MXPA06004614A - Amine-based gas hydrate inhibitors - Google Patents
Amine-based gas hydrate inhibitorsInfo
- Publication number
- MXPA06004614A MXPA06004614A MXPA/A/2006/004614A MXPA06004614A MXPA06004614A MX PA06004614 A MXPA06004614 A MX PA06004614A MX PA06004614 A MXPA06004614 A MX PA06004614A MX PA06004614 A MXPA06004614 A MX PA06004614A
- Authority
- MX
- Mexico
- Prior art keywords
- formula
- alkyl
- coo
- composition according
- alkenyl
- Prior art date
Links
- 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 43
- 150000001412 amines Chemical class 0.000 title claims abstract description 18
- 239000003112 inhibitor Substances 0.000 title claims description 56
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 26
- 125000005263 alkylenediamine group Chemical class 0.000 claims abstract description 10
- 229920000768 polyamine Chemical class 0.000 claims abstract description 6
- 230000002401 inhibitory effect Effects 0.000 claims abstract description 5
- 125000001424 substituent group Chemical group 0.000 claims abstract description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 89
- 239000000203 mixture Substances 0.000 claims description 64
- 125000000217 alkyl group Chemical group 0.000 claims description 53
- -1 2-ethylhexyl Chemical group 0.000 claims description 43
- 150000002430 hydrocarbons Chemical class 0.000 claims description 35
- 125000003342 alkenyl group Chemical group 0.000 claims description 32
- 125000003118 aryl group Chemical group 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 24
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 24
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 24
- 230000002829 reductive effect Effects 0.000 claims description 18
- 229930195733 hydrocarbon Natural products 0.000 claims description 17
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 150000004677 hydrates Chemical class 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 9
- 239000010779 crude oil Substances 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 239000003345 natural gas Substances 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000001488 beta-D-galactosyl group Chemical group C1([C@H](O)[C@@H](O)[C@@H](O)[C@H](O1)CO)* 0.000 claims description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- WTXXSZUATXIAJO-OWBHPGMISA-N (Z)-14-methylpentadec-2-enoic acid Chemical compound CC(CCCCCCCCCC\C=C/C(=O)O)C WTXXSZUATXIAJO-OWBHPGMISA-N 0.000 claims description 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 description 53
- 238000005755 formation reaction Methods 0.000 description 20
- 239000012530 fluid Substances 0.000 description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 5
- 150000001204 N-oxides Chemical class 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- 239000008103 glucose Substances 0.000 description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 240000008042 Zea mays Species 0.000 description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 3
- 150000001350 alkyl halides Chemical class 0.000 description 3
- 235000005822 corn Nutrition 0.000 description 3
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 3
- APTOPAJNUNTEQS-UHFFFAOYSA-N n,n'-didodecyl-n,n'-dimethylethane-1,2-diamine Chemical compound CCCCCCCCCCCCN(C)CCN(C)CCCCCCCCCCCC APTOPAJNUNTEQS-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 235000000346 sugar Nutrition 0.000 description 3
- 239000006188 syrup Substances 0.000 description 3
- 235000020357 syrup Nutrition 0.000 description 3
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 2
- 125000005916 2-methylpentyl group Chemical group 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- 229930091371 Fructose Natural products 0.000 description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 2
- 239000005715 Fructose Substances 0.000 description 2
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 150000002016 disaccharides Chemical class 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- MNQZXJOMYWMBOU-UHFFFAOYSA-N glyceraldehyde Chemical compound OCC(O)C=O MNQZXJOMYWMBOU-UHFFFAOYSA-N 0.000 description 2
- 150000002334 glycols Chemical class 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
- 239000007791 liquid phase Substances 0.000 description 2
- 150000002772 monosaccharides Chemical class 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 150000008163 sugars Chemical class 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical class CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- YQIGLEFUZMIVHU-UHFFFAOYSA-N 2-methyl-n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C(C)=C YQIGLEFUZMIVHU-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
- MXRGSJAOLKBZLU-UHFFFAOYSA-N 3-ethenylazepan-2-one Chemical compound C=CC1CCCCNC1=O MXRGSJAOLKBZLU-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 241001562081 Ikeda Species 0.000 description 1
- 208000007976 Ketosis Diseases 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000004948 alkyl aryl alkyl group Chemical group 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000008121 dextrose Substances 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- FBPFZTCFMRRESA-GUCUJZIJSA-N galactitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-GUCUJZIJSA-N 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 150000002303 glucose derivatives Chemical group 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical class C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical class O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002584 ketoses Chemical class 0.000 description 1
- 239000000832 lactitol Substances 0.000 description 1
- 235000010448 lactitol Nutrition 0.000 description 1
- VQHSOMBJVWLPSR-JVCRWLNRSA-N lactitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@@H]1O[C@H](CO)[C@H](O)[C@H](O)[C@H]1O VQHSOMBJVWLPSR-JVCRWLNRSA-N 0.000 description 1
- 229960003451 lactitol Drugs 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000845 maltitol Substances 0.000 description 1
- 235000010449 maltitol Nutrition 0.000 description 1
- VQHSOMBJVWLPSR-WUJBLJFYSA-N maltitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O VQHSOMBJVWLPSR-WUJBLJFYSA-N 0.000 description 1
- 229940035436 maltitol Drugs 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- NRDCHXHBLQDNIZ-UHFFFAOYSA-N n'-dodecyl-n,n'-dimethylethane-1,2-diamine Chemical compound CCCCCCCCCCCCN(C)CCNC NRDCHXHBLQDNIZ-UHFFFAOYSA-N 0.000 description 1
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- YRVUCYWJQFRCOB-UHFFFAOYSA-N n-butylprop-2-enamide Chemical compound CCCCNC(=O)C=C YRVUCYWJQFRCOB-UHFFFAOYSA-N 0.000 description 1
- HOZLHJIPBBRFGM-UHFFFAOYSA-N n-dodecyl-2-methylprop-2-enamide Chemical compound CCCCCCCCCCCCNC(=O)C(C)=C HOZLHJIPBBRFGM-UHFFFAOYSA-N 0.000 description 1
- PNLUGRYDUHRLOF-UHFFFAOYSA-N n-ethenyl-n-methylacetamide Chemical compound C=CN(C)C(C)=O PNLUGRYDUHRLOF-UHFFFAOYSA-N 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- ZIWDVJPPVMGJGR-UHFFFAOYSA-N n-ethyl-2-methylprop-2-enamide Chemical compound CCNC(=O)C(C)=C ZIWDVJPPVMGJGR-UHFFFAOYSA-N 0.000 description 1
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- CNWVYEGPPMQTKA-UHFFFAOYSA-N n-octadecylprop-2-enamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)C=C CNWVYEGPPMQTKA-UHFFFAOYSA-N 0.000 description 1
- AWGZKFQMWZYCHF-UHFFFAOYSA-N n-octylprop-2-enamide Chemical compound CCCCCCCCNC(=O)C=C AWGZKFQMWZYCHF-UHFFFAOYSA-N 0.000 description 1
- BPCNEKWROYSOLT-UHFFFAOYSA-N n-phenylprop-2-enamide Chemical compound C=CC(=O)NC1=CC=CC=C1 BPCNEKWROYSOLT-UHFFFAOYSA-N 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000005932 reductive alkylation reaction Methods 0.000 description 1
- 238000006268 reductive amination reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- AGDSCTQQXMDDCV-UHFFFAOYSA-M sodium;2-iodoacetate Chemical compound [Na+].[O-]C(=O)CI AGDSCTQQXMDDCV-UHFFFAOYSA-M 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
Abstract
Certain substituted amines, alkylenediamines or polyamines, and derivatives of these, are suitable for use in preventing, inhibiting, or otherwise modifying crystalline gas hydrate formation. The substituents R 1 - R 5 may be hydrocarbyl groups or, in some cases, polyhydroxyalkyl groups or (CH 2 ) p -COO - in which p is either 1 or 2.
Description
HYDRO-BASED GAS HYDRATE INHIBITORS BACKGROUND OF THE INVENTION Lower hydrocarbons such as methane, ethane, propane, n-butane and isobutane are frequently found in crude oil, and are also present in natural gas streams. Water is also among the components typically present in oil-bearing formations. Under conditions of high pressure and reduced temperature, mixtures of water and many lower hydrocarbons tend to form hydrocarbon hydrates known as clathrates. Such hydrates are crystalline structures in which the water has formed a cage structure around a host molecule such as the lower hydrocarbon. For example, at a pressure of about 1 MPa, ethane can form gas hydrates with water at temperatures below 4 ° C; at a pressure of 3 MPa, this can form gas hydrates. with water at temperatures below 14 ° C. Lap temperatures and pressures such as these are commonly found for many environments in which natural gas and crude oil are produced and transported. Gas hydrates are of particular interest because of the blockages in the pipeline that can be produced during the production and transport of natural gas or crude oil. As gas hydrates form and develop inside a pipe or conduit, they can block or damage associated pipe and valves and other equipment. The prevention or inhibition of gas hydrate formation and agglomeration in this way is sought in order to minimize unscheduled stoppages, maintenance and repair, and to provide the safest production operation and / or installation facilities. transport. BRIEF DESCRIPTION OF THE INVENTION In one aspect, the invention provides a composition that includes water, a stream of crude natural gas or stream of crude oil that includes one or more lower hydrocarbons, and at least one compound capable of modifying hydrate formation Of gas. The compound is selected from the group consisting of: a) compounds according to formula (1)
(1) wherein i is selected from the group consisting of branched C4-C18 alkyl, linear alkyl, alkenyl, cycloalkyl, aryl, alkaryl and aralkyl; R 2 is selected from the group consisting of C 1 -C 8 alkyl, alkenyl, cycloalkyl, aryl, alkaryl, aralkyl and portions of the formula (A) (A)
R 3 is C 1 -C 8 alkyl, alkenyl, cycloalkyl, aryl, alkaryl or (CH 2) p ~ COO "wherein p is either 1 or 2, n is an integer from 2 to 14, is an integer of 0 to 2; R 4 is H, aD-glucopyranosyl, β-D-pyranosyl or β-D-galactopyranosyl, and X "is Cl", Br-, I ", OH", CH 3 COO ", 1/2 S04" 2 or 1/3 P04"3, with the proviso that the number of portions X" in formula (1) be reduced by one for each R3 that is (CH2) P-COO "; b) compounds according to formula (2)
(2)
wherein Ri, R2 and n are as defined above in relation to formula (1); c) compounds according to formula (3)
wherein m and R4 are as defined in relation to formula (1), R2 and R3 are each independently selected from the group consisting of C1 to C6 alkyl, alkenyl, aryl or alkylaryl groups, ethyl or propyl groups they carry an alkoxy substituent of Ci to Cie, and cycloalkyl groups of C5 or C6, and wherein R3 can also be H or have a structure according to formula (B)
(B)
wherein Ri is an alkyl group of C3 to Ci2, alkenyl, aryl or alkylaryl; d) compounds according to formula (3b)
wherein my R2-R4 are as defined in relation to formula (3) and R3 may also be (CH2) p-COO "where p is either 1 or 2, wherein Rs is an alkyl group of C? -C8, alkenyl, cycloalkyl, aryl or alkylaryl, and wherein X "is Cl", Br ", I", OH ", CH3COO", 1/2 S04"2 or 1/3 P04" 3, with the proviso that that the number of portions of X "in formula (3b) be reduced by one for each R3 that is (CH2) p-COO ~;
e) compounds according to the formula (4)
(4)
wherein m and R4 are defined as in formula (A) above, each R2 is independently defined as in formula (3) above and may also be of formula (B) above, and n is an integer from 2 to 14; f) compounds according to the formula (5)
(5)
wherein Ri is branched alkyl of C3 -; - C2, linear alkyl, alkenyl, cycloalkyl or branched or linear alkyl substituted with aryl; R2 and R3 with each individually selected from the group consisting of C1-C4 alkyl, benzyl, C3-C5 alkenyl and (CH2) p-COO "; where p is either 1 or 2, with the proviso that no both of R2 and R3 are (CH2) P-COO "; R4 and R5 are independently selected from C2-C6 alkylene; n is an integer from 0 to 4; and X "is Cl", Br ", I", OH ", CH3COO", 1/2 S04"2 or 1/3 P04" 3, with the proviso that the number of X "portions in the formula (5) be reduced by one for each R or R3 that is (CH2) p-C00; g) compounds according to the formula (6)
(6)
wherein i, R2, R4 and R5 are as defined above for formula (5) except that R2 can not be (CH2) p-COO "; h) compounds according to formula (7a)
(7a)
wherein each Ri is independently alkyl of Cj.-C2o or benzyl; R2 is hydrogen or methyl; R3 is C? -C? 8 alkyl; ra is 1 or 2, n is an integer from 2 to 10; and X "is Cl", Br ", I", OH ", CH3COO", 1/2 SO4"2 or 1/3 P04" 3; and i) compounds according to the formula (7b)
2X_ (7b) where Ri, R3, n and X are as defined above for formula (7a). In another aspect, the invention provides a method for modifying the formation of gas hydrate. The method comprises contacting a stream of crude natural gas or stream of crude oil containing water and one or more lower hydrocarbons with at least one compound capable of modifying the formation of gas hydrate selected from groups a) to i) as defined above. In yet another aspect, the invention provides a compound according to formula (7b) as shown above. DETAILED DESCRIPTION OF THE INVENTION The invention provides certain substituted amines, alkylene diamines or polyamines and derivatives thereof, suitable for use in preventing, inhibiting, or otherwise modifying the formation of crystalline gas hydrate. Such modification can, for example, stop, reduce or eliminate the nucleation, growth and / or agglomeration of gas hydrates. A number of classes of compounds are disclosed herein for this use, each of which will now be discussed in detail. As used herein, the term "gas hydrate" means a crystalline hydrate of a lower hydrocarbon.The term "lower hydrocarbon" means any of methane, ethane, propane, any isomer of butane and any isomer of pentane. of gas hydrate inhibitors suitable for use according to the invention consists of certain derivatives, of N, N'-dialkylalkylenediamines as shown in formula (1) below.
(1) In formula (1), Rx is selected from the group consisting of branched alkyl of C 4 -C 8, linear alkyl, alkenyl, cycloalkyl, aryl, alkaryl and aralkyl; R 2 is selected from the group consisting of C 1 -C 8 alkyl, alkenyl, cycloalkyl, aryl, alkaryl, aralkyl and portions of the formula (A)
(TO)
R3 is C?-C8 alkyl, alkenyl, cycloalkyl, aryl, alkaryl or (CH2) p-C00"wherein p is either 1 or 2; n is an integer from 2 to 14; m is a whole number from 0 to 2, R4 is H, aD-glucopyranosyl, β-D-pyranosyl or β-D-galactopyranosyl, and X "is Cl", Br ", I", OH ", CH2C00 ~, 1/2 S04" 2 or 1/3 P04 ~ 3, with the proviso that the number of portions X "of the formula (1) is reduced by one for each R3 that is (CH2) p-C00." The substituents of the formula (A) above, without considering the identity of R4, will be referred to herein as "polyhydroxyalkyl" groups It will be understood by the person of ordinary skill in the art to use the term "2X" in formula (1) and formula 1 (a) it is then proposed to indicate the amount of anion necessary to provide charge neutrality. The groups Rj. Suitable examples include straight chain or branched chain alkyl groups such as n-butyl, 2-butyl, tert-butyl, isobutyl, n-pentyl, 2-pentyl, ter-pentyl, isopentyl, neopentyl, 2-methylpentyl, n-hexyl, isohexyl, heptyl, 2-ethylhexyl, octyl, nonyl,
3, 5-dimethyloctyl, 3,7-dimethyloctyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, 3-methyl-10-ethyldodecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, cocoalkyl
(C8H1-7-C16H33) and tallow (C16H33-C18H37), as well as aralkyl, aryl, alkaryl, alicyclic, bicyclic and similar groups. Examples of such groups are cyclohexylmethyl, benzyl, pinyl, pinylmethyl, phenethyl, p-methylbenzyl, phenyl, tolyl, xylyl, naphthyl, ethylphenyl, methylnaphthyl, dimethylnaphthyl, norbornyl and norbornylmethyl. Suitable exemplary groups R 2 and R include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, tert-butyl, isobutyl, n-pentyl, 2-pentyl, tert-pentyl, isopentyl, neopentyl, methylpentyl, n-hexyl, isohexyl, heptyl, 2-ethylhexyl, octyl, cyclohexylmethyl, benzyl, phenethyl, p-methylbenzyl, phenyl, tolyl, xylyl and ethylphenyl. Suitable exemplary R2 groups also include polyhydroxyalkyl groups such as 1-deoxyglucityl, 2,3-dihydroxypropyl and 1-deoxy analogues groups derived from mannitol, xylitol, galactitol, maltitol and lactitol. The compounds according to formula (1) can be prepared by any method known in the synthetic organic chemistry art. For example, they can be prepared by reacting the corresponding N, N'-di (R?) - N, Nf-di (R2) alkylene diamine with an alkyl halide to introduce the R3 group, according to well-known methods in the chemical technique. In the case where R3 is
(CH2) p-COO ", the reaction with a halocarboxylic acid salt can be used, for example a salt of a haloacetic acid (see, for example, Example 1 of the US Patent No. 3,839,425; from The DuPont de Nemours and Company.) If R2 is a polyhydroxyalkyl group, a number of variations of R2 are possible, depending on the value of R4 and m, to form a variety of compounds according to formula (a) below,
(1a)
The compounds according to formula (la) can be obtained by any suitable method, for example that reported by V.l. Ve sier and collaborators, Zhumal Obshchel Khi il. 50 (9), 2120-2123 (1980). Although any of a variety of polyhydroxyalkyl groups can be incorporated into compounds useful in the practice of the invention, they are more typically derived from the open chain forms of reducing sugars, for example glucose. Exemplary polyhydroxyalkyl groups are glucose derivatives; that is, they are 1-deoxyglucityl groups. In general, polyhydroxyalkyl groups of N- (polyhydroxyalkyl) alkylamines useful for making N, N'-dialkyl-N, N'-bis (polyhydroxyalkyl) alkylenediamines for use according to the invention can be derived from any group of reducing sugars which consist of glucose, fructose, maltose, lactose, galactose, mannose and xylose. Typically, the reducing sugar will be an aldose, although the ketoses can also be used, and both monosaccharides and disaccharides can be used, with convenient sources of the latter including high-dextrose corn syrup, high-content corn syrup. of fructose, high maltose corn syrup. Other useful polyhydroxyalkyl groups can be derivatives of glyceraldehydes. In some embodiments, R 2 is a polyhydroxyalkyl group derived from glucose; that is, the group is 1-deoxyglucityl. In this case, m is 2 and R4 is hydrogen. The second class of gas hydrate inhibitors useful in the practice of this invention include bis N-oxides of the general formula (2)
(2)
where Ri, R2 and n are as defined above in relation to the compounds of the formula (1). The compounds according to formula (2) can be prepared by any method known in the synthetic organic chemistry art. For example, they can be prepared by treating the corresponding di-tertiary amine with an oxidizing agent such as hydrogen peroxide (see, for example, U.S. Patent No. 5,710,332, Example 4, for the preparation of N-N-oxides, N-dialkylglucamines). The case where R2 is a polyhydroxyalkyl group constitutes a subclass of formula (2), shown below as formula (2a), wherein Ri, R4, m and n have the same meanings as defined above in relation to formula (la) .
In one embodiment, the polyhydroxyalkyl group is derived from glucose; that is, the group is 1-deoxyglucityl. In this case, m is 2 and R4 is hydrogen. The third class of gas hydrate inhibitors useful in the practice of this invention include the polyhydroxyalkyl [(di) alkyl] amines according to structure (3). If R is H, the product is a polyhydroxyalkyl [alkyl] amine, and if R3 is an alkyl or substituted alkyl group the product is a polyhydroxyalkyl [dialkyl] amine.
(3)
In (3), m and R4 are as defined in relation to formula (1), and R2 and R3 are each independently selected from the group consisting of Ci to Ci6, alkenyl, aryl or alkylaryl alkyl groups, ethyl or propyl bearing an alkoxy substituent from Ci to Cie, and cycloalkyl groups of C5 or Cß. R3 can also be H, or it can have a structure according to formula (B).
(B)
If R3 is (B), the resulting compound is that shown below by (3a), in which Ri is an alkyl group of C3 to C12, alkenyl, aryl or alkylaryl.
The polyhydroxyalkyl [alkyl] amines, ie the compounds according to formula (3) wherein Rs-H- can be obtained by the standard reductive amination of glucose or other suitable mono- or disaccharide with the desired amine (e.g. , Example 1 of U.S. Patent 5,625,098, to The Procter and Gamble Company). A similar process can also be used for the preparation of polyhydroxyalkyl [dialkyl] amines (3) wherein R3 is a hydrocarbyl group (for example, example 3 of EP 663,389, to BASF). The polyhydroxyalkyl [dialkyl] amines of the formula (3a) can be obtained by treating the corresponding polyhydroxyalkyl [alkyl] amines (structure (3), R3 = H) with a glycidyl ether of the formula shown below, for example using methods such as those described by S. War el, et al., Tenside Surt. Det., 38
The quaternary salts of amines according to structure (3) are also included within the scope of this invention and are represented immediately by structure (3b).
In (3b), and R2-R4 are as defined in relation to formula (3), and R3 can also be (CH2) p-COO "in which p is either 1 or 2. The group R5, which can be introduced by a quaternizing agent is an alkyl group of C? -C8, alkenyl, cycloalkyl, aryl, or alkylaryl, and X "is Cl", Br ", I", OH ", CH3COO", 1/2 SO4" 2 or 1/3 P04"3, with the proviso that the number of portions X" in the formula (3b) is reduced by one for each R3 that is (CH2) p-COO ~. It will be understood by the person of ordinary skill in the art that the use of the term "X" "in formula (3b) is proposed to indicate the amount of anion necessary to provide charge neutrality." Quaternary salts (3b) can be prepared by reacting the corresponding dialkylamine precursor (3) with an alkyl halide (eg, Synthetic Organic Chemistry, RB Wagner and HD Zook, John Wiley and Sons, New York, 1953, page 668) or a haloacetic acid salt (e.g., Example 1 of U.S. Patent 3,839,425; The DuPont of Nemours and Company.) The fourth class of gas hydrate inhibitors useful in the practice of this invention include N, N'-bis (polyhydroxyalkyl) alkylenediamines which they have structure (4), where m and R4 are as defined in relation to formula (a) above, each R2 is independently defined as formula (3) above and can also be of formula (B) as described and n the above, and n is an integer from 2 to 14. In some embodiments of the invention, each of the two groups R2 in structure (4) is different. For example, one can be butyl and one can be octyl. In some embodiments, the product of structure (4) may be a statistical mixture, such as, for example, about 25 mol% of molecules containing two butyl groups, about 25 mol% having two octyl groups, and about 50 mol. % in mol that has one of each.
(4)
In the case where R2 is according to formula (B), the compound according to structure (4) has the structure shown below as formula (4a).
The compounds according to formula (4a) can be prepared by the reaction of compounds according to formula (4), wherein R2 = H, with glycidyl ethers in a manner analogous to that used to prepare polyhydroxyalkyl [dialkyl] amines (3a) Compounds (4) can be obtained by reductive alkylation of the corresponding N, Nr-di (1-deoxyglucityl) alkylenediamine with the appropriate aldehyde, for example as described on pages 4 and 5 of WO 00/076954 of SmithKline Beecham PLC and by ML Fielden, et al., Eur. J. Biochem., 268, 1269-1279 (2000). The preparation of compounds (4a) is discussed and exemplified in U.S. Patent Publication No. 2004/0180970 Al. The fifth class of gas hydrate inhibitors useful in the practice of this invention consists of quaternary derivatives of N, N ' -dialkyl polyalkylene polyamines of the general formula (5).
(5)
In the formula (5), Ri is branched alkyl of C3-C2, linear alkyl, alkenyl, cycloalkyl or branched or linear alkyl substituted with aryl; R and R3 are each individually selected from the group consisting of C1-C4 alkyl, benzyl, C3-C5 alkenyl and (CH2) p-COO ~ in which p is either 1 or 2, with the proviso that not both of R2 and R3 are
(CH2) p-COO "; R4 and 5 are independently selected from C2-C6 alkylene, n is an integer from 0 to 4, and X" is Cl ", Br", I ", OH", CH3COO ", 1/2 S04"2 or 1/3 P04" 3, with the proviso that the number of portions X "in formula (5) be reduced by one for each R2 and R3 that is (CH2) p-COO". It will be understood by the person of ordinary skill in the art that the use of the term "(n + 2) X" "in formula (5) is proposed to indicate the amount of anion necessary to provide charge neutrality. Suitable exemplary Ri groups include straight chain or branched chain alkyl groups such as n-propyl, isopropyl, n-butyl, 2-butyl, tert-butyl, isobutyl, n-pentyl, 2-pentyl, tert-pentyl, isopentyl, neopentyl , 2-methylpentyl, n-hexyl, isohexyl, heptyl, 2-ethylhexyl, octyl, nonyl, 3,5-dimethyloctyl, 3,7-dimethyloctyl, decyl, undecyl and dodecyl, as well as cyclohexylmethyl, benzyl, phenethyl and p-methylbenzyl . Suitable exemplary groups R2 and R3 include ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, tert-butyl, isobutyl and benzyl. In some modalities R and R5 are both
(CH2) 2, (CH2) 3, (CH2) 6 or (CH2) 3CH (CH3) CH2. The compounds according to formula (5) can be prepared by any method known in the synthetic organic chemistry art. For example, they can be prepared by alkylation under conditions known in the art of the corresponding polyamine (6), which in turn can be obtained for example according to the procedures of any of the US Pat. Nos. 4,126,640; 4,195,152 and 6,015,852;
R2 R2 R2 (6)
wherein Ri, R2, R4 and R-s are as defined for formula (5) except that R2 can not be (CH2) p-COO ~. Such alkylation can be carried out, for example, via the reaction with an alkyl halide (see, for example, Synthetic Organic Chemistry, RB Wagner and HD Zook, John Wiley and Sons, New York, 1953, page 668) . The compounds according to the formula (6) by themselves constitute a sixth class of gas hydrate inhibitors suitable for use according to the invention. In some embodiments, R4 and R5 are both (CH2) 2, (CH2) 3, (CH2) 6 or (CH2) 3CH (CH3) CH2. A final class of gas hydrate inhibitors suitable for use in accordance with the invention consist of bis quat derivatives of alkylene diamines, as shown in formulas (7a) and (7b) below. Here, each Ri is independently C? -C20 alkyl or benzyl; R2 is hydrogen or methyl; R3 is C? -C? 8 alkyl; m is 1 or 2; n is an integer from 2 to 10; and X "is Cl", Br ", I", OH ", CH3COO", 1/2 S04"2 or 1/3 P04" 3.
(7a) 2X- (7b)
It will be understood by the person of ordinary skill in the art that the use of the term "2X-" in the formulas (7a) and
(7b) is proposed to indicate the amount of anion necessary to provide charge neutrality. Examples of compounds (7a) have been described in Japanese Patent JP9111660 of Lion Corp., published on April 28, 1997, and by T. Tatsumi, W. Zhang, T. Kida, Y. Nakatsuji, D. Ono, T Takeda e 1. Ikeda in Journal of Surfactants and Detergents. 4, (3), 279-285 (2001). The compounds can be prepared, for example, by reaction of the corresponding tertiary amine with a dialkyl, α-alkylene, under conditions known to those skilled in the art. The inventors believe that the compounds (7b) are new compositions of matter. These can be prepared in a manner analogous to (7a), that is, by the reaction of the corresponding tertiary amine (which can be prepared, for example according to the procedures disclosed in Japanese Patent 2002201165, July 16, 2002 from Kao Corp.) with an α, β-alkylene dihalide. Suitable exemplary Ri groups include straight-chain alkyl groups such as methyl, ethyl, n-propyl and n-butyl, 2-ethylhecyl and benzyl. Suitable R groups include straight chain alkyl, branched chain alkyl or mixed alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, cyclohexyl, n-heptyl, 2-ethylhexyl, n-octyl, isooctyl, n-ninyl, n-decyl, isodecyl, dodecyl, isododecyl, isotridecyl, tetradecyl, mixed octyl / decyl, dodecyl / mixed tetradecyl, tetradecyl / mixed dodecyl, mixed dodecyl / pentadecyl and octadecyl / mixed hexadecyl, and mixed alkyl groups derived from natural sources such as cocoalkyl, oleyl, tallow and stearyl. Suitable values per n include 2, 3, 4 and 6. Use of Gas Hydrate Inhibitors Inhibitors useful in the practice of this invention may provide protection against the formation of gas hydrate either by themselves, or in any mixture desired with any or other inhibitors known in the art, or with solvents or other additives included for purposes other than inhibition of gas hydrate. The desired mixtures can be obtained by mixing prior to introduction to potential hydrate formation fluids, or by simultaneous or sequential introduction to potential hydrate formation fluids. Non-limiting examples of other inhibitors that can be used in combination with the inhibitors of the invention include tertiodynamic inhibitors (including, but not limited to, methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol), kinetic inhibitors
(including, but not limited to homopolymers or copolymers of vinylpyrrolidone, vinylcaprolactam, vinylpyridine, vinylformamide, N-vinyl-N-methylacetamide, acrylamide, methacrylamide, ethacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N-ethylacrylamide, N-isopropylacrylamide , N-butylacrylamide, Nt-butylacrylamide, N-octylacrylamide, Nt-octylacrylamide, N-octadecyl acrylamide, N-phenylacrylamide, N-methylmethacrylamide, N-ethyl methacrylamide, N-isopropylmethacrylamide, N-dodecylmethacrylamide, 1-vinylidexol and l-vinyl-2 -methylvinylimidazole) and agglomeration inhibitors (including, but not limited to, tetralkylammonium salts, tetralquiphosphonium salts, trialkyl acyloxylalkyl ammonium salts, dialkyl diakyloxyalkyl ammonium salts, alkoxylated diamines, trialkylalkyloxyalkyl ammonium salts and trialkylalkylpolyalkoxyalkyl ammonium salts). Exemplary solvents suitable for making formulations containing the gas hydrate inhibitors include the thermodynamic inhibitors mentioned above as well as water, C4-C6 alcohols, C-C6 glycols, C4-C10 ethers, monoalkyl ethers of C-C6. Cß of C2-C6 glycols, C3-C10 esters and C3-C10 ketones. Other additives that can be mixed with the inhibitors of the invention include, but are not limited to, corrosion inhibitors, wax inhibitors, scale inhibitors, asphaltene inhibitors, de-emulsifiers, defoamers and biocides. The amount of gas hydrate inhibitors of the invention in such a mixture can be varied over a range of 1 to 100% by weight, preferably 5 to 50% by weight. It will be appreciated that it is very difficult, if not impossible, to predict a priori dosages or proportions of components that will be effective in inhibiting gas hydrates in a given application. There are a number of interrelated, complex factors that must be taken into account, including, but not limited to, the salinity of the water, the composition of the hydrocarbon stream, the relative amounts of water and hydrocarbon, and the temperature and pressure. For these reasons, dosages and proportions of components are generally optimized through laboratory and field testing for a given application, using techniques well known to those of ordinary skill in the art. Two non-limiting gas hydrate inhibitor formulations, exemplary using the inventive inhibitors are as follows: Typical Gas Hydrate Inhibitor Formulation A 10-30% by weight of Invention Inhibitor 70-90% by weight of Methanol Formulation B of Typical Gas Hydrate Inhibitor 10-30% by weight of Invention Inhibitor 10-30% by weight of polymeric kinetic inhibitor 20-40% by weight of water 20-40% by weight of 2-butoxyethanol The presence of a Gas hydrate inhibitor as described above may result in a reduced proportion and / or a reduced amount of hydrate formation. This may also, or instead, result in a reduction in hydrate crystal size relative to what will be observed in a given environment in the absence of the inhibitor. When added to a combined stream or static mass of water and lower hydrocarbon (s) capable of gas hydrate formation, the compounds described herein may also reduce the tendency of the gas hydrates to agglomerate. This may be of benefit during the production and / or transportation of these hydrocarbons. Methods for such addition are well known in the art, and are disclosed for example in U.S. Patent No. 6,331,508 to Oakulski. The gas hydrate inhibitors are added to a composition comprising water and one or more lower hydrocarbons in an amount that is effective to reduce or modify the formation of gas hydrate. Typically, such hydrate formation occurs at high pressures, generally at least 0.2 MPa, more typically at least 0.5 MPa and more typically at least 1.0 MPa. The inhibitor can be added to a composition containing a lower hydrocarbon before water is added, or vice versa, or a composition can be added which already contains both. The addition can be carried out before the composition is subjected to high pressures or at reduced temperatures, or afterwards. Compositions that can be treated in accordance with the present invention include fluids comprising water and host molecules, in which water and host molecules together can form hydrate hydrates. The fluid mixtures may comprise any or all of gaseous water or organic phase, an aqueous liquid phase and an organic liquid phase, in any proportion. Typical fluids that are treated include crude oil or natural gas streams, for example those that come out of an oil or gas well, particularly an oil or gas well under the sea, where temperatures can be very low and conducive to the formation of gas hydrate. The gas hydrate inhibitors of the present invention can be added to the fluid mixture in a variety of ways, the only requirement is that the additive be efficiently incorporated into the fluid mixture to control hydrate formation. For example, the additive hydrate inhibitor can be mixed in the fluid system, such as in a flow of fluid in flow. Thus, the inhibitor can be injected into a downstream location in a production well to control the formation of hydrate in the fluids that are produced through the well. In the same way, the additive can be injected into the fluid stream produced in a location above the well, or even in the pipeline that extends through an elevator, through which the fluids produced are transported in coastal production operations. outside from the ocean floor to the offshore production facility located at or above the surface of the water. Additionally, the additive can be injected into a mixture of the fluid before the transport of the mixture, for example by way of an underwater pipeline from an offshore production location to a ground collection and / or processing facility. The incorporation of the mixing of the inhibitor into the fluid mixture can be aided by mechanical means such as are well known in the art, including for example the use of a static line mixer in a pipeline. In most pipeline transportation applications, however, sufficient mixing and contact will occur due to the turbulent nature of the fluid flow, and mechanical mixing aids are not necessary. The amount of additive required to effectively inhibit the formation of hydrate in any particular fluid mixture will depend on the composition of that system and the conditions of temperature and pressure at which the fluid mixture will be subjected. Generally, however, the hydrate inhibitor will be added to the fluid mixture to be present in an amount of from about 0.01 to about 5% by weight, and more typically from about 0.01 to about 1% by weight of the water present in the mixture. of fluid. The performance properties of the present inhibitors can be optimized for a specific application by appropriate modification of the structure of the inhibitor and the selection of the substituents Ri, R2, R3, R and R5, the number of repeat units on the groups of bond, and the length of the alkylene groups between the nitrogen atoms. Such optimization is routine, and within the skill of the person of ordinary skill in the art in the particular application area. Thus the manipulation of these variables produces compounds that can find utility as gas hydrate inhibitors in a variety of applications, including, for example, those summarized in the above description. In addition to their activity as gas hydrate inhibitors, the compounds (la), (2a), (3), (3a) (3b), (4) and (4a) of the present invention may exhibit increased biodegradation and lower toxicity aquatic in relation to inhibitors of the previous technique. More generally, the inhibitors of (1), (5), (6), (7a) and (7b) of the present invention, which are diamine or polyamine compounds, may exhibit less aquatic toxicity, relative to some existing inhibitors. . The invention is further illustrated by the following examples, which are presented for purposes of demonstrating, but not limiting the methods and compositions of this invention. EXAMPLES Examples 1-36 describe the preparation of compounds suitable for inhibiting the formation of gas hydrate according to the invention. Examples 37 and 38 describe experiments showing the inhibition of gas hydrate formation by the use of such compounds.
Example 1 illustrates the preparation of N, '-dimethyl-N, N' -dilaurylethylenediamine, an example of an intermediate in the synthesis of the gas hydrate inhibitors of the formula (1). (This is also an example of an inhibitor according to formula (6) in which n = 0). Examples 2-10 illustrate the preparation of other N, '-di (R?) - N, N'-di (R2) alkylenediamines. Examples 1 -10 A 300 mL Autoclave Engineers stainless steel reactor was charged with 72.4 g (0.40 mol) of lauronitrile, 16.8 g (0.19 mol) of N, '-dimethylethylenediamine, 1.45 g (dry basis weight) of a catalyst of 5% palladium on carbon and 48 g of isopropanol. The reactor was closed, purged with nitrogen and hydrogen, and pressurized to approximately 600 psig with hydrogen. The mixture was heated with stirring
(1000 rpm) at 125 ° C, pressurized with hydrogen at 1000 psig and maintained at this temperature and pressure by the regulated hydrogen feed path. After 7 hours, the mixture was cooled to room temperature and the product was removed from the reactor with filtration through a 0.5 μm internal sintered metal element. The analysis of the product by GC (Gas Chromatography) and GC-MS (Gas Chromatography-Mass Spectrometry) indicated that the conversion was completed, and that the product consisted of 98 +% of N, N '-dimethyl-N, N '-dilaurylethylenediamine and only above 1% of N, Nf -dimethyl-N-laurylethylenediamine. Vacuum distillation (190-200 ° C / 80-100 Torr) provided the pure N, N'-dimethyl-N, N'-dilaurylethylenediamine. The additional N, N '-di (Rx) -N, N' -di (R2) alkylenediamines can be prepared and characterized using procedures similar to those described above. Some of these diamines are shown as Examples 2-10 in Table 1.
TABLE 1 Example Ri R2 n 1 C C1122HH2255 C CHH33 2 2 C CsgHHii C C22HH55 2 3 C CßßHHin! C C22HH55 6 4 C C88HH1? 55 C CHH33 2 5 C88HH ?? 55 C CHH33 6 6 C C ?? ooHH22 ?? C CHH33 2 7 C C1122HH2255 C C22HH55 2 Cocoalkyl CH3 2 (C8Hp-Cl6H33) Cocoalkyl C2H5 (C8H17-Ci6H33) 10 Sebo CH3 (C16H33-C18H37) Examples 11-15 illustrate the preparation of a dicoutary salt, an example of the first class of gas hydrate inhibitor, specifically a salt derived from Example 1 of Table 1. Examples 11 -15 To a 250 mL three-necked flask equipped with a magnetic stirrer, reflux condenser, thermometer, septum and nitrogen purge , 20 g (0.0472 mol) of N, N 'dimethyl-N, Nr -laurylethylenediamine and 80 mL of isopropanol were added at room temperature. After the diamine was dissolved, 12.08 g (0.0851 mol) of methyl iodide were added dropwise via syringe through the septum. The mixture was heated with stirring at 50 ° C and kept at temperature for 16 hours. After cooling to room temperature, removal of a solvent under vacuum with a rotary evaporator yielded the N, N, N ', Nf-tetramethyl-N, Nr -dilaurylethylenediamonium diiodide, shown as Example 11 in Table 2. The identity and the purity of the product were determined by NMR analysis. The alkylenediamonium iodides can be prepared and characterized using procedures similar to those in the foregoing. Some of these are shown in Table 2, where X = l in all cases.
0) TABLE 2 E j us Ri Ri R3 n 11 C 2H25 CH3 CH3 2
12 CßHii C2H5 CH3 2 13 C8Hi5 CH3 CH3 2 14 Cocoalkyl CH3 CH3 2 (C8H17-C16? 33) 15 Sebo CH3 CH3 2 (Cl6H33-Cl8H37) Examples 16-20 illustrate the preparation of bis betaine salts, ie, examples of the class (1) of gas hydrate inhibitor where R3 is (CH2) p-COO ", and specifically of Example 16 in Table 3. Examples 16-20 To a 250 mL three-necked flask equipped with a stirrer magnetic, reflux condenser, thermometer and nitrogen purge, 20 g (0.0472 mol) of N, N'-dimethyl-N, N'-dilaurylethylenediamine, 25.54 (0.1180 mol) of sodium iodoacetate, 80 mL of isopropanol and mL of deionized water at room temperature The mixture was heated with stirring at 80 ° C and maintained at that temperature for 4.5 hours After cooling to room temperature, the solvent was removed under vacuum with a rotary evaporator. The addition of isopropanol (approximately 100 mL), vacuum filtration and subsequent removal of isopropanol under vacuum with a rotary evaporator produced an internal N, N'-di (carboxymethyl) -N, N'-dimethyl-dihydroxide salt. Pure N, N '-dilaurylethylenediamonium shown as Example 16 in Table 3. The additional bis betaines can be prepared and characterized using procedures similar to those described in the foregoing. Some of these are shown in Table 3, in which the compounds have the following structure.
TABLE 3 Example i R2 Rs n 16 C 2 H 25 CH 3 CH 2 COO
18 C8Hi5 CH3 CH2COO "2 19 Cocoalkyl CH3 CH2COO ~ 2 (C8Hi7-C16H33) 20 Sebo CH3 CH2COO ~ 2 (C16H33- Examples 21-25 illustrate the preparation of several bis N-oxides, examples of class (2) of inhibitors of gas hydrate in which none of the substituents on any nitrogen is a polyhydroxyalkyl group Examples 21 -25 To a 100 L three-necked flask equipped with a magnetic stirrer, reflux condenser, thermometer, septum and nitrogen purge, 5 g (0.0118 mol) of N, N 'dimethyl-N, N' -laurylethylenediamine and 25 L of isopropanol were added at room temperature The mixture was heated with stirring at 60 ° C after which 3.2 g (0.028 mol; 2.4 eq.) Of 30 wt% aqueous hydrogen peroxide was added dropwise from a syringe The reaction was maintained at 60 ° C for 6 hours After cooling to room temperature, removal of the solvent under vacuum with a rotary evaporator produced N, N '-dimethyl-N, N' -dilauri letile diamine-N, N '-bis (N-oxide), shown as in Example 21 in Table 4. The identity and purity of the product were determined by NMR analysis. Additional alkylene diamine bis (N-oxides) analogs can be prepared and characterized using procedures similar to those described above. Some of these are shown 'in Table 4.
(2)
TABLE 4 Example Ri R2 n 21 C? 2H25 CH3 2
22 CgHi C2H5 2 23 C8Hi5 CH3 2 24 Cocoalkyl CH3 2 (C8Hi7-C16H33) 25 Sebo CH3 2 (C1SH33-Cl8H37) Examples 26-29 illustrate the preparation of several bis N-oxides in which both nitrogen atoms are substituted with polyhydroxyalkyl groups; that is, compounds of subclass (2a). EXAMPLES 26-29 The procedure of Example 21 is repeated with N, N'-dioctyl-N, N'-bis (1-deoxyglucityl) ethylenediamine, with the use of methanol before isopropanol as solvent, to prepare the compounds shown in Table 5, where R4 = H and m and n are both 2. TABLE 5
(2a)
Example Ri 26 C8Hi7 28 C4Hg 29 C12H25 Examples 30-36 illustrate the preparation of compounds (7b). Examples 30-36 To a 250 mL three-necked flask equipped with a magnetic stirrer, reflux condenser, thermometer, septum and nitrogen purge, 21.5 g (0.1 mol) of 3 (2-ethylhexyloxy-1-dimethylaminopropane and 80 mL of isopropanol were added at room temperature.After the diamine was dissolved, 4.95 g (0.05 mol) of 1,2-dichloroethane was added dropwise via syringe through the septum.The mixture was heated with stirring to 50.degree. C and was maintained at that temperature for 16 hours After cooling to room temperature, removal of the solvent under vacuum with a rotary evaporator produced N, N, N, N'-tetramethyl, N, N'-bis dichloride [3- (2-ethyl) hexyloxypropyl] ethylene diammonium, shown as Example 30 in Table 6. The identity and purity of the product were determined by NMR analysis.The additional alkylene diamine chlorides are prepared and characterized using procedures similar to those in the foregoing, and are shown as Examples 31-36 in Table 6.
TABLE 6 Example Ri R3 n 30 CH3 2-ethylhexyl 2 31 CH3 n- C8Hi7 / n- CIQH2I 2 32 CH3 Iso-C? 0H2? 2 34 CH3 C14H29 2 35 CH3 2-ethylhexyl 3 36 CH3 2-ethylhexyl Example 38 illustrates the use of the compounds described herein as gas hydrate inhibitors, with Example 37 being a control sample. Example 37 - Performance Test - Control Sample In this example, 100 mL of salt water (NaCl at
3. 5% by weight) is charged to a 500 cm3 stainless steel autoclave equipped with a turbine agitator. The system is pressurized to 6.5 MPa with methane and the pressure is maintained by the gas supply. The temperature of the autoclave is rapidly reduced at a rate of approximately 5 ° C per hour, at a temperature of 15 ° C. The temperature is then further reduced slowly in controlled aspect at a rate of 1 ° C per hour. Significant hydrate formation occurs at 9 ° C. Example 38 - Performance Test - Use of Inhibitors The operation is the same as in Example 37, but 0.5% by weight, with respect to water, of a gas hydrate inhibitor as described herein is added to the autoclave prior to pressurization with methane. The ratio of nucleation, growth and / or agglomeration of gas hydrates is less than that observed in Control Example 37. Although the invention is illustrated and described herein with reference to specific embodiments, it is not proposed that the appended claims be limited to the details shown. Rather, it is expected that various modifications can be made in these details by those skilled in the art, modifications that are still within the spirit and scope of the subject matter claimed and it is proposed that these claims be considered accordingly.
Claims (34)
- CLAIMS 1. A composition, characterized in that it comprises water, a stream of crude natural gas or stream of crude oil comprising one or more lower hydrocarbons, and at least one compound capable of modifying the formation of gas hydrate selected from the group consisting of of: a) compounds according to the formula (1)(1)wherein Ri is selected from the group consisting of branched alkyl of C 4 -C 8, linear alkyl, alkenyl, cycloalkyl, aryl, alkaryl and aralkyl; R 2 is selected from the group consisting of C 1 -C 8 alkyl, alkenyl, cycloalkyl, aryl, alkaryl, aralkyl and portions of the formula (A)(TO)R 3 is C 1 -C 8 alkyl, alkenyl, cycloalkyl, aryl, alkaryl or (CH 2) p -COO "wherein p is either 1 or 2, n is an integer from 2 to 14, m is a whole number from 0 to 2; R 4 is H, aD-glucopyranosyl, β-D-pyranosyl or β-D-galactopyranosyl, and X "is Cl", Br ", T, OH", CH 3 COO ", 1/2 S04" 2 or 1/3 PO4"3, with the proviso that the number of portions X" in formula (1) be reduced by one for each R3 that is (CH2) P-C00"; b) compounds according to formula (2)(2)wherein Ri, R2 and n are as defined above in relation to formula (1); c) compounds according to formula (3)(3)wherein m and R4 are as defined in relation to formula (1), R2 and R3 are each independently selected from the group consisting of C1 to C6 alkyl, alkenyl, aryl or alkylaryl groups, ethyl or propyl groups they carry an alkoxy substituent from Ci to Cie, and cycloalkyl groups of C5 or C6, and wherein R3 may also be H or have a structure according to formula (B) (B)wherein i is an alkyl group of C3 to C2, alkenyl, aryl or alkylaryl; d) compounds according to formula (3b)(3b)wherein m and R2-R4 are as defined in relation to formula (3) and R3 may also be (CH2) p-COO ~ where p is either 1 or 2; wherein R5 is an alkyl group of C? -C8, alkenyl, cycloalkyl, aryl or alkylaryl; and where X "is Cl", Br ", I", OH ", CH3COO", 1/2 S04 ~ 2 or 1/3 P04"3, with the proviso that the number of X" portions in the formula (3b) is reduced by one for each R3 that is (CH2) P-COO ~; e) compounds according to formula (4)(4)wherein and R4 are defined as in formula (A) above, each R2 is independently defined as in formula (3) above and may also be of formula (B) above, and n is an integer from 2 to 14; f) compounds according to the formula (5)(5)wherein Ri is branched C3-C12 alkyl, linear alkyl, alkenyl, cycloalkyl or branched or linear alkyl substituted with aryl; R2 and R3 with each individually selected from the group consisting of C1-C4 alkyl, benzyl, C3-C5 alkenyl and (CH2) p-COO "; where p is either 1 or 2, with the proviso that no both of R2 and R3 are (CH2) p-COO "; R4 and R5 are independently selected from C-C6 alkylene; n is an integer from 0 to 4; and X "is Cl", Br ", I", OH ", CH3COO", 1/2 SO4"2 or 1/3 P04" 3, with the proviso that the number of X "portions in the formula (5) be reduced by one for each R2 or R3 that is (CH2) p-COO "; g) compounds according to the formula (6)(6) wherein Ri, R2, R4 and R5 are as defined above for formula (5) except that R2 can not be (CH2) p-COO "; h) compounds according to formula (7a)(7a)wherein each Rx is independently C1-C20 alkyl or benzyl; R2 is hydrogen or methyl; R3 is C? -C? 8 alkyl; m is 1 or 2, n is an integer from 2 to 10; and X "is Cl", Br ",I ", OH", CH3COO ", 1/2 S04" 2 or 1/3 P04"3, and i) compounds according to the formula (7b)
- 2 X- (7b)wherein Ri, R3, n and X are as defined above for formula (7a). The composition according to claim 1, characterized in that at least a portion of the water and at least a portion of one or more lower hydrocarbons is in the form of one or more gas hydrates.
- 3. The composition according to claim 1, characterized in that the at least one compound comprises a compound according to the formula (1).
- 4. The composition according to claim 3, characterized in that R2 is a portion of the formula (A).
- 5. The composition according to claim 3, characterized in that R2 is 1-deoxyglucityl.
- 6. The composition according to claim 1, characterized in that at least one compound comprises a compound according to formula (2).
- The composition according to claim 6, characterized in that R2 is a portion of the formula (A).
- 8. The composition according to claim 6, characterized in that R2 is 1-deoxyglucityl.
- 9. The composition according to claim 1, characterized in that the at least one compound comprises a compound according to formula (3).
- 10. The composition according to claim 9, characterized in that R3 is a portion of the formula (B).
- 11. The composition according to claim 9, characterized in that m is 2 and R4 is H.
- 12. The composition according to claim 1, characterized in that the at least one compound comprises a compound according to the formula (3b). ).
- The composition according to claim 12, characterized in that R3 is a portion of the formula (B).
- 14. The composition according to claim 12, characterized in that R3 is (CH) p-COO. "
- 15. The composition according to claim 12, characterized in that m is 2 and R4 is H.
- 16. The composition of compliance with claim 1, characterized in that the at least one compound comprises a compound according to formula (4) 17.
- The composition according to claim 16, characterized in that R2 is a portion of the formula (B).
- The composition according to claim 16, characterized in that m is 2 and R is H.
- The composition according to claim 1, characterized in that the at least one compound comprises a compound according to the formula (5)
- 20. The composition according to claim 19, characterized in that one of R2 and R3 is (CH2) p-COO ".
- 21. The composition according to claim 19, characterized in that R4 and R5 are both (CH2) 2, (CH2) 3, (CH2) 6 or (CH2) 3CH (CH3) CH2.
- 22. The composition according to claim 1, characterized in that the at least one compound comprises a compound according to formula (6).
- 23. The composition according to claim 22, characterized in that R4 and R5 with both (CH2) 2, (CH2) 3, (CH2) 6 or (CH2) 3CH (CH3) CH2.
- 24. The composition according to claim 1, characterized in that the at least one compound comprises a compound according to formula (7a).
- 25. The composition according to claim 24, characterized in that n is 2, 3, 4, 6 or a mixture thereof.
- 26. The composition according to claim 1, characterized in that the at least one compound comprises a compound according to formula (7b).
- 27. The composition according to claim 26, characterized in that n is 2.
- 28. The composition according to claim 26, characterized in that R? it is methyl and R3 is 2-ethylhexyl.
- 29. A method for modifying gas hydrate formation, the method characterized in that it comprises contacting a stream of crude natural gas or stream of crude oil comprising water and one or more lower hydrocarbons with at least one compound capable of modifying the formation of gas hydrate selected from the group consisting of: a) compounds according to formula (1)0) wherein Ri is selected from the group consisting of branched alkyl of C 4 -C 8, linear alkyl, alkenyl, cycloalkyl, aryl, alkaryl and aralkyl; R 2 is selected from the group consisting of C 1 -C 8 alkyl, alkenyl, cycloalkyl, aryl, alkaryl, aralkyl and portions of the formula (A)(A) R3 is C? -C8 alkyl, alkenyl, cycloalkyl, aryl, alkaryl or (CH2) p-COO "where p is either 1 or 2; n is an integer from 2 to 14; m is an integer from 0 to 2, R4 is H, aD-glucopyranosyl, β-D-pyranosyl or β-D-galactopyranosyl, and X "is Cl", Br ", I", OH ", CH3COO", 1/2 SO4"2 or 1/3 PO4" 3, with the proviso that the number of portions X "in formula (1) be reduced by one for each R3 that is (CH2) p-COO"; b) compounds in accordance to the formula (2)(2)wherein Ri, R2 and n are as defined above in relation to formula (1); c) compounds according to formula (3)(3)where m and R4 are as defined in relation to the formula(1), R2 and R3 are each independently selected from the group consisting of Ci to C6 alkyl, alkenyl, aryl or alkylaryl groups, ethyl or propyl groups bearing an alkoxy substituent of Ci to Cie, and cycloalkyl groups of C5 or Cs, and where R3 can also be H or have a structure according to the formula (B)(B)wherein Ri is an alkyl group of C3 to C12, alkenyl, aryl or alkylaryl; d) compounds according to formula (3b)(3b)wherein my R2-R4 are as defined in relation to formula (3) and R3 may also be (CH2) p-COO "where p is either 1 or 2, wherein R5 is an alkyl group of C? -C8, alkenyl, cycloalkyl, aryl or alkylaryl, and wherein X "is Cl", Br ", I", OH ", CH3C00", 1/2 S04 ~ 2 or 1/3 P04"3, with the proviso that that the number of portions of X "in the formula (3b) be reduced by one for each R3 that is (CH2) P-COO ~; e) compounds according to the formula (4)(4) where m and R4 are defined as in formula (A) above, each R2 is independently defined as in formula (3) above and may also be of formula (B) above, and n is an integer of 2 to 14; f) compounds according to the formula (5)Ri -Ri N + / / \ -H / ^ \ n / \ - 1"+2> X 'Rg R3 Rg 3 R2 R3(5)wherein Ri is branched alkyl of C3-C2, linear alkyl, alkenyl, cycloalkyl or branched or linear alkyl substituted with aryl; R2 and R3 with each individually selected from the group consisting of C? -C alkyl, benzyl, C3-Cs alkenyl and (CH2) p-COO "; where p is either 1 or 2, with the proviso that not both R2 and R3 are (CH2) p-COO "; R4 and R5 are independently selected from C2-Cß alkylene; n is an integer from 0 to 4; and X "is Cl", Br ", I", OH ", CH3COO", 1/2 SO4"2 or 1/3 P04" 3, with the proviso that the number of X "portions in the formula (5) be reduced by one for each R2 or R3 that is (CH2) p-COO "; g) compounds according to the formula (6)(6) where Ri, R2, R4 and s are as defined above for formula (5) except that R2 can not be (CH) p-COO "; h) compounds according to formula (7a)wherein each Ri is independently C 1 -C 20 alkyl or benzyl; R2 is hydrogen or methyl; R3 is C? -C? 8 alkyl; m is 1 or 2, n is an integer from 2 to 10; and X "is Cl ', Br",I ", OH", CH3COO ", 1/2 S0 ~ 2 or 1/3 P04" 3; and i) compounds according to the formula (7b)2 X-(7b)wherein R 1 R 3, n and X are as defined above for formula (7a).
- 30. The method according to claim 29, characterized in that the at least one compound comprises a compound according to formula (3).
- 31. The method according to claim 29, characterized in that the at least one compound comprises a compound according to formula (4).
- 32. A compound according to the formula (7b)2X- (7b)characterized in that Ri is C1-C20 alkyl or benzyl; R is C? -C? 8 alkyl; m is 1 or 2; n is an integer from 2 to 10; and X "is Cl", Br ", I", OH ", CH3C00", 1/2 S04"2 or 1/3 P04" 3.
- 33. The compound according to claim 32, characterized in that R3 is 2-ethylhexyl.
- 34. The compound according to claim 32, characterized in that Ri is methyl.SUMMARY. INVENTION Certain substituted amines, alkylene diamines or polyamines and derivatives thereof, are suitable for use in preventing, inhibiting or otherwise modifying the formation of crystalline gas hydrate. These inhibitors include compounds from any of the following groupsd) (2)(4) (5) (6)(7a)2 X- (7b)The substituents R1-R5 can be hydrocarbyl groups or, in some cases, polyhydroxyalkyl groups or (CH2) p-COO ~ in which p is either 1 or 2.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11114274 | 2005-04-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| MXPA06004614A true MXPA06004614A (en) | 2006-12-13 |
Family
ID=
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7452848B2 (en) | Amine-based gas hydrate inhibitors | |
| US8821754B2 (en) | Additive for preserving the fluidity of fluids containing gas hydrates | |
| EP1676831B1 (en) | N,N-dialkylpolyhydroxyalkylamines | |
| CA2535675A1 (en) | Polyamine-based corrosion inhibitors | |
| US8833450B2 (en) | Nitrogen containing compounds as corrosion inhibitors | |
| US11542427B2 (en) | Corrosion inhibitor compositions and methods of use in acid stimulation operations | |
| DK2683849T3 (en) | QUARTERLY AMMONIUM COMPOSITION TO INHIBIT CORROSION | |
| NO328094B1 (en) | Use of an inhibitor and additives to inhibit gas hydrate formation | |
| RU2439120C2 (en) | Additive for preserving fluidity of fluids containing gaseous hydrates | |
| CA3039069C (en) | Hydroxyalkylurethane kinetic hydrate inhibitors | |
| US20040163307A1 (en) | Corrosion and gas hydrate inhibitors having improved water solubility and increased biodegradability | |
| CA3129073A1 (en) | Multifunctional additive compounds | |
| MXPA06004614A (en) | Amine-based gas hydrate inhibitors | |
| WO2021115974A1 (en) | A method of and a composition for controlling gas hydrate blockage through the addition of a synergistically acting blend with n-alkanoyl-polyhydroxyalkylamines | |
| RU2298555C1 (en) | Oxyethylated alkyl- (or phenol)methyl- or ethyl phosphites of n-methyl- or ethylalkylammonium as corrosion inhibitors possessing bactericidal activity with respect to sulfate-reducing microorganisms | |
| NO20191199A1 (en) | Method for inhibiting the agglomeration of gas hydrates | |
| AU5368100A (en) | Corrosion inhibition |