
In this embodiment, the oxidation initiator and the reduction initiator are used to initiate in situ polymerization of the three monomers to copolymerize to form the above-described polyhydroxy polymer. The auxiliary initiator plays an auxiliary role and is matched with an oxidation initiator and a reduction initiator for use, so that the polymerization efficiency is improved.
In some preferred embodiments, the oxidant initiator is at least one of potassium persulfate, sodium persulfate, hydrogen peroxide, and dibenzoyl peroxide.
In some preferred embodiments, the reducing initiator is at least one of sodium sulfite, sodium bisulfite, sodium metabisulfite, and sodium formaldehyde sulfoxylate.
In some preferred embodiments, the co-initiator is at least one of azobisisobutylamidine hydrochloride, azobisisobutyronitrile, azobisisobutylimidazoline hydrochloride, and azobisisoheptonitrile.
According to a second aspect of the present application there is provided a high temperature resistant alcohol-based fracturing fluid system, the components of which comprise a polyhydroxy thickener as described above.
In the embodiment, the polyhydroxy thickening agent is used as a main agent for endowing the alcohol-based fracturing fluid system with high temperature resistance, so that the heating stability of the alcohol-based fracturing fluid system is improved.
In some preferred embodiments, the high temperature resistant alcohol-based fracturing fluid system is formed by crosslinking reaction of raw materials comprising the following components:
the weight percentage of the material is as follows: 0.5-1% of polyhydroxy thickening agent, 0.3-0.6% of composite cross-linking agent, 0.05-0.2% of regulator, 20-99% of high-flash-point alcohol and 0-50% of water.
In the embodiment, the composite cross-linking agent is another factor capable of improving the high temperature resistance of the alcohol-based fracturing fluid system, and can be used for increasing the space network junction of the polymerThe structural density is that the polyhydroxy thickening agent and the composite cross-linking agent form a compact beam-shaped cross stereo microstructure after cross-linking, on one hand, the gelling strength is improved, on the other hand, the heat resistance and the shearing resistance are better, so that the high temperature resistance of the copolymer reaches over 160 ℃, and is 170s-1Continuously shearing for 2h at the shearing speed, and stabilizing the viscosity to be more than 100 mPas.
In the embodiment, when the dosage of the polyhydroxy thickening agent is 0.5-1%, and the dosage of the composite crosslinking agent is 0.3-0.6%, the prepared alcohol-based fracturing fluid system has good delayed crosslinking performance, low initial viscosity and good economic applicability.
In some preferred embodiments, the composite cross-linking agent is obtained by contact reaction of borax, zirconium oxychloride, glycerol, triethanolamine, lactic acid, sodium gluconate and water. In the embodiment, the organic zirconium cross-linking agent is synthesized by using borax and zirconium oxychloride as raw materials and using glycerol, lactic acid and sodium gluconate as ligands, and has the advantages of improving cross-linking strength and cross-linking structure stability.
The preparation method of the composite cross-linking agent comprises the following steps:
adding 10-25% of glycerol and 10-40% of water into a reaction kettle according to mass percentage, adding 5-20% of zirconium oxychloride, stirring and dissolving, and adjusting the pH value to 7-8;
heating to 50-70 ℃, adding 5-20% of borax, and stirring for dissolving; then adding 10-15% of triethanolamine, 5-10% of lactic acid and 5-10% of sodium gluconate, and stirring for dissolving;
and heating to 70-90 ℃, and continuously stirring for reacting for 2-4 hours to obtain the composite cross-linking agent.
In some preferred embodiments, the conditioning agent is an aqueous solution of hydrochloric acid, acetic acid, or formic acid for adjusting the pH of the alcohol-based fracturing fluid system.
In some preferred embodiments, the high flash point alcohol is one or a mixture of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, glycerol, 1, 2-butylene glycol, 1, 3-butylene glycol, 1, 4-butylene glycol, n-amyl alcohol, and n-hexyl alcohol.
In some preferred embodiments, raw materials such as a polyhydroxy thickening agent, a composite cross-linking agent, a high-flash-point alcohol and a regulator for preparing the high-temperature-resistant alcohol-based fracturing fluid system are separately packaged, the mass ratio of the raw materials is calculated according to the actual condition of a stratum during use, and then the raw materials are compounded and cross-linked in proportion and then pumped into the stratum for use, so that the raw materials are prepared and used at present to ensure the fracturing effect.
In some preferred embodiments, the alcohol/water ratio of the high temperature resistant alcohol-based fracturing fluid system is in the range of 20 to 100%.
In some preferred embodiments, the alcohol/water ratio of the refractory alcohol-based fracturing fluid system is 60% or greater.
In some more preferred embodiments, the alcohol/water ratio of the refractory alcohol-based fracturing fluid system is 100%, i.e., the refractory alcohol-based fracturing fluid system is free of water and the amount of alcohol is 100%.
In the present application, the use of a polyol instead of conventional methanol has at least the following advantages: 1) the polyol has higher flash point, is not flammable and is safe in site construction; 2) no toxicity, safety and environmental protection; 3) the alcohol/water ratio in an alcohol-based fracturing fluid system can be improved to at least more than 60 percent, and even a waterless system with 100 percent of alcohol/water ratio can be adopted, so that the complete formation inhibition hydration expansion can be achieved, the water lock problem is solved, and the flowback of the fracturing fluid is facilitated.
Example 1
Preparation of N-acrylamidopropyl-N, N, N-dimethylhydroxyethylammonium chloride (MPP):
adding 120.0g of N, N-dimethylaminopropyl acrylamide into a 500mL three-neck flask, then adding 110mL of ethanol, heating to 50 ℃, slowly dropwise adding 68.0g of 2-chloroethanol, continuously reacting for 12h after the dropwise adding is finished, and then evaporating the solvent ethanol in vacuum to obtain the MPP monomer.
The molecular structural formula of the MPP monomer is shown as follows, and the infrared identification map of the MPP monomer is shown as figure 1.
As can be seen from FIG. 1, the FTIR spectrum of the MPP monomer is 3354.54cm-1Presence of-CONH2In the radical-NH2Has a peak of absorption of stretching vibration of 1651.29cm-1Presence of-CONH2The peak of the C ═ O bond absorption by stretching vibration in the radical was 1379.23cm-1And 1454.70cm-1Characteristic peaks for methyl groups are present.
Example 2
Preparing a polyhydroxy thickening agent POP-1:
538.0g of deionized water is added into a 1L beaker, 173.0g of comonomer Acrylamide (AM), 25.2g of N-vinyl pyrrolidone (NVP) and 11.3g of N-acrylamidopropyl-N, N, N-dimethylhydroxyethylammonium chloride (MPP) are added under the mechanical stirring of 400rpm, and then 8.5g of urea and 0.025g of EDTA are added for full dissolution; and at the temperature of 18 ℃, transferring the mixed solution into a 1L polymerization bottle, introducing nitrogen for 30min, adding 2.4ml of prepared 1% potassium persulfate solution, 2.4ml of prepared 1% sodium bisulfite solution and 4ml of prepared 1% azodiisobutyl amidine hydrochloride solution, sealing the polymerization bottle, waiting for reaction for 6h, taking out the rubber block, granulating, drying, crushing and screening to obtain the polyhydroxy POP-1 thickener.
Example 3
Preparing a polyhydroxy thickening agent POP-2:
540.0g of deionized water is added into a 1L beaker, 160.0g of comonomer Acrylamide (AM), 33.5g of N-vinyl pyrrolidone (NVP) and 17.6g of N-acrylamidopropyl-N, N, N-dimethylhydroxyethylammonium chloride (MPP) are added under the mechanical stirring of 400rpm, and then 8.5g of urea and 0.03g of EDTA are added for full dissolution; and at the temperature of 20 ℃, transferring the mixed solution into a 1L polymerization bottle, introducing nitrogen for 30min, adding 2.4ml of prepared 1% sodium persulfate solution, 2.4ml of prepared 1% sodium sulfite solution and 4ml of prepared 1% azodiisobutyronitrile solution, sealing the polymerization bottle, reacting for 5h, taking out the rubber block, granulating, drying, crushing and screening to obtain the polyhydroxy thickener POP-2.
Example 4
Preparing a polyhydroxy thickener POP-3:
adding 400.0g of deionized water into a 1L beaker, adding 80.0g of comonomer Acrylamide (AM), 70.0g of N-vinyl pyrrolidone (NVP) and 50.0g of N-acrylamidopropyl-N, N, N-dimethylhydroxyethylammonium chloride (MPP) under the mechanical stirring of 400rpm, then adding 6.0g of urea and 0.1g of EDTA to dissolve fully; and at the temperature of 18 ℃, transferring the mixed solution into a 1L polymerization bottle, introducing nitrogen for 30min, adding 2.0ml of prepared 0.1% hydrogen peroxide solution, 2.0ml of prepared 0.1% sodium metabisulfite solution and 2.0ml of prepared 0.1% azobisisobutylimidazoline hydrochloride solution, sealing the polymerization bottle, reacting for 6h, taking out the rubber block, granulating, drying, crushing and screening to obtain the polyhydroxy thickener POP-3.
Example 5
Preparing a polyhydroxy thickener POP-4:
adding 800.0g of deionized water into a 1L beaker, adding 170.0g of comonomer Acrylamide (AM), 10.0g of N-vinyl pyrrolidone (NVP) and 20.0g of N-acrylamidopropyl-N, N, N-dimethylhydroxyethylammonium chloride (MPP) under the mechanical stirring of 400rpm, then adding 10.0g of urea and 0.06g of EDTA to dissolve fully; and at the temperature of 18 ℃, transferring the mixed solution into a 1L polymerization bottle, introducing nitrogen for 30min, adding 2.4ml of prepared 1% dibenzoyl peroxide solution, 2.4ml of prepared 1% rongalite solution and 4ml of prepared 1% azobisisoheptonitrile solution, sealing the polymerization bottle, waiting for reaction for 6h, taking out the rubber block, granulating, drying, crushing and screening to obtain the polyhydroxy thickening agent POP-4.
Example 6
Preparation of a composite cross-linking agent JCA-10:
adding 1220g of glycerol and 1680g of water into a 10L reaction kettle, starting stirring at 300rpm, adding 720.5g of zirconium oxychloride, stirring for dissolution, and adjusting the pH to 7.0 by using 152g of 2mol/L NaOH solution; raising the temperature of the reaction kettle to 50 ℃, adding 706.4g of borax, and stirring for dissolving; then 760.6g triethanolamine, 448.4g lactic acid and 312.2g sodium gluconate are added; heating to 75 ℃, and continuously stirring for reaction for 4 hours to obtain the composite cross-linking agent JCA-10.
Example 7
Preparation of a composite cross-linking agent JCA-20:
1250g of glycerol and 1550g of water are added into a 10L reaction kettle, stirring is started at 300rpm, 778.0g of zirconium oxychloride is added, and after stirring and dissolution, 158g of NaOH solution with the concentration of 2mol/L is used for adjusting the pH value to 7.2; raising the temperature of the reaction kettle to 50 ℃, adding 660.5g of borax, and stirring for dissolving; then 750.2g triethanolamine, 502.3g lactic acid and 350.0g sodium gluconate are added; heating to 80 ℃, and continuously stirring for reaction for 4 hours to obtain the composite cross-linking agent JCA-20.
Example 8
Preparation of a composite cross-linking agent JCA-30:
adding 600g of glycerol and 2235g of water into a 10L reaction kettle, starting stirring at 300rpm, adding 1200g of zirconium oxychloride, stirring for dissolution, and adjusting the pH value to 8.0 by using 165g of 2mol/L NaOH solution; raising the temperature of the reaction kettle to 50 ℃, adding 300g of borax, and stirring for dissolving; then 600g of triethanolamine, 300g of lactic acid and 600g of sodium gluconate are added; heating to 90 ℃, and continuously stirring for reaction for 4 hours to obtain the composite cross-linking agent JCA-30.
Example 9
Preparation of a composite cross-linking agent JCA-40:
adding 1500g of glycerol and 1050g of water into a 10L reaction kettle, starting stirring at 300rpm, adding 300g of zirconium oxychloride, stirring for dissolving, and adjusting the pH to 7.0 by using 150g of 2mol/L NaOH solution; raising the temperature of the reaction kettle to 50 ℃, adding 1200g of borax, and stirring for dissolving; then adding 900g of triethanolamine, 600g of lactic acid and 300g of sodium gluconate; heating to 70 ℃, and continuously stirring for reaction for 4 hours to obtain the composite cross-linking agent JCA-40.
Example 10
Preparing an alcohol-based fracturing fluid system GC-801:
according to the mass percent, the polyhydroxy thickening agent POP-10.6 percent prepared in the embodiment of the invention is dissolved in a mixed solution of 80 percent of glycol and 19 percent of water, then 0.1 percent of acetic acid and a compound cross-linking agent JCA-100.3 percent are added, the mixture is uniformly stirred to obtain the polyhydroxy thickening agent POP-10 percent, and the time of cross-linking and hanging into glue is recorded, and the results are shown in Table 1. Then 0.05% ammonium persulfate is added to break the gel after 2h at 90 ℃, and the viscosity of the gel breaking liquid is tested, and the result is shown in table 1.
Example 11
Preparing an alcohol-based fracturing fluid system GC-802:
according to the mass percent, the polyhydroxy thickening agent POP-20.6 percent prepared in the embodiment of the invention is dissolved in a mixed solution of 80 percent of 1, 2-propylene glycol and 19 percent of water, then 0.1 percent of acetic acid and a composite cross-linking agent JCA-200.3 percent are added, the mixture is obtained after uniform stirring, the time of cross-linking and hanging into glue is recorded, and the result is shown in table 1. Then 0.05% ammonium persulfate is added to break the gel after 2h at 90 ℃, and the viscosity of the gel breaking liquid is tested, and the result is shown in table 1.
Example 12
Preparing an alcohol-based fracturing fluid system GC-100:
according to the mass percent, the polyhydroxy thickening agent POP-20.8 percent prepared in the embodiment of the invention is dissolved in a mixed solution of 80 percent of ethylene glycol and 19 percent of 1, 2-propylene glycol, then 0.15 percent of acetic acid and a composite cross-linking agent JCA-200.5 percent are added, the mixture is obtained after uniform stirring, the time of cross-linking and hanging glue is recorded, and the result is shown in table 1. Then 0.05% ammonium persulfate is added to break the gel after 2h at 90 ℃, and the viscosity of the gel breaking liquid is tested, and the result is shown in table 1.
Example 13
Preparing an alcohol-based fracturing fluid system GC-803:
according to the mass percent, the polyhydroxy thickening agent POP-30.5% prepared in the embodiment of the invention is dissolved in a mixed solution of 20% of 1, 3-propylene glycol, 20% of glycerol, 30% of 1, 2-butanediol, 24.2% of 1, 3-butanediol and 4.65% of water, then 0.05% of formic acid and a composite crosslinking agent JCA-300.6% are added, and the mixture is uniformly stirred to obtain the polyhydroxy thickening agent POP-1, and the time for which crosslinking can be selected and hung into glue is recorded, and the result is shown in Table 1. Then 0.05% ammonium persulfate is added to break the gel after 2h at 90 ℃, and the viscosity of the gel breaking liquid is tested, and the result is shown in table 1.
Example 14
Preparing an alcohol-based fracturing fluid system GC-804:
according to the mass percentage, the polyhydroxy thickening agent POP-41.0% prepared in the embodiment of the invention is dissolved in a mixed solution of 30% of 1, 4-butanediol, 30% of n-amyl alcohol, 37.3% of n-hexyl alcohol and 1.0% of water, then 0.2% of hydrochloric acid and a composite cross-linking agent JCA-400.5% are added, the mixture is uniformly stirred to obtain the polyhydroxy thickening agent POP-41.0%, and the time for hanging the cross-linking agent into glue is recorded, and the result is shown in Table 1. Then 0.05% ammonium persulfate is added to break the gel after 2h at 90 ℃, and the viscosity of the gel breaking liquid is tested, and the result is shown in table 1.
Comparative example 1
Preparing an alcohol-based fracturing fluid system DB-1:
dissolving 0.6% of hydroxypropyl guar gum in a mixed solution of 80% of ethylene glycol and 19% of water according to mass percentage, then adding 0.1% of acetic acid and 100.3% of a composite cross-linking agent JCA, uniformly stirring to obtain the hydroxypropyl guar gum, and recording the time for which cross-linking can be hung into the gum, wherein the results are shown in Table 1. Then 0.05% ammonium persulfate is added to break the gel after 2h at 90 ℃, and the viscosity of the gel breaking liquid is tested, and the result is shown in table 1.
TABLE 1 Performance of alcohol-based fracturing fluid systems
| Alcohol-based fracturing system | GC-801 | GC-802 | GC-100 | GC-803 | GC-804 | DB-1 |
| Gel forming time | 216s | 260s | 185s | 240s | 228s | 358s |
| Viscosity of gel breaker | 2.3mPa·s | 1.8mPa·s | 2.8mPa·s | 2.5mPa·s | 2.2mPa·s | 8.3mPa·s |
The fracturing fluid system can break gel by using a common gel breaker, the gel is broken thoroughly, the viscosity of the gel breaking liquid after gel breaking is less than 3mPa & s, the gel breaking liquid is easy to flow back, and the damage to a reservoir is greatly reduced. The viscosity of the gel breaking liquid of the comparative example is more than 8mPa · s, which shows that the damage to the reservoir stratum is large.
Further, the shear rheology of the fracturing fluid system is measured by a GRACE type high-temperature high-pressure rheology tester at 170s-1At a shear rate of 2 h. FIG. 2 shows the high temperature shear rheology curve of the alcohol-based fracturing fluid system GC-100 provided herein at 160 deg.C, and it can be seen that the fracturing fluid system is at 160 deg.C for 170s-1Under the condition, the viscosity is still more than 100mPa & s after continuous shearing for 2 hours, which shows that the fracturing liquid system disclosed by the application has good temperature resistance and shearing resistance, and the temperature resistance can reach 160 ℃. While the fracturing fluid system DB-1 of comparative example 1 is at 160 ℃ for 170s-1Under the condition, the viscosity is less than 30mPa & s after continuous shearing for 2h, which shows that the high temperature resistance and the shearing resistance are poor.
In conclusion, the alcohol-based fracturing liquid system disclosed by the application gets rid of the defects of low flash point, toxicity and the like caused by the traditional adoption of methanol, and better safety and environmental protection performance can be obtained by adopting the alcohol with high flash point to replace the methanol. And the range of the alcohol/water ratio applied by the alcohol-based fracturing liquid system is improved to more than 60 percent, and even a waterless system with 100 percent of alcohol/water ratio can be adopted, so that the complete formation inhibition hydration expansion can be achieved, the water lock problem is solved, and the flowback of the fracturing liquid is greatly facilitated. And, the flowback liquid of the alcohol-based fracturing fluid of this application can also recycle through simple processing, has saved the cost of fracturing operation so greatly.
Compared with the traditional alcohol-based fracturing fluid using vegetable gum as a thickening agent, the polyhydroxy thickening agent and the composite cross-linking agent system provided by the application have the excellent effects of temperature resistance of more than 160 ℃, excellent solubility, extremely low formation damage and the like. The system is at 170s-1The viscosity is stabilized to be more than 100mPa.s after continuously shearing for 2 hours at the shearing speed of (1); the system has good gel breaking performance, after gel breaking is carried out by adopting 0.3% ammonium persulfate solution, the viscosity is less than 3mPa.s, and the industrial application of drilling and exploitation of high-water-sensitivity stratum oil-gas wells can be met.
The above description is only a preferred embodiment of the application and is illustrative of the principles of the technology employed. It will be appreciated by a person skilled in the art that the scope of the invention as referred to in the present application is not limited to the embodiments with a specific combination of the above-mentioned features, but also covers other embodiments with any combination of the above-mentioned features or their equivalents without departing from the inventive concept. For example, the above features may be replaced with (but not limited to) features having similar functions disclosed in the present application.
Claims (10)
1. The polyhydroxy thickening agent is characterized in that the polyhydroxy thickening agent is formed by copolymerizing three monomers, namely acrylamide, N-vinyl pyrrolidone and N-acrylamidopropyl-N, N, N-dimethylhydroxyethyl ammonium chloride, in an aqueous solution, wherein the three monomers are prepared according to the following ratio in terms of the total mass of the monomers: 40-85% of acrylamide, 5-35% of N-vinylpyrrolidone, and 3-25% of N-acrylamidopropyl-N, N, N-dimethylhydroxyethylammonium chloride; wherein the structural formula of the N-acrylamidopropyl-N, N, N-dimethylhydroxyethylammonium chloride is shown as follows:
2. the polyhydroxy thickener of claim 1, wherein the polyhydroxy thickener is prepared by a process comprising the steps of:
dissolving acrylamide, N-vinylpyrrolidone and N-acrylamidopropyl-N, N, N-dimethylhydroxyethylammonium chloride in water 2-4 times of the total mass of the monomers, and stirring for dissolving; then adding urea accounting for 3-5% of the total mass of the monomers and EDTA accounting for 0.01-0.05% of the total mass of the monomers, and fully dissolving to obtain a mixed solution;
introducing nitrogen into the mixed solution for 30min at 15-30 ℃, adding an oxidation initiator accounting for 0.001-0.01% of the total mass of the monomers, a reduction initiator accounting for 0.001-0.01% of the total mass of the monomers and an auxiliary initiator accounting for 0.001-0.02% of the total mass of the monomers, carrying out polymerization reaction for 3-6 h, and then granulating, drying, crushing and screening the obtained colloid to obtain the polyhydroxy thickening agent.
3. The polyhydroxy thickener of claim 2 wherein said oxidation initiator is at least one of potassium persulfate, sodium persulfate, hydrogen peroxide, and dibenzoyl peroxide; the reduction initiator is at least one of sodium sulfite, sodium bisulfite, sodium metabisulfite and sodium formaldehyde sulfoxylate; the auxiliary initiator is at least one of azodiisobutyl amidine hydrochloride, azodiisobutyronitrile, azodiisobutyl imidazoline hydrochloride and azodiisoheptanonitrile.
4. A high temperature resistant alcohol-based fracturing fluid system, wherein the components of the high temperature resistant alcohol-based fracturing fluid system comprise the polyhydroxy thickener according to any one of claims 1 to 3.
5. The high temperature resistant alcohol-based fracturing fluid system of claim 4, wherein the high temperature resistant alcohol-based fracturing fluid system is formed by cross-linking reaction of raw materials comprising:
the weight percentage of the material is as follows: 0.5-1% of polyhydroxy thickening agent, 0.3-0.6% of composite cross-linking agent, 0.05-0.2% of regulator, 20-99% of high-flash-point alcohol and 0-50% of water.
6. The high-temperature-resistant alcohol-based fracturing fluid system of claim 5, wherein the composite cross-linking agent is obtained by contact reaction of borax, zirconium oxychloride, glycerol, triethanolamine, lactic acid, sodium gluconate and water;
the preparation method of the composite cross-linking agent comprises the following steps:
adding 10-25% of glycerol and 10-40% of water into a reaction kettle according to mass percentage, adding 5-20% of zirconium oxychloride, stirring and dissolving, and adjusting the pH value to 7-8;
heating to 50-70 ℃, adding 5-20% of borax, and stirring for dissolving; then adding 10-15% of triethanolamine, 5-10% of lactic acid and 5-10% of sodium gluconate, and stirring for dissolving;
and heating to 70-90 ℃, and continuously stirring for reacting for 2-4 hours to obtain the composite cross-linking agent.
7. The high temperature resistant alcohol-based fracturing fluid system of claim 5, wherein the conditioning agent is an aqueous solution of hydrochloric acid, acetic acid, or formic acid.
8. The high temperature resistant alcohol-based fracturing fluid system of claim 5, wherein the high flash point alcohol is one or a mixture of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, glycerol, 1, 2-butylene glycol, 1, 3-butylene glycol, 1, 4-butylene glycol, n-amyl alcohol and n-hexyl alcohol.
9. A high temperature resistant alcohol-based fracturing fluid system according to any one of claims 4 to 8, wherein the alcohol/water ratio of the high temperature resistant alcohol-based fracturing fluid system is in the range of 20 to 100%.
10. Use of a high temperature resistant alcohol-based fracturing fluid system according to any of claims 4 to 8 in oil field exploitation.
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