WO2021169480A1 - Fracturing fluid for seabed natural gas hydrate mineral resources - Google Patents
Fracturing fluid for seabed natural gas hydrate mineral resources Download PDFInfo
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- WO2021169480A1 WO2021169480A1 PCT/CN2020/135068 CN2020135068W WO2021169480A1 WO 2021169480 A1 WO2021169480 A1 WO 2021169480A1 CN 2020135068 W CN2020135068 W CN 2020135068W WO 2021169480 A1 WO2021169480 A1 WO 2021169480A1
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- Prior art keywords
- fracturing fluid
- hydrate
- natural gas
- fracturing
- gas hydrate
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- 239000012530 fluid Substances 0.000 title claims abstract description 57
- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052500 inorganic mineral Inorganic materials 0.000 title abstract description 7
- 239000011707 mineral Substances 0.000 title abstract description 7
- 239000004927 clay Substances 0.000 claims abstract description 36
- 239000003381 stabilizer Substances 0.000 claims abstract description 20
- 239000013535 sea water Substances 0.000 claims abstract description 17
- 239000003112 inhibitor Substances 0.000 claims abstract description 16
- 239000002562 thickening agent Substances 0.000 claims abstract description 14
- 239000002455 scale inhibitor Substances 0.000 claims abstract description 13
- 239000012190 activator Substances 0.000 claims abstract description 11
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 10
- 239000003899 bactericide agent Substances 0.000 claims abstract description 10
- 239000003002 pH adjusting agent Substances 0.000 claims abstract description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052796 boron Inorganic materials 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 54
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 48
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 16
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003431 cross linking reagent Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- 239000001103 potassium chloride Substances 0.000 claims description 8
- 235000011164 potassium chloride Nutrition 0.000 claims description 8
- 229920013818 hydroxypropyl guar gum Polymers 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 235000002639 sodium chloride Nutrition 0.000 claims description 7
- 229920002554 vinyl polymer Polymers 0.000 claims description 7
- 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 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- -1 hydroxypropyl Chemical group 0.000 claims description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 244000007835 Cyamopsis tetragonoloba Species 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical group C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 229920006322 acrylamide copolymer Polymers 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 239000010426 asphalt Substances 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical compound C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- UJNSFDHVIBGEJZ-CMRIBGNTSA-N (1S,2R,4R,7Z,11S,12S)-12-[(dimethylamino)methyl]-4,8-dimethyl-3,14-dioxatricyclo[9.3.0.02,4]tetradec-7-en-13-one Chemical compound CN(C)C[C@@H]1[C@@H]2CC\C(C)=C/CC[C@@]3(C)O[C@@H]3[C@H]2OC1=O UJNSFDHVIBGEJZ-CMRIBGNTSA-N 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 229910021538 borax Inorganic materials 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 229940045803 cuprous chloride Drugs 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 235000007715 potassium iodide Nutrition 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- 239000004328 sodium tetraborate Substances 0.000 claims description 2
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 2
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical compound S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 claims 1
- 235000019270 ammonium chloride Nutrition 0.000 claims 1
- 150000001642 boronic acid derivatives Chemical class 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- PZNOBXVHZYGUEX-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine;hydrochloride Chemical compound Cl.C=CCNCC=C PZNOBXVHZYGUEX-UHFFFAOYSA-N 0.000 claims 1
- 238000006068 polycondensation reaction Methods 0.000 claims 1
- 230000005764 inhibitory process Effects 0.000 abstract description 17
- 230000036571 hydration Effects 0.000 abstract description 9
- 238000006703 hydration reaction Methods 0.000 abstract description 9
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 239000004971 Cross linker Substances 0.000 abstract 1
- 238000005065 mining Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 9
- 150000004677 hydrates Chemical class 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229920002907 Guar gum Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000665 guar gum Substances 0.000 description 4
- 235000010417 guar gum Nutrition 0.000 description 4
- 229960002154 guar gum Drugs 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- FJWSMXKFXFFEPV-UHFFFAOYSA-N prop-2-enamide;hydrochloride Chemical compound Cl.NC(=O)C=C FJWSMXKFXFFEPV-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- ZCGQZLKPUVGCBQ-HLMPTVQRSA-N (2S,4R)-1-[(2S)-2-[3-[3-[(2S)-2-[[7-(8-chloronaphthalen-1-yl)-4-[(3S)-3-(cyanomethyl)-4-(2-fluoroprop-2-enoyl)piperazin-1-yl]-6,8-dihydro-5H-pyrido[3,4-d]pyrimidin-2-yl]oxymethyl]pyrrolidin-1-yl]propoxy]propanoylamino]-3,3-dimethylbutanoyl]-4-hydroxy-N-[[4-(4-methyl-1,3-thiazol-5-yl)phenyl]methyl]pyrrolidine-2-carboxamide Chemical compound CC1=C(SC=N1)C2=CC=C(C=C2)CNC(=O)[C@@H]3C[C@H](CN3C(=O)[C@H](C(C)(C)C)NC(=O)CCOCCCN4CCC[C@H]4COC5=NC6=C(CCN(C6)C7=CC=CC8=C7C(=CC=C8)Cl)C(=N5)N9CCN([C@H](C9)CC#N)C(=O)C(=C)F)O ZCGQZLKPUVGCBQ-HLMPTVQRSA-N 0.000 description 1
- LVSCGHXBWWOJLY-UHFFFAOYSA-N 1-chloropropane;n-methylmethanamine Chemical compound CNC.CCCCl LVSCGHXBWWOJLY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009933 burial Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 150000004662 dithiols Chemical class 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical class C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Images
Classifications
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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
- 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
- C09K8/887—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
-
- 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
- C09K8/84—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
- C09K8/90—Compositions based on water or polar solvents containing organic compounds macromolecular compounds of natural origin, e.g. polysaccharides, cellulose
- C09K8/905—Biopolymers
Definitions
- the invention relates to a fracturing fluid for seabed natural gas hydrate deposits.
- Hydraulic fracturing is a common reservoir improvement and stimulation operation in conventional and shale oil and gas exploitation, but this technology has not been studied in depth in the exploitation of natural gas hydrate deposits.
- the main characteristics of natural gas hydrate reservoirs are silt and muddy and low permeability.
- the results of single well gas production obtained from several gas hydrate test productions at home and abroad are still far from commercial production, and the gas production cycle is also different. It is not ideal, so realizing hydraulic fracturing of hydrate deposits is the only way to realize commercial hydrate mining.
- fracturing fluids suitable for submarine gas hydrate deposits need to meet the following properties: 1
- the formation temperature of hydrate reservoirs is relatively low (Hydrate reservoirs in the Shenhu area of the South China Sea)
- the average layer temperature is 14.15°C), which belongs to ultra-low temperature oil and gas wells, and the hydrate dissociates and absorbs heat during the mining process, and the temperature near the wellbore will be further reduced.
- the low temperature environment will cause the gel breaking and flowback process after the fracturing to be incomplete. , Long gel breaking time and incomplete flowback will cause serious damage to the reservoir.
- the fracturing fluid first needs to have good low temperature gel breaking performance and low temperature effective performance; 2
- the clay content in the hydrate reservoir is very high. Water swelling with high content of clay will cause serious shaft wall safety problems and seepage damage. Therefore, the fracturing fluid should improve its ability to inhibit clay hydration as much as possible; 3
- the low-temperature and high-pressure environment in the wellbore may generate hydrates during the mining process.
- a fracturing fluid for submarine natural gas hydrate deposits is composed of the following components by weight percentage: thickener: 0.15-0.6%; clay stabilizer: 0.5-4.0%; organic boron Cross-linking agent: 0.05-1.0%; gel breaker: 0.2-0.5%; low-temperature activator: 0.05-0.3%; scale inhibitor: 0.1-0.6%; fungicide: 0.05-0.1%; pH regulator: 0.1 ⁇ 1.0%; Hydrate inhibitor: 0.5 ⁇ 1.0%; the remaining component is the base liquid; the thickener is a mixture of instant hydroxypropyl guar powder and ethylene glycol, or instant hydroxypropyl guar Gum powder and polyethylene glycol are mixed, the mass ratio of hydroxypropyl guar powder and ethylene glycol or polyethylene glycol is 90-95:5-10; instant hydroxypropyl guar powder increases The effect of the viscosity of the fracturing fluid, ethylene glycol and hydroxypropyl guar powder
- the clay stabilizer is a mixture of polyvinyl caprolactam (PVCap) or vinylpyrrolidone-acrylate quaternary ammonium salt copolymer, potassium chloride and potassium hydroxide, and the mass ratio of the three is 3-5:55-57: 40.
- PVCap polyvinyl caprolactam
- vinylpyrrolidone-acrylate quaternary ammonium salt copolymer potassium chloride and potassium hydroxide
- the potassium hydroxide of the present invention has four energy effects for the fracturing fluid: firstly, potassium hydroxide is a good clay stabilizer for oil and gas wells, which can permanently change the chemical structure of clay minerals and inhibit the hydration expansion and particle size of the clay.
- potassium hydroxide is a strong hydrate thermodynamic inhibitor
- potassium hydroxide is a conventional scale inhibitor for barite scale.
- Part of potassium chloride and sodium chloride can be directly provided by seawater. They can be used as hydrate thermodynamic inhibitors as well as conventional clay stabilizers.
- EDTA is an effective gel breaker for guar gum fracturing fluid and a good hydraulic fracturing scale inhibitor for oil and gas wells.
- Ethylene glycol can increase the viscosity of guar gum and strongly inhibit the formation of hydrates. It is also the main component of the organoboron crosslinking agent.
- PVP and PVCap are good inhibitors of hydrate kinetics, and they can also stabilize the reservoir.
- the present invention selects fracturing fluid components that can adapt to the special and harsh physical and chemical environment of natural gas hydrate reservoirs through screening, and selects fracturing fluid components with multiple functions and energy efficiency from them, which can further strengthen the fracturing fluid by increasing the addition amount. Reduce production costs while maintaining performance.
- the performance of the fracturing fluid is mainly low temperature gel breaking performance, clay hydration inhibition performance, hydrate inhibition performance and scale inhibition performance.
- the invention can further change the composition and mass ratio of the fracturing fluid according to the requirements of different working conditions to adapt to the natural gas hydrate deposits in different physical and chemical environments.
- the preparation method of fracturing fluid is: first add filtered seawater or fracturing flowback fluid to the mixing tank, then slowly add the thickener and stir until it is completely dissolved, and then add the clay stabilizer according to the mass ratio under stirring. , Scale inhibitor, hydrate inhibitor, pH adjuster and bactericide, and finally add crosslinking agent, low temperature activator and gel breaker to obtain seawater-based fracturing fluid for fracturing of natural gas hydrate mineral reservoir.
- the present invention provides for the first time a sea-based submarine natural gas hydrate deposit with good low-temperature gel breaking performance, good clay hydration inhibition performance, good hydrate inhibition performance and scale inhibition ability
- the fracturing fluid has a synergistic effect between the components.
- Ethylene glycol can increase the viscosity of guar gum, and it also strongly inhibits the formation of hydrates. It is also the main component of the organoboron crosslinking agent.
- PVP and PVCap are good hydrate kinetic inhibitors, and they can also stabilize the clay in the reservoir.
- the clay stabilizer also has a synergistic effect on the decomposition of hydrates.
- the obtained low-temperature gel breaking performance is good, and the clay is well inhibited. Hydration performance, good hydrate inhibition performance and scale inhibition ability, suitable for submarine natural gas hydrate deposits.
- the present invention selects fracturing fluid components with multiple functions and energy efficiency, which can increase the added amount to further enhance the performance of the fracturing fluid while reducing production costs.
- Figure 1 is the methane hydrate phase equilibrium curve diagram of the clay stabilizer potassium hydroxide solution in Example 1 and Example 2.
- the square in the figure represents the pure water phase equilibrium, and the circle represents the methane hydrate phase equilibrium of a 2% mass concentration solution.
- the upper triangle is the methane hydrate phase equilibrium of a solution with a mass concentration of 5%
- the lower triangle is the methane hydrate phase equilibrium of a solution with a mass concentration of 10%
- the diamond is the methane hydrate phase equilibrium of a solution with a mass concentration of 15%;
- Fig. 2 is a graph showing the kinetics of methane hydrate formation in the potassium hydroxide solution of clay stabilizer with a mass concentration of 5% in Example 1.
- a seawater-based fracturing fluid for the fracturing of natural gas hydrate mineral reservoirs consisting of the following weight percentage components: thickener 0.15%, clay stabilizer 4.0%, scale inhibitor 0.6 %, hydrate inhibitor 0.8%, pH adjuster 0.5%, bactericide 0.1%, cross-linking agent 0.1%, low temperature activator 0.15%, gel breaker 0.3%, and the remaining components are base liquid.
- the thickening agent is a mixture of hydroxypropyl guar gum powder and ethylene glycol, and the mass ratio of the two is 95:5;
- the clay stabilizer is polyvinyl caprolactam (PVCap) or vinyl pyrrolidone-acrylate Quaternary ammonium salt copolymer, a mixture of potassium chloride and potassium hydroxide, the mass ratio of the three is 5:55:40;
- the scale inhibitor is polyacrylate;
- the hydrate inhibitor is sodium chloride and polyvinylpyrrolidone (PVP ) Is mixed, the mass ratio of the two is 6:4;
- the pH value adjuster is sodium bicarbonate;
- the bactericide is mercaptobenzimidazole;
- the crosslinking agent is an organoboron crosslinking agent.
- the low temperature activator is citric acid
- the gel breaker is a mixture of ammonium persulfate, sodium sulfite and hydrogen peroxide with a mass ratio of 7:1:2
- the base fluid is Filter sea water.
- the seawater-based fracturing fluid of this embodiment can be used in gas hydrate reservoirs with low temperature and high pressure (temperature less than 285K, pressure greater than 4MPa), high clay content (5-30wt%), and high hydrate content (-40wt%).
- the fracturing fluid is broken at low temperature, to inhibit the impact of hydration and expansion of clay on mining, and to inhibit the formation of hydrate in the wellbore and pipeline under the conditions of low temperature, high pressure and high water content.
- Example 1 Refer to Example 1, except that the thickener of Comparative Example 1 is conventional guar gum.
- Comparative Example 2 Refer to Example 1, except that the thickener of Comparative Example 1 is ethylene glycol.
- Example 1 shows that the synergistic effect between the components, ethylene glycol not only enhances the thickening effect of a single hydroxypropyl guar gum thickener, but also strongly inhibits the formation of hydrates. Here comes the role of hydrate inhibitors.
- a seawater-based fracturing fluid for the fracturing of natural gas hydrate mineral deposits is 100%, and it is composed of the following weight percentage components: thickener 0.15%, clay stabilizer 3.5%, scale inhibitor 0.7%, hydrate inhibitor 0.6%, pH value adjuster 0.5%, bactericide 0.1%, crosslinking agent 0.1%, low temperature activator 0.15%, gel breaker 0.3%, and the remaining components are base fluids.
- the thickener is a mixture of hydroxypropyl guar gum powder and ethylene glycol, and the mass ratio of the two is 95:5; the clay stabilizer is dimethyldiallylammonium chloride-acrylamide copolymer A mixture of potassium chloride and potassium hydroxide, the mass ratio of the three is 3:57:40; the scale inhibitor is EDTA; the hydrate inhibitor is a mixture of ethylene glycol and polyvinyl caprolactam (PVCap), two The mass ratio is 6:4; the pH regulator is sodium bicarbonate; the bactericide is pentanediol; the cross-linking agent is an organoboron cross-linking agent; the low-temperature activator is triethanolamine, and the gel breaker is a mass ratio of 7: 1:2 ammonium persulfate, ferrous chloride and hydrogen peroxide are mixed; the base fluid is filtered seawater.
- the seawater-based fracturing fluid of this embodiment can be used in gas hydrate reservoirs with low temperature and high pressure (temperature less than 285K, pressure greater than 4MPa), high clay content (5-30 wt%), and high hydrate content (-40 wt%).
- the fracturing fluid can be broken at low temperature to inhibit the impact of hydration and expansion of clay on mining, and to inhibit the formation of hydrate in the wellbore and pipeline under the conditions of low temperature, high pressure and high water content.
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Abstract
Disclosed is a fracturing fluid for seabed natural gas hydrate mineral resources. The fracturing fluid is comprised of the following components in percentages by weight, with the total percentage by weight being 100%: a thickener: 0.15-0.6%; a clay stabilizer: 0.5-4.0%; an organic boron crosslinker: 0.05-1.0%; a gel breaker: 0.2-0.5%; a low temperature activator: 0.05-0.3%; a scale inhibitor: 0.1-0.6%; a bactericide: 0.05-0.1%; a pH adjusting agent: 0.1-1.0%; a hydrate inhibitor: 0.5-1.0%; and the remaining component being a base liquid. The fracturing fluid is a seawater-based fracturing fluid for seabed natural gas hydrate mineral resources, which has a good low temperature gel breaking performance, a good clay hydration inhibiting performance, and a good hydrate inhibition performance and scale inhibition ability.
Description
本发明涉及一种海底天然气水合物矿藏用压裂液。The invention relates to a fracturing fluid for seabed natural gas hydrate deposits.
水力压裂是一项在常规以及页岩油气开采中常见的储层改造增产作业，但这项技术在天然气水合物矿藏开采中还没有深入研究。天然气水合物储层的主要特点为粉砂泥质,而且渗透率较低，近年来国内外几次天然气水合物试采所得的单井产气量结果与商业开采还有一段距离，产气周期也不理想，所以，实现水合物矿藏储层的水力压裂是实现水合物商业开采的必由之路。Hydraulic fracturing is a common reservoir improvement and stimulation operation in conventional and shale oil and gas exploitation, but this technology has not been studied in depth in the exploitation of natural gas hydrate deposits. The main characteristics of natural gas hydrate reservoirs are silt and muddy and low permeability. In recent years, the results of single well gas production obtained from several gas hydrate test productions at home and abroad are still far from commercial production, and the gas production cycle is also different. It is not ideal, so realizing hydraulic fracturing of hydrate deposits is the only way to realize commercial hydrate mining.
天然气水合物储层的贮藏条件较为复杂，埋藏浅、温度低、黏土含量高、渗透率低，而且开采过程涉及储层内以及井筒内水合物的相变，开采和压裂的难度较大。因此开发适用于海底天然气水合物矿藏的压裂液用以解决这些重要问题，对水合物商业开采的意义重大。The storage conditions of natural gas hydrate reservoirs are relatively complex, with shallow burial, low temperature, high clay content, and low permeability, and the mining process involves phase changes of hydrate in the reservoir and in the wellbore, making mining and fracturing more difficult. Therefore, the development of fracturing fluids suitable for submarine gas hydrate deposits to solve these important problems is of great significance to the commercial exploitation of hydrates.
对比于常规压裂液，根据水合物储层开采的特点，适用于海底天然气水合物矿藏的压裂液需要满足以下性能：①水合物储层的地层温度较低(南海神狐海域水合物储层平均温度14.15℃)，属于超低温油气井，而且开采过程中水合物解离吸热，井筒附近温度会进一步降低，低温环境会使压裂结束后的破胶和返排过程出现破胶不彻底、破胶时间长、返排不彻底等问题，会导致严重的储层伤害，所以压裂液首先需要具有良好的低温破胶性能以及低温有效性能；②水合物储层内黏土含量非常高，高含量的黏土吸水膨胀会造成严重的井壁安全问题和渗透伤害问题，因此压裂液应尽可能提高其抑制黏土水化的性能；③开采过程中井筒内低温高压的环境可能会生成水合物，造成井筒或管线的堵塞，使开采作业无法正常进行，所 以压裂液应该具有有效抑制水合物生成的能力；④为了降低压裂液成本，海上天然气水合物开采会选择来源广泛且现取现用的海水作为压裂液的基液，但海水矿化度较高，压裂过后会产生较多盐垢与残渣，影响压裂液返排，还会制约水合物矿藏的连续生产，因此压裂液需要有良好的阻垢能力以避免这一风险。但至今仍没有特定的用于天然气水合物矿藏的压裂液体系。Compared with conventional fracturing fluids, according to the characteristics of hydrate reservoir mining, fracturing fluids suitable for submarine gas hydrate deposits need to meet the following properties: ①The formation temperature of hydrate reservoirs is relatively low (Hydrate reservoirs in the Shenhu area of the South China Sea) The average layer temperature is 14.15℃), which belongs to ultra-low temperature oil and gas wells, and the hydrate dissociates and absorbs heat during the mining process, and the temperature near the wellbore will be further reduced. The low temperature environment will cause the gel breaking and flowback process after the fracturing to be incomplete. , Long gel breaking time and incomplete flowback will cause serious damage to the reservoir. Therefore, the fracturing fluid first needs to have good low temperature gel breaking performance and low temperature effective performance; ②The clay content in the hydrate reservoir is very high. Water swelling with high content of clay will cause serious shaft wall safety problems and seepage damage. Therefore, the fracturing fluid should improve its ability to inhibit clay hydration as much as possible; ③The low-temperature and high-pressure environment in the wellbore may generate hydrates during the mining process. , Causing blockage of the wellbore or pipeline, making the mining operation impossible, so the fracturing fluid should have the ability to effectively inhibit the formation of hydrate; ④In order to reduce the cost of fracturing fluid, offshore natural gas hydrate mining will choose a wide range of sources and use it now The seawater is used as the base fluid of the fracturing fluid, but the seawater has a high degree of salinity. After fracturing, more salt scale and residue will be produced, which will affect the flowback of the fracturing fluid and restrict the continuous production of hydrate deposits. Therefore, fracturing The liquid needs to have good scale resistance to avoid this risk. However, there is still no specific fracturing fluid system for natural gas hydrate deposits.
发明内容：Summary of the invention:
本发明的目的是针对天然气水合物矿藏储层的特点，首次提供一种低温破胶性能好、有良好抑制黏土水化性能、良好水合物抑制性能和阻垢能力的海水基海底天然气水合物矿藏用压裂液。The purpose of the present invention is to provide for the first time a sea-based submarine natural gas hydrate deposit with good low-temperature gel breaking performance, good clay hydration inhibition performance, good hydrate inhibition performance and scale inhibition ability based on the characteristics of natural gas hydrate mineral reservoirs Use fracturing fluid.
本发明是通过以下技术方案予以实现的：The present invention is realized through the following technical solutions:
一种海底天然气水合物矿藏用压裂液，按总重量百分比为100％计，由如下重量百分比的组分构成：增稠剂：0.15～0.6％；黏土稳定剂：0.5～4.0％；有机硼交联剂：0.05～1.0％；破胶剂：0.2～0.5％；低温激活剂：0.05～0.3％；阻垢剂：0.1～0.6％；杀菌剂：0.05～0.1％；pH值调节剂：0.1～1.0％；水合物抑制剂：0.5～1.0％；剩余组分为基液；增稠剂为速溶型羟丙基瓜尔胶粉和乙二醇混合而成，或速溶型羟丙基瓜尔胶粉和聚乙二醇混合而成，羟丙基瓜尔胶粉和乙二醇或聚乙二醇的质量比为90-95:5-10；速溶型羟丙基瓜尔胶粉起增加压裂液粘度的作用，乙二醇与羟丙基瓜尔胶产生胶凝作用，增加压裂液粘度，稳定压裂液中的盐类，还可以将储层伤害降到最低；黏土稳定剂为聚二甲基二烯丙基氯化铵、聚三甲基烯丙基氯化铵、聚乙烯基己内酰胺(PVCap)、二甲基二烯丙基氯化铵-丙烯酰胺共聚物、环氧氯丙烷-二甲胺缩聚物、乙烯基吡咯烷酮-丙烯酸酯季铵盐共聚物中的一种或多种，与氯化钾和氢氧化钾等复 配使用，一同组成黏土稳定剂；有机硼交联剂由硼砂、乙二醇、氢氧化钾组成；所述破胶剂由破胶氧化剂、破胶还原剂与过氧化氢组合混配而成；其中破胶氧化剂选自过硫酸钾、过硫酸铵、EDTA或SD02中的一种以上，破胶还原剂选自氯化亚铁、氯化亚铜、碘化钾、亚硫酸钠、硫代硫酸钠或亚硫酸氢钠中的一种以上；低温激活剂为柠檬酸、二乙醇胺、三乙醇胺、LC-1或LC-2中的一种或多种；阻垢剂为EDTA、氢氧化钾、聚丙烯酸盐、磺化沥青或磺化聚丙烯酸共聚物中的一种或多种，聚丙烯酸盐适用于硼交联压裂液，磺化沥青在较低温度下有效；杀菌剂为巯基苯并咪唑、1,3,4-噻二唑-2,5-二硫醇和戊二醇中的一种或多种；所述pH值调节剂为碳酸钠、碳酸氢钠中的一种或多种；所述水合物抑制剂为氯化钠、氢氧化钾、乙二醇、聚乙二醇、聚乙烯乙二醇、聚乙烯吡咯烷酮(PVP)、聚乙烯基己内酰胺(PVCap)或1-乙基-3-甲基咪唑四氟硼酸盐中的一种或多种；所述基液为过滤海水或压裂返排液，过滤海水中除水之外的主要成分为氯化钠、氯化钾、硫酸镁、氯化钙等。A fracturing fluid for submarine natural gas hydrate deposits, based on a total weight percentage of 100%, is composed of the following components by weight percentage: thickener: 0.15-0.6%; clay stabilizer: 0.5-4.0%; organic boron Cross-linking agent: 0.05-1.0%; gel breaker: 0.2-0.5%; low-temperature activator: 0.05-0.3%; scale inhibitor: 0.1-0.6%; fungicide: 0.05-0.1%; pH regulator: 0.1 ～1.0%; Hydrate inhibitor: 0.5～1.0%; the remaining component is the base liquid; the thickener is a mixture of instant hydroxypropyl guar powder and ethylene glycol, or instant hydroxypropyl guar Gum powder and polyethylene glycol are mixed, the mass ratio of hydroxypropyl guar powder and ethylene glycol or polyethylene glycol is 90-95:5-10; instant hydroxypropyl guar powder increases The effect of the viscosity of the fracturing fluid, ethylene glycol and hydroxypropyl guar gum produce gelation, increase the viscosity of the fracturing fluid, stabilize the salts in the fracturing fluid, and minimize the damage of the reservoir; clay stabilizer It is polydimethyldiallylammonium chloride, polytrimethylallylammonium chloride, polyvinylcaprolactam (PVCap), dimethyldiallylammonium chloride-acrylamide copolymer, epoxy One or more of chloropropane-dimethylamine polycondensate, vinylpyrrolidone-acrylate quaternary ammonium salt copolymer, used in combination with potassium chloride and potassium hydroxide to form a clay stabilizer; organic boron cross The coupling agent is composed of borax, ethylene glycol, and potassium hydroxide; the breaker is a combination of a breaker oxidant, a breaker reducing agent and hydrogen peroxide; wherein the breaker oxidant is selected from potassium persulfate and persulfuric acid One or more of ammonium, EDTA or SD02, the breaking reducing agent is selected from more than one of ferrous chloride, cuprous chloride, potassium iodide, sodium sulfite, sodium thiosulfate or sodium bisulfite; the low-temperature activator is One or more of citric acid, diethanolamine, triethanolamine, LC-1 or LC-2; scale inhibitor is EDTA, potassium hydroxide, polyacrylate, sulfonated asphalt or sulfonated polyacrylic acid copolymer One or more, polyacrylate is suitable for boron cross-linking fracturing fluid, sulfonated asphalt is effective at lower temperature; the bactericide is mercaptobenzimidazole, 1,3,4-thiadiazole-2,5- One or more of dithiol and pentanediol; the pH adjusting agent is one or more of sodium carbonate and sodium bicarbonate; the hydrate inhibitor is sodium chloride, potassium hydroxide, Ethylene glycol, polyethylene glycol, polyethylene glycol, polyvinylpyrrolidone (PVP), polyvinyl caprolactam (PVCap) or one of 1-ethyl-3-methylimidazole tetrafluoroborate or Multiple; the base fluid is filtered seawater or fracturing flowback fluid, and the main components in the filtered seawater except water are sodium chloride, potassium chloride, magnesium sulfate, calcium chloride and the like.
优选地，黏土稳定剂为聚乙烯基己内酰胺(PVCap)或乙烯基吡咯烷酮-丙烯酸酯季铵盐共聚物与氯化钾和氢氧化钾的混合物，三者质量比为3-5:55-57:40。Preferably, the clay stabilizer is a mixture of polyvinyl caprolactam (PVCap) or vinylpyrrolidone-acrylate quaternary ammonium salt copolymer, potassium chloride and potassium hydroxide, and the mass ratio of the three is 3-5:55-57: 40.
由于天然气水合物储层的特殊性，它在低温有效、黏土稳定、水合物抑制和阻垢能力方面对压裂液的性能有着更高的要求，因此在压裂液组分选择时需要着重考虑这几方面的因素，选出有多种能效的组分物质，提高加入量以增强压裂液不同种类的性能的同时降低生产成本。例如，本发明氢氧化钾对该压裂液而言有四种能效：首先氢氧化钾是良好的油气井用黏土稳定剂，可以永久改变黏土矿物的化学结构，抑制黏土的水化膨胀和颗粒运移；其次氢氧化钾是一种较强的水合物热力学抑制剂；氢氧化钾是常规的针对重晶石垢的阻垢剂。氯化钾和氯化钠部分可由海水直接提供，它们既可以做水合物热力学抑制剂，又可以做常规的黏土稳定 剂。EDTA是针对瓜尔胶压裂液的有效破胶剂，又是良好的油气井水力压裂阻垢剂。乙二醇可以起到对瓜尔胶的增粘效果，还强烈抑制水合物的生成，又是有机硼交联剂的主要成分。PVP和PVCap是良好的水合物动力学抑制剂，又可以对储层起到黏土稳定的效果。Due to the particularity of natural gas hydrate reservoirs, it has higher requirements for the performance of fracturing fluids in terms of low temperature effectiveness, clay stability, hydrate inhibition and scale inhibition. Therefore, the selection of fracturing fluid components needs to be considered. Based on these factors, a variety of energy-efficient components are selected, and the addition amount is increased to enhance the performance of different types of fracturing fluids while reducing production costs. For example, the potassium hydroxide of the present invention has four energy effects for the fracturing fluid: firstly, potassium hydroxide is a good clay stabilizer for oil and gas wells, which can permanently change the chemical structure of clay minerals and inhibit the hydration expansion and particle size of the clay. Transport; secondly, potassium hydroxide is a strong hydrate thermodynamic inhibitor; potassium hydroxide is a conventional scale inhibitor for barite scale. Part of potassium chloride and sodium chloride can be directly provided by seawater. They can be used as hydrate thermodynamic inhibitors as well as conventional clay stabilizers. EDTA is an effective gel breaker for guar gum fracturing fluid and a good hydraulic fracturing scale inhibitor for oil and gas wells. Ethylene glycol can increase the viscosity of guar gum and strongly inhibit the formation of hydrates. It is also the main component of the organoboron crosslinking agent. PVP and PVCap are good inhibitors of hydrate kinetics, and they can also stabilize the reservoir.
因此本发明通过筛选可以适应天然气水合物储层特殊、苛刻理化环境的压裂液成分，并从中选出具有多种作用能效的压裂液成分物质，可以在提高加入量而进一步强化压裂液性能的同时降低生产成本。所述压裂液性能主要为低温破胶性能、抑制黏土水化性能、水合物抑制性能和阻垢性能。本发明还可以根据不同工况要求，进一步改变压裂液成分及质量比以适应不同理化环境的天然气水合物矿藏储层。Therefore, the present invention selects fracturing fluid components that can adapt to the special and harsh physical and chemical environment of natural gas hydrate reservoirs through screening, and selects fracturing fluid components with multiple functions and energy efficiency from them, which can further strengthen the fracturing fluid by increasing the addition amount. Reduce production costs while maintaining performance. The performance of the fracturing fluid is mainly low temperature gel breaking performance, clay hydration inhibition performance, hydrate inhibition performance and scale inhibition performance. The invention can further change the composition and mass ratio of the fracturing fluid according to the requirements of different working conditions to adapt to the natural gas hydrate deposits in different physical and chemical environments.
压裂液的制备方法为：先将过滤海水或压裂返排液加入到配液罐中，再缓慢加入增稠剂并搅拌至完全溶解，之后在搅拌下按质量配比依次加入黏土稳定剂、阻垢剂、水合物抑制剂、pH值调节剂和杀菌剂，最后加入交联剂、低温激活剂和破胶剂而得到天然气水合物矿藏储层压裂用海水基压裂液。The preparation method of fracturing fluid is: first add filtered seawater or fracturing flowback fluid to the mixing tank, then slowly add the thickener and stir until it is completely dissolved, and then add the clay stabilizer according to the mass ratio under stirring. , Scale inhibitor, hydrate inhibitor, pH adjuster and bactericide, and finally add crosslinking agent, low temperature activator and gel breaker to obtain seawater-based fracturing fluid for fracturing of natural gas hydrate mineral reservoir.
本发明的有益效果如下：The beneficial effects of the present invention are as follows:
1)本发明针对天然气水合物矿藏储层的特点，首次提供一种低温破胶性能好、有良好抑制黏土水化性能、良好水合物抑制性能和阻垢能力的海水基海底天然气水合物矿藏用压裂液，组分间协同作用，乙二醇可以起到对瓜尔胶的增粘效果，还强烈抑制水合物的生成，又是有机硼交联剂的主要成分。PVP和PVCap是良好的水合物动力学抑制剂，又可以对储层起到黏土稳定的效果，粘土稳定剂同时对水合物的分解也有协同作用，得到的低温破胶性能好、有良好抑制黏土水化性能、良好水合物抑制性能和阻垢能力，适合于海底天然气水合物矿藏用。1) Aiming at the characteristics of natural gas hydrate deposits, the present invention provides for the first time a sea-based submarine natural gas hydrate deposit with good low-temperature gel breaking performance, good clay hydration inhibition performance, good hydrate inhibition performance and scale inhibition ability The fracturing fluid has a synergistic effect between the components. Ethylene glycol can increase the viscosity of guar gum, and it also strongly inhibits the formation of hydrates. It is also the main component of the organoboron crosslinking agent. PVP and PVCap are good hydrate kinetic inhibitors, and they can also stabilize the clay in the reservoir. The clay stabilizer also has a synergistic effect on the decomposition of hydrates. The obtained low-temperature gel breaking performance is good, and the clay is well inhibited. Hydration performance, good hydrate inhibition performance and scale inhibition ability, suitable for submarine natural gas hydrate deposits.
2)本发明选出具有多种作用能效的压裂液成分物质，可以在提高加入量而进一步强化压 裂液性能的同时降低生产成本。2) The present invention selects fracturing fluid components with multiple functions and energy efficiency, which can increase the added amount to further enhance the performance of the fracturing fluid while reducing production costs.
图1是实施例1和实施例2中黏土稳定剂氢氧化钾溶液的甲烷水合物相平衡曲线图，图中方形代表纯水相平衡，圆形为质量浓度2％溶液的甲烷水合物相平衡，上三角为质量浓度5％溶液的甲烷水合物相平衡，下三角为质量浓度10％溶液的甲烷水合物相平衡，菱形为质量浓度15％溶液的甲烷水合物相平衡；Figure 1 is the methane hydrate phase equilibrium curve diagram of the clay stabilizer potassium hydroxide solution in Example 1 and Example 2. The square in the figure represents the pure water phase equilibrium, and the circle represents the methane hydrate phase equilibrium of a 2% mass concentration solution. , The upper triangle is the methane hydrate phase equilibrium of a solution with a mass concentration of 5%, the lower triangle is the methane hydrate phase equilibrium of a solution with a mass concentration of 10%, and the diamond is the methane hydrate phase equilibrium of a solution with a mass concentration of 15%;
图2是实施例1中质量浓度5％黏土稳定剂氢氧化钾溶液的甲烷水合物生成动力学曲线图。Fig. 2 is a graph showing the kinetics of methane hydrate formation in the potassium hydroxide solution of clay stabilizer with a mass concentration of 5% in Example 1.
以下是对本发明的进一步说明，而不是对本发明的限制。The following is a further description of the present invention, but not a limitation of the present invention.
实施例1：Example 1:
一种天然气水合物矿藏储层压裂用海水基压裂液，按总重量百分比为100％计，由如下重量百分比组分组成：增稠剂0.15％，黏土稳定剂4.0％，阻垢剂0.6％，水合物抑制剂0.8％，pH值调节剂0.5％，杀菌剂0.1％，交联剂0.1％，低温激活剂0.15％，破胶剂0.3％，其余组分为基液。A seawater-based fracturing fluid for the fracturing of natural gas hydrate mineral reservoirs, based on a total weight percentage of 100%, consisting of the following weight percentage components: thickener 0.15%, clay stabilizer 4.0%, scale inhibitor 0.6 %, hydrate inhibitor 0.8%, pH adjuster 0.5%, bactericide 0.1%, cross-linking agent 0.1%, low temperature activator 0.15%, gel breaker 0.3%, and the remaining components are base liquid.
所述增稠剂为羟丙基瓜尔胶粉和乙二醇混合而成，二者质量比为95:5；所述黏土稳定剂为聚乙烯基己内酰胺(PVCap)或乙烯基吡咯烷酮-丙烯酸酯季铵盐共聚物，与氯化钾和氢氧化钾的混合物，三者质量比为5:55:40；阻垢剂为聚丙烯酸盐；水合物抑制剂为氯化钠和聚乙烯吡咯烷酮(PVP)混合而成，二者质量比为6:4；pH值调节剂为碳酸氢钠；杀菌剂为巯基苯并咪唑；交联剂为有机硼交联剂，选择商用产品，例如由陕西森瑞石油技术开发有限公司 生产，型号SRJL-YL4；低温激活剂为柠檬酸，破胶剂由质量比为7:1:2的过硫酸铵、亚硫酸钠和过氧化氢三者混合而成；基液为过滤海水。The thickening agent is a mixture of hydroxypropyl guar gum powder and ethylene glycol, and the mass ratio of the two is 95:5; the clay stabilizer is polyvinyl caprolactam (PVCap) or vinyl pyrrolidone-acrylate Quaternary ammonium salt copolymer, a mixture of potassium chloride and potassium hydroxide, the mass ratio of the three is 5:55:40; the scale inhibitor is polyacrylate; the hydrate inhibitor is sodium chloride and polyvinylpyrrolidone (PVP ) Is mixed, the mass ratio of the two is 6:4; the pH value adjuster is sodium bicarbonate; the bactericide is mercaptobenzimidazole; the crosslinking agent is an organoboron crosslinking agent. Produced by Petroleum Technology Development Co., Ltd., model SRJL-YL4; the low temperature activator is citric acid, and the gel breaker is a mixture of ammonium persulfate, sodium sulfite and hydrogen peroxide with a mass ratio of 7:1:2; the base fluid is Filter sea water.
如图1所示，黏土稳定剂中的高浓度(2-15wt％)的氢氧化钾对甲烷水合物有着强烈的热力学抑制作用，相同状态下，水合物的成核需要更高的压力和更低的温度，水合物的解离更加容易。如图2所示，温度277K下，5wt％的氢氧化钾溶液生成甲烷水合物诱导时间超过300min，动力学抑制性能优异。多种具有水合物抑制性能、促进分解性能的化学剂的使用将助力水合物开采过程，减少井筒及管道堵塞，加强水合物的分解转化，增强了压裂改造的开采效果。As shown in Figure 1, the high concentration (2-15wt%) of potassium hydroxide in the clay stabilizer has a strong thermodynamic inhibitory effect on methane hydrate. Under the same state, the nucleation of hydrate requires higher pressure and more At lower temperatures, the dissociation of hydrates is easier. As shown in Figure 2, at a temperature of 277K, the induction time for the formation of methane hydrates from 5wt% potassium hydroxide solution exceeds 300 minutes, and the kinetic inhibition performance is excellent. The use of a variety of chemical agents with hydrate inhibition and decomposition properties will help the hydrate mining process, reduce wellbore and pipeline blockage, strengthen the decomposition and transformation of hydrate, and enhance the mining effect of fracturing.
本实施例海水基压裂液可以用于低温高压(温度小于285K,压力大于4MPa)、黏土含量高(5-30wt％)、水合物含量高(～40wt％)的天然气水合物储层，可以在低温下完成压裂液的破胶，抑制黏土的水化膨胀对开采的影响，并在低温高压和含水量高的情况下抑制井筒和管道中水合物的生成。The seawater-based fracturing fluid of this embodiment can be used in gas hydrate reservoirs with low temperature and high pressure (temperature less than 285K, pressure greater than 4MPa), high clay content (5-30wt%), and high hydrate content (-40wt%). The fracturing fluid is broken at low temperature, to inhibit the impact of hydration and expansion of clay on mining, and to inhibit the formation of hydrate in the wellbore and pipeline under the conditions of low temperature, high pressure and high water content.
对比例1：Comparative example 1:
参考实施例1，不同之处在于对比例1增稠剂为常规瓜尔胶。Refer to Example 1, except that the thickener of Comparative Example 1 is conventional guar gum.
对比例2：参考实施例1，不同之处在于对比例1增稠剂为乙二醇。Comparative Example 2: Refer to Example 1, except that the thickener of Comparative Example 1 is ethylene glycol.
实施例1和对比例1、2比较可知，组分间协同作用，乙二醇不仅增强了单一羟丙基瓜尔胶增稠剂的增粘效果，同时还强烈抑制了水合物的生成，起到了水合物抑制剂的作用。Comparison of Example 1 and Comparative Examples 1 and 2 shows that the synergistic effect between the components, ethylene glycol not only enhances the thickening effect of a single hydroxypropyl guar gum thickener, but also strongly inhibits the formation of hydrates. Here comes the role of hydrate inhibitors.
实施例2：Example 2:
一种天然气水合物矿藏储层压裂用海水基压裂液，按总重量百分比为100％计，由如下重量百分比的组分组成：增稠剂0.15％，黏土稳定剂3.5％，阻垢剂0.7％，水合物抑制剂0.6％， pH值调节剂0.5％，杀菌剂0.1％，交联剂0.1％，低温激活剂0.15％，破胶剂0.3％，其余组分为基液。A seawater-based fracturing fluid for the fracturing of natural gas hydrate mineral deposits. The total weight percentage is 100%, and it is composed of the following weight percentage components: thickener 0.15%, clay stabilizer 3.5%, scale inhibitor 0.7%, hydrate inhibitor 0.6%, pH value adjuster 0.5%, bactericide 0.1%, crosslinking agent 0.1%, low temperature activator 0.15%, gel breaker 0.3%, and the remaining components are base fluids.
所述增稠剂为羟丙基瓜尔胶粉和乙二醇混合而成，二者质量比为95:5；所述黏土稳定剂为二甲基二烯丙基氯化铵-丙烯酰胺共聚物与氯化钾、氢氧化钾的混合物，三者质量比为3:57:40；阻垢剂为EDTA；水合物抑制剂为乙二醇、聚乙烯基己内酰胺(PVCap)混合而成，二者质量比为6:4；pH值调节剂为碳酸氢钠；杀菌剂为戊二醇；交联剂为有机硼交联剂；低温激活剂为三乙醇胺，破胶剂为质量比为7:1:2的过硫酸铵、氯化亚铁和过氧化氢混合而成；基液为过滤海水。The thickener is a mixture of hydroxypropyl guar gum powder and ethylene glycol, and the mass ratio of the two is 95:5; the clay stabilizer is dimethyldiallylammonium chloride-acrylamide copolymer A mixture of potassium chloride and potassium hydroxide, the mass ratio of the three is 3:57:40; the scale inhibitor is EDTA; the hydrate inhibitor is a mixture of ethylene glycol and polyvinyl caprolactam (PVCap), two The mass ratio is 6:4; the pH regulator is sodium bicarbonate; the bactericide is pentanediol; the cross-linking agent is an organoboron cross-linking agent; the low-temperature activator is triethanolamine, and the gel breaker is a mass ratio of 7: 1:2 ammonium persulfate, ferrous chloride and hydrogen peroxide are mixed; the base fluid is filtered seawater.
本实施例海水基压裂液的可以低温高压(温度小于285K,压力大于4MPa)、黏土含量高(5-30wt％)、水合物含量高(～40wt％)的天然气水合物储层，可以在低温下完成压裂液的破胶，抑制黏土的水化膨胀对开采的影响，并在低温高压和含水量高的情况下抑制井筒和管道中水合物的生成。The seawater-based fracturing fluid of this embodiment can be used in gas hydrate reservoirs with low temperature and high pressure (temperature less than 285K, pressure greater than 4MPa), high clay content (5-30 wt%), and high hydrate content (-40 wt%). The fracturing fluid can be broken at low temperature to inhibit the impact of hydration and expansion of clay on mining, and to inhibit the formation of hydrate in the wellbore and pipeline under the conditions of low temperature, high pressure and high water content.
以上列举仅仅是对本发明的举例说明，并不构成对本发明的保护范围的限制，在上述说明的基础上还可以做出其它不同形式的变化或变动,凡是与本发明相同或相似的设计均属于本发明的保护范围之内。The above list is merely illustrative of the present invention, and does not constitute a limitation to the scope of protection of the present invention. On the basis of the above description, other changes or changes in different forms can also be made. Any design identical or similar to the present invention belongs to Within the protection scope of the present invention.
Claims (3)
- 一种海底天然气水合物矿藏用压裂液，其特征在于，按总重量百分比为100％计，由如下重量百分比的组分构成：增稠剂：0.15～0.6％；黏土稳定剂：0.5～4.0％；有机硼交联剂：0.05～1.0％；破胶剂：0.2～0.5％；低温激活剂：0.05～0.3％；阻垢剂：0.1～0.6％；杀菌剂：0.05～0.1％；pH值调节剂：0.1～1.0％；水合物抑制剂：0.5～1.0％；剩余组分为基液；增稠剂为速溶型羟丙基瓜尔胶粉和乙二醇混合而成，或速溶型羟丙基瓜尔胶粉和聚乙二醇混合而成，羟丙基瓜尔胶粉和乙二醇或聚乙二醇的质量比为90-95:5-10；黏土稳定剂为聚二甲基二烯丙基氯化铵、聚三甲基烯丙基氯化铵、聚乙烯基己内酰胺、二甲基二烯丙基氯化铵-丙烯酰胺共聚物、环氧氯丙烷-二甲胺缩聚物、乙烯基吡咯烷酮-丙烯酸酯季铵盐共聚物中的一种或多种，与氯化钾和氢氧化钾复配使用；有机硼交联剂由硼砂、乙二醇、氢氧化钾组成；所述破胶剂由破胶氧化剂、破胶还原剂与过氧化氢组合混配而成；其中破胶氧化剂选自过硫酸钾、过硫酸铵、EDTA或SD02中的一种以上，破胶还原剂选自氯化亚铁、氯化亚铜、碘化钾、亚硫酸钠、硫代硫酸钠或亚硫酸氢钠中的一种以上；低温激活剂为柠檬酸、二乙醇胺、三乙醇胺、LC-1或LC-2中的一种或多种；阻垢剂为EDTA、氢氧化钾、聚丙烯酸盐、磺化沥青或磺化聚丙烯酸共聚物中的一种或多种；杀菌剂为巯基苯并咪唑、1,3,4-噻二唑-2,5-二硫醇和戊二醇中的一种或多种；所述pH值调节剂为碳酸钠、碳酸氢钠中的一种或多种；所述水合物抑制剂为氯化钠、氢氧化钾、乙二醇、聚乙二醇、聚乙烯乙二醇、聚乙烯吡咯烷酮、聚乙烯基己内酰胺或1-乙基-3-甲基咪唑四氟硼酸盐中的一种或多种；所述基液为过滤海水或压裂返排液。A fracturing fluid for submarine natural gas hydrate deposits, characterized in that, based on a total weight percentage of 100%, it is composed of the following components by weight percentage: thickener: 0.15 to 0.6%; clay stabilizer: 0.5 to 4.0 %; Organoboron crosslinking agent: 0.05～1.0%; Breaker: 0.2～0.5%; Low temperature activator: 0.05～0.3%; Scale inhibitor: 0.1～0.6%; Bactericide: 0.05～0.1%; pH value Conditioner: 0.1-1.0%; Hydrate inhibitor: 0.5-1.0%; the remaining component is the base liquid; the thickener is a mixture of fast-dissolving hydroxypropyl guar powder and ethylene glycol, or fast-dissolving hydroxy Propyl guar gum powder and polyethylene glycol are mixed, the mass ratio of hydroxypropyl guar gum powder and ethylene glycol or polyethylene glycol is 90-95:5-10; the clay stabilizer is polyethylene glycol Diallyl ammonium chloride, polytrimethylallyl ammonium chloride, polyvinyl caprolactam, dimethyldiallyl ammonium chloride-acrylamide copolymer, epichlorohydrin-dimethylamine polycondensation One or more of vinylpyrrolidone-acrylate quaternary ammonium salt copolymer, used in combination with potassium chloride and potassium hydroxide; the organic boron crosslinking agent is composed of borax, ethylene glycol, and potassium hydroxide; The gel breaker is a combination of a gel breaker oxidant, a gel breaker reducing agent and hydrogen peroxide; wherein the gel breaker oxidant is selected from one or more of potassium persulfate, ammonium persulfate, EDTA or SD02, and the gel breaker reduces The agent is selected from one or more of ferrous chloride, cuprous chloride, potassium iodide, sodium sulfite, sodium thiosulfate or sodium bisulfite; the low-temperature activator is citric acid, diethanolamine, triethanolamine, LC-1 or LC -2; the scale inhibitor is one or more of EDTA, potassium hydroxide, polyacrylate, sulfonated asphalt or sulfonated polyacrylic acid copolymer; the bactericide is mercaptobenzimidazole, One or more of 1,3,4-thiadiazole-2,5-dithiol and pentanediol; said pH adjusting agent is one or more of sodium carbonate and sodium bicarbonate; The hydrate inhibitor is sodium chloride, potassium hydroxide, ethylene glycol, polyethylene glycol, polyethylene glycol, polyvinylpyrrolidone, polyvinyl caprolactam or 1-ethyl-3-methylimidazole tetrafluoroethylene One or more of borates; the base fluid is filtered seawater or fracturing flowback fluid.
- 根据权利要求1所述的海底天然气水合物矿藏用压裂液，其特征在于，黏土稳定剂为聚 乙烯基己内酰胺或乙烯基吡咯烷酮-丙烯酸酯季铵盐共聚物与氯化钾和氢氧化钾的混合物，三者质量比为3-5:55-57:40。The fracturing fluid for submarine natural gas hydrate deposits according to claim 1, wherein the clay stabilizer is a combination of polyvinyl caprolactam or vinyl pyrrolidone-acrylate quaternary ammonium salt copolymer and potassium chloride and potassium hydroxide. For the mixture, the mass ratio of the three is 3-5:55-57:40.
- 权利要求1所述的海底天然气水合物矿藏用压裂液的制备方法，其特征在于，包括以下步骤：先将过滤海水或压裂返排液加入到配液罐中，再缓慢加入增稠剂并搅拌至完全溶解，之后在搅拌下按质量配比依次加入黏土稳定剂、阻垢剂、水合物抑制剂、pH值调节剂和杀菌剂，最后加入交联剂、低温激活剂和破胶剂而得到天然气水合物矿藏储层压裂用海水基压裂液。The preparation method of fracturing fluid for submarine natural gas hydrate deposits according to claim 1, characterized in that it comprises the following steps: firstly adding filtered seawater or fracturing flowback fluid to the mixing tank, and then slowly adding the thickener Stir until completely dissolved, then add clay stabilizer, scale inhibitor, hydrate inhibitor, pH adjuster and bactericide according to the mass ratio under stirring, and finally add cross-linking agent, low-temperature activator and gel breaker The seawater-based fracturing fluid for fracturing the natural gas hydrate deposit is obtained.
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