CN115057964A - 一种用于高温压裂液的交联剂的制备方法 - Google Patents
一种用于高温压裂液的交联剂的制备方法 Download PDFInfo
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- CN115057964A CN115057964A CN202210815611.6A CN202210815611A CN115057964A CN 115057964 A CN115057964 A CN 115057964A CN 202210815611 A CN202210815611 A CN 202210815611A CN 115057964 A CN115057964 A CN 115057964A
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- zirconium
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- 239000003431 cross linking reagent Substances 0.000 title claims abstract description 43
- 239000012530 fluid Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims description 16
- 239000003446 ligand Substances 0.000 claims abstract description 42
- 239000000178 monomer Substances 0.000 claims abstract description 36
- 125000000129 anionic group Chemical group 0.000 claims abstract description 19
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 150000003755 zirconium compounds Chemical class 0.000 claims abstract description 9
- -1 zirconium ions Chemical class 0.000 claims abstract description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 6
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 7
- 239000004310 lactic acid Substances 0.000 claims description 7
- 235000014655 lactic acid Nutrition 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 6
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 4
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 229930195725 Mannitol Natural products 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000594 mannitol Substances 0.000 claims description 4
- 235000010355 mannitol Nutrition 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 4
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- XESUCHPMWXMNRV-UHFFFAOYSA-M sodium;2-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1C=C XESUCHPMWXMNRV-UHFFFAOYSA-M 0.000 claims description 3
- PFXYQVJESZAMSV-UHFFFAOYSA-K zirconium(iii) chloride Chemical compound Cl[Zr](Cl)Cl PFXYQVJESZAMSV-UHFFFAOYSA-K 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 2
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 claims description 2
- MXRGSJAOLKBZLU-UHFFFAOYSA-N 3-ethenylazepan-2-one Chemical compound C=CC1CCCCNC1=O MXRGSJAOLKBZLU-UHFFFAOYSA-N 0.000 claims description 2
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 claims description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 claims description 2
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229960003330 pentetic acid Drugs 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims 1
- 229960001484 edetic acid Drugs 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 10
- 239000002562 thickening agent Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 6
- 229920002521 macromolecule Polymers 0.000 abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 238000010008 shearing Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 238000000034 method Methods 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000013110 organic ligand Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 150000003754 zirconium Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 2
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 description 1
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/30—Sulfur
-
- 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
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
- C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
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- 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
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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
- C09K8/62—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
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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
- C09K8/84—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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- 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
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- General Life Sciences & Earth Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明通过将功能单体、丙烯酰胺等非离子单体、2‑丙烯酰胺基‑2‑甲基丙磺酸等阴离子单体共聚,制备含有羟基、羧基、磺酸基、多位点配位结构的高分子,作为锆离子的高分子配体,在此基础上,以无机锆化物、非离子配体、阴离子配体、高分子配体为原料,制备压裂液用交联剂。经过测试,该产品对于常规压裂液稠化剂具有良好的交联作用,形成的压裂液体系在高温、高盐、剪切作用下仍然可以保持良好的粘度,可以适用于苛刻条件下的压裂作业。
Description
技术领域
本发明涉及一种用于高温压裂液的交联剂,属于油田化学技术领域。
背景技术
石油是目前世界上使用量最大、使用领域最广的能源,其使用优势和基础性作用在未来一段时期内仍然不可替代。随着油气勘探开发的不断深入,低渗、超低渗储层、致密油气储层比重加大,低渗透油气资源占到了总资源的50%以上。深层超高温储层由于埋藏深,储层渗透率低,射孔后自然产能低甚至无产量,对于那些投产初期产量很低甚至没有产量的油气井,经过压裂增产改造后,具备了一定的生产价值和经济效益。因此,压裂技术在低渗油藏中得到了广泛的应用,成为这类储层最为有效的增产措施,取得了较好的增产效果。
交联剂作为压裂液中最重要的添加剂之一,通过化学键或配位键与稠化剂发生交联反应,使稠化剂中的大分子链相互交结形成体型网状结构,进一步增稠形成典型的粘弹冻胶,进而有效提高压裂液的携砂能力和造缝能力。交联剂对压裂体系的成胶速度、耐温稳定性和剪切稳定性以及对地层渗透率都有较大的影响。在抗高温压裂液体系中,稠化剂通常选用丙烯酰胺类聚合物,交联剂通常为有机金属离子化合物。交联剂中的金属离子通过与稠化剂分子中的羧基、酰胺基等基团形成配位作用,实现交联。通过改进交联剂的分子结构,可以提升压裂液体系的性能。
中国专利文件CN104927828 A公开了一种有机锆交联剂、压裂液冻胶及其制备方法,以无机锆盐(5%-10%)、多元醇(5%-15%)、有机配体(5%-10%)络合交联剂(1%-5%)、高温稳定剂(1%-5%)为原料制备。其中,无机锆盐为四氯化锆、氧氯化锆,多元醇为乙二醇、丙三醇、甘露醇,有机配体为醋酸、乳酸、二羟乙基甘氨酸、葡萄糖酸钠、三乙醇胺,络合交联剂为N,N-亚甲基双丙烯酰胺,高温稳定剂为磷酸丁三酯、硫代硫酸钠、氯化钾、四乙烯五胺。所得的有机锆交联剂应用于高温地层中,在160℃条件下剪切一段时间后,其粘度仍能满足施工要求。
中国专利文件CN105199 706 A公开了一种有机锆交联剂的制备方法,以无机锆盐(5%-25%)、有机醇(15%-55%)、有机配体(10%-50%)为原料制备。其中,无机锆盐为三氯化锆、四氯化锆、氧氯化锆、硫酸锆、醋酸锆,有机醇为乙二醇、丙三醇、异丙醇、正丁醇、甘露醇,有机配体为丙三醇、二甘醇、β-二酮、乳酸、三乙醇胺、二乙醇胺、异丙醇胺。所得有机锆交联剂可应用于压裂液的配制。
发明内容
针对现有技术的不足,本发明提供了一种高温用压裂液交联剂的制备方法。
发明概述
本发明涉及一种高温用压裂液交联剂的制备方法,属于油田化学技术领域。通过合成具有多络合位点的高分子作为交联剂配体,使得压裂液具有良好的耐温性能。利用高分子的分子量分布,以及小分子配体与高分子配体之间的分子量差异,实现不同尺度的交联,提高交联效率。最终制备带有羟基、羧基、磺酸基的高分子,利用这些基团协同作用下对锆离子强烈的配位作用,提升交联结构在高温下的稳定能力,实现压裂液性能的提升。
发明目的
丙烯酰胺类聚合物配制成水溶液后会与多价的金属离子交联而形成凝胶,常用的有机锆交联剂在引入配体后稳定性提高,单位交联点强度增加,从而提高压裂液冻胶的稳定性。目前的技术手段来看,交联剂往往存在以下不足之处:交联剂的交联效果不佳,压裂液体系中稠化剂和交联剂的用量多;有机配体等用量大,交联剂中的高价金属离子有效含量少;交联结构在高温条件下容易被破坏,长时间剪切后粘度急剧下降,影响产品的使用性能。针对现有技术的不足之处,本发明提供一种用于高温条件下的压裂液用交联剂。
发明详述
本发明的技术方案如下。
一种高温用压裂液交联剂,其制备方法如下:
(1)高分子配体的制备
将功能单体、非离子单体、阴离子单体、引发剂、去离子水加入到装有搅拌器、通氮管、温度计的三颈玻璃瓶中,搅拌待所有原料溶解后,将pH调到6~9,通入氮气30min,聚合温度控制在40~80℃,聚合反应1~24h,将产物干燥、粉碎、即得;功能单体、非离子单体、阴离子单体的摩尔比为(2~10):(60~90):(5~30),三类单体、引发剂、去离子水的质量比为1:(0.005~0.05):(1~10);
(2)交联剂的制备
将无机锆化物、非离子配体、阴离子配体、高分子配体、去离子水加入到装有搅拌器、冷凝管和温度计的三颈玻璃瓶中,搅拌待所有原料溶解后,将pH调至3~7.5,温度控制在50~90℃,反应1~10h,即得;无机锆化物、非离子配体、阴离子配体、高分子配体、去离子水的质量比为1:(0.5~5):(0.2~2):(0.1~2):(2~7)。
根据本发明,优选的,步骤(1)中所述的功能单体为功能单体-A、功能单体-B中的一种,
优选的,所述的非离子单体为丙烯酰胺、甲基丙烯酸二甲氨基乙酯、乙烯基吡咯烷酮、乙烯基己内酰胺、甲基丙烯酰胺、N-乙基丙烯酰胺、N,N-二甲基丙烯酰胺、N,N-二乙基丙烯酰胺、N-异丙基丙烯酰胺中的一种或者两种以上混合物;
优选的,所述的阴离子单体为2-丙烯酰胺基-2-甲基丙磺酸、乙烯基苯磺酸钠、乙烯基磺酸钠、烯丙基磺酸钠中的一种或者两种以上混合物;
优选的,所述的引发剂为过硫酸钾、过硫酸铵、过硫酸钠、偶氮二异丁咪唑啉盐酸盐、偶氮二异丁脒盐酸盐中的一种或者两种以上混合物;
优选的,功能单体、非离子单体、阴离子单体的摩尔比为(5~10):(60~80):(20~30);
优选的,三类单体、引发剂、去离子水的质量比为1:(0.005~0.03):(1~8);
优选的,聚合温度为40~70℃,时间为4~10h。
根据本发明,优选的,步骤(2)中所述的无机锆化物为氧氯化锆、三氯化锆、四氯化锆、醋酸锆中的一种;
优选的,所述的非离子配体为三乙醇胺、二乙醇胺、丙三醇、异丙醇、正丁醇、甘露醇、甲醇、乙醇、丙醇中的一种或者两种以上混合物;
优选的,所述的阴离子配体为羟基乙酸、乳酸、羟基丙酸、葡萄糖酸、柠檬酸、乙二酸、丙二酸、丁二酸、乙二胺四乙酸、二乙烯三胺五乙酸中的一种或者两种以上混合物;
优选的,无机锆化物、非离子配体、阴离子配体、高分子配体、去离子水的质量比为1:(0.5~2):(0.5~1.5):(0.2~1):(3~7);
优选的,交联剂制备反应pH为6~7,温度为60~80℃,时间为2~6h。
本发明的优良效果如下:
1.本发明原料易得,过程简单安全,生产成本低。
2.制备带有羟基、羧基、磺酸基的高分子,利用这些基团协同作用下对锆离子强烈的配位作用,提升交联结构在高温下的稳定能力,实现压裂液抗温性能的提升。
3.高分子配体具有多个强配位结构,将锆离子负载于高分子配位上,形成稳固的多位点的交联结构,可以降低压裂液体系中稠化剂和交联剂的用量。
4.利用高分子的分子量分布,以及小分子配体与高分子配体之间的分子量差异,实现不同尺度的交联,提高交联效率。
5.本发明产品后处理简单,容易实现连续生产。
6.本发明制备的产品与常规压裂液体系的配伍性好。
具体实施方式
下述实施例中所使用的实验方法如无特殊说明,均为常规方法。
下述实施例中所用的药剂,包括稠化剂、助排剂、高温稳定剂等,均从北京弘毅恩泽能源技术有限公司购买,其它的材料、试剂等,如无特殊说明,均可从商业途径得到。
下面结合具体实施例对本发明做进一步说明,但本发明保护范围不仅限于此。
实施例1:
(1)高分子配体的制备
将30g功能单体-A、130g丙烯酰胺、140g 2-丙烯酰胺基-2-甲基丙磺酸、3g过硫酸钾、500g去离子水加入到装有搅拌器、通氮管、温度计的三颈玻璃瓶中,搅拌至所有的原料溶解后,通入氮气30min,将温度升至55℃,反应8h,将产物干燥、粉碎,即得到高分子配体。
(2)交联剂的制备
将20g氧氯化锆、10g三乙醇胺、10g乳酸、15g高分子配体、60g去离子水加入到装有搅拌器、冷凝管和温度计的三颈玻璃瓶中,搅拌待所有原料溶解后,加入25%的氢氧化钠溶液将pH调节为7,温度升高至80℃,反应4h,即得交联剂。
实施例2:
如实施例1所述,所不同的是步骤(1)中功能单体为功能单体-B,加量为30g。
实施例3:
如实施例1所述,所不同的是步骤(1)中功能单体为功能单体-A、功能单体-B的混合物,加量为15g功能单体-A,15g功能单体-B。
实施例4:
如实施例1所述,所不同的是步骤(1)中非离子单体为80g丙烯酰胺和50g N,N-二乙基丙烯酰胺。
实施例5:
如实施例1所述,所不同的是步骤(1)中非离子单体为50g丙烯酰胺和30g甲基丙烯酰胺和30g N,N-二甲基丙烯酰胺。
实施例6:
如实施例1所述,所不同的是步骤(1)中阴离子单体为乙烯基苯磺酸钠,加量为100g。
实施例7:
如实施例1所述,所不同的是步骤(1)中2-丙烯酰胺基-2-甲基丙磺酸加量为170g。
实施例8:
如实施例1所述,所不同的是步骤(1)中引发剂为偶氮二异丁咪唑啉盐酸盐,加量为5g。
实施例9:
如实施例1所述,所不同的是步骤(1)中聚合反应,温度为70℃,反应时间为5h。
实施例10:
如实施例1所述,所不同的是步骤(2)中三乙醇胺的加量为16g。
实施例11:
如实施例1所述,所不同的是步骤(2)中非离子配体为6g三乙醇胺和4g二乙醇胺。
实施例12:
如实施例1所述,所不同的是步骤(2)中阴离子配体为8g乳酸和5g柠檬酸。
实施例13:
如实施例1所述,所不同的是步骤(2)中高分子配体的加量为10g。
实施例14:
如实施例1所述,所不同的是步骤(2)中高分子配体的加量为20g。
实施例15:
如实施例1所述,所不同的是步骤(2)中反应pH为6,温度为70℃,时间为2h。
对比例1:
将20g氧氯化锆、10g三乙醇胺、10g乳酸、60g去离子水加入到装有搅拌器、冷凝管和温度计的三颈玻璃瓶中,搅拌待所有原料溶解后,将pH调节为7,温度升高至80℃,反应4h,即得。
对比例2:
北京弘毅恩泽能源技术有限公司,GL-3。
性能评价
评价了对比例1~2和实施例1~15产品配制压裂液体系,在高温下的流变性能,评价按SY/T 5107-2016《水基压裂液性能评价方法》规定,高温下170s-1剪切90min后测定表观粘度,测试温度分别为160℃,180℃和200℃,压裂液体系的组成如下所示,评价结果如表1所示。
压裂液体系配方:475g去离子水+24g NaCl+1g CaCl2+3.5g稠化剂+10g交联剂+12.5g高温稳定剂+15g铁离子稳定剂+5g破乳剂+5g助排剂。
表1性能评价结果
由表中数据可以看出,使用本发明交联剂配制的压裂液,具有更好的抗高温稳定性,可以满足200℃压裂施工的要求。
Claims (6)
1.一种高温用压裂液交联剂,其制备方法包括步骤如下:
(1)高分子配体的制备
将功能单体、非离子单体、阴离子单体、引发剂、去离子水加入到装有搅拌器、通氮管、温度计的三颈玻璃瓶中,搅拌待所有原料溶解后,将pH调到6~9,通入氮气30min,聚合温度控制在40~80℃,聚合反应1~24h,将产物干燥、粉碎、即得;功能单体、非离子单体、阴离子单体的摩尔比为(2~10):(60~90):(5~30),三类单体、引发剂、去离子水的质量比为1:(0.005~0.05):(1~10);
所述的功能单体为功能单体-A、功能单体-B中的一种,
所述的非离子单体为丙烯酰胺、甲基丙烯酸二甲氨基乙酯、乙烯基吡咯烷酮、乙烯基己内酰胺、甲基丙烯酰胺、N-乙基丙烯酰胺、N,N-二甲基丙烯酰胺、N,N-二乙基丙烯酰胺、N-异丙基丙烯酰胺中的一种或者两种以上混合物;
所述的阴离子单体为2-丙烯酰胺基-2-甲基丙磺酸、乙烯基苯磺酸钠、乙烯基磺酸钠、烯丙基磺酸钠中的一种或者两种以上混合物;
所述的引发剂为过硫酸钾、过硫酸铵、过硫酸钠、偶氮二异丁咪唑啉盐酸盐、偶氮二异丁脒盐酸盐中的一种或者两种以上混合物;
(2)交联剂的制备
将无机锆化物、非离子配体、阴离子配体、高分子配体、去离子水加入到装有搅拌器、冷凝管和温度计的三颈玻璃瓶中,搅拌待所有原料溶解后,将pH调至3~7.5,温度控制在50~90℃,反应1~10h,即得;无机锆化物、非离子配体、阴离子配体、高分子配体、去离子水的质量比为1:(0.5~5):(0.2~2):(0.1~2):(2~7);
所述的无机锆化物为氧氯化锆、三氯化锆、四氯化锆、醋酸锆中的一种;
所述的非离子配体为三乙醇胺、二乙醇胺、丙三醇、异丙醇、正丁醇、甘露醇、甲醇、乙醇、丙醇中的一种或者两种以上混合物;
所述的阴离子配体为羟基乙酸、乳酸、羟基丙酸、葡萄糖酸、柠檬酸、乙二酸、丙二酸、丁二酸、乙二胺四乙酸、二乙烯三胺五乙酸中的一种或者两种以上混合物。
2.根据权利要求1所述的高温用压裂液交联剂,其特征在于,步骤(1)中功能单体、非离子单体、阴离子单体的摩尔比为(5~10):(60~80):(20~30)。
3.根据权利要求1所述的高温用压裂液交联剂,其特征在于,步骤(1)中三类单体、引发剂、去离子水的质量比为1:(0.005~0.03):(1~8)。
4.根据权利要求1所述的高温用压裂液交联剂,其特征在于,步骤(1)中聚合温度为40~70℃,时间为4~10h。
5.根据权利要求1所述的高温用压裂液交联剂,其特征在于,步骤(2)中无机锆化物、非离子配体、阴离子配体、高分子配体、去离子水的质量比为1:(0.5~2):(0.5~1.5):(0.2~1):(3~7)。
6.根据权利要求1所述的高温用压裂液交联剂,其特征在于,步骤(2)中交联剂制备反应pH为6~7,温度为60~80℃,时间为2~6h。
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