CN114349608A - Alcohol ether compound and process for producing the same - Google Patents
Alcohol ether compound and process for producing the same Download PDFInfo
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- CN114349608A CN114349608A CN202111674884.5A CN202111674884A CN114349608A CN 114349608 A CN114349608 A CN 114349608A CN 202111674884 A CN202111674884 A CN 202111674884A CN 114349608 A CN114349608 A CN 114349608A
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- Prior art keywords
- alcohol ether
- aluminum
- alcohol
- acid
- compound
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- -1 Alcohol ether compound Chemical class 0.000 title claims abstract description 142
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 32
- 230000008569 process Effects 0.000 title abstract description 23
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000002808 molecular sieve Substances 0.000 claims abstract description 35
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000002253 acid Substances 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 238000006266 etherification reaction Methods 0.000 claims abstract description 26
- 239000007800 oxidant agent Substances 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000001590 oxidative effect Effects 0.000 claims abstract description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 20
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 14
- 230000009471 action Effects 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 43
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 32
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 23
- 229910052719 titanium Inorganic materials 0.000 claims description 23
- 239000010936 titanium Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 6
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 6
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 6
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 6
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 5
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 4
- 238000004537 pulping Methods 0.000 claims description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims description 3
- 229910015900 BF3 Inorganic materials 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- FGGJBCRKSVGDPO-UHFFFAOYSA-N hydroperoxycyclohexane Chemical compound OOC1CCCCC1 FGGJBCRKSVGDPO-UHFFFAOYSA-N 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- CZPZWMPYEINMCF-UHFFFAOYSA-N propaneperoxoic acid Chemical compound CCC(=O)OO CZPZWMPYEINMCF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 3
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
- 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 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 abstract description 52
- 150000001875 compounds Chemical class 0.000 abstract description 17
- 238000002360 preparation method Methods 0.000 abstract description 10
- 230000001105 regulatory effect Effects 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 5
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001336 alkenes Chemical class 0.000 description 42
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 35
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 25
- YTTFFPATQICAQN-UHFFFAOYSA-N 2-methoxypropan-1-ol Chemical class COC(C)CO YTTFFPATQICAQN-UHFFFAOYSA-N 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 7
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([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
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- BWPAALSUQKGDBR-UHFFFAOYSA-N 1-hexoxypropan-2-ol Chemical compound CCCCCCOCC(C)O BWPAALSUQKGDBR-UHFFFAOYSA-N 0.000 description 2
- 125000004917 3-methyl-2-butyl group Chemical group CC(C(C)*)C 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 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 2
- 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 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- WGKZYJXRTIPTCV-UHFFFAOYSA-N 2-butoxypropan-1-ol Chemical class CCCCOC(C)CO WGKZYJXRTIPTCV-UHFFFAOYSA-N 0.000 description 1
- UPGSWASWQBLSKZ-UHFFFAOYSA-N 2-hexoxyethanol Chemical compound CCCCCCOCCO UPGSWASWQBLSKZ-UHFFFAOYSA-N 0.000 description 1
- 125000004398 2-methyl-2-butyl group Chemical group CC(C)(CC)* 0.000 description 1
- 125000004918 2-methyl-2-pentyl group Chemical group CC(C)(CCC)* 0.000 description 1
- 125000004922 2-methyl-3-pentyl group Chemical group CC(C)C(CC)* 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- 125000004919 3-methyl-2-pentyl group Chemical group CC(C(C)*)CC 0.000 description 1
- 125000004921 3-methyl-3-pentyl group Chemical group CC(CC)(CC)* 0.000 description 1
- 125000004920 4-methyl-2-pentyl group Chemical group CC(CC(C)*)C 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 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 1
- 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 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of an alcohol ether compound. In the preparation method of the alcohol ether compound, an alcohol compound shown in a formula (1), an olefin compound shown in a formula (2) and an oxidant are subjected to oxidation reaction and etherification reaction under the action of a catalyst to obtain alcohol ether compounds with structures shown in the formulae (3) and (4); wherein the catalyst is an acid modified titanium silicon aluminum molecular sieve, which can improve the selectivity of alcohol ether compounds, and because the acid modified titanium silicon aluminum molecular sieve increases the acid active center, when the olefin compound contains three or more carbon atoms, the selectivity of isomers in the etherification reaction process can be regulated, so that R in the alcohol compounds1The moieties tend to be linked to ether linkages, thereby modulating the composition of the isomers, e.g. when the olefinic compound isWhen propylene is used, not only the selectivity of the alcohol ether compound is improved, but also the regioselectivity of the isomer 1-methoxy-2-propanol is improved.
Description
Technical Field
The invention relates to the technical field of compound synthesis, in particular to a preparation method of an alcohol ether compound.
Background
Alcohol ether compounds are a class of solvents having oxygen-containing functional groups, which may be hydroxyl and ether linkages, including alcohols and ether compounds such as ethylene glycol, ethylene glycol ethers, propylene glycol ethers, and other lower alcohols or lower alcohol ethers. The alcohol ether compound has ether bond and hydroxyl, the former has lipophilicity and can dissolve hydrophobic compound, the latter has hydrophilicity and can dissolve water-soluble compound. Therefore, the alcohol ether compound is widely applied as a good solvent of oil-soluble paint, can improve the leveling property of a paint film, has good intermiscibility with water, and can be used as a cosolvent of water-based paint.
At present, the industrial production of alcohol ether compounds is mainly prepared by carrying out alkoxy ring-opening etherification reaction on alcohol and epoxy monomers, but the synthesis process of the epoxy monomer is complex, so that the process of the process method is complex and the cost is high. Therefore, the technical personnel propose to directly prepare the alcohol ether compound by one-pot reaction of alcohol and olefin under the action of an oxidant. However, in the conventional process for directly preparing an alcohol ether compound by using an alcohol and an olefin under the action of an oxidant, during the reaction process, the olefin compound is converted into alcohol ether compounds such as a mono-alcohol ether compound and a diol compound, and meanwhile, complicated side reactions are also accompanied, so that the alcohol ether compound has low selectivity and low yield. More importantly, during the process of converting the olefin containing three carbon atoms and more into the alcohol ether compound by the reaction with the alcohol, isomers can be generated, and the isomers with different structures have different purposes and economic benefits. For example, when methanol and propylene are used for preparing alcohol ether compounds comprising propylene glycol monomethyl ether and propylene glycol, the main product of the alcohol ether compounds, namely propylene glycol monomethyl ether, comprises two isomers of 1-methoxy-2-propanol and 2-methoxy-1-propanol, and compared with 2-methoxy-1-propanol, the 1-methoxy-2-propanol has lower biological toxicity and is more beneficial to application, so that the price of the 1-methoxy-2-propanol is higher than that of the 2-methoxy-1-propanol, and the economic benefit is greater. However, in the conventional method for directly preparing the alcohol ether compound by using the alcohol and the olefin under the action of the oxidant, the regioselectivity of different isomers is difficult to control.
Thus, the prior art remains to be improved.
Disclosure of Invention
Based on the method, the invention provides the preparation method of the alcohol ether compound, which can improve the selectivity of the alcohol ether compound and regulate and control the isomer composition of the alcohol ether compound.
The technical scheme of the invention is as follows.
In one aspect of the present invention, there is provided a method for preparing an alcohol ether compound, comprising the steps of:
carrying out oxidation reaction and etherification reaction on an alcohol compound shown in a formula (1), an olefin compound shown in a formula (2) and an oxidant under the action of a catalyst to obtain alcohol ether compounds with structures shown in the formulae (3) and (4);
R1-OH (1)，CH2＝CHR2 (2)，
wherein R is1And R2Each independently selected from H or alkyl with 1-8 carbon atoms:
the catalyst is an acid modified titanium-silicon-aluminum molecular sieve.
In some of the embodiments, the ratio of the amounts of the alcohol compound, the olefin compound and the oxidant is (4-8): 1: (1.5-4).
In some embodiments, the temperature of the oxidation reaction and the etherification reaction is 40 ℃ to 100 ℃ and the pressure is 2MP to 4 MP; and/or
The oxidant is at least one selected from hydrogen peroxide, tert-butyl hydroperoxide, cumyl peroxide, cyclohexyl hydroperoxide, peroxyacetic acid and peroxypropionic acid.
In some of the embodiments, the alcohol compound is selected from any one of water, methanol, ethanol, propanol, butanol, t-butanol, pentanol, hexanol, heptanol, and octanol; and/or
The olefin compound is any one selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene and 1-octene.
In some of these embodiments, the method of making the acid-modified titanium silicalite molecular sieve comprises the steps of:
mixing and pulping a titanium silicalite molecular sieve and organic acid, and carrying out first heat treatment to obtain a first solid;
and mixing the first solid, an aluminum source, a titanium source, a silicon source, an acid source and water, carrying out second heat treatment, and then roasting to obtain the acid modified titanium-silicon-aluminum molecular sieve.
In some of these embodiments, the mass ratio of the first solid, the aluminum source, the titanium source, the silicon source, the acid source, and the water is 100: (0.05-7): (0.05-7): (0.05-7): (1-50): (100-1000).
In some of these embodiments, the acid source is selected from at least one of fluoroboric acid, boron trifluoride, aluminum trichloride, and boron trifluoride etherate; and/or
The aluminum source is selected from at least one of aluminum sol, aluminum salt, aluminum hydroxide, aluminum sulfate, sodium metaaluminate, aluminum chloride, aluminum nitrate and aluminum oxide; and/or
The titanium source is selected from at least one of isopropyl titanate, n-propyl titanate and tetraethyl titanate; and/or
The silicon source is at least one of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and butyl orthosilicate.
In some embodiments, the temperature of the first heat treatment is 50-150 ℃ and the time is 10-30 h; and/or
The temperature of the second heat treatment is 10-200 ℃, and the time is 5-20 h; and/or
The roasting temperature is 150-250 ℃, and the roasting time is 1-10 h.
In some of these embodiments, the step of performing the oxidation reaction and the etherification reaction comprises the steps of:
and (2) placing the catalyst in a reactor to form a catalyst bed layer, then conveying the alcohol compound, the olefin compound and the oxidant into the reactor to contact with the catalyst bed layer, and continuously carrying out the oxidation reaction and the etherification reaction.
In some of the embodiments, the reaction space velocity of the oxidation reaction and the etherification reaction is 2h-1～5h-1。
In the preparation method of the alcohol ether compound, the alcohol compound shown in the formula (1), the olefin compound shown in the formula (2) and an oxidant are subjected to oxidation reaction and etherification reaction under the action of a catalyst to obtain the alcohol ether compound comprising the mono-alcohol ether compound shown in the formula (3) and the glycol compound shown in the formula (4); the catalyst is an acid modified titanium-silicon-aluminum molecular sieve, so that the selectivity of converting an olefin compound into an alcohol ether compound can be improved, and the acid modified titanium-silicon-aluminum molecular sieve increases an acid active center, so that when the olefin compound contains three or more carbon atoms, the selectivity of an isomer in the etherification reaction process can be regulated, the formed ether bond tends to be connected with the carbon atom with a smaller substituent group, and the composition of the isomer is regulated, for example, when the olefin compound is propylene, the selectivity of converting the olefin compound into the alcohol ether compound is improved, and the regioselectivity of the isomer 1-methoxy-2-propanol is improved.
Further, the ratio of the amounts of the alcohol compound, the olefin compound and the oxidant is regulated to further improve the selectivity of the alcohol ether compound and the regioselectivity of its isomer.
Further, the catalyst is placed in a reactor to form a catalyst bed layer, then the alcohol compound, the olefin compound and the oxidant are conveyed into the reactor to contact with the catalyst bed layer, and the oxidation reaction and the etherification reaction are continuously carried out.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
As used herein, the term "alkyl" refers to a monovalent residue resulting from the loss of one hydrogen atom from a saturated hydrocarbon containing a primary (normal) carbon atom, or a secondary carbon atom, or a tertiary carbon atom, or a quaternary carbon atom, or a combination thereof. The phrase including the term, for example, "C1-8 alkyl" which is an alkyl group having 1-8 carbon atoms means an alkyl group having 1-8 carbon atoms, and at each occurrence, may be independently C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, or C8 alkyl.
Suitable examples include, but are not limited to: methyl (Me, -CH)3) Ethyl (Et-CH)2CH3) 1-propyl (n-Pr, n-propyl, -CH)2CH2CH3) 2-propyl (i-Pr, i-propyl, -CH (CH)3)2) 1-butyl (n-Bu, n-butyl, -CH)2CH2CH2CH3) 2-methyl-1-propyl (i-Bu, i-butyl, -CH)2CH(CH3)2) 2-butyl (s-Bu, s-butyl, -CH (CH)3)CH2CH3) 2-methyl-2-propyl (t-Bu, t-butyl, -C (CH)3)3) 1-pentyl (n-pentyl, -CH)2CH2CH2CH2CH3) 2-pentyl (-CH (CH)3)CH2CH2CH3) 3-pentyl (-CH (CH)2CH3)2) 2-methyl-2-butyl (-C (CH)3)2CH2CH3) 3-methyl-2-butyl(-CH(CH3)CH(CH3)2) 3-methyl-1-butyl (-CH)2CH2CH(CH3)2) 2-methyl-1-butyl (-CH)2CH(CH3)CH2CH3) 1-hexyl (-CH)2CH2CH2CH2CH2CH3) 2-hexyl (-CH (CH)3)CH2CH2CH2CH3) 3-hexyl (-CH (CH)2CH3)(CH2CH2CH3) 2-methyl-2-pentyl (-C (CH))3)2CH2CH2CH3) 3-methyl-2-pentyl (-CH (CH)3)CH(CH3)CH2CH3) 4-methyl-2-pentyl (-CH (CH)3)CH2CH(CH3)2), 3-methyl-3-pentyl (-C (CH)3)(CH2CH3)2) 2-methyl-3-pentyl (-CH (CH)2CH3)CH(CH3)2)2, 3-dimethyl-2-butyl (-C (CH)3)2CH(CH3)2) 3, 3-dimethyl-2-butyl (-CH (CH)3)C(CH3)3And octyl (- (CH)2)7CH3)。
Alcohol and olefin react under the action of an oxidant, the olefin can be converted to obtain corresponding alcohol ether compounds such as glycol compounds and mono-alcohol ether compounds, and isomers can be generated in the process of converting the olefin containing three carbon atoms or more into the alcohol ether compounds through the reaction of the olefin and the alcohol, and the isomers with different structures have different purposes and economic benefits. For example, propylene glycol monomethyl ether prepared from methanol and propylene has two isomers of 1-methoxy-2-propanol and 2-methoxy-1-propanol, and compared with 2-methoxy-1-propanol, the 1-methoxy-2-propanol has lower biotoxicity, so that the price difference between the 1-methoxy-2-propanol and the 2-methoxy-1-propanol is huge, the market price of the 1-methoxy-2-propanol reaches 12500 yuan/ton, and the market price of the 2-methoxy-1-propanol is only 5500 yuan/ton, so that the benefit influence is great.
The traditional method for directly preparing the alcohol ether compound by adopting alcohol and olefin under the action of an oxidant is difficult to control the selectivity of different isomers. Based on this, the skilled person further has discovered, by chance, when conducting extensive studies on the reaction mechanism involved in the preparation of alcohol ether compounds: in the process of preparing the alcohol ether compound by taking an alcohol compound and olefin as raw materials and acting an oxidant through a one-step method, the acid-modified titanium-silicon-aluminum molecular sieve is used as a catalyst, so that the selectivity of the alcohol ether compound can be effectively improved, the selectivity of isomers can be regulated, and the alcohol ether compound preparation method is obtained after a large number of experimental researches.
An embodiment of the present invention provides a method for preparing an alcohol ether compound, including the following step S10.
Step S10, carrying out oxidation reaction and etherification reaction on the alcohol compound shown in the formula (1), the olefin compound shown in the formula (2) and an oxidant under the action of a catalyst to obtain alcohol ether compounds with structures shown in the formulas (3) and (4);
R1-OH(1)，CH2＝CHR2(2)，
wherein R is1And R2Each independently selected from H or alkyl with 1-8 carbon atoms:
the catalyst is an acid modified titanium-silicon-aluminum molecular sieve.
In the preparation method of the alcohol ether compound, the alcohol compound shown in the formula (1), the olefin compound shown in the formula (2) and an oxidant are subjected to oxidation reaction and etherification reaction under the action of a catalyst to obtain the alcohol ether compound comprising the mono-alcohol ether compound shown in the formula (3) and the glycol compound shown in the formula (4); the catalyst is an acid modified titanium-silicon-aluminum molecular sieve, which can improve the selectivity of converting an olefin compound into an alcohol ether compound, and the acid modified titanium-silicon-aluminum molecular sieve increases an acid active center, so that when the olefin compound contains three or more carbon atoms, the selectivity of an isomer in the etherification reaction process can be regulated, the formed ether bond tends to be connected with the carbon atom with a smaller substituent group, and the composition of the isomer is regulated, for example, when the olefin compound is propylene, the selectivity of the alcohol ether compound is improved, and the regioselectivity of the isomer 1-methoxy-2-propanol is improved.
It should be noted that since water molecules contain hydroxyl groups, they can be theoretically regarded as alcohols in the art.
It can be understood that when R in formula (1)1When the compound is H, the compound shown in the formula (1) is water, and the products obtained by the reaction have the same structures shown in the formula (3) and the formula (4); in other words, when R in the formula (1)1When the compound is H, i.e. the compound represented by the formula (1) is water, the olefin is converted into a diol compound.
In some embodiments, the ratio of the amounts of the alcohol compound, the olefin compound and the oxidant is (4-8): 1: (1.5-4).
Further, the ratio of the amounts of the alcohol compound, the olefin compound and the oxidizing agent is controlled to further improve the selectivity of the alcohol ether compound and the selectivity of its isomer, so that the formed ether bond tends to be connected to a carbon atom having a smaller substituent group. For example, when the olefin compound is propylene, the regioselectivity of the isomer 1-methoxy-2-propanol is further improved.
In some of these embodiments, the oxidation and etherification reactions are carried out at temperatures of 40 ℃ to 100 ℃ and pressures of 2MP to 4 MP.
In some of these embodiments, the oxidizing agent is selected from at least one of hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, cyclohexyl hydroperoxide, peroxyacetic acid, and peroxypropionic acid.
In some of these embodiments, the oxidizing agent is added as an aqueous solution thereof in step S10.
Further, the oxidizing agent is hydrogen peroxide; further, it is added in the form of an aqueous hydrogen peroxide solution having a concentration of 27.5 to 35 wt%.
In some embodiments, the alcohol compound is selected from any one of water, methanol, ethanol, propanol, butanol, t-butanol, pentanol, hexanol, heptanol, and octanol.
In some of whichIn (1), the above R2Selected from alkyl with 2-8 carbon atoms.
In other words, the olefin compound contains three or more carbon atoms, and the substituents on both sides of the double bond have different volumes, and isomers are formed during the subsequent etherification reaction.
In some of these embodiments, the olefin is selected from any one of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene.
In some embodiments, the preparation method of the modified titanium-silicon-aluminum molecular sieve comprises the following steps of S11-S12.
And step S11, mixing and pulping the titanium silicalite molecular sieve and organic acid, and carrying out first heat treatment to obtain a first solid.
And step S12, mixing the first solid, the aluminum source, the titanium source, the silicon source, the acid source and water, carrying out second heat treatment, and then roasting to obtain the acid modified titanium-silicon-aluminum molecular sieve.
The active component of the titanium-silicon molecular sieve is modified by adopting an acid source to form an acid active center at the catalytic active center of titanium-silicon-aluminum so as to further improve the selectivity of the alcohol ether compound, and the acid active center is increased by the acid modified titanium-silicon-aluminum molecular sieve, so that when an olefin compound contains three or more carbon atoms, the selectivity of an isomer in the etherification reaction process can be regulated, the formed ether bond tends to be connected with the carbon atom with a smaller substituent group, and the composition of the isomer is regulated.
In some of these embodiments, the first solid has a relative crystallinity of 70% to 90%.
In some of the embodiments, in step S11, the above titanium silicalite molecular sieve is selected from at least one of a MFI structure titanium silicalite molecular sieve, a MEL structure titanium silicalite molecular sieve, a BEA structure titanium silicalite molecular sieve, a MWW structure titanium silicalite molecular sieve, an MOR structure titanium silicalite molecular sieve, a TUN structure titanium silicalite molecular sieve, and a two-dimensional hexagonal structure titanium silicalite molecular sieve.
In some embodiments, the mass ratio of the first solid, the aluminum source, the titanium source, the silicon source, the acid source, and the water is 100: (0.05-7): (0.05-7): (0.05-7): (1-50): (100-1000).
In some of these embodiments, the organic acid is selected from at least one of citric acid, malic acid, tartaric acid, oxalic acid, acetic acid, and sulfonic acid.
In some embodiments, the mass ratio of the titanium silicalite molecular sieve to the organic acid is (0.01-0.5): 1.
In some of these embodiments, the acid source is selected from at least one of fluoroboric acid, boron trifluoride, aluminum trichloride, and boron trifluoride etherate.
In some of these embodiments, the aluminum source is selected from at least one of aluminum sol, aluminum salt, aluminum hydroxide, aluminum sulfate, sodium metaaluminate, aluminum chloride, aluminum nitrate, and aluminum oxide.
In some of these embodiments, the titanium source is selected from at least one of isopropyl titanate, n-propyl titanate, and tetraethyl titanate.
In some embodiments, the silicon source is at least one of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, and butyl orthosilicate.
In some embodiments, the temperature of the first heat treatment is 50-150 ℃ and the time is 10-30 h.
In some embodiments, the temperature of the second heat treatment is 100 ℃ to 200 ℃ and the time is 5h to 20 h.
In some embodiments, the roasting temperature is 150-250 ℃ and the roasting time is 1-10 h.
In some embodiments, the step of performing the oxidation reaction and the etherification reaction comprises the steps of:
and (2) placing the catalyst in a reactor to form a catalyst bed layer, then conveying the alcohol compound, the olefin compound and the oxidant into the reactor to contact with the catalyst bed layer, and continuously carrying out oxidation reaction and etherification reaction.
Thus, the method can continuously carry out oxidation reaction and etherification reaction, and has simple and feasible process, environmental protection, high catalytic efficiency and high selectivity.
And further, discharging the reacted product from the top of the reactor, cooling the product by a cooler, removing olefin after cooling, performing gas-liquid separation, circularly pressurizing and liquefying the olefin in the gas phase for reuse, and rectifying the mixed liquid in the liquid phase to obtain corresponding alcohol ether compound products respectively. Simple process, environmental protection, high catalytic efficiency, and good safety and environmental benefits.
In some embodiments, the reaction space velocity of the oxidation reaction and the etherification reaction is 2h-1～5h-1。
While the present invention will be described with respect to particular embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but is intended to cover by the appended claims the scope of the invention, and that certain changes in the embodiments of the invention will be suggested to those skilled in the art and are intended to be covered by the appended claims.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
(1) The prepared modified titanium-silicon-aluminum molecular sieve is placed in a fixed bed to react and is arranged in a fixed bed tubular reactor with the diameter of 2cm and the length of 60cm, and the volume of a catalyst bed layer is 13cm2The apparatus was then purged with nitrogen.
The preparation process of the modified titanium-silicon-aluminum molecular sieve comprises the following steps:
mixing and pulping an MFI structure titanium silicalite molecular sieve and sulfonic acid according to the mass ratio of 0.2 to 1 at the normal temperature of 25 ℃ and under the normal pressure, carrying out heat treatment on the obtained slurry at 80 ℃ for 20 hours, and carrying out solid-liquid separation to obtain a first solid with the relative crystallinity of 80%.
Mixing a first solid with an aluminum source (aluminum sol, 20 wt%), titanium source n-propyl titanate, silicon source methyl orthosilicate, acid source fluoboric acid and water according to a mass ratio of 100: 3: 5: 5: 20: 500 is put into a stainless steel sealed reaction kettle, the second heat treatment is carried out for 15h at the temperature of 150 ℃, the obtained solution is dried for 2h at the temperature of 200 ℃ after discharging, and finally the solution is roasted for 6h at the temperature of 500 ℃, thus obtaining the acid modified titanium-silicon-aluminum molecular sieve.
(2) Methanol, hydrogen peroxide and ethylene are mixed according to the mol ratio of 41: 2 (hydrogen peroxide is provided by 30 wt% of aqueous hydrogen peroxide solution) is fed into a reactor for continuous reaction, the reaction is carried out at the temperature of 60 ℃ and the pressure of 2.5MPa, and the space velocity of the reaction is 2h-1. And obtaining a reaction product after the reaction is finished.
(3) The prepared reaction product is subjected to gas chromatography detection, and the ethylene conversion rate and the selectivity of the alcohol ether compound, namely ethylene glycol monomethyl ether and ethylene glycol, are calculated according to the following modes.
Olefin conversion ═ (moles of olefin feed-moles of olefin in reaction product)/moles of olefin feed 100%
Ethylene glycol monomethyl ether selectivity ═ ethylene glycol monomethyl ether mole/(moles of olefin feed-moles of olefins in reaction product) × 100%
Ethylene glycol selectivity ═ ethylene glycol moles/(moles of olefin feed-moles of olefin in reaction product) × 100%
The results show that: the conversion rate of olefin is 99.7%, and the selectivity of alcohol ether compound ethylene glycol monomethyl ether and ethylene glycol is 76.5% and 22% respectively.
Example 2
Example 2 is essentially the same as example 1, except that: in the step (2), the methanol, the hydrogen peroxide and the ethylene are fed into a reactor for continuous reaction according to the mol ratio of the methanol to the hydrogen peroxide to the ethylene of 6: 1: 3, the reaction is carried out at the temperature of 60 ℃ and the pressure of 2.5MPa, and the space velocity of the reaction is 3h-1. And obtaining a reaction product after the reaction is finished.
The remaining process conditions were the same as in example 1.
The results show that: the conversion rate of olefin is 99.7%, and the selectivity of alcohol ether compound ethylene glycol monomethyl ether and ethylene glycol is 83.5% and 14.2%, respectively.
Example 3
Example 3 is essentially the same as example 1, except that: in the step (2), the methanol, the hydrogen peroxide and the propylene are fed into a reactor for continuous reaction according to the mol ratio of the methanol to the hydrogen peroxide to the propylene of 4: 1: 2, the reaction is carried out at the temperature of 60 ℃ and the pressure of 2.5MPa, and the space velocity of the reaction is 3h-1. Inverse directionAfter the reaction, a reaction product is obtained.
The remaining process conditions were the same as in example 2. The results show that: the conversion rate of olefin is 98.8%, and the selectivity of alcohol ether compound propylene glycol monomethyl ether and propylene glycol is 69.6% and 28.8%, respectively. Further, the gas chromatography results showed that the ratio of the moles of the two isomers of propylene glycol methyl ether, 1-methoxy-2-propanol and 2-methoxy-1-propanol, was 66: 3.6.
wherein the calculation formula of the olefin conversion rate was the same as in step (3) of example 1.
Propylene glycol monomethyl ether selectivity ═ total moles of propylene glycol monomethyl ether/(moles of olefin feed-moles of olefin in reaction product) × 100%
Propylene glycol selectivity ═ propylene glycol moles/(moles of olefin feed-moles of olefin in reaction product) × 100%
Example 4
Example 4 is essentially the same as example 3, except that: in the step (2), the reaction is carried out at the temperature of 80 ℃ and the pressure of 3MPa, and the reaction space velocity is 3h-1. The remaining conditions and process conditions were the same as in example 3.
The results show that: the conversion rate of olefin is 99.5%, and the selectivity of alcohol ether compound propylene glycol monomethyl ether and propylene glycol is 58.6% and 38.8%, respectively. Further, the gas chromatography results showed that the molar ratio of the two isomers of propylene glycol monomethyl ether, 1-methoxy-2-propanol and 2-methoxy-1-propanol, was 55.1: 3.5.
example 5
Example 5 is essentially the same as example 4, except that: in the step (2), the methanol, the hydrogen peroxide and the propylene are fed into a reactor for continuous reaction according to the mol ratio of the methanol to the hydrogen peroxide to the propylene of 4: 1: 1.5. The remaining conditions and process conditions were the same as in example 4.
The results show that: the conversion rate of olefin is 99.4%, and the selectivity of alcohol ether compound propylene glycol methyl ether and propylene glycol is 58.6% and 41.8%, respectively. Further, the gas chromatography results showed that the molar ratio of the two isomers of propylene glycol methyl ether, 1-methoxy-2-propanol and 2-methoxy-1-propanol, was 55: 3.6.
example 6
Example 6 is essentially the same as example 4, except that: in the step (2), methanol, hydrogen peroxide and propylene are fed into a reactor according to the molar ratio of 4: 1: 5 for continuous reaction. The remaining conditions and process conditions were the same as in example 4.
The results show that: the conversion rate of olefin is 99.2%, and the selectivity of alcohol ether compound propylene glycol methyl ether and propylene glycol is 50.3% and 32.3%, respectively. Further, the gas chromatography results showed that the ratio of the moles of the two isomers of propylene glycol methyl ether, 1-methoxy-2-propanol and 2-methoxy-1-propanol, was 27.3: 30.
example 7
Example 7 is essentially the same as example 4, except that: in the step (2), the butanol, the hydrogen peroxide and the propylene are fed into a reactor for continuous reaction according to the molar ratio of 4: 1: 1.5. The remaining conditions and process conditions were the same as in example 4. The results show that: the conversion rate of olefin is 99.4%, and the selectivity of alcohol ether compound propylene glycol butyl ether and propylene glycol is 54.6% and 41.8%, respectively. Further, the gas chromatography results showed that the ratio of the moles of the two isomers of propylene glycol butyl ether, 1-butoxy-2-propanol and 2-butoxy-1-propanol, was 53: 1.6.
wherein the calculation formulas of the olefin conversion rate and the propylene glycol selectivity are the same as those in the step (3) of the example 1.
Propylene glycol butyl ether selectivity ═ propylene glycol butyl ether total moles/(moles of olefin feed-moles of olefin in reaction product) × 100%
Example 8
Example 8 is essentially the same as example 1, except that: in the step (2), hexanol, hydrogen peroxide and ethylene are fed into a reactor according to the molar ratio of 5: 1: 1.5 for continuous reaction, the reaction is carried out at the temperature of 100 ℃ and the pressure of 2.5MPa, and the space velocity of the reaction is 4h-1. The remaining conditions and process conditions were the same as in example 1. The results show that: the conversion rate of olefin is 99.8%, and the selectivity of alcohol ether compound ethylene glycol hexyl ether and ethylene glycol is 43.5% and 54.2%, respectively.
Wherein, the calculation formulas of the olefin conversion rate and the propylene glycol selectivity are the same as those in the step (3) of the example 1.
Propylene glycol hexyl ether selectivity ═ total moles of propylene glycol hexyl ether/(moles of olefin feed-moles of olefin in reaction product) × 100%
Comparative example 1
Example 7 is essentially the same as example 4, except that: in step (1), an unmodified titanium silicalite molecular sieve TS-1 is provided. The remaining conditions and process conditions were the same as in example 4.
The results show that: the conversion rate of olefin is 99.5%, and the selectivity of alcohol ether compound propylene glycol monomethyl ether and propylene glycol is 57.7% and 33.3%, respectively. Further, the gas chromatography results showed that the ratio of the moles of the two isomers of propylene glycol monomethyl ether, 1-methoxy-2-propanol and 2-methoxy-1-propanol, was 35.9: 21.8.
the above examples only show some embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A method for producing an alcohol ether compound, characterized by comprising the steps of:
carrying out oxidation reaction and etherification reaction on an alcohol compound shown in a formula (1), an olefin compound shown in a formula (2) and an oxidant under the action of a catalyst to obtain alcohol ether compounds with structures shown in the formulae (3) and (4);
wherein R is1And R2Each independently selected from H or alkyl with 1-8 carbon atoms:
the catalyst is an acid modified titanium-silicon-aluminum molecular sieve.
2. The method for producing an alcohol ether compound according to claim 1, wherein the ratio of the amounts of the alcohol compound, the olefin compound and the oxidant is (4 to 8): 1: (1.5-4).
3. The method for producing an alcohol ether compound according to claim 1, wherein the temperature of the oxidation reaction and the etherification reaction is 40 ℃ to 100 ℃ and the pressure is 2MP to 4 MP; and/or
The oxidant is at least one selected from hydrogen peroxide, tert-butyl hydroperoxide, cumyl peroxide, cyclohexyl hydroperoxide, peroxyacetic acid and peroxypropionic acid.
4. The method for producing an alcohol ether compound according to any one of claims 1 to 3, wherein the alcohol compound is any one selected from the group consisting of water, methanol, ethanol, propanol, butanol, t-butanol, pentanol, hexanol, heptanol, and octanol; and/or
The olefin compound is any one selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene and 1-octene.
5. The method for preparing an alcohol ether compound according to any one of claims 1 to 3, wherein the method for preparing the acid-modified titanium-silicon-aluminum molecular sieve comprises the following steps:
mixing and pulping a titanium silicalite molecular sieve and organic acid, and carrying out first heat treatment to obtain a first solid;
and mixing the first solid, an aluminum source, a titanium source, a silicon source, an acid source and water, carrying out second heat treatment, and then roasting to obtain the acid modified titanium-silicon-aluminum molecular sieve.
6. The method for producing an alcohol ether compound according to claim 5, wherein the mass ratio of the first solid, the aluminum source, the titanium source, the silicon source, the acid source, and the water is 100: (0.05-7): (0.05-7): (0.05-7): (1-50): (100-1000).
7. The method for producing an alcohol ether compound according to claim 5, wherein the acid source is at least one selected from the group consisting of fluoroboric acid, boron trifluoride, aluminum trichloride and boron trifluoride etherate; and/or
The aluminum source is selected from at least one of aluminum sol, aluminum salt, aluminum hydroxide, aluminum sulfate, sodium metaaluminate, aluminum chloride, aluminum nitrate and aluminum oxide; and/or
The titanium source is selected from at least one of isopropyl titanate, n-propyl titanate and tetraethyl titanate; and/or
The silicon source is at least one of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and butyl orthosilicate.
8. The method for producing an alcohol ether compound according to claim 5, wherein the temperature of the first heat treatment is 50 to 150 ℃ for 10 to 30 hours; and/or
The temperature of the second heat treatment is 100-200 ℃, and the time is 5-20 h; and/or
The roasting temperature is 150-250 ℃, and the roasting time is 1-10 h.
9. The method for producing an alcohol ether compound according to any one of claims 1 to 3, wherein the step of performing the oxidation reaction and the etherification reaction comprises the steps of:
and (2) placing the catalyst in a reactor to form a catalyst bed layer, then conveying the alcohol compound, the olefin compound and the oxidant into the reactor to contact with the catalyst bed layer, and continuously carrying out the oxidation reaction and the etherification reaction.
10. The method for producing an alcohol ether compound according to claim 9, wherein the reaction space velocity of the oxidation reaction and the etherification reaction is 2 hours-1～5h-1。
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| CN103012078A (en) * | 2011-09-28 | 2013-04-03 | 中国石油化工股份有限公司 | Method for preparing propylene glycol monomethyl ether by catalyzing propylene oxide |
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