WO2017048424A1 - Improved poly(vinyl caprolactam) kinetic gas hydrate inhibitor and method for preparing the same - Google Patents
Improved poly(vinyl caprolactam) kinetic gas hydrate inhibitor and method for preparing the same Download PDFInfo
- Publication number
- WO2017048424A1 WO2017048424A1 PCT/US2016/046667 US2016046667W WO2017048424A1 WO 2017048424 A1 WO2017048424 A1 WO 2017048424A1 US 2016046667 W US2016046667 W US 2016046667W WO 2017048424 A1 WO2017048424 A1 WO 2017048424A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hydrate inhibitor
- vinyl caprolactam
- polymerization
- poly
- lactate
- Prior art date
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- -1 poly(vinyl caprolactam) Polymers 0.000 title claims abstract description 103
- 239000003112 inhibitor Substances 0.000 title claims abstract description 68
- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims description 38
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 56
- 239000002904 solvent Substances 0.000 claims abstract description 41
- 229920000642 polymer Polymers 0.000 claims abstract description 40
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 26
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 22
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 17
- MXRGSJAOLKBZLU-UHFFFAOYSA-N 3-ethenylazepan-2-one Chemical compound C=CC1CCCCNC1=O MXRGSJAOLKBZLU-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 10
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 10
- 239000003345 natural gas Substances 0.000 claims abstract description 9
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 51
- 239000012530 fluid Substances 0.000 claims description 22
- 229920001519 homopolymer Polymers 0.000 claims description 17
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 claims description 13
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 claims description 9
- 230000002401 inhibitory effect Effects 0.000 claims description 9
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 8
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 8
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 5
- 229940017144 n-butyl lactate Drugs 0.000 claims description 5
- 229940116333 ethyl lactate Drugs 0.000 claims description 4
- ILVGAIQLOCKNQA-UHFFFAOYSA-N propyl 2-hydroxypropanoate Chemical compound CCCOC(=O)C(C)O ILVGAIQLOCKNQA-UHFFFAOYSA-N 0.000 claims description 4
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 3
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 3
- WBPAQKQBUKYCJS-UHFFFAOYSA-N 2-methylpropyl 2-hydroxypropanoate Chemical compound CC(C)COC(=O)C(C)O WBPAQKQBUKYCJS-UHFFFAOYSA-N 0.000 claims description 3
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical group C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 claims description 3
- 229940057867 methyl lactate Drugs 0.000 claims description 3
- KIWATKANDHUUOB-UHFFFAOYSA-N propan-2-yl 2-hydroxypropanoate Chemical compound CC(C)OC(=O)C(C)O KIWATKANDHUUOB-UHFFFAOYSA-N 0.000 claims description 3
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 claims description 2
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 claims description 2
- JJRDRFZYKKFYMO-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-ylperoxy)butane Chemical compound CCC(C)(C)OOC(C)(C)CC JJRDRFZYKKFYMO-UHFFFAOYSA-N 0.000 claims description 2
- UVWVIEBLYRKAFQ-UHFFFAOYSA-N 4,4-bis(tert-butylperoxy)butyl pentanoate Chemical compound CCCCC(=O)OCCCC(OOC(C)(C)C)OOC(C)(C)C UVWVIEBLYRKAFQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005755 formation reaction Methods 0.000 description 24
- 239000007789 gas Substances 0.000 description 23
- 150000004677 hydrates Chemical class 0.000 description 17
- 150000002430 hydrocarbons Chemical class 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000178 monomer Substances 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229920001897 terpolymer Polymers 0.000 description 6
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000005764 inhibitory process Effects 0.000 description 5
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003139 biocide Substances 0.000 description 4
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 241001082241 Lythrum hyssopifolia Species 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000005553 drilling Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 150000003895 L-lactate salts Chemical class 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- MRABAEUHTLLEML-LURJTMIESA-N butyl (2s)-2-hydroxypropanoate Chemical compound CCCCOC(=O)[C@H](C)O MRABAEUHTLLEML-LURJTMIESA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- PNLUGRYDUHRLOF-UHFFFAOYSA-N n-ethenyl-n-methylacetamide Chemical compound C=CN(C)C(C)=O PNLUGRYDUHRLOF-UHFFFAOYSA-N 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- ZLMORGKRXPNOBO-UHFFFAOYSA-N (2-methylcyclohexyl) 2-hydroxypropanoate Chemical compound CC(O)C(=O)OC1CCCCC1C ZLMORGKRXPNOBO-UHFFFAOYSA-N 0.000 description 1
- DJABNVJZYFGAJE-UHFFFAOYSA-N 1-ethenyl-5-ethylpyrrolidin-2-one Chemical compound CCC1CCC(=O)N1C=C DJABNVJZYFGAJE-UHFFFAOYSA-N 0.000 description 1
- HQGPZXPTJWUDQR-UHFFFAOYSA-N 1-ethenyl-5-methylpyrrolidin-2-one Chemical compound CC1CCC(=O)N1C=C HQGPZXPTJWUDQR-UHFFFAOYSA-N 0.000 description 1
- GIQLJJKZKUIRIU-UHFFFAOYSA-N 1-ethenyl-6-ethylpiperidin-2-one Chemical compound CCC1CCCC(=O)N1C=C GIQLJJKZKUIRIU-UHFFFAOYSA-N 0.000 description 1
- FFDNCQYZAAVSSF-UHFFFAOYSA-N 1-ethenyl-6-methylpiperidin-2-one Chemical compound CC1CCCC(=O)N1C=C FFDNCQYZAAVSSF-UHFFFAOYSA-N 0.000 description 1
- PBGPBHYPCGDFEZ-UHFFFAOYSA-N 1-ethenylpiperidin-2-one Chemical compound C=CN1CCCCC1=O PBGPBHYPCGDFEZ-UHFFFAOYSA-N 0.000 description 1
- FECDACOUYKFOOP-UHFFFAOYSA-N 2-ethylhexyl 2-hydroxypropanoate Chemical compound CCCCC(CC)COC(=O)C(C)O FECDACOUYKFOOP-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- LWLOKSXSAUHTJO-UHFFFAOYSA-N 4,5-dimethyl-1,3-dioxolan-2-one Chemical compound CC1OC(=O)OC1C LWLOKSXSAUHTJO-UHFFFAOYSA-N 0.000 description 1
- NTOXAXQNZZXUQQ-UHFFFAOYSA-N C1(OC(=C(C)C)O1)=O Chemical compound C1(OC(=C(C)C)O1)=O NTOXAXQNZZXUQQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- LCXXNKZQVOXMEH-UHFFFAOYSA-N Tetrahydrofurfuryl methacrylate Chemical compound CC(=C)C(=O)OCC1CCCO1 LCXXNKZQVOXMEH-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- SAQPWCPHSKYPCK-UHFFFAOYSA-N carbonic acid;propane-1,2,3-triol Chemical compound OC(O)=O.OCC(O)CO SAQPWCPHSKYPCK-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- MLXVQJMYSKICMT-UHFFFAOYSA-N cyclohexyl 2-hydroxypropanoate Chemical compound CC(O)C(=O)OC1CCCCC1 MLXVQJMYSKICMT-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- PZSYRGVIJCBHDE-UHFFFAOYSA-N heptyl 2-hydroxypropanoate Chemical compound CCCCCCCOC(=O)C(C)O PZSYRGVIJCBHDE-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 150000003951 lactams Chemical group 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- ILCQQHAOOOVHQJ-UHFFFAOYSA-N n-ethenylprop-2-enamide Chemical compound C=CNC(=O)C=C ILCQQHAOOOVHQJ-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- SFBIZPBTKROSDE-UHFFFAOYSA-N octyl 2-hydroxypropanoate Chemical compound CCCCCCCCOC(=O)C(C)O SFBIZPBTKROSDE-UHFFFAOYSA-N 0.000 description 1
- 150000004010 onium ions Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- 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
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
-
- 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
- C08F126/00—Homopolymers 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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F126/06—Homopolymers 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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
-
- 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
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/035—Organic additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
- C10G75/04—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of antifouling agents
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
- C10L1/2368—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing heterocyclic compounds containing nitrogen in the ring
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/107—Limiting or prohibiting hydrate formation
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
-
- 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
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/22—Hydrates inhibition by using well treatment fluids containing inhibitors of hydrate formers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/80—Additives
Definitions
- This disclosure relates to kinetic hydrate inhibitors, in particular kinetic gas hydrate inhibitors, and methods for preparing such hydrate inhibitors.
- the kinetic hydrate inhibitors find application in a variety of fields including, but not limited to, gas hydrate inhibition in well drilling, completion, natural gas production, processing, transportation and storage.
- Gas hydrates are solids that form from a combination of water and one or more hydrocarbon or non-hydrocarbon gases. In physical appearance, gas hydrates resemble packed snow or ice. In a gas hydrate, the gas molecules are "caged" within a crystal structure composed of water molecules. Sometimes gas hydrates are called “gas clathrates". Clathrates are substances in which molecules of one compound are completely “caged” within the crystal structure of another. Thus, gas hydrates are one type of clathrate.
- thermodynamic and kinetic Two broad techniques are generally used to overcome or control hydrate formation, namely thermodynamic and kinetic, which can be used alone or in conjunction.
- thermodynamic approach there are a number of reported or attempted methods, including water Attorney Docket No. D#81816 PATENT
- U.S. Pat. No, 6,867,262 discloses a graft polymer gas hydrate inhibitor wherein the graft polymer comprises a base polymer and vinyl caprolactam (in ethylene glycol) grafted onto the base polymer;
- U.S. Pat. No. 6,451,892 discloses a composition that includes a homopolymer of vinyl caprolactam, a glycol ether polymerization solvent, a carrier solvent and optionally water or methanol;
- U.S. Pat. No. 6,359,047 discloses a composition comprising a copolymer based on vinyl caprolactam and ⁇ , ⁇ -diethylaminoethyl meth(acrylate) in admixture with a low molecular weight glycol ether as a hydrate inhibitor;
- U.S. Pat. No. 6,281,274 discloses the use of a hydrate inhibitor composition comprising a copolymer of vinyl caprolactam and vinyl pyridine made in 2-butoxyethanol;
- U.S. Pat. No. 6,242,518 teaches a gas hydrate inhibitor composition comprising a homopolymer of vinyl caprolactam made in a mixture of a glycol ether and water; Attorney Docket No. D#81816 PATENT
- U.S. Pat. No. 6,194,622 teaches a method for inhibiting hydrate formation using a copolymer of a surfactant monomer and vinyl caprolactam in admixture with an alcohol or glycol;
- U.S. Pat. No. 6,180,699 discloses the use of a homopolymer of vinyl caprolactam, made in a glycol ether, and a polyoxyalkyldiamine or polyoxyaryldiamine as a hydrate inhibiting composition;
- U.S. Pat. No. 6,096,815 discloses a composition for preventing the formation of gas hydrates comprising a homopolymer of vinyl caprolactam and an alcohol containing 3 to 5 carbon atoms;
- U.S. Pat. No. 5,880,319 teaches a method for using an N-vinyl lactam polymer and an alcohol to reduce the tendency of clathrate agglomeration
- U.S. Pat. No. 5,874,660 discloses a method for inhibiting hydrate formation using a kinetic hydrate inhibitor comprising a polymer formed from N-methyl-N-vinylacetamide and vinyl caprolactam in water, brine or low molecular weight alcohols;
- U.S. Pat. No. 5,432,292 discloses a method for controlling clathrate hydrates in fluid systems utilizing a terpolymer comprising N-vinyl caprolactam.
- the present disclosure provides a kinetic hydrate inhibitor containing a poly(vinyl caprolactam) polymer which has been made and is used in a polymerization solvent system comprising an alkylene carbonate and/or an alkyl lactate.
- the poly(vinyl lactam) polymer is a poly(N-vinyl caprolactam) homopolymer.
- a method for preparing the kinetic hydrate inhibitor of the present disclosure in a polymerization medium comprising a vinyl caprolactam compound, a polymerization solvent system and a polymerization initiator.
- kinetic hydrate inhibitor of the present disclosure in methods for inhibiting the formation of natural gas and/or liquid hydrocarbon hydrates in a system by adding the kinetic hydrate inhibitor to the system.
- the system may be a fluid and/or conduit.
- Figure 1 depicts the % hydrate conversion in 0.5 wt. % aqueous solutions in the presence of Green Canyon gas at a temperature of 2° (12° sub-cooling).
- an alkylene carbonate means one alkylene carbonate or more than one alkylene carbonate.
- the phrases “in one embodiment”, “according to one embodiment” and the like generally mean the particular feature, structure, or characteristic following the phrase is included in at least one embodiment of the present disclosure, and may be included in more than one embodiment of the present disclosure. Importantly, such phrases do not necessarily refer to the same embodiment. If the specification states a component or feature “may”, “can”, “could”, or “might” be included or have a characteristic, that particular component or feature is not required to be included or have the characteristic.
- monomer refers to the repeat units that comprise a polymer.
- a monomer is a compound that chemically bonds to other molecules, including other monomers, to form a polymer.
- polymer refers to a molecule comprising multiple monomer units connected by covalent chemical bonds.
- a polymer encompasses molecules wherein the number of monomer units ranges from very few, which more commonly may be called Attorney Docket No. D#81816 PATENT
- Non-limiting examples of polymers include homopolymers which comprise like monomer units, copolymers which comprise two unlike monomer units and which may be in random, blocked or alternating order, and terpolymers which comprise three unlike monomer units and which may be in random, blocked, or alternating order.
- performance chemicals refers to non-personal care compositions that serve a broad variety of applications, and include non-limiting compositions such as, adhesives, agricultural, biocides, coatings, electronics, household- industrial-institutional (HI&I), inks, membranes, metal fluids, paper, paints, plastics, printing, plasters, and wood-care compositions.
- personal care composition refers to such illustrative non-limiting compositions as skin, sun, oil, hair, cosmetic, and preservative compositions, including those to alter the color and appearance of the skin.
- Potential personal care compositions include, but are not limited to, polymers for increased flexibility in styling, durable styling, and increased humidity resistance for hair, skin, and color cosmetics, sun care water-proof/resistance, wear- resistance, and thermal protecting/enhancing compositions.
- fluid means production fluids which, in turn, includes, but is not limited to, formation fluids, crude oil, crude natural gas, and any other fluids encountered in the production of oil and gas.
- the present disclosure provides a poly(vinyl caprolactam) polymer obtained by polymerizing a vinyl caprolactam compound in a polymerization solvent system comprising an alkylene carbonate and/or an alkyl lactate and a polymerization initiator.
- the present disclosure also provides a kinetic hydrate inhibitor comprising the poly(vinyl caprolactam) polymer in Attorney Docket No. D#81816 PATENT
- poly(vinyl caprolactam) polymers may be produced having a similar number- and weight-average molecular weight and distribution as state of the art poly(vinyl caprolactam) polymers which have been prepared in state of the art solvents, such as 2-butoxyethanol or other alcohols or glycols, with the state of the art solvents being replaced by an alkylene carbonate and/or an alkyl lactate.
- the present method thus represents an improvement with regards to state of the art polymers and methods since the inventive polymerization solvent system has low-toxicity and a VOC-exempt status.
- the resultant polyvinyl caprolactam) polymer/polymerization solvent system blend exhibits superior hydrate inhibitor performance relative to state of the art poly(vinyl caprolactam) polymer/solvent blends.
- the poly(vinyl caprolactam) polymer is a poly(vinyl caprolactam) homopolymer.
- the poly( vinyl caprolactam) homopolymer may be derived from a vinyl caprolactam compound such as N-vinyl caprolactam, N-vinyl-7-methyl-2-caprolactam and N-vinyl-7-ethyl-2-caprolactam.
- the poly(vinyl caprolactam) homopolymer is poly(N-vinyl caprolactam) homopolymer.
- the poly(vinyl caprolactam) homopolymer may have a weight average molecular weight of about 400 to about 4000, especially about 500 to about 2500, as determined by GPC using polyethylene glycol as the standard.
- the poly(vinyl caprolactam) polymer is a copolymer derived from a vinyl caprolactam compound and one other vinyl lactam compound, such as N- vinyl pyrrolidone, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-2- piperidone, N-vinyl-6-methyl-2-piperidone and N-vinyl-6-ethyl-2-piperidone.
- N- vinyl pyrrolidone N-vinyl-5-methyl-2-pyrrolidone
- N-vinyl-5-ethyl-2-pyrrolidone N-vinyl-2- piperidone
- N-vinyl-6-methyl-2-piperidone N-vinyl-6-ethyl-2-piperidone
- the polyvinyl caprolactam) copolymer has a weight average molecular weight average of about 400 to about 4000, especially about 500 to about 2500 as determined by GPC using polyethylene glycol as the standard.
- the poly(vinyl caprolactam) polymer is a copolymer or terpolymer derived from a vinyl caprolactam compound and at least one other vinyl lactam compound and/or other monomer, such as a linear, acrylic N-vinylamide monomer (for e.g. N- vinyl formamide, N-vinyl acetamide or N-vinyl-N-methylacetamide), an acrylamide, an N-alkyl acrylamide (for e.g. ⁇ , ⁇ -dimethylamino acrylamide; N-[l-(2-pyrrolidonylethyl)] acrylamide, an ⁇ , ⁇ -dialkyl aminoalkyl methacrylamide (for e.g.
- the poly(vinyl caprolactam) copolymer or terpolymer has a molecular weight average of about 400 to about 4000, especially about 500 to about 2500, as determined by GPC using polyethylene glycol as the standard.
- such poly(vinyl caprolactam) copolymers and terpolymers should contain at least about 40% by weight of vinyl caprolactam, and especially at least about 50% by weight of vinyl caprolactam, based on the total weight of the copolymer or terpolymer.
- the amount of vinyl caprolactam compound in the polymerization medium may be up to about 60% by weight, based on the total weight of the polymerization medium. In other embodiments, the amount of vinyl caprolactam compound in the polymerization medium may be from about 10% by weight to about 50% by weight, based on the total weight of the polymerization medium.
- the polymerization solvent system includes an alkylene carbonate.
- the alkylene carbonate is a compound represented by the structure:
- Ri, R 2 , R 3 and R4 are each, independently, hydrogen, hydroxymethyl or a linear or branched Q-CJO alkyl group.
- the alkylene carbonate may be produced by a number of known processes, including the reaction of a glycol with phosgene, transesterification of a glycol with a diethyl carbonate, or by the reaction of the corresponding 1,2-epoxide with carbon dioxide in the presence of a catalyst, as such methods are known in the art.
- alkylene carbonates include, but are not limited to, ethylene carbonate, propylene carbonate, trimethylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, iso-butylene carbonate, glycerine carbonate and mixtures thereof.
- the alkylene carbonate is selected from ethylene carbonate, propylene carbonate, 1 ,2-butylene carbonate and a mixture thereof.
- the alkylene carbonate is propylene carbonate.
- the polymerization solvent system includes an alkyl lactate.
- the alkyl lactate is an aliphatic linear or branched Cj-Qo alkyl lactate.
- the alkyl lactate is a linear or branched aliphatic Cj-C 4 alkyl Attorney Docket No. D#81816 PATENT
- the alkyl lactates may be present in the form of D- and/or L-lactates, with particular embodiments preferring the L-lactates.
- alkyl lactates include methyl lactate, ethyl lactate, n-propyl lactate, iso- propyl lactate, n-butyl lactate, iso-butyl lactate, cyclohexyl lactate, 2-ethylhexyl lactate, 2- methylcyclohexyl lactate, heptyl lactate, octyl lactate and mixtures thereof.
- the alkyl lactate is selected from methyl lactate, ethyl lactate, n-propyl lactate, iso-propyl lactate, n-butyl lactate, iso-butyl lactate and a mixture thereof.
- the alkyl lactate is selected from an ethyl lactate, n-propyl lactate, n-butyl lactate and a mixture thereof. In still another embodiment, the alkyl lactate is n-butyl lactate.
- the polymerization medium may contain up to about 75% by weight of the polymerization solvent system, based on the total weight of the polymerization medium. In other embodiments, the polymerization medium may contain from about 5% by weight to about 60% by weight of the polymerization solvent system, based on the total weight of the polymerization medium. In still another embodiment, the polymerization may contain from about 10%) by weight to about 50% by weight, based on the total weight of the polymerization medium.
- the polymerization medium contains a polymerization initiator.
- initiators for polymerization it is possible to use peroxide compounds, including di-tert-butyl peroxide, di-tert-amyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis-(tert-butylperoxy)- hexane, 2,2-bis(tert-butylperoxy)-butane, 1 , 1 -bis-(tert-butylperoxy)-3 ,3 ,5 -trimethylcyclohexane or 4,4-di-(tert-butylperoxy)-butyl valerate, 2,5-dimethyl-2,5-di-(t-buylperoxyl)hexane and Attorney Docket No. D#81816 PATENT
- the polymerization initiator may generally be used in an amount of about 0.01-10% by weight, based on the total weight of the polymerization medium. In other embodiments, the polymerization initiator may be used in an amount of about 0.02-5% by weight, based on the total weight of the polymerization medium.
- the polymerization may be carried out by means of a batch process or a (semi)continuous feed process.
- the polymerization may take place at a temperature ranging from about 40° C to about 200° C, in other embodiments from about 60° C to about 170° C, while in still other embodiments from about 85° C to about 150° C.
- Polymerization is normally conducted under atmospheric pressure but may also proceed under reduced or elevated pressure, such as between 1 and 10 bar
- the polymerization may also be carried out in an inert gas atmosphere, for example nitrogen.
- the kinetic hydrate inhibitor of the present disclosure includes the poly(vinyl caprolactam) polymer, for e.g. poly(N-vinyl caprolactam) homopolymer, in admixture with the polymerization solvent system.
- the poly(vinyl caprolactam) polymer, for e.g. poly(N-vinyl caprolactam) homopolymer and polymerization solvent system may, during the polymerization or after the polymerization, be diluted with water or methanol to form a homogeneous aqueous solution of a desired concentration. The water can be added continuously, intermittently or all at once.
- the thus- formed poly(vinyl caprolactam) polymer for e.g. poly(N-vinyl caprolactam) homopolymer, and polymerization solvent system can be further diluted with a dilution liquid, such as water or methanol, or mixtures thereof, if desired, to form a diluted composition.
- a dilution liquid such as water or methanol, or mixtures thereof
- poly(vinyl caprolactam) polymer/polymerization solvent system to dilution liquid may range from 0.5: 1 to 5:1, such as about 1 :1.
- the amount of poly(vinyl caprolactam) polymer that may be in admixture with the polymerization solvent system in the kinetic hydrate inhibitor may range from about 20% to about 80% by weight, such as about 25% to 55% by weight, based on the total weight of poly(vinyl caprolactam) polymer and polymerization solvent system.
- the % by weight ratio of polymerization solvent system to poly(vinyl caprolactam) polymer is from about 90:10 to 10:90, in other embodiments from 75:25 to 25:75, and in further embodiments from 60:40 to 40:60.
- the kinetic hydrate inhibitor of the present disclosure may be used in methods for inhibiting the formation of natural gas and/or liquid hydrocarbon hydrates in a system, the method comprising adding the kinetic hydrate inhibitor of the present disclosure to the system.
- the present disclosure provides the use of the kinetic hydrate inhibitor as described herein as a kinetic gas hydrate inhibitor for inhibiting the formation of hydrates in a system, such as a system for hydrocarbon drilling, production, storage and/or transportation, including production, drilling, completion, fracturing, stimulation and injection and re-injection operations.
- a system such as a system for hydrocarbon drilling, production, storage and/or transportation, including production, drilling, completion, fracturing, stimulation and injection and re-injection operations.
- the "system” referred to herein is a fluid and/or a conduit.
- a method of inhibiting the formation of hydrates in a fluid which includes the step of adding the kinetic gas hydrate inhibitor to the fluid.
- Addition of the kinetic gas hydrate inhibitor to the system may be achieved through any known means and in amounts typical in the art. However, due to the surprising efficacy of the kinetic gas hydrate inhibitor of the present disclosure, lower amounts may be required than of Attorney Docket No. D#81816 PATENT
- typical kinetic gas hydrate inhibitor use concentrations, calculated as 100% of active substance may be from about 0.005% by weight to about 8% by weight, for instance, about 0.0075% by weight to about 5% by weight, especially about 0.01% by weight to about 3% by weight and even concentrations of from about 0.02% by weight to about 1% by weight (100-10,000 ppm), based on the total amount of water in the system.
- the present disclosure is useful for inhibiting hydrate formation for many hydrocarbons and hydrocarbon mixtures, for e.g. those which include methane, ethane, propane, n-butane, isobutane, isopentane and mixtures thereof.
- hydrocarbons may also comprise other compounds including, but not limited to C0 2 , hydrogen sulphide, and other compounds commonly found in gas/oil formations or processing plants, either naturally occurring or used in recovering/processing hydrocarbons from the formation or both, and mixtures thereof.
- the methods and uses of the present disclosure involve contacting a system with the kinetic gas hydrate inhibitor as described herein. When an effective amount of such kinetic gas hydrate inhibitor is used, hydrate blockage in a conduit is inhibited.
- the contacting may be achieved by means of standard equipment such as injection pumps or the like, resulting in rapid and uniform distribution of the inhibitor in the aqueous phase which has a tendency to form hydrates.
- the contacting can be made in-line or off-line or both. If needed or desired, the kinetic gas hydrate inhibitor, or some of its components, may be optionally removed or separated Attorney Docket No. D#81816 PATENT
- the pressure at which the kinetic gas hydrate inhibitor is contacted with fluid is usually at or greater than atmospheric pressure, (i.e. about 101 kPa), such as greater than about 1 MPa, and even more greater than about 5 MPa.
- atmospheric pressure i.e. about 101 kPa
- the pressure in certain formation or processing plants or units could be much higher, for example greater than about 20 MPa.
- the present kinetic gas hydrate inhibitor can be used at any pressure that allows formation of gas hydrates.
- the kinetic gas hydrate inhibitor primarily retards or prevents the formation of gas hydrates
- the addition of the inhibitor should ideally take place before hydrates are formed, i.e. at above the equilibrium temperature of hydrate formation.
- the temperature for contacting is usually below, the same as, or not much higher than the ambient or room temperature. Lower temperatures tend to favor hydrate formation, thus requiring the treatment with the kinetic gas hydrate inhibitor of the present disclosure. At much higher temperatures, however, hydrocarbon hydrates may not form, thus obviating the need of carrying out any treatments.
- the kinetic gas hydrate inhibitor described herein may be added to the system at any stage or location suitable to inhibit formation of hydrates.
- the conduits into which the kinetic gas hydrate inhibitor may be added are typically hydrocarbon conduits extending for at least part of the length from the site within a hydrocarbon well at which hydrocarbon enters the borehole to the facility remote from the well at which hydrocarbon compositions are processed.
- the kinetic gas hydrate inhibitor is added to a process stream containing hydrocarbons and water by injection via a single port or multiple Attorney Docket No. D#81816 PATENT
- the kinetic gas hydrate inhibitor may be injected into the reservoir matrix surrounding a hydrocarbon production well. In a further aspect, the kinetic gas hydrate inhibitor may be injected into a hydrocarbon production well. In another aspect, the kinetic gas hydrate inhibitor is injected at the well head.
- the kinetic gas hydrate inhibitor of this disclosure may be used alone or in combination with an additional component(s), including, but not limited to, salts, weighting agents, inert solids, fluid loss control agents, emulsifiers, dispersion aids, corrosion inhibitors, emulsion thinners, emulsion thickeners, viscosifying agents, gelling agents, high-pressure, high- temperature emulsifler-filtration control agents, surfactants, particulates, proppants, gravel particulates, lost circulation materials, foaming agents, gases, pH control additives, breakers, biocides, crosslinkers, stabilizers, chelating agents, scale inhibitors, thermodynamic hydrate inhibitors, second kinetic hydrate inhibitors, mutual solvents, oxidizers, reducers, friction reducers, clay stabilizing agents, or any combination thereof.
- additional component(s) including, but not limited to, salts, weighting agents, inert solids, fluid loss control agents, emulsifiers, dispersion aids, corrosion
- the described poly(vinyl caprolactam) polymers may provide benefits outside of the oil and gas industry. These benefits may include rheology control, de-emulsification, biocidal activity, shale-swelling inhibition, scale inhibition, solubilization, wax inhibition, and deposition of actives (such as biocides or fragrances). Consequently, the poly(vinyl caprolactam) polymers are expected to be useful in other performance chemicals compositions and personal care compositions. For example, the poly(vinyl caprolactam) polymers may be combined with Attorney Docket No . D#81816 PATENT
- the addition funnel Prior to transfer, the addition funnel was wrapped with heating tape that was adjusted such to maintain the contents in a molten state throughout the addition (40-60° C).
- the butyl cellosolve solvent present in the reaction flask was heated to 150° C with stirring while simultaneously purging the assembly with nitrogen. Once the solvent stabilized at 150° C and the assembly purged with nitrogen for at least 30 minutes, the aforementioned mixture containing N-vinyl caprolactam was charged dropwise to the flask over 1 hour while maintaining a reaction temperature of 150° C. After completion of the addition, the flask contents were further maintained at 150° C for 1.5 hours. The resulting product was cooled and discharged below 60° C. The resulting product was a light yellow liquid.
- GPC THF solvent, 1.0 wt. % t-butyl amine, PPG standards
- the contents of the flask were stirred whi le simultaneously being heated to 150° C and purging with nitrogen. Once the stirring flask contents stabilized at 150° C and the assembly purged with nitrogen for at least 30 minutes, the afore-mentioned mixture containing N-vinyl caprolactam was charged dropwise to the flask over I hour while mamtaining a reaction temperature of 150° C. After completion of the addition, the flask contents were further maintained at 150 p C for 1.5 hours.
- Example 2 The procedure given in Example 1 was repeated except that 1.8 g Luperox® 101 (2,5- dimethyl-2,5-di(t-butylperoxy)hexane 5 Arkema) was used as the initiating species in place of di-t- butylperoxide.
- the resulting product was a pale yellow liquid. 25 wt, % theoretical solids.
- Example 2 The procedure given in Example 1 was repeated except that (S)-n-butyl lactate was used as solvent in place of propylene carbonate. 120.0 g butyl lactate was added to the reaction flask and the blend containing N-vinyl caprolactam consisted of 180.0 g N-vinyl caprolactam, 150.0 g butyl lactate, and 4.0 g di-t-butylperoxide. 40 wt. % theoretical solids.
- Example 2 The procedure given in Example 1 was repeated except that (S)-n-butyl lactate was used as the solvent in place of propylene carbonate and Luperox® 101 was used as initiator in place of di-t-butylperoxide. 1028.9 g butyl lactate was added to the reaction flask and the blend containing N-vinyl caprolactam consisted of 1234.0 g N-vinyl caprolactam, 823.1 g butyl lactate, and 17.1 g Luperox® 101. 40 wt. % theoretical solids.
- hydrate conversion defined as v i , where f and ; are the final and initial pressures, respectively, reached 10%.
- a stirring speed of 250 rpm was maintained throughout the procedure.
- the fluid was warmed to 40-45° C and maintained at that temperature for six hours to completely melt the hydrates formed during the test.
- the fluid was then cooled to the same initial pressure-temperature conditions employed above and duplicate tests was conducted in the same manner as the first.
- the test fluids consisted of 0.5 wt. % aqueous solutions of materials prepared according to the above examples. Each was monitored for hydrate formation in the presence Green Canyon gas (87.2 mol % methane, 7.6 mol % ethane, 3.1 mol % propane, 0.8 mol % n-butane, 0.5 mol % isobutene, 0.4 mol % nitrogen, 0.2 mol % isopentane, 0.2 mol % n-pentane) at an initial pressure of -550 psi and a temperature of 2° C (12° C sub-cooling).
- the % hydrate conversion calculated as detailed above, was plotted as a function of time in hours. ( Figure 1).
- Hydrate inhibitor performance data displayed in Figure 1 indicate that poly(vinyl caprolactam) polymer obtained in Example 4 is a significantly better kinetic gas hydrate inhibitor than the one produced in Comparative Example 1.
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Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
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MX2017012497A MX2017012497A (en) | 2015-09-18 | 2016-08-12 | Improved poly(vinyl caprolactam) kinetic gas hydrate inhibitor and method for preparing the same. |
BR112017020844-0A BR112017020844A2 (en) | 2015-09-18 | 2016-08-12 | kinetic hydrate inhibitor, methods for preparing a kinetic hydrate inhibitor and for inhibiting formation of natural gas hydrates and / or liquid hydrocarbon in a system, and performance chemical and kinetic gas hydrate inhibitor compositions |
CN201680019200.9A CN107429154B (en) | 2015-09-18 | 2016-08-12 | Improved poly (vinyl caprolactam) kinetic gas hydrate inhibitors and methods of making the same |
RU2017133954A RU2722387C2 (en) | 2015-09-18 | 2016-08-12 | Improved kinetics of poly(vinylcaprolactam) inhibitor of formation of gas hydrates and a method for production thereof |
US15/559,852 US10731070B2 (en) | 2015-09-18 | 2016-08-12 | Poly (vinyl carprolactam) kinetic gas hydrate inhibitor and method for preparing the same |
MYPI2017001381A MY194732A (en) | 2015-09-18 | 2016-08-12 | Improved poly(vinyl caprolactam) kinetic gas hydrate inhibitor and method for preparing the same |
AU2016322891A AU2016322891B2 (en) | 2015-09-18 | 2016-08-12 | Improved poly(vinyl caprolactam) kinetic gas hydrate inhibitor and method for preparing the same |
EP16847020.1A EP3350283B1 (en) | 2015-09-18 | 2016-08-12 | Improved poly(vinyl caprolactam) kinetic gas hydrate inhibitor and method for preparing the same |
CA2980007A CA2980007C (en) | 2015-09-18 | 2016-08-12 | Poly(vinyl caprolactam) kinetic gas hydrate inhibitor and method for preparing the same |
SA517390065A SA517390065B1 (en) | 2015-09-18 | 2017-09-30 | Improved poly(vinyl caprolactam) kinetic gas hydrate inhibitor and method for preparing the same |
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US201562220374P | 2015-09-18 | 2015-09-18 | |
US62/220,374 | 2015-09-18 |
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WO2017048424A1 true WO2017048424A1 (en) | 2017-03-23 |
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PCT/US2016/046667 WO2017048424A1 (en) | 2015-09-18 | 2016-08-12 | Improved poly(vinyl caprolactam) kinetic gas hydrate inhibitor and method for preparing the same |
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US (1) | US10731070B2 (en) |
EP (1) | EP3350283B1 (en) |
CN (1) | CN107429154B (en) |
AR (1) | AR106030A1 (en) |
AU (1) | AU2016322891B2 (en) |
BR (1) | BR112017020844A2 (en) |
CA (1) | CA2980007C (en) |
MX (1) | MX2017012497A (en) |
MY (1) | MY194732A (en) |
RU (1) | RU2722387C2 (en) |
SA (1) | SA517390065B1 (en) |
WO (1) | WO2017048424A1 (en) |
Cited By (2)
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WO2023106989A1 (en) | 2021-12-07 | 2023-06-15 | Rise Research Institutes of Sweden AB | Process for preparing lignin ester and lignin oil |
WO2024030389A1 (en) * | 2022-07-31 | 2024-02-08 | Baker Hughes Oilfield Operations Llc | Application of carbonates and their derivatives in formulations for gas hydrate inhibitors |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN111285969A (en) * | 2020-03-06 | 2020-06-16 | 中国科学院广州能源研究所 | Hyperbranched amide hydrate kinetic inhibitor and preparation method and application thereof |
CN115403702B (en) * | 2022-09-01 | 2023-09-26 | 深圳市弘毅海洋智能装备有限公司 | Inhibitor and preparation method and application thereof |
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WO2024030389A1 (en) * | 2022-07-31 | 2024-02-08 | Baker Hughes Oilfield Operations Llc | Application of carbonates and their derivatives in formulations for gas hydrate inhibitors |
Also Published As
Publication number | Publication date |
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CN107429154A (en) | 2017-12-01 |
MX2017012497A (en) | 2018-01-18 |
AU2016322891A1 (en) | 2017-10-05 |
CA2980007A1 (en) | 2017-03-23 |
AR106030A1 (en) | 2017-12-06 |
RU2017133954A (en) | 2019-10-18 |
SA517390065B1 (en) | 2021-04-04 |
RU2017133954A3 (en) | 2020-02-06 |
MY194732A (en) | 2022-12-15 |
RU2722387C2 (en) | 2020-05-29 |
BR112017020844A2 (en) | 2018-07-10 |
CN107429154B (en) | 2020-11-20 |
EP3350283B1 (en) | 2020-01-08 |
CA2980007C (en) | 2023-05-23 |
US20190249069A1 (en) | 2019-08-15 |
US10731070B2 (en) | 2020-08-04 |
EP3350283A4 (en) | 2019-03-27 |
AU2016322891B2 (en) | 2020-02-27 |
EP3350283A1 (en) | 2018-07-25 |
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