CN113646381B - 用于水力压裂的反相乳液 - Google Patents
用于水力压裂的反相乳液 Download PDFInfo
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- CN113646381B CN113646381B CN202080025877.XA CN202080025877A CN113646381B CN 113646381 B CN113646381 B CN 113646381B CN 202080025877 A CN202080025877 A CN 202080025877A CN 113646381 B CN113646381 B CN 113646381B
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- Prior art keywords
- water
- fracturing fluid
- salt
- preparing
- inverse emulsion
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- 239000000839 emulsion Substances 0.000 title claims abstract description 64
- 239000003921 oil Substances 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 229920003118 cationic copolymer Polymers 0.000 claims abstract description 12
- 125000002091 cationic group Chemical group 0.000 claims abstract description 12
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001593 sorbitan monooleate Substances 0.000 claims abstract description 9
- 229940035049 sorbitan monooleate Drugs 0.000 claims abstract description 9
- 235000011069 sorbitan monooleate Nutrition 0.000 claims abstract description 9
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 6
- 239000000194 fatty acid Substances 0.000 claims abstract description 6
- 229930195729 fatty acid Natural products 0.000 claims abstract description 6
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 6
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical class CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003784 tall oil Substances 0.000 claims abstract description 6
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Polymers OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 claims abstract description 3
- JNYAEWCLZODPBN-UHFFFAOYSA-N 2-(1,2-dihydroxyethyl)oxolane-3,4-diol Polymers OCC(O)C1OCC(O)C1O JNYAEWCLZODPBN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000001298 alcohols Chemical class 0.000 claims abstract description 3
- 229920000847 nonoxynol Polymers 0.000 claims abstract description 3
- JNYAEWCLZODPBN-CTQIIAAMSA-N sorbitan Polymers OCC(O)C1OCC(O)[C@@H]1O JNYAEWCLZODPBN-CTQIIAAMSA-N 0.000 claims abstract description 3
- 239000012530 fluid Substances 0.000 claims description 46
- 150000003839 salts Chemical class 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 36
- 239000012267 brine Substances 0.000 claims description 34
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 34
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 16
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 13
- 238000002347 injection Methods 0.000 claims description 13
- 239000007924 injection Substances 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 claims description 8
- 229940050176 methyl chloride Drugs 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229920006317 cationic polymer Polymers 0.000 claims description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 5
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 3
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 claims description 3
- 229920003169 water-soluble polymer Polymers 0.000 claims description 3
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 claims description 2
- 239000012313 reversal agent Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 238000007046 ethoxylation reaction Methods 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 150000002191 fatty alcohols Chemical class 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 description 22
- 235000019198 oils Nutrition 0.000 description 20
- 239000000243 solution Substances 0.000 description 17
- 239000007789 gas Substances 0.000 description 15
- -1 alkyl ether sulfates Chemical class 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 11
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 11
- 235000010262 sodium metabisulphite Nutrition 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 229940001584 sodium metabisulfite Drugs 0.000 description 10
- 239000007762 w/o emulsion Substances 0.000 description 10
- 239000008186 active pharmaceutical agent Substances 0.000 description 9
- 239000008346 aqueous phase Substances 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 235000021317 phosphate Nutrition 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- 230000000638 stimulation Effects 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 235000011148 calcium chloride Nutrition 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000003750 conditioning effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000005553 drilling Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- LQPLDXQVILYOOL-UHFFFAOYSA-I pentasodium;2-[bis[2-[bis(carboxylatomethyl)amino]ethyl]amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC(=O)[O-])CCN(CC([O-])=O)CC([O-])=O LQPLDXQVILYOOL-UHFFFAOYSA-I 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000011435 rock Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 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 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 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
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000003079 shale oil Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- VUWCWMOCWKCZTA-UHFFFAOYSA-N 1,2-thiazol-4-one Chemical class O=C1CSN=C1 VUWCWMOCWKCZTA-UHFFFAOYSA-N 0.000 description 1
- MTJHSRBOHBCBPX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile;hydrochloride Chemical compound Cl.N#CC(C)(C)N=NC(C)(C)C#N MTJHSRBOHBCBPX-UHFFFAOYSA-N 0.000 description 1
- QMYCJCOPYOPWTI-UHFFFAOYSA-N 2-[(1-amino-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidamide;hydron;chloride Chemical compound Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N QMYCJCOPYOPWTI-UHFFFAOYSA-N 0.000 description 1
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-M 3-carboxy-2,3-dihydroxypropanoate Chemical compound OC(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-M 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical class ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 1
- 235000019743 Choline chloride Nutrition 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000015076 Shorea robusta Nutrition 0.000 description 1
- 244000166071 Shorea robusta Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 125000005600 alkyl phosphonate group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000002579 anti-swelling effect Effects 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- ZETCGWYACBNPIH-UHFFFAOYSA-N azane;sulfurous acid Chemical compound N.OS(O)=O ZETCGWYACBNPIH-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 229910001622 calcium bromide Inorganic materials 0.000 description 1
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 1
- 229960003178 choline chloride Drugs 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920006007 hydrogenated polyisobutylene Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
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Abstract
本申请涉及油包水反相乳液及其用于水力压裂的用途,该油包水反相乳液包含:‑油;‑水;‑至少一种平均摩尔质量大于3百万道尔顿的水溶性阳离子共聚物,其包含18‑32摩尔%的阳离子单体和68‑82摩尔%的非离子单体;‑至少一种反转剂和至少一种乳化剂,反转剂总量与乳化剂总量的质量比R大于1.8,‑该反转剂选自优选具有4‑10个乙氧基化的乙氧基化壬基酚;优选具有乙氧基化/丙氧基化以具有C12‑C25的总碳数的乙氧基化/丙氧基化醇,乙氧基化十三醇和乙氧基化/丙氧基化脂肪醇,‑该乳化剂选自单油酸脱水山梨糖醇酯,聚乙氧基化脱水山梨糖醇酯或者妥尔油脂肪酸的二乙醇酰胺。
Description
技术领域
本发明涉及油包水乳液(也被称作反相乳液)形式的聚合物的技术领域。更具体地,本发明涉及一种包含在非常高盐度条件下稳定的阳离子聚合物的反相乳液。
本发明的其他方面涉及用于制备压裂流体的方法以及使用所述反相乳液对非常规油气地下储层(réservoirs)进行水力压裂的方法,并且最后,本发明的最后方面涉及在水力压裂操作中减小压裂流体摩擦的方法。
背景技术
非常规地下储层中的油(烃)和气的生产已经发展了数年,并且需要在储层中打开裂缝以实现油气的经济生产。
在现有技术和本发明的以下描述中,“非常规地下储层”用于指需要特殊开采技术的矿层,因为它们不是以堆积形式存在于多孔和可渗透的岩石中(参见Les hydrocarburesde roche-mère en France Rapport proviso ire–CGIET No.2011-04-G–Ministère del’écologie,du développement durable,des transports et du logement-2011年4月)。非常规气包括页岩气(英文为“shale gas”)、煤层甲烷(英文为“coal bed methane”)和致密气(英文为“tight gas”)。非常规油包括重油(英文为“heavy oil”)、页岩油(英文为“shale oil”)和致密油(英文为“tight oil”)。
非常规储层中所含储量巨大,并且在以前无法开采的区域中是极其广泛的(如基岩如泥质页岩的烃,致密气和煤层甲烷)。在美国,页岩气被广泛开采,且目前占美国天然气总产量的46%,而1998年仅占28%。非常大的盆地已知有Barnett页岩、Ville Fayette页岩、Mowry页岩、Marcellus页岩、Utica页岩等。钻井技术的发展使致密储层的开采成为可能。
实际上,生产技术已经从竖直井发展到水平井,减少了所需生产井的数量及其占地面积,并允许更好地覆盖储层体积以尽可能多地回收天然气。然而,渗透性的不足无法使气体容易从基岩向井中迁移并因此经济地、大量地生产气或油。因此有必要通过增产操作并且特别是通过对与井接触的岩石进行水力压裂来增加渗透性和生产面。
水力压裂
水力压裂的目的是产生额外的渗透性并产生更大的气或油的生产区域。这是因为,低渗透性、致密层的天然屏障以及钻井作业的不渗透性极大地限制了产量。非常规储层中所含的气或油在没有增产措施的情况下无法容易地从岩石迁移到井中。
这些水平井水力压裂作业始于1960年的Appalaches,并且如今在美国已进行了数万次作业。
研究、储层建模、钻井、固井和增产的技术变得越来越复杂,并且使用使得这些操作在越来越短的时间内实施并准确分析结果的设备。
通过水力压裂的储层的增产(stimulation)
这些操作在于在高压和非常高的流速下注入水,以产生垂直于生产井分布的裂缝。这通常分几个步骤来进行,以沿水平井的整个长度形成裂缝,从而覆盖储层的最大体积。
为了使这些裂缝保持开放,添加支撑剂(例如砂、塑料或梯度陶瓷)以防止这些裂缝闭合并保持一旦注射停止产生的毛细管作用。
为了减少将水或盐水快速注入地下地层所需的液压动力,使用了被称为减摩剂(réducteurs de frictions)的聚合物。此类聚合物的使用使得能够将由于流体内部摩擦引起的压力损失降低多达70%。
反相乳液形式的聚合物因其易于实施而被普遍使用。它们的使用基于聚合物在水中或盐水中的溶解。为此,反相乳液反转,以使得包含在该反相乳液的水相中的聚合物被释放。在释放之后,该聚合物处于在其中添加了反相乳液的水或盐水中。
压裂流体越来越多地基于包含大量溶解盐的水。在此背景下,工业上需要在高盐水(具有高浓度溶解盐的盐水)中有效工作的减摩剂,其中的一些高盐水可包含超过30,000mg.L-1的溶解盐,甚至超过100,000mg.L-1,尤其具有高含量的二价盐。
发明内容
本申请人已经令人惊讶地发现,特定组成的油包水反相乳液在具有高含量二价盐的非常高盐度条件下在减摩方面提供优异的性能。
本发明还涉及使用本发明的乳液制备压裂流体的方法。
本发明的第三方面涉及一种水力压裂方法,其中已根据前述本发明方法制备了注入流体。
最后,本发明的最后方面涉及使用本发明乳液在水力压裂操作中减少压裂流体摩擦的方法。
更具体地,本发明首先涉及一种油包水反相乳液,其包含:
-油;
-水;
-至少一种平均分子量大于3百万道尔顿的水溶性阳离子共聚物,其包含18-32摩尔%的阳离子单体和68-82摩尔%的非离子单体;
-至少一种反转剂和至少一种乳化剂,反转剂总量与乳化剂总量的质量比R大于1.8,
ο该反转剂选自优选具有4-10个乙氧基化(éthoxylations)的乙氧基化壬基酚;优选具有乙氧基化/丙氧基化以具有C12-C25的总碳数的乙氧基化/丙氧基化醇,乙氧基化十三醇和乙氧基化/丙氧基化脂肪醇。
ο该乳化剂选自单油酸脱水山梨糖醇酯,聚乙氧基化脱水山梨糖醇酯或者妥尔油脂肪酸的二乙醇酰胺。
用于制备本发明的油包水乳液的油可以是矿物油、植物油、合成油或多种这些油的混合物。矿物油的实例是包含脂族、环烷烃、石蜡烃、异构石蜡烃、环状石蜡烃或萘基类型的饱和烃的矿物油。合成油的实例是氢化聚癸烯或氢化聚异丁烯,酯如硬脂酸辛酯或油酸丁酯。Exxon的产品系列是非常合适的。
通常,该反相乳液中水相与油相的重量比优选为50/50至90/10,优选70/30至80/20。
该油包水乳液有利地包含12-24重量%、更有利地为15-22重量%的油。
该油包水乳液有利地包含30-55重量%、更有利地为35-48重量%的水。
如本文所用的术语“水溶性聚合物”是指当在25℃下搅拌溶解4小时且在水中的浓度为20g.L-1时产生无不溶性颗粒的水溶液的聚合物。
在本发明中,术语“乳化剂”是指能够乳化油包水的试剂,“反转剂”是能够乳化水包油的试剂。更具体地,反转剂被认为是HLB大于或等于10的表面活性剂,乳化剂被认为是HLB严格小于10的表面活性剂。
化合物的亲水亲油平衡值(HLB)是其亲水性或亲油性程度的量度,通过计算分子不同区域的值来确定,如Griffin在1949年所描述的(Griffin WC,Classification ofSurface-Active Agents by HLB,Journal of the Society of Cosmetic Chemists,1949,1,第311-326页)。
在本发明中,我们采用了以基于分子化学基团的值计算为基础的Griffin方法。Griffin指定了一个介于0和20之间的无量纲数,以提供有关在水和油中的溶解度的信息。HLB值为10的物质分布在两相之间,使得亲水基团(分子量Mh)完全伸入水中,而疏水烃基基团(分子量Mp)被吸附在非水相中。
其亲水部分的分子量为Mh的总分子量为M的物质的HLB值为:
HLB=20(Mh/M)
根据本发明的油包水乳液可根据本领域技术人员已知的任何方法制备。典型地,包含单体和乳化剂的水溶液在油相中乳化。然后通过添加自由基引发剂进行聚合。可以参考氧化还原对,氧化剂中有氢过氧化枯烯、叔丁基羟基过氧化物或过硫酸盐,还原剂中有亚硫酸钠、焦亚硫酸钠和莫尔盐。也可以使用偶氮化合物,例如2,2’-偶氮双(异丁腈)盐酸盐和2,2’-偶氮双(2-脒基丙烷)盐酸盐。
典型地,该聚合在等温、绝热或在受控温度下进行。也就是说,该温度保持恒定,通常为10-60℃(等温),或者让温度自然升高(绝热)并且在这种情况下,反应通常在低于10℃的温度下开始并且最终温度通常高于50℃,或者最后控制升温,以使温度曲线介于等温和绝热曲线之间。
典型地,反转剂在聚合反应结束时加入,优选在低于50℃的温度下加入。
优选地,本发明的乳液包含12-50质量%、优选12-40质量%、甚至更优选12-30质量%的水溶性聚合物(干重)。
根据另一优选项,对于本发明乳液来说,反转剂总量与乳化剂总量的质量比R大于1.8,优选大于2,甚至更优选大于2.5,甚至更优选大于3,甚至更优选大于3.5,甚至更优选大于4。
本发明乳液中所含的水溶性阳离子聚合物是非离子和阳离子单体的共聚物。
非离子单体优选选自丙烯酰胺、甲基丙烯酰胺、N-烷基丙烯酰胺、N-烷基甲基丙烯酰胺、N,N-二烷基丙烯酰胺、N,N-二烷基甲基丙烯酰胺、丙烯酸酯和甲基丙烯酸酯。优选的非离子单体是丙烯酰胺。
阳离子单体优选选自丙烯酸二甲氨基乙酯(ADAME)或其季铵盐、甲基丙烯酸二甲氨基乙酯(MADAME)或其季铵盐、二甲基二烯丙基氯化铵(DADMAC)、丙烯酰胺基丙基三甲基氯化铵(APTAC)和甲基丙烯酰胺基丙基三甲基氯化铵(MAPTAC)。优选地,单体ADAME或MADAME的季铵盐通过用烷基氯、优选甲基氯进行季铵化获得。优选的阳离子单体是用甲基氯季铵化的丙烯酸二甲氨基乙酯。
可以选择多种非离子和阳离子单体来形成阳离子共聚物。有利地,水溶性阳离子聚合物是丙烯酰胺和用甲基氯季铵化的丙烯酸二甲氨基乙酯的共聚物。
水溶性阳离子聚合物的平均分子量大于3百万道尔顿。优选地,这个平均分子量为3-30百万道尔顿,甚至更优选8-18百万道尔顿。
根据本发明的“平均分子量”通过特性粘度确定。特性粘度可通过本领域技术人员已知的方法测量,并且可特别通过图形方法由不同浓度的比浓粘度值计算,该图形方法在于绘制随浓度(在x轴上)变化的比浓粘度值(在y轴上)并将该曲线外推到零浓度。在y轴上或使用最小二乘法读取特性粘度值。重均分子量则可通过著名的Mark-Houwink方程确定:
[η]=KMα
[η]是通过溶液粘度法测定的聚合物的特性粘度,
K是经验常数,
M是聚合物的分子量,
α是Mark-Houwink系数
α和K取决于特定的聚合物-溶剂体系。
本发明的乳液优选包含0.5-10质量%的反转剂和0.5-16质量%的乳化剂。
该油包水乳液有利地包含0.8-2重量%的至少一种乳化剂。
该油包水乳液有利地包含3-6重量%的至少一种反转剂。
任选地,该油包水乳液包含1-40重量%的盐,优选3-30重量%、更优选5-25重量%且甚至更优选7-17重量%的盐。
该油包水乳液中存在的盐可以是例如钠盐、锂盐、钾盐、镁盐、铝盐、铵盐、磷酸盐、硫酸盐、氯化物盐、柠檬酸盐、醋酸盐、磷酸氢酒石酸盐、水溶性无机盐或其他无机盐及其混合物。这些盐包括氯化钠、硫酸钠、溴化钠、氯化钙、硫酸铵、氯化铵、氯化锂、溴化锂、氯化钾、溴化钾、硫酸镁、硫酸铝、磷酸氢钠、磷酸氢钾及其混合物。优选氯化钠、氯化钙、氯化铵、硫酸铵,并且进一步优选它们的混合物。
本发明的另一方面涉及一种制备压裂流体的方法,包括:
a)提供根据本发明的反相乳液,
b)通过将反相乳液添加到盐水(saumure)中来反转该反相乳液,该盐水包含大于30,000ppm的盐并且二价比R+≥0.15,R+=质量比:二价盐/总盐,
c)任选地,添加至少一种支撑剂。
总盐是指盐水中盐的总量。
该盐水可包含单价和/或多价盐或其组合。盐的实例包括但不限于钠盐、锂盐、钾盐、铝盐、铵盐、磷酸盐、硫酸盐、镁盐、钡盐、硝酸盐和其他无机盐及其混合物。
该盐水优选包含以下成分中的至少一种:氯化钠、氯化钙、溴化钠、溴化钙、氯化钡、氯化镁、溴化锌、甲酸钠和甲酸钾。
优选地,用于制备压裂流体的盐水包含大于70,000ppm的盐并且优选大于100,000ppm的盐,优选地,该盐水包含70,000-350,000ppm、优选100,000-350,000ppm的盐。
根据制备压裂流体的方法的一种有利实施方案:
-当该盐水包含30,000ppm-70,000ppm(排除上限)的盐时(步骤b),乳液(步骤a)的比率R优选大于1.8,
-当该盐水包含70,000ppm-100,000ppm(排除上限)时,乳液的比率R优选大于2,
-当该盐水包含100,000ppm-150,000ppm(排除上限)的盐时,乳液的比率R优选大于2.5,
-当该盐水包含150,000ppm-200,000ppm(排除上限)的盐时,乳液的比率R优选大于3,
-当该盐水包含200,000ppm-250,000ppm(排除上限)的盐时,乳液的比率R优选大于3.5,并且
-当该盐水包含大于250,000ppm(排除上限)的盐时,乳液的比率R优选大于4。
优选地,二价比R+=质量比:二价盐/总盐大于或等于0.20,甚至更优选R+≥0.25。
本发明的乳液在盐水中的反转可有利地通过文献US 8 383 560的装置和方法实现,其中乳液用多静态混合器布置连续溶解。
本发明还涉及通过本发明方法获得的压裂流体,特别是包含以下项的压裂流体:
-盐水溶液;
-根据本发明的水溶性阳离子(共)聚合物;
-本发明的反相乳液的油;
-水。
支撑剂可不受限制地选自砂、陶瓷、铝土矿、玻璃珠和树脂浸渍的砂。它优选占压裂流体重量的0.5-40%,更优选1-25%,甚至更优选1.5-20%。
根据本发明的压裂流体优选包含0.01%-3%重量并且甚至更优选0.05%-1%重量的本发明的水溶性阳离子(共)聚合物(以乳液的形式添加)。
构成压裂流体的盐水可包含本领域技术人员已知的其他化合物,例如在SPE152596中列出的那些,例如:
-粘土防膨胀剂,如氯化钾或氯化胆碱,和/或
-防止细菌滋生的杀生物剂,所述细菌尤其是硫酸盐还原菌,它可形成减少通道表面的粘性物质。实例包括最常用的戊二醛,或甲醛或异噻唑啉酮,和/或
-氧还原剂如亚硫酸氢铵,以避免其他组分的氧化性破坏和注射管道的腐蚀,和/或
-防腐蚀添加剂,以防止管道被残余量的氧所氧化,优选N,N二甲基甲酰胺,和/或
-润滑剂,如石油馏分,和/或
-铁螯合剂,如柠檬酸、EDTA(乙二胺四乙酸)、膦酸盐,和/或
-防结垢产品,如磷酸酯、膦酸酯、聚丙烯酸酯或乙二醇。
根据一种优选的实施方案,制备压裂流体的方法包括:
a)提供根据本发明的反相乳液,该反相乳液包含至少12-30质量%的水溶性阳离子共聚物,该水溶性阳离子共聚物包含18-32摩尔%的利用甲基氯季铵化的丙烯酸二甲氨基乙酯和68-82摩尔%的丙烯酰胺;至少一种反转剂和至少一种乳化剂,反转剂总量与乳化剂总量的质量比R大于2.5,
b)通过将反相乳液添加到盐水中来反转该反相乳液,该盐水包含大于100,000ppm的盐并且二价比R+≥0.2,R+=质量比:二价盐/总盐,以获得水溶性阳离子共聚物在注射流体中的质量浓度为0.05-1%。
c)任选地,添加至少一种支撑剂。
本发明的第三方面涉及一种用于水力压裂非常规油或气地下储层的方法,包括制备如上所述的压裂流体,并将所述压裂流体注入地下地层。
更特别地,本发明涉及一种压裂地下地层的方法,包括:
aa)提供根据上述制备方法获得的压裂流体,
bb)将注入流体引入到地下地层的一部分中,
cc)用注入流体压裂地下地层,
dd)回收气体、油和水性流体的混合物。
注入在压力下进行,以产生沿生产井长度分布的裂缝。
任选地,在产生裂缝之后,将至少一种氧化性化合物和/或至少一种表面活性剂化合物注入到储层中。
这些化合物的注入使得能够恢复接近水的粘度的流体粘度。
氧化性化合物的实例是漂白剂(次氯酸盐的水溶液)、过氧化氢、臭氧、氯胺、过硫酸盐、高锰酸盐或高氯酸盐。
表面活性剂的化学类型并不是关键的。它们可以是阴离子的、非离子的、两性的、两性离子的和/或阳离子的。优选地,本发明的表面活性化合物带有阴离子电荷。
优选地,所使用的表面活性化合物选自阴离子表面活性剂和它们的两性离子,从包括以下物质的衍生物的组中选择:烷基硫酸盐、烷基醚硫酸盐、芳基烷基硫酸盐、芳基烷基醚硫酸盐、烷基磺酸盐、烷基醚磺酸盐、芳基烷基磺酸盐、芳基烷基醚磺酸盐、烷基磷酸盐、烷基醚磷酸盐、芳基烷基磷酸盐、芳基烷基醚磷酸盐、烷基膦酸盐、烷基醚膦酸盐、芳基烷基膦酸盐、芳基烷基醚膦酸盐、烷基羧酸盐、烷基醚羧酸盐、芳基烷基羧酸盐、芳基烷基醚羧酸盐、聚烷基醚和芳基烷基聚醚。
最后,本发明的第四个也是最后一个方面涉及一种用于在非常规油或气地下储层的水力压裂操作中减少压裂流体摩擦的方法,包括制备如上所述的压裂流体,并将所述压裂流体注入到地下地层中。
减摩使得能够减少或消除压裂流体注入过程中与摩擦相关的损失。
对于水力压裂,减摩涉及压裂流体中的聚合物为溶液提供流变流化(rhéofluidifiantes)性能,使其在注入期间(在高剪切下)具有相对较低的粘度并且在剪切减小时具有高粘度以保持支撑剂悬浮在裂缝处。
具体实施方式
本发明和由此产生的优点将从以下实施例中变得明显。
实施例
实施例1(反例):包含20重量%的含有15摩尔%阳离子单体的聚合物的乳液
用27.00重量%的丙烯酰胺溶液(水中50重量%)、8.12重量%的ADAME-MC溶液(甲基氯季铵化的二甲氨基乙基,水中80重量%)、39.87重量%的去离子水和0.02重量%的Versenex 80制备水相。
油相由以下物质制备:23.45重量%的油(D100S)和以下乳化剂:1.16重量%的/>(妥尔油脂肪酸二乙醇胺)、0.16重量%的/>80(单油酸脱水山梨糖醇酯)和0.23重量%的/>81(单油酸脱水山梨糖醇酯5EO)。
在混合的同时将水相加入油相中以形成乳液。所得分散体用氮气鼓泡30分钟,同时温度稳定在25℃,此时将0.002重量%的过氧化物加入乳液中,并将0.075重量%的焦亚硫酸钠(MBS)溶液以0.1毫升/分钟的流量引入到分散体中。聚合温度控制在38℃-42℃约90分钟。通过以1.0毫升/分钟的流量引入0.03重量%的焦亚硫酸钠(MBS)溶液来捕获残余单体。得到包含20%的丙烯酰胺和ADC的活性共聚物的油包水聚合物乳液。
将1.75重量%的反转剂(NP 8,壬基酚聚乙二醇醚8OE)添加到该油包水聚合物乳液中以促进使用过程中的调节。质量比R为1.5。
实施例2(反例):包含20重量%的含有20摩尔%阳离子单体的聚合物的乳液
用23.78重量%的丙烯酰胺溶液(水中50重量%)、10.14重量%的ADAME-MC溶液(甲基氯季铵化的二甲氨基乙基,水中80重量%)、41.08重量%的去离子水和0.02重量%的Versenex 80制备水相。
油相由以下物质制备:23.45重量%的油(D100S)和以下乳化剂:1.16重量%的/>(妥尔油脂肪酸二乙醇胺)、0.16重量%的/>80(单油酸脱水山梨糖醇酯)和0.23重量%的/>81(单油酸脱水山梨糖醇酯5EO)。
在混合的同时将水相加入油相中以形成乳液。所得分散体用氮气鼓泡30分钟,同时温度稳定在25℃,此时将0.002重量%的过氧化物加入乳液中,并将0.075重量%的焦亚硫酸钠(SMBS)溶液以0.1毫升/分钟的流量引入到分散体中。聚合温度控制在38℃-42℃约90分钟。通过以1.0毫升/分钟的流量引入0.03重量%的焦亚硫酸钠(SMBS)溶液来捕获残余单体。得到包含20%的丙烯酰胺和ADAME-MC的活性共聚物的油包水聚合物乳液。
将1.75重量%的反转剂(NP 8,壬基酚聚乙二醇醚8OE)添加到该油包水聚合物乳液中以促进使用过程中的调节。质量比R为1.5。
实施例3(反例):包含20重量%的含有35摩尔%阳离子单体的聚合物的乳液
用16.20重量%的丙烯酰胺溶液(水中50重量%)、14.87重量%的ADAME-MC溶液(甲基氯季铵化的二甲氨基乙基,水中80重量%)、43.92重量%的去离子水和0.02重量%的Versenex 80制备水相。
油相由以下物质制备:23.45重量%的油(D100S)和以下乳化剂:1.16重量%的/>(妥尔油脂肪酸二乙醇胺)、0.16重量%的/>80(单油酸脱水山梨糖醇酯)和0.23重量%的/>81(单油酸脱水山梨糖醇酯5EO)。
在混合的同时将水相加入油相中以形成乳液。所得分散体用氮气鼓泡30分钟,同时温度稳定在25℃,此时将0.002重量%的过氧化物加入乳液中,并将0.075重量%的焦亚硫酸钠(SMBS)溶液以0.1毫升/分钟的流量引入到分散体中。聚合温度控制在38℃-42℃约90分钟。通过以1.0毫升/分钟的流量引入0.03重量%的焦亚硫酸钠(SMBS)溶液来捕获残余单体。得到包含20%的丙烯酰胺和ADC的活性共聚物的油包水聚合物乳液。
将1.75重量%的反转剂(NP 8,壬基酚聚乙二醇醚8OE)添加到该油包水聚合物乳液中以促进使用过程中的调节。质量比R为1.5。
以下实施例是以根据本发明的质量比R进行的。实施例4和7、然后是实施例5和8、最后是实施例6和9使用与实施例1、2和3相同的过程制造,但使用了更高量的NP 8(反转剂)。表1描述了每个实施例的质量比R。
[表1]
表1:油包水乳液的质量比R
摩擦流回路测试
摩擦流回路由总长为20英尺的1/4"外径不锈钢管构成。测试溶液被泵送到5升锥形罐的底部。溶液通过管并返回罐。流量是通过配备变速驱动器的三缸泵来获得的。
在样品罐中制备4升的9%的CaCl2盐水,或API或2xAPI盐水,并且启动泵并设置为输送1.5加仑/分钟。9%的CaCl2盐水对应于100ml水中9g的CaCl2,其R+为1.00。API盐水被定义为100ml水中8.5g NaCl+2.5g CaCl2,其R+等于0.20。2xAPI盐水对应于100ml水中17gNaCl+5g CaCl2,其R+等于0.20。将盐水溶液再循环,直到温度平衡到25℃并达到稳定的压差。此压力被记录为9%的CaCl2或API或2xAPI盐水的“初始压力”。
用注射器将测试量的纯油包水乳液聚合物快速注入包含9%的CaCl2或API或2xAPI盐水的样品罐中,并启动计时器。剂量以每千加仑9%的CaCl2或API或2xAPI盐水的油包水乳液的加仑数(gpt)来记录。每秒记录一次压力,持续5分钟。给定时间“t”的减摩百分比(%FRt)由初始压降ΔPi和时间t的压降ΔPt使用以下公式来计算:
结果
在表2中,所有乳液均包含20重量%的阳离子聚合物。
[表2]
结果表明,当质量比R增加时,减摩性能得到改善。随着盐浓度的增加,减摩性能下降。
但当选择和调整质量比R时(在本发明的范围内),则可在盐水甚至高盐水中获得非常好的摩擦性能。
当聚合物的阳离子度为20摩尔%时,减摩性能得到改善。较低的阳离子度(15%)和较高的阳离子度(35%)提供较低的性能。
Claims (11)
1.制备压裂流体的方法,包括:
a)提供反相乳液,该反相乳液包含:
-油;
-水;
-至少一种平均摩尔质量大于3百万道尔顿的水溶性阳离子共聚物,其包含18-32摩尔%的阳离子单体和68-82摩尔%的非离子单体;
-至少一种反转剂和至少一种乳化剂,反转剂总量与乳化剂总量的质量比R大于2.5,
-该反转剂选自乙氧基化壬基酚和乙氧基化/丙氧基化醇,
-该乳化剂选自单油酸脱水山梨糖醇酯,聚乙氧基化脱水山梨糖醇酯和妥尔油脂肪酸的二乙醇酰胺,
b)通过将反相乳液添加到盐水中来反转该反相乳液,该盐水包含大于30,000ppm的盐并且二价比R+≥0.15,R+=二价盐/总盐的质量比,
c)任选地,添加至少一种支撑剂。
2.根据权利要求1的制备压裂流体的方法,其特征在于,对于步骤b)来说,该盐水包含大于70,000ppm的盐。
3.根据权利要求1或2的制备压裂流体的方法,其特征在于,对于步骤b)来说,该盐水的二价比R+≥0.20。
4.根据权利要求1或2的制备压裂流体的方法,其特征在于,该反相乳液包含12-50质量%的至少一种水溶性聚合物。
5.根据权利要求1或2的制备压裂流体的方法,其特征在于,该反相乳液的水溶性阳离子共聚物的非离子单体选自丙烯酰胺,甲基丙烯酰胺,N-烷基丙烯酰胺,N-烷基甲基丙烯酰胺,N,N-二烷基丙烯酰胺,N,N-二烷基甲基丙烯酰胺,丙烯酸酯;甲基丙烯酸酯。
6.根据权利要求1或2的制备压裂流体的方法,其特征在于,该反相乳液的水溶性阳离子共聚物的阳离子单体选自丙烯酸二甲氨基乙酯或其季铵盐,甲基丙烯酸二甲氨基乙酯或其季铵盐,二甲基二烯丙基氯化铵,丙烯酰胺基丙基三甲基氯化铵和甲基丙烯酰胺基丙基三甲基氯化铵。
7.根据权利要求1或2的制备压裂流体的方法,其特征在于,该反相乳液的水溶性阳离子聚合物的平均摩尔质量为3-30百万道尔顿。
8.根据权利要求1或2的制备压裂流体的方法,其特征在于,该反相乳液包含0.5-10质量%的反转剂和0.5-16质量%的乳化剂。
9.根据权利要求1或2的制备压裂流体的方法,包括:
a)提供反相乳液,该反相乳液包含至少12-30质量%的水溶性阳离子共聚物,该水溶性阳离子共聚物包含18-32摩尔%的利用甲基氯季铵化的丙烯酸二甲氨基乙酯和68-82摩尔%的丙烯酰胺;根据权利要求1的至少一种反转剂和至少一种乳化剂,反转剂总量与乳化剂总量的质量比R大于2.5,
b)通过将反相乳液添加到盐水中来反转该反相乳液,该盐水包含大于100,000ppm的盐并且二价比R+≥0.20,R+=二价盐/总盐的质量比,以获得水溶性阳离子共聚物在注射流体中的质量浓度为0.05-1%,
c)任选地,添加至少一种支撑剂。
10.压裂地下地层的方法,包括:
aa)提供根据权利要求1-9中任一项的制备方法获得的压裂流体,
bb)将注入流体引入到地下地层的一部分中,
cc)用注入流体压裂地下地层,
dd)回收气体、油和水性流体的混合物。
11.在非常规油或气地下储层的水力压裂操作中减少压裂流体摩擦的方法,包括根据权利要求1-9中任一项制备压裂流体,并将所述压裂流体注入到地下地层中。
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