CN112724954A - 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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- CN112724954A CN112724954A CN202011175074.0A CN202011175074A CN112724954A CN 112724954 A CN112724954 A CN 112724954A CN 202011175074 A CN202011175074 A CN 202011175074A CN 112724954 A CN112724954 A CN 112724954A
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- Prior art keywords
- weight
- water
- emulsion
- salt
- oil
- Prior art date
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- Granted
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- 239000000839 emulsion Substances 0.000 title claims abstract description 78
- 239000003921 oil Substances 0.000 claims abstract description 53
- 239000000178 monomer Substances 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 25
- 125000000129 anionic group Chemical group 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 229920006318 anionic polymer Polymers 0.000 claims abstract description 21
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical group FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001593 sorbitan monooleate Substances 0.000 claims abstract description 11
- 229940035049 sorbitan monooleate Drugs 0.000 claims abstract description 11
- 235000011069 sorbitan monooleate Nutrition 0.000 claims abstract description 11
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 10
- 239000000194 fatty acid Substances 0.000 claims abstract description 10
- 229930195729 fatty acid Natural products 0.000 claims abstract description 10
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical group CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003784 tall oil Substances 0.000 claims abstract description 7
- 238000007046 ethoxylation reaction Methods 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000001298 alcohols Chemical class 0.000 claims abstract description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 3
- 229920000847 nonoxynol Polymers 0.000 claims abstract description 3
- 239000012313 reversal agent Substances 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
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical class CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000012530 fluid Substances 0.000 claims description 45
- 150000003839 salts Chemical class 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 30
- 239000012267 brine Substances 0.000 claims description 21
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 21
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 19
- 239000011780 sodium chloride Substances 0.000 claims description 13
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 12
- 238000002347 injection Methods 0.000 claims description 12
- 239000007924 injection Substances 0.000 claims description 12
- 230000001603 reducing effect Effects 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 8
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 7
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical group OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 7
- 159000000000 sodium salts Chemical class 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- KFNGWPXYNSJXOP-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propane-1-sulfonic acid Chemical compound CC(=C)C(=O)OCCCS(O)(=O)=O KFNGWPXYNSJXOP-UHFFFAOYSA-N 0.000 claims description 3
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- JTFZVTZBHCHYGA-UHFFFAOYSA-N 2-methyl-2-(2-methylprop-2-enoylamino)propanoic acid Chemical compound CC(=C)C(=O)NC(C)(C)C(O)=O JTFZVTZBHCHYGA-UHFFFAOYSA-N 0.000 claims description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 229940047670 sodium acrylate Drugs 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims 1
- 235000019198 oils Nutrition 0.000 description 29
- 229920000642 polymer Polymers 0.000 description 27
- 239000000243 solution Substances 0.000 description 21
- 239000012071 phase Substances 0.000 description 20
- 239000007789 gas Substances 0.000 description 16
- -1 shale Chemical class 0.000 description 14
- 239000008346 aqueous phase Substances 0.000 description 11
- 239000007762 w/o emulsion Substances 0.000 description 11
- 239000008186 active pharmaceutical agent Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 9
- 229940001584 sodium metabisulfite Drugs 0.000 description 9
- 235000010262 sodium metabisulphite Nutrition 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 8
- 238000005755 formation reaction Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 206010017076 Fracture Diseases 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 239000001110 calcium chloride Substances 0.000 description 5
- 229910001628 calcium chloride Inorganic materials 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- FPQQERRFPULCIK-UHFFFAOYSA-N 5-(5-methoxypyridin-3-yl)-3-methyl-8-(piperidin-4-ylamino)-1H-1,7-naphthyridin-2-one Chemical compound COC=1C=C(C=NC=1)C1=C2C=C(C(NC2=C(N=C1)NC1CCNCC1)=O)C FPQQERRFPULCIK-UHFFFAOYSA-N 0.000 description 4
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 230000003750 conditioning effect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 4
- 238000005553 drilling Methods 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 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 4
- 230000035699 permeability Effects 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- FWFUWXVFYKCSQA-UHFFFAOYSA-M sodium;2-methyl-2-(prop-2-enoylamino)propane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(C)(C)NC(=O)C=C FWFUWXVFYKCSQA-UHFFFAOYSA-M 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 235000011148 calcium chloride Nutrition 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
- 238000011161 development Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 239000011435 rock Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 230000000638 stimulation Effects 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
- 208000010392 Bone Fractures Diseases 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
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical class [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920000570 polyether Polymers 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
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 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
- 229920003169 water-soluble polymer Polymers 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
- IYXGAVFNZJFSBQ-UHFFFAOYSA-N 2,3-dihydroxybutanedioic acid;phosphoric acid Chemical compound OP(O)(O)=O.OC(=O)C(O)C(O)C(O)=O IYXGAVFNZJFSBQ-UHFFFAOYSA-N 0.000 description 1
- CCTFAOUOYLVUFG-UHFFFAOYSA-N 2-(1-amino-1-imino-2-methylpropan-2-yl)azo-2-methylpropanimidamide Chemical class NC(=N)C(C)(C)N=NC(C)(C)C(N)=N CCTFAOUOYLVUFG-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical class N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-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
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 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
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 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
- 208000002565 Open Fractures Diseases 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
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 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
- 238000004458 analytical method Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 230000003416 augmentation Effects 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
- 230000005540 biological transmission Effects 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
- 238000004364 calculation method Methods 0.000 description 1
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Abstract
本申请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高于3百万道尔顿的水溶性阴离子聚合物,该聚合物含有4‑14mol%的磺化阴离子单体,0‑17mol%的羧化阴离子单体和69‑94mol%的非离子单体;‑至少一种反相剂和至少一种乳化剂,反相剂的总量与乳化剂的总量的重量比R高于1.8;‑该反相剂选自优选具有4‑10乙氧化度的乙氧化的壬基酚;优选具有乙氧化度/丙氧化度来获得C12‑C25的总碳数的乙氧化的/丙氧化的醇,乙氧化的十三烷基醇,和乙氧化的/丙氧化的脂肪醇;‑该乳化剂选自山梨聚糖单油酸酯,聚乙氧化山梨聚糖酯,或妥尔油脂肪酸、聚乙氧化脂肪酸的二乙醇酰胺,及其用于水力压裂的用途。
Description
本发明涉及油包水乳液形式的聚合物(也称作反相乳液)的技术领域。更具体地,本发明的主题是一种有在高盐度条件下稳定的阴离子聚合物的反相乳液。
本发明的其他方面涉及一种制备压裂流体的方法和一种使用所述反相乳液来水力压裂非常规地下油和气储层的方法,最后本发明的最后一方面涉及一种减少水力压裂作业中压裂流体的摩擦的方法。
现有技术
包含在非常规地下储层中的油(烃)和气的生产已经经历一些年的发展,并且需要打开储层中的裂缝来经济地生产油和气。
在现有技术和本发明的说明书的其余部分中,“非常规地下储层”表示必需使用特殊提取技术的沉积物,因为它们不是以在多孔的可透过的岩床中的聚集物形式存在(参见Les hydrocarbures de roche-mère en France Rapport provisoire–CGIET n°2011-04-G Ministère de l’écologie,du développement durable,des transports et dulogement-Avril 2011)(法国的源岩烃,临时报告–涉及生态、可持续发展,运输和住房的政府部门–2011年4月)。对于非常规气,可以提及的是页岩气、煤床甲烷或致密气。对于非常规油,可以提及的是重质油、页岩油或致密油。
包含在非常规储层中的沉积物在以前不能提取的区域中大量和广泛分布,例如源岩烃例如泥质页岩、致密气和煤床甲烷。在美国,页岩气是广泛生产的,并且目前占美国所生产的天然气总量的46%,而它在1998年时仅占28%。已知最大的气田在Barnett Shale、Ville Fayette Shale、Mowry Shale、Marcellus Shale、Utica Shale……名下。通过钻探技术的发展,已经可以进行致密储层的钻探了。
生产技术已经从垂直井发展到水平井,这减少了所需的生产井的数目,并且其占地规模允许更好地覆盖储层体积来采收最大量的气体。但是,渗透性不足以使气体从岩床容易地迁移到井中来经济地生产大量的气或油。所以必需经由增产作业,特别是经由水力压裂与所述井接触的岩石,来增加渗透性和生产面。
水力压裂
水力压裂的目标是产生另外的渗透性和产生更大的气或油生产面。低渗透性、致密地质层的天然阻隔和通过钻探作业的不可穿透性明显限制了生产。不使用增产时,包含在非常规储层中的气或油不能从岩床中容易地迁移到井中。
这些在水平井上的水力压裂作业在1960年开始于阿帕拉契地区,并且迄今已经在美国进行了数万次作业。
研究、储层模拟、钻探、水泥灌浆和增产技术已经变得日益复杂,使用的装置允许这些作业在不断缩短的时间内进行,并且对结果进行精确分析。
经由水力压裂的储层增产
对于这些作业来说,水在高压和强流量下注入,来产生垂直于生产井分布的裂缝。通常,这在几个步骤中进行来产生沿着水平井的整个长度的裂缝,其能够覆盖最大的储层体积。
为了使这些裂缝保持开放,添加支撑剂(例如砂、塑性材料、校准陶瓷)来在注入停止时,防止这些裂缝闭合和保持所产生的毛细管。
为了降低将水或盐水快速注入到地下地层所需的水功率,使用了被称作减摩剂的聚合物。使用所述聚合物能够减少高至70%的由于流体内的内摩擦造成的压力损失。
反相乳液形式的聚合物通常由于它们的易用性而被使用。其作用是基于聚合物在水或盐水中的溶解。为此目的,反相乳液反转来释放出该反相乳液的水相中所包含的聚合物。在释放后,聚合物开始包含在已经添加到反相乳液的水或盐水中。
压裂流体越来越多地基于含有大量的溶解盐的水。在本文上下文中,工业需要在高盐度的盐水(具有高浓度的溶解盐)中有效起作用的减摩剂,其中一些可以包含大于30000mg·L-1的溶解盐,甚至大于100000mg·L-1,特别是具有高含量的二价盐。
发明内容
申请人已经令人惊讶地发现一种特殊组成的反相油包水乳液在具有高含量的二价盐的非常强的盐度条件下产生了更高的减摩性能。
本发明还涉及一种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,用于该方法的注入流体根据前述本发明的方法制备。
最后,本发明的最后一方面涉及一种使用本发明的乳液来减少水力压裂作业中压裂流体的摩擦的方法。
更具体地,本发明首先涉及一种反相油包水乳液,其包含:
-油;
-水;
-至少一种平均分子量高于3百万道尔顿的水溶性阴离子聚合物,该聚合物含有4-14mol%的磺化阴离子单体,0-17mol%的羧化阴离子单体和69-96mol%的非离子单体;
-至少一种反相剂和至少一种乳化剂,反相剂的总量与乳化剂的总量的重量比R高于1.8;
该反相剂选自优选具有4-10乙氧化度的乙氧化的壬基酚;优选具有乙氧化度/丙氧化度来获得C10-C25的总碳数的乙氧化的/丙氧化的醇,乙氧化的十三烷基醇和乙氧化的/丙氧化的脂肪醇;
该乳化剂选自山梨聚糖单油酸酯,聚乙氧化山梨聚糖酯,妥尔油脂肪酸或聚乙氧化脂肪酸的二乙醇酰胺。
在本发明中,用表述xxx至yyy表示包括端值xxx和yyy的范围。
用于制备本发明的油包水乳液的油可以是矿物油、植物油、合成油或这些油中几种的混合物。
矿物油的例子是含有脂族、环烃、链烷烃、异链烷烃、环烷烃或萘基类型的饱和烃的矿物油。
通常,反相乳液中的水相与油相的重量比优选是50:50-90:10,和更优选70:30-80:20。
油包水乳液有利地包含12-24重量%的油,更有利地15-22%,相对于乳液的总重量计。
油包水乳液有利地包含30-55重量%的水,更有利地35-48重量%,相对于乳液的总重量计。
如在本文中所使用,术语“水溶性聚合物”表示这样的聚合物,其当在25℃水中搅拌4小时以10g·L-1的浓度溶解时,产生了没有不溶性颗粒的水溶液。
在本发明中,术语“乳化剂”表示能够在油中将水乳化的试剂,“反相剂”是能够在水中将油乳化的试剂。更具体地,据认为反相剂是HLB值高于或等于10的表面活性剂,乳化剂是HLB值严格低于10的表面活性剂。
化学化合物的亲水亲油平衡值(HLB)是它是亲水性还是亲油性的程度的度量,其通过计算分子不同区域的值来测定,如Griffin在1949年(Griffin WC,Classification ofSurface-Active Agents by HLB,Journal of the Society of Cosmetic Chemists,1949,1,第311-326页)中所述。
在本发明中,采用了Griffin方法,由此值的计算是基于分子的化学基团。Griffin赋予0到20的无量纲值来产生关于在水中和在油中的溶解度的信息。HLB值为10的物质在两相之间分布,由此亲水性基团(分子量Mh)具有对水的完全亲和性,而疏水性烃基(分子量Mp)吸附在非含水相中。
总分子量M的物质(其中亲水部分的分子量是Mh)的HLB是HLB=20(Mh/M)。
本发明的油包水乳液可以用本领域技术人员已知的任何方法来制备。通常,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来进行聚合。提及氧化还原对时,在氧化剂中是异丙基苯过氧化氢、叔丁基过氧化氢或过硫酸盐,在还原剂中是亚硫酸钠、偏亚硫酸氢钠和Mohr盐。还可以使用偶氮化合物例如2,2’-偶氮二(异丁腈)和2,2’-偶氮二(2-脒基丙烷)的盐酸盐。
常规上,聚合通常是等温的、绝热的或在受控的温度进行。也就是说,温度保持恒定,通常是10-60℃(等温),或者使温度自然增加(绝热),并且在这种情况中,反应通常在低于10℃的温度开始,且最终的温度通常高于50℃,或者最后,控制温度的增加来获得处于等温曲线和绝热曲线之间的温度曲线。
通常,在聚合反应结束时添加反相剂,优选在低于50℃的温度添加。
优选地,本发明的乳液包含15-50干重%的水溶性聚合物,更优选15-40干重%,进一步优选15-25干重%,相对于乳液的总重量计。
在本发明乳液的另一优选的实施方案中,反相剂的总量与乳化剂的总量的重量比R高于2,优选高于2.5,更优选高于3,进一步优选高于3.5,仍然进一步优选高于4。
包含在本发明乳液中的水溶性阴离子聚合物包含非离子单体和磺化阴离子单体,和任选的羧化阴离子单体。
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;甲基丙烯酸酯。优选的非离子单体是丙烯酰胺。
磺化阴离子单体优选选自2-丙烯酰氨基-2-甲基丙烷磺酸(ATBS)、2-甲基丙烯酰氨基-2-甲基丙酸、苯乙烯磺酸、乙烯基磺酸、甲基丙烯酸3-磺丙基酯,所述阴离子单体是未成盐的、部分或完全成盐的,和甲基丙烯酸3-磺丙基酯的盐。优选的磺化阴离子单体是2-丙烯酰氨基-2-甲基丙烷磺酸的盐。
羧化阴离子单体优选选自丙烯酸、甲基丙烯酸、衣康酸、马来酸,所述阴离子单体是未成盐的、部分或完全成盐的。优选的羧化阴离子单体是丙烯酸的钠盐。
任选地包括在水溶性阴离子聚合物中的羧化阴离子单体也可以是聚合物的水解的反应产物,其是本领域技术人员公知的。例如,丙烯酸可以是丙烯酰胺水解的产物。
可以选择几种非离子和阴离子单体来形成本发明的水溶性阴离子聚合物。有利地,水溶性阴离子聚合物是丙烯酰胺和2-丙烯酰氨基-2-甲基丙烷磺酸的钠盐的聚合物。
水溶性阴离子聚合物的平均分子量高于3百万道尔顿。优选地,这个平均分子量是3-30百万道尔顿,更优选8-18百万道尔顿。
在本发明中,“平均分子量”通过特性粘度来测定。特性粘度可以用本领域技术人员已知的方法来测量,并且可以具体地由作为不同浓度的函数的减少的粘度值,使用图形方法,将减少的粘度值(沿着Y轴)相对于浓度(沿着X轴)绘图,并且将该曲线外推到零浓度来计算。特性粘度值沿着Y轴读取,或者使用最小平方方法来获得。平均分子量因此可以使用公知的Mark-Houwink等式来测定:
[η]=KMα
[η]表示聚合物的特性粘度,通过测量溶液中粘度的方法来测定;
K表示经验常数;
M表示聚合物的平均分子量;
α表示Mark-Houwink系数;
α和K取决于具体的聚合物-溶剂体系。
本发明的乳液优选包含0.5-10重量%的反相剂和0.5-16重量%的乳化剂,相对于乳液的总重量计。
油包水乳液有利地包含0.8-2重量%的至少一种乳化剂,相对于乳液的总重量计。
油包水乳液优选包含1.5-8重量%的至少一种反相剂,相对于乳液的总重量计。
任选地,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%,进一步优选7-17重量%的盐,相对于乳液的总重量计。
例如,油包水乳液中所含的盐可以是钠盐、锂盐、钾盐、镁盐、铝盐、铵盐、磷酸盐、硫酸盐、盐酸盐、柠檬酸盐、醋酸盐、磷酸酒石酸氢盐、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,并且进一步优选其混合物。
本发明另一方面涉及一种制备压裂流体的方法,其包括:
a)提供本发明的反相乳液,
b)通过将其添加到含有大于30000ppm的盐和二价比R+高于或等于0.15的盐水中,来反转该反相乳液,R+是二价盐/总盐的重量比,
c)任选地添加至少一种支撑剂。
总盐表示盐水中盐的总量。
盐水可以包含一价和/或多价盐或其组合。盐的例子包括但不限于钠、锂、钾、铝、磷酸盐、硫酸盐、镁、钡、硝酸盐和其他无机盐及其混合物。
盐水优选包含至少一种以下成分: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70000ppm的盐和更优选大于100000ppm的盐,优选该盐水包含70000-350000ppm的盐,更优选100000-350000ppm。
在制备压裂流体的方法的一个有利的实施方案中:
-当盐水包含30000ppm-70000ppm(不包括上限)的盐时(步骤b),乳液的比率R(步骤a)优选高于1.8;
-当盐水包含70000ppm-100000ppm(不包括上限)时,乳液的比率R优选高于2;
-当盐水包含100000ppm-150000ppm(不包括上限)的盐时,乳液的比率R优选高于2.5;
-当盐水包含150000ppm-200000ppm(不包括上限)的盐时,乳液的比率R优选高于3;
-当盐水包含200000ppm-250000ppm(不包括上限)的盐时,乳液的比率R优选高于3.5;和
-当盐水包含大于250000ppm(不包括上限)的盐时,乳液的比率R优选高于4。
优选地,二价比率R+(其等于二价盐/总盐的重量比)高于或等于0.20,更优选R+高于或等于0.25。
本发明的乳液在盐水中的反转可以有利地用US8383560的装置和方法来进行,其中该乳液用多个静态混合器布置来连续溶解。
本发明还涉及用本发明的方法获得的压裂流体,特别是包含以下的压裂流体:
-盐水溶液;
-本发明的水溶性阴离子聚合物;
-本发明的反相乳液的油;
-水。
支撑剂可以选自但不限于砂、陶瓷、铝矾土、玻璃珠、树脂浸渍的砂。它优选占压裂流体的0.5-40重量%,更优选1-25重量%,进一步优选1.5-20重量%。
本发明的压裂流体优选包含0.01-3重量%的本发明的水溶性阴离子聚合物(以乳液形式添加),更优选0.025-1重量%,相对于压裂流体的总重量计。
形成压裂流体的盐水可以包含本领域技术人员已知的其他化合物,例如在文献SPE 152596中引述的那些,例如:
–抗粘土溶胀剂例如氯化钾或氯化胆碱;和/或
–杀生物剂,用于防止细菌发展,特别是硫酸盐还原性细菌,其能够形成减少通道表面的粘性物质。可以提及的是例如戊二醛(其是最广泛使用的)或甲醛或异噻唑啉酮;和/或
–氧还原剂例如亚硫酸铵,用于防止其他组分经由注入管的氧化和腐蚀而受到破坏;和/或
–抗腐蚀添加剂,用于保护管防止残留量的氧的氧化,优选的是N,N-二甲基甲酰胺;和/或
–润滑剂例如油蒸馏物;和/或
–铁螯合剂例如柠檬酸,EDTA(乙二胺四乙酸)、膦酸酯;和/或
–防垢剂例如磷酸盐、膦酸盐、聚丙烯酸盐或乙二醇。
在一个优选的实施方案中,制备压裂流体的方法包括:
a)提供本发明的反相乳液,该乳液含有至少15-25重量%的水溶性阴离子聚合物,相对于该乳液的总重量计,含有4-14mol%的2-丙烯酰氨基-2-甲基丙烷磺酸的钠盐,0-17%的丙烯酸钠,和69-96mol%的丙烯酰胺;至少一种反相剂和至少一种乳化剂,反相剂的总量与乳化剂的总量的重量比R高于2.5;
b)通过将其添加到含有大于100000ppm的盐和二价比R+高于或等于0.2的盐水中,来反转该反相乳液,以获得水溶性阴离子聚合物在注入流体中0.05-1%的重量浓度,R+是二价盐/总盐的重量比,
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水力压裂油或气的非常规地下储层的方法,其包括如前所述制备压裂流体和将所述压裂流体注入地下地层中。
更具体地,本发明涉及一种压裂地下地层的方法,该方法包括:
aa)提供根据前述制备方法获得的压裂流体;
bb)将注入流体注入到地下地层的一部分中;
cc)用该注入流体压裂该地下地层;
dd)采收气、油和含水流体的混合物。
注入在压力下进行,来产生沿着生产井长度的裂缝。
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储层中。
这些化合物的注入使流体粘度恢复到接近于水。
作为氧化性化合物,可以提及漂白剂(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。
表面活性剂化合物的化学性质不是关键的。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,本发明的表面活性剂化合物带有阴离子电荷。
优选地,所用的表面活性剂化合物选自阴离子表面活性剂及其两性离子,其选自包含以下的衍生物的组: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、烷基聚醚、芳基烷基聚醚。
最后,本发明第四和最后方面涉及一种在油或气的非常规地下储层上的水力压裂作业中减少压裂流体摩擦的方法,其包括如前所述制备压裂流体,和将所述压裂流体注入地下地层中。
通过减少摩擦,可以减少或消除当注入压裂流体时由于摩擦导致的损失。
对于水力压裂,减少摩擦意味着压裂流体的聚合物赋予溶液以流体流化性能,来在注入时获得相对低的粘度(在高剪切下)和强的粘度来在剪切减少时保持裂缝处悬浮液中的支撑剂。
本发明及其获得的优势将从下面的实施例而变得清楚可见。
实施例
实施例1:含有20.00重量%的包含2mol%的磺化单体的聚合物的乳液。
用37.50重量%的丙烯酰胺溶液(水中50重量%),2.50重量%的ATBS.Na溶液(水中50重量%的2-丙烯酰氨基-2-甲基丙烷磺酸钠),34.90重量%的去离子水和0.02重量%的Versenex 80来制备含水相。
用23.45重量%的油(D100S)和以下乳化剂来制备油相:1.16重量%的511(妥尔油脂肪酸的二乙醇胺),0.16重量%的80(山梨聚糖单油酸酯)和0.23重量%的81(山梨聚糖单油酸酯5EO)。
在混合下将含水相添加到油相来形成乳液。将所形成的分散体置于氮气鼓泡下30分钟,同时将温度稳定在25℃,此时将0.002重量%的过氧化物添加到乳液和将0.075重量%的偏亚硫酸氢钠(MBS)溶液以0.1毫升/分钟的流量添加到分散体。将聚合温度控制在38℃-42℃持续约90分钟。通过以1.0毫升/分钟的流量添加0.03重量%的偏亚硫酸氢钠(MBS)溶液来捕集残留单体。获得油包水聚合物乳液,其含有20%的活性丙烯酰胺聚合物和ATBS.Na。
实施例2:含有20.00重量%的包含10mol%的磺化单体的聚合物的乳液。
用29.50重量%的丙烯酰胺溶液(水中50重量%),10.50重量%的ATBS.Na溶液(水中50重量%的2-丙烯酰氨基-2-甲基丙烷磺酸钠),34.90重量%的去离子水和0.02重量%的Versenex 80来制备含水相。
用23.45重量%的油(D100S)和以下乳化剂来制备油相:1.16重量%的511(妥尔油脂肪酸的二乙醇胺),0.16重量%的80(山梨聚糖单油酸酯)和0.23重量%的81(山梨聚糖单油酸酯5EO)。
在混合下将含水相添加到油相来形成乳液。将所形成的分散体置于氮气鼓泡下30分钟,同时将温度稳定在25℃,此时将0.002重量%的过氧化物添加到乳液和将0.075重量%的偏亚硫酸氢钠(MBS)溶液以0.1毫升/分钟的流量添加到分散体。将聚合温度控制在38℃-42℃持续约90分钟。通过以1.0毫升/分钟的流量添加0.03重量%的偏亚硫酸氢钠(MBS)溶液来捕集残留单体。获得油包水聚合物乳液,其含有20%的活性丙烯酰胺聚合物和ATBS.Na。
实施例3:含有20.00重量%的包含18mol%的磺化单体的聚合物的乳液。
用23.40重量%的丙烯酰胺溶液(水中50重量%),16.60重量%的ATBS.Na溶液(水中50重量%的2-丙烯酰氨基-2-甲基丙烷磺酸钠),34.90重量%的去离子水和0.02重量%的Versenex 80来制备含水相。
用23.45重量%的油(D100S)和以下乳化剂来制备油相:1.16重量%的511(妥尔油脂肪酸的二乙醇胺),0.16重量%的80(山梨聚糖单油酸酯)和0.23重量%的81(山梨聚糖单油酸酯5EO)。
在混合下将含水相添加到油相来形成乳液。将所形成的分散体置于氮气鼓泡下30分钟,同时将温度稳定在25℃,此时将0.002重量%的过氧化物添加到乳液和将0.075重量%的偏亚硫酸氢钠(MBS)溶液以0.1毫升/分钟的流量添加到分散体。将聚合温度控制在38℃-42℃持续约90分钟。通过以1.0毫升/分钟的流量添加0.03重量%的偏亚硫酸氢钠(MBS)溶液来捕集残留单体。获得油包水聚合物乳液,其含有20%的活性丙烯酰胺聚合物和ATBS.Na。
实施例4-9:
实施例10:含有20.00重量%的包含5mol%的磺化单体和15mol%的羧化单体的聚
合物的乳液
用28.70重量%的丙烯酰胺溶液(水中50重量%),5.14重量%的ATBS.Na溶液(水中50重量%的2-丙烯酰氨基-2-甲基丙烷磺酸钠),2.42%重量的丙烯酸(100%),2.69重量%的氢氧化钠溶液(水中50重量%),35.95重量%的去离子水和0.02重量%的Versenex80来制备含水相。
用23.45重量%的油(D100S)和以下乳化剂来制备油相:1.16重量%的511(妥尔油脂肪酸的二乙醇胺),0.16重量%的80(山梨聚糖单油酸酯)和0.23重量%的81(山梨聚糖单油酸酯5EO)。
在混合下将含水相添加到油相来形成乳液。将所形成的分散体置于氮气鼓泡下30分钟,同时将温度稳定在25℃,此时将0.002重量%的过氧化物添加到乳液和将0.075重量%的偏亚硫酸氢钠(MBS)溶液以0.1毫升/分钟的流量添加到分散体。将聚合温度控制在38℃-42℃持续约90分钟。通过以1.0毫升/分钟的流量添加0.03重量%的偏亚硫酸氢钠(MBS)溶液来捕集残留单体。获得油包水聚合物乳液,其含有20%的活性丙烯酰胺聚合物和ATBS.Na。
实施例11和12:
表1描述了每个实施例的重量比R。
表1油包水乳液的重量比R
摩擦流回路测试
用1/4”外径和20英尺总长的不锈钢管构成摩擦流回路。将测试溶液从5升圆锥形存储器的底部泵出。溶液经过管路并返回存储器。使用装备有变速器的三缸泵来获得流量。
在样品存储器中制备4升的9%CaCl2或API或2×API的盐水,并且在作业中设定泵并调节来传输1.5加仑/分钟的流量。9%CaCl2的盐水对应于在100ml水中9g的CaCl2,其R+值是1.00。API盐水对应于在100ml水中8.5g的NaCl+2.5g的CaCl2,其R+是0.20。2×API盐水对应于在100ml水中17g的NaCl+5g的CaCl2,其R+是0.20。将盐水溶液再循环,直到温度在25℃平衡且达到稳定的压力差。这个压力记录为9%CaCl2或API或2×API盐水的“初始压力”。
将样品量的纯油包水聚合物乳液用注射器快速注入含有9%CaCl2或API或2×API的盐水的样品存储器中,并且启动计时器。剂量记录为油包水乳液的加仑/每千加仑的9%CaCl2或API或2×API(gpt)。在5分钟内每秒记录压力。在给定时间’t’的摩擦减少百分比(%FRt)在初始压降ΔPi和时间t时的压降ΔP之t时或之后,用下面的等式来计算:
结果:
在表2中,全部乳液包含20重量%的阴离子聚合物。
结果表明,当重量比R增加时,减摩性能改进。当盐浓度增加时,减摩性能下降。但是,当选择和改变重量比R时(根据本发明的范围),在盐水和甚至高盐度的盐水中获得非常好的减摩性能变成可能。
当聚合物中的磺化单体的百分比是10mol%时,减摩性能改进。较低的磺化单体百分比(2%)和较高的百分比(18%)表现出较差的性能。除了磺化单体之外,以0-17%存在的阴离子单体也能够获得良好的减摩性能。
Claims (14)
1.油包水反相乳液,其包含:
-油;
-水;
-至少一种平均分子量高于3百万道尔顿的水溶性阴离子聚合物,该聚合物含有4-14mol%的磺化阴离子单体,0-17mol%的羧化阴离子单体,和69-96mol%的非离子单体;
-至少一种反相剂和至少一种乳化剂,所述反相剂的总量与所述乳化剂的总量的重量比R高于1.8;
-该反相剂选自优选具有4-10乙氧化度的乙氧化的壬基酚;优选具有乙氧化度/丙氧化度来获得C12-C25的总碳数的乙氧化的/丙氧化的醇,乙氧化的十三烷基醇,和乙氧化的/丙氧化的脂肪醇;
-该乳化剂选自山梨聚糖单油酸酯,聚乙氧化山梨聚糖酯,妥尔油脂肪酸、聚乙氧化脂肪酸的二乙醇酰胺。
2.根据权利要求1所述的乳液,特征在于它包含15-50重量%的水溶性阴离子聚合物,优选15-40重量%,更优选15-25重量%,相对于该乳液的总重量计。
3.根据权利要求1或2所述的乳液,特征在于反相剂的总量与乳化剂的总量的重量比R高于2,优选高于2.5,更优选高于3,进一步优选高于3.5,仍然进一步优选高于4。
4.根据权利要求1-3中任一项所述的乳液,特征在于该水溶性阴离子聚合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;优选的单体是丙烯酰胺。
5.根据权利要求1-4中任一项所述的乳液,特征在于该水溶性阴离子聚合物的磺化阴离子单体选自2-丙烯酰氨基-2-甲基丙烷磺酸(ATBS)、2-甲基丙烯酰氨基-2-甲基丙酸、苯乙烯磺酸、乙烯基磺酸、甲基丙烯酸3-磺丙基酯,所述阴离子单体是未成盐的、部分或完全成盐的,优选的磺化阴离子单体是2-丙烯酰氨基-2-甲基丙烷磺酸的钠盐。
6.根据权利要求1-5中任一项所述的乳液,特征在于该水溶性阴离子聚合物的羧化阴离子单体选自丙烯酸、甲基丙烯酸、衣康酸、马来酸,所述阴离子单体是未成盐的、部分或完全成盐的,优选的羧化阴离子单体是丙烯酸的钠盐。
7.根据权利要求1-6中任一项所述的乳液,特征在于该水溶性阴离子聚合物的平均分子量是3-30百万道尔顿,优选8-18百万道尔顿。
8.根据权利要求1-7中任一项所述的乳液,特征在于它包含0.5-10重量%的反相剂和0.5-16重量%的乳化剂,相对于该乳液的总重量计。
9.制备压裂流体的方法,其包括:
a)提供根据权利要求1-8中任一项所述的反相乳液,
b)通过将其添加到含有大于30000ppm的盐和二价比R+≥0.15的盐水中,来反转该反相乳液,R+=二价盐/总盐的重量比,
c)任选地添加至少一种支撑剂。
10.根据权利要求8所述的制备压裂流体的方法,特征在于在步骤b)时,该盐水包含大于70000ppm的盐,优选大于100000ppm的盐。
11.根据权利要求9或10之一所述的制备压裂流体的方法,特征在于在步骤b)时,该盐水的二价比R+高于或等于0.20,优选R+高于或等于0.25。
12.根据权利要求9-11之一所述的制备压裂流体的方法,其包括:
a)提供本发明的反相乳液,该乳液含有相对于压裂流体重量计至少15-25重量%的水溶性阴离子聚合物,该聚合物含有4-14mol%的2-丙烯酰氨基-2-甲基丙烷磺酸的钠盐,0-17%的丙烯酸钠和69-96mol%的丙烯酰胺;至少一种反相剂和至少一种乳化剂,反相剂的总量与乳化剂的总量的重量比R高于2.5,
b)通过将其添加到含有大于100000ppm的盐和二价比R+高于或等于0.20的盐水中,来反转该反相乳液,以获得水溶性阴离子聚合物在注入流体中0.05-1%的重量浓度,R+=二价盐/总盐的重量比,
c)任选地,添加至少一种支撑剂。
13.压裂地下地层的方法,其包括:
aa)提供根据权利要求9-12中任一项所述的制备方法获得的压裂流体,
bb)将注入流体注入到地下地层的一部分中,
cc)用该注入流体压裂该地下地层,
dd)采收气、油和含水流体的混合物。
14.用于在油或气的非常规地下储层的水力压裂作业中减少压裂流体摩擦的方法,其包括制备根据权利要求9-12中任一项所述的压裂流体,和将所述压裂流体注入地下地层中。
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