CN114349608B - Alcohol ether compound preparation method - Google Patents
Alcohol ether compound preparation method Download PDFInfo
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- CN114349608B CN114349608B CN202111674884.5A CN202111674884A CN114349608B CN 114349608 B CN114349608 B CN 114349608B CN 202111674884 A CN202111674884 A CN 202111674884A CN 114349608 B CN114349608 B CN 114349608B
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- -1 Alcohol ether compound Chemical class 0.000 title claims abstract description 141
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 64
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000002808 molecular sieve Substances 0.000 claims abstract description 45
- 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 45
- 239000002253 acid Substances 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims description 63
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 62
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 57
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 50
- 150000001336 alkenes Chemical class 0.000 claims description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 20
- 229910052719 titanium Inorganic materials 0.000 claims description 20
- 239000010936 titanium Substances 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000007795 chemical reaction product Substances 0.000 claims description 15
- YTTFFPATQICAQN-UHFFFAOYSA-N 2-methoxypropan-1-ol Chemical compound COC(C)CO YTTFFPATQICAQN-UHFFFAOYSA-N 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 8
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000004537 pulping Methods 0.000 claims description 7
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- UYVDGHOUPDJWAZ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical class COCC(C)O.COCC(C)O UYVDGHOUPDJWAZ-UHFFFAOYSA-N 0.000 claims description 4
- WGKZYJXRTIPTCV-UHFFFAOYSA-N 2-butoxypropan-1-ol Chemical compound CCCCOC(C)CO WGKZYJXRTIPTCV-UHFFFAOYSA-N 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims 4
- 239000007800 oxidant agent Substances 0.000 abstract description 22
- 238000006266 etherification reaction Methods 0.000 abstract description 21
- 238000000034 method Methods 0.000 abstract description 21
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 20
- 238000007254 oxidation reaction Methods 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 15
- 230000001590 oxidative effect Effects 0.000 abstract description 14
- 230000009471 action Effects 0.000 abstract description 11
- 230000001105 regulatory effect Effects 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 5
- 230000001276 controlling effect Effects 0.000 abstract description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 25
- 125000000217 alkyl group Chemical group 0.000 description 11
- 238000004817 gas chromatography Methods 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 6
- 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 description 6
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 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
- BWPAALSUQKGDBR-UHFFFAOYSA-N 1-hexoxypropan-2-ol Chemical compound CCCCCCOCC(C)O BWPAALSUQKGDBR-UHFFFAOYSA-N 0.000 description 3
- 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
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 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 3
- 239000003973 paint Substances 0.000 description 3
- 239000008194 pharmaceutical composition Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 3
- 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 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 2
- 125000004398 2-methyl-2-butyl group Chemical group CC(C)(CC)* 0.000 description 2
- 125000004918 2-methyl-2-pentyl group Chemical group CC(C)(CCC)* 0.000 description 2
- 125000004922 2-methyl-3-pentyl group Chemical group CC(C)C(CC)* 0.000 description 2
- 125000004917 3-methyl-2-butyl group Chemical group CC(C(C)*)C 0.000 description 2
- 125000004919 3-methyl-2-pentyl group Chemical group CC(C(C)*)CC 0.000 description 2
- 125000004921 3-methyl-3-pentyl group Chemical group CC(CC)(CC)* 0.000 description 2
- 125000004920 4-methyl-2-pentyl group Chemical group CC(CC(C)*)C 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- FGGJBCRKSVGDPO-UHFFFAOYSA-N hydroperoxycyclohexane Chemical compound OOC1CCCCC1 FGGJBCRKSVGDPO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 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
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- CZPZWMPYEINMCF-UHFFFAOYSA-N propaneperoxoic acid Chemical compound CCC(=O)OO CZPZWMPYEINMCF-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium(IV) ethoxide Substances [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- 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 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
- UPGSWASWQBLSKZ-UHFFFAOYSA-N 2-hexoxyethanol Chemical compound CCCCCCOCCO UPGSWASWQBLSKZ-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 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
- 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
- 238000001354 calcination Methods 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
- 238000007599 discharging Methods 0.000 description 1
- 239000007789 gas Substances 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 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
- 238000005580 one pot reaction Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 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
- 239000000243 solution Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
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- 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, the alcohol compound shown in the formula (1), the alkene compound shown in the formula (2) and the oxidant are subjected to oxidation reaction and etherification reaction under the action of a catalyst to obtain the alcohol ether compound with the structures shown in the formulas (3) and (4); the catalyst is acid modified titanium silicon aluminum molecular sieve, which can improve the selectivity of alcohol ether compound, and can regulate and control the selectivity of isomer in the etherification reaction process when the olefin compound contains three or more carbon atoms because the acid modified titanium silicon aluminum molecular sieve increases the acid active center, so that the R 1 part in the alcohol compound tends to be connected with ether bond, thereby regulating and controlling the composition of isomer, for example, when the olefin compound is propylene, the selectivity of alcohol ether compound is improved, and the regioselectivity of 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 functionalities that may be hydroxyl and ether linkages, including alcohols and ether compounds, such as ethylene glycol, glycol ethers, propylene glycol ethers, and other lower alcohols or lower alcohol ethers. The alcohol ether compound has both ether bond and hydroxyl group, the former has lipophilicity and can dissolve hydrophobic compound, and the latter has hydrophilicity and can dissolve water-soluble compound. Therefore, the alcohol ether compound is widely used as a good solvent of oil-soluble paint, can improve the leveling property of a paint film, has good compatibility with water, and can be used as a cosolvent of water-based paint.
At present, the industrialized production of the alcohol ether compound is mainly prepared by the alkoxy ring-opening etherification reaction of alcohol and epoxy monomers, but the synthesis process of the epoxy monomer is complex, so that the technological process of the technological method is complex and the cost is high. Thus, the skilled artisan proposes the direct preparation of alcohol ether compounds by one-pot reaction of an alcohol with an olefin under the action of an oxidizing agent. However, in the conventional process for directly preparing the alcohol ether compound by using alcohol and olefin under the action of an oxidant, the olefin compound is converted into the alcohol ether compound such as a mono-alcohol ether compound, a diol compound and the like, and complicated side reactions are accompanied in the reaction process, so that the alcohol ether compound has low selectivity and low yield. More importantly, the olefin containing three or more carbon atoms can generate isomers in the process of converting the olefin into the alcohol ether compound by the reaction with alcohol, and the use and the economic benefits of the isomers with different structures are different. For example, when methanol and propylene are used to prepare alcohol ether compounds including propylene glycol monomethyl ether and propylene glycol, the main product propylene glycol monomethyl ether exists 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 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, it is difficult to control the regioselectivity of the different isomers by conventional methods for directly preparing alcohol ether compounds using alcohols and olefins under the action of an oxidizing agent.
Thus, there is a need in the art for improvement.
Disclosure of Invention
Based on the above, the invention provides a 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 invention, a method for preparing an alcohol ether compound is provided, comprising the following steps:
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 an alcohol ether compound with structures shown in a formula (3) and a formula (4);
R1-OH (1),CH2＝CHR2 (2)，
Wherein R 1 and R 2 are each independently selected from H or an alkyl group having 1 to 8 carbon atoms:
the catalyst is an acid modified titanium-silicon-aluminum molecular sieve.
In some of these embodiments, the ratio of the amounts of the substances of the alcohol compound, the olefin compound, and the oxidizing agent is (4 to 8): 1: (1.5-4).
In some of these embodiments, the oxidation and etherification reactions are carried out at a temperature of 40 ℃ to 100 ℃ and a pressure of 2MP to 4MP; and/or
The oxidant is at least one selected from hydrogen peroxide, tert-butyl hydroperoxide, cumene peroxide, cyclohexyl hydroperoxide, peracetic acid and peroxypropionic acid.
In some 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 selected from any one 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-silicon molecular sieve and an organic acid, and performing first heat treatment to obtain a first solid;
And mixing the first solid, the aluminum source, the titanium source, the silicon source and the acid source with water, performing second heat treatment, and 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 at least one selected from aluminum sol, aluminum salt, aluminum hydroxide, aluminum sulfate, sodium metaaluminate, aluminum chloride, aluminum nitrate and aluminum oxide; and/or
The titanium source is 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 hours; 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 and etherification reactions comprises the steps of:
And placing the catalyst in a reactor to form a catalyst bed, and then conveying the alcohol compound, the olefin compound and the oxidant into the reactor to contact with the catalyst bed, so as to continuously perform the oxidation reaction and the etherification reaction.
In some of these embodiments, the reaction space velocity of the oxidation and etherification reactions is 2h -1～5h-1.
In the preparation method of the alcohol ether compound, the alcohol compound shown in the formula (1), the alkene compound shown in the formula (2) and the oxidant are subjected to oxidation reaction and etherification reaction under the action of a catalyst to obtain the alcohol ether compound comprising the monoalcohol ether compound shown in the formula (3) and the diol compound shown in the formula (4); the catalyst is acid modified titanium silicon aluminum molecular sieve, which can improve the selectivity of converting olefin compounds into alcohol ether compounds, and can regulate and control the selectivity of isomers in the etherification reaction process when the olefin compounds contain three or more carbon atoms, so that the formed ether bonds tend to be connected with carbon atoms with smaller substituent groups, and the composition of isomers is regulated and controlled, for example, when the olefin compounds are propylene, the selectivity of converting olefin compounds into alcohol ether compounds is improved, and the regioselectivity of isomers 1-methoxy-2-propanol is improved.
Further, the ratio of the amounts of the substances of the alcohol compound, the olefin compound and the oxidizing agent is regulated to further improve the selectivity of the alcohol ether compound and the regioselectivity of the isomer thereof.
Further, the catalyst is placed in the reactor to form a catalyst bed, and then the alcohol compound, the olefin compound and the oxidant are conveyed into the reactor to contact with the catalyst bed, so that the oxidation reaction and the etherification reaction are continuously carried out, and the process is simple and feasible, environment-friendly and high in catalytic efficiency and selectivity.
Detailed Description
The present invention will be described more fully hereinafter in order to facilitate an understanding of the present invention, and preferred embodiments of the present invention are set forth. 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 herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Herein, the term "alkyl" refers to a monovalent residue of a saturated hydrocarbon containing a primary (positive) carbon atom, or a secondary carbon atom, or a tertiary carbon atom, or a quaternary carbon atom, or a combination thereof, losing one hydrogen atom. The phrase containing the term, for example, an alkyl group having 1 to 8 carbon atoms, i.e., "C1-8 alkyl" refers to an alkyl group containing 1 to 8 carbon atoms, which may be, for each occurrence, independently of one another, 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), a catalyst for the preparation of a pharmaceutical composition, 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)), a catalyst for the preparation of a pharmaceutical composition, 2-methyl-2-butyl (-C (CH 3)2CH2CH3), 3-methyl-2-butyl (-CH (CH 3)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)), a catalyst, 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)), a catalyst for the preparation of a pharmaceutical composition, 2, 3-dimethyl-2-butyl (-C (CH 3)2CH(CH3)2), 3-dimethyl-2-butyl (-CH (CH 3)C(CH3)3 and octyl (- (CH 2)7CH3)).
The alcohol and the alkene react under the action of the oxidant, the alkene can be converted into the corresponding alcohol ether compound such as the dihydric alcohol compound, the mono-alcohol ether compound and the like, and the alkene containing three carbon atoms and more can generate isomerides in the process of converting the alkene into the alcohol ether compound by the reaction with the alcohol, so that the purposes and the economic benefits of the isomerides with different structures are different. For example, propylene glycol monomethyl ether prepared from methanol and propylene has two isomers of 1-methoxy-2-propanol and 2-methoxy-1-propanol, compared with 2-methoxy-1-propanol, the 1-methoxy-2-propanol has lower biotoxicity, so that the price difference between the two isomers is huge, the market selling price of 1-methoxy-2-propanol reaches 12500 yuan/ton, and the selling price of 2-methoxy-1-propanol is only 5500 yuan/ton, thereby having great benefit influence.
The traditional method for directly preparing alcohol ether compound by alcohol and olefin under the action of oxidant is difficult to control the selectivity of different isomers. Based on this, those skilled in the art have further carried out extensive studies on the reaction mechanism involved in the preparation of alcohol ether compounds, and have found by chance that: in the process of preparing alcohol ether compound by using alcohol compound and olefin as raw materials under the action of oxidant by 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 controlled, and the preparation method of the alcohol ether compound is obtained after a large amount 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 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 an alcohol-ether compound with structures shown in a formula (3) and a formula (4);
R1-OH(1),CH2＝CHR2(2)，
Wherein R 1 and R 2 are each independently selected from H or an alkyl group having 1 to 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 alkene compound shown in the formula (2) and the oxidant are subjected to oxidation reaction and etherification reaction under the action of a catalyst to obtain the alcohol ether compound comprising the monoalcohol ether compound shown in the formula (3) and the diol compound shown in the formula (4); the catalyst is acid modified titanium silicon aluminum molecular sieve, which can improve the selectivity of converting olefin compounds into alcohol ether compounds, and can regulate and control the selectivity of isomers in the etherification reaction process when the olefin compounds contain three or more carbon atoms, so that the formed ether bonds tend to be connected with carbon atoms with smaller substituent groups, and the composition of isomers is regulated and controlled, for example, when the olefin compounds are propylene, the selectivity of the alcohol ether compounds is improved, and the regioselectivity of the isomer 1-methoxy-2-propanol is improved.
Since water molecules contain hydroxyl groups, they can be regarded as alcohols theoretically in the art.
It is understood that when R 1 in formula (1) is H, the compound shown in formula (1) is water, and the structures of the product formula (3) and formula (4) obtained by the reaction are the same; in other words, when R 1 in the formula (1) is H, that is, the compound represented by the formula (1) is water, the olefin is converted into the diol compound.
In some embodiments, the ratio of the amounts of the alcohol compound, the olefin compound, and the oxidizing agent is (4 to 8): 1: (1.5-4).
Further, the ratio of the amounts of the substances of the alcohol compound, the olefin compound and the oxidizing agent is regulated to further increase the selectivity of the alcohol ether compound and the selectivity of the isomer thereof, so that the formed ether bond tends to be connected with the smaller carbon atom of the 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 4MP.
In some embodiments, the oxidizing agent is selected from at least one of hydrogen peroxide, t-butyl hydroperoxide, cumene peroxide, cyclohexyl hydroperoxide, peracetic acid, and peroxypropionic acid.
In some of these embodiments, in step S10, the above-described oxidizing agent is added in the form of an aqueous solution thereof.
Further, the oxidant is hydrogen peroxide; further, the hydrogen peroxide is added in the form of an aqueous hydrogen peroxide solution with 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 embodiments, R 2 is selected from alkyl groups having 2 to 8 carbon atoms.
In other words, the olefinic compound contains three or more carbon atoms, and the volume of substituents on both sides of the double bond are different, and isomers are formed during the subsequent etherification reaction.
In some embodiments, the olefin is selected from any one of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene.
In some embodiments, the method for preparing the modified titanium silicon aluminum molecular sieve comprises the following steps S11 to S12.
And S11, mixing and pulping the titanium-silicon molecular sieve and the organic acid, and performing first heat treatment to obtain a first solid.
And step S12, mixing the first solid, the aluminum source, the titanium source, the silicon source and the acid source with water, performing second heat treatment, and roasting to obtain the acid modified titanium-silicon-aluminum molecular sieve.
The acid source is adopted to modify the active component of the titanium-silicon molecular sieve 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 the olefin compound contains three or more carbon atoms, the selectivity of the isomer in the etherification reaction process can be regulated and controlled, and the formed ether bond tends to be connected with the carbon atom with smaller substituent groups, thereby regulating and controlling the composition of the isomer.
In some embodiments, the first solid has a relative crystallinity of 70% to 90%.
In some embodiments, in step S11, the titanium silicalite molecular sieve is at least one selected from MFI structure titanium silicalite molecular sieve, MEL structure titanium silicalite molecular sieve, BEA structure titanium silicalite molecular sieve, MWW structure titanium silicalite molecular sieve, MOR structure titanium silicalite molecular sieve, TUN structure titanium silicalite molecular sieve and two-dimensional hexagonal structure titanium silicalite molecular sieve.
In some embodiments, the first solid, the aluminum source, the titanium source, the silicon source, the acid source, and the water have a mass ratio of 100: (0.05-7): (0.05-7): (0.05-7): (1-50): (100-1000).
In some embodiments, the organic acid is at least one selected from the group consisting 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 embodiments, the acid source is selected from at least one of fluoroboric acid, boron trifluoride, aluminum trichloride, and boron trifluoride etherate.
In some 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 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 100-200 ℃ and the time is 5-20 h.
In some embodiments, the calcination temperature is 150 to 250 ℃ for 1 to 10 hours.
In some embodiments, the step of performing the oxidation reaction and the etherification reaction comprises the steps of:
And placing the catalyst in a reactor to form a catalyst bed, and then conveying the alcohol compound, the olefin compound and the oxidant into the reactor to contact with the catalyst bed, so as to continuously perform oxidation reaction and etherification reaction.
Thus, the oxidation reaction and the etherification reaction can be continuously carried out, and the process is simple and feasible, environment-friendly and high in catalytic efficiency and selectivity.
Further, the product after the reaction is discharged from the top of the reactor, cooled by a cooler, then subjected to olefin removal for gas-liquid separation, the olefin in the gas phase is circularly reused after being circularly pressurized and liquefied, and the mixed liquid in the liquid phase is rectified to respectively obtain the corresponding alcohol ether compound product. Simple process, environmental protection, high catalytic efficiency, and good safety and environmental benefit.
In some of these embodiments, the reaction space velocity of the oxidation and etherification reactions described above is 2h -1～5h-1.
The invention will be described in connection with specific embodiments, but the invention is not limited thereto, and it will be appreciated that the appended claims outline the scope of the invention, and those skilled in the art, guided by the inventive concept, will appreciate that certain changes made to the embodiments of the invention will be covered by the spirit and scope of 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 reactor with a diameter of 2cm and a length of 60cm for fixed bed reaction, the volume of a catalyst bed is 13cm 2, and then the device is purged by nitrogen.
The preparation process of the modified titanium-silicon-aluminum molecular sieve comprises the following steps:
At normal temperature and pressure of 25 ℃, mixing and pulping the titanium-silicon molecular sieve with an MFI structure and the sulfonic acid in a mass ratio of 0.2 to 1, carrying out heat treatment on the obtained slurry for 20 hours at 80 ℃, and carrying out solid-liquid separation to obtain a first solid with a relative crystallinity of 80%.
Mixing the 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 the 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 15 hours at 150 ℃, the obtained solution is dried for 2 hours at 200 ℃ after discharging, and finally the acid modified titanium-silicon-aluminum molecular sieve is obtained after roasting for 6 hours at 500 ℃.
(2) Methanol, hydrogen peroxide and ethylene were fed into a reactor in a molar ratio of methanol, hydrogen peroxide and ethylene of 4:1:2 (hydrogen peroxide was supplied as a 30wt% aqueous hydrogen peroxide solution) for continuous reaction at a temperature of 60℃under a pressure of 2.5MPa, and a reaction space velocity of 2h -1. After the reaction is completed, a reaction product is obtained.
(3) The reaction product thus obtained was subjected to gas chromatography detection, and ethylene conversion, alcohol ether compound ethylene glycol monomethyl ether and ethylene glycol selectivity were calculated as follows.
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 moles/(moles of olefin feedstock-moles of olefin in reaction product) ×100%
Ethylene glycol selectivity = moles of ethylene glycol/(moles of olefin feedstock-moles of olefin in reaction product) ×100% of ethylene glycol
The results show that: the conversion of olefin was 99.7%, and the selectivity of the alcohol ether compound ethylene glycol monomethyl ether and ethylene glycol was 76.5% and 22%, respectively.
Example 2
Example 2 is substantially the same as example 1 except that: in the step (2), methanol, hydrogen peroxide and ethylene are fed into a reactor according to the molar ratio of 6:1:3 of methanol, hydrogen peroxide and ethylene to carry out continuous reaction, and the reaction is carried out at the temperature of 60 ℃ and the pressure of 2.5MPa, and the reaction space velocity is 3h -1. After the reaction is completed, a reaction product is obtained.
The remaining process conditions were the same as in example 1.
The results show that: the conversion of olefin was 99.7%, and the selectivity of the alcohol ether compound ethylene glycol monomethyl ether and ethylene glycol was 83.5% and 14.2%, respectively.
Example 3
Example 3 is substantially the same as example 1 except that: in the step (2), methanol, hydrogen peroxide and propylene are fed into a reactor according to the molar ratio of 4:1:2 of methanol, hydrogen peroxide and propylene to carry out continuous reaction, and the reaction is carried out at the temperature of 60 ℃ and the pressure of 2.5MPa, and the reaction space velocity is 3h -1. After the reaction is completed, a reaction product is obtained.
The remaining process conditions were the same as in example 2. The results show that: the olefin conversion was 98.8%, and the selectivity of the alcohol ether compound propylene glycol monomethyl ether and propylene glycol was 69.6% and 28.8%, respectively. Further, the gas chromatography result shows that the mole ratio of the two isomers of propylene glycol methyl ether 1-methoxy-2-propanol to 2-methoxy-1-propanol is 66:3.6.
Wherein, the calculation formula of the olefin conversion rate is the same as that of the step (3) of the example 1.
Propylene glycol monomethyl ether selectivity = propylene glycol monomethyl ether total moles/(moles of olefin feedstock-moles of olefin in reaction product) ×100% of the total moles of propylene glycol monomethyl ether
Propylene glycol selectivity = moles of propylene glycol/(moles of olefin feedstock-moles of olefin in reaction product) 100%
Example 4
Example 4 is substantially the same as example 3 except that: in the step (2), the reaction is carried out at a temperature of 80 ℃ and a pressure of 3MPa, and the reaction space velocity is 3h -1. The other conditions and the step conditions were the same as in example 3.
The results show that: the conversion of olefin was 99.5%, and the selectivity of the alcohol ether compound propylene glycol monomethyl ether and propylene glycol was 58.6% and 38.8%, respectively. Further, the gas chromatography result shows that the mole ratio of the two isomers of propylene glycol monomethyl ether, namely 1-methoxy-2-propanol and 2-methoxy-1-propanol, is 55.1:3.5.
Example 5
Example 5 is substantially the same as example 4 except that: in the step (2), methanol, hydrogen peroxide and propylene are fed into a reactor for continuous reaction according to the molar ratio of the methanol, the hydrogen peroxide and the propylene being 4:1:1.5. The other conditions and the step conditions were the same as in example 4.
The results show that: the conversion of olefin was 99.4%, and the selectivity of alcohol ether compound propylene glycol methyl ether and propylene glycol was 58.6% and 41.8%, respectively. Further, the gas chromatography result shows that the mole ratio of the two isomers of propylene glycol methyl ether 1-methoxy-2-propanol to 2-methoxy-1-propanol is 55:3.6.
Example 6
Example 6 is substantially the same as example 4 except that: in the step (2), methanol, hydrogen peroxide and propylene are fed into a reactor according to the mol ratio of 4:1:5 for continuous reaction. The other conditions and the step conditions were the same as in example 4.
The results show that: the conversion of olefin was 99.2%, and the selectivity of the alcohol ether compound propylene glycol methyl ether and propylene glycol was 50.3% and 32.3%, respectively. Further, the gas chromatography result shows that the mole ratio of the two isomers of propylene glycol methyl ether, 1-methoxy-2-propanol and 2-methoxy-1-propanol, is 27.3:30.
Example 7
Example 7 is substantially the same as example 4 except that: in the step (2), butanol, hydrogen peroxide and propylene are fed into a reactor according to the mol ratio of 4:1:1.5 for continuous reaction. The other conditions and the step conditions were the same as in example 4. The results show that: the conversion of olefin was 99.4%, and the selectivity of alcohol ether compound propylene glycol butyl ether and propylene glycol was 54.6% and 41.8%, respectively. Further, the gas chromatography result shows that the mole ratio of the two isomers of propylene glycol butyl ether, 1-butoxy-2-propanol and 2-butoxy-1-propanol, is 53:1.6.
Wherein, the calculation formula of the conversion rate of olefin and the selectivity of propylene glycol is the same as that of the step (3) of the example 1.
Propylene glycol butyl ether selectivity = propylene glycol Ding Mizong moles/(moles of olefin feed-moles of olefin in reaction product) 100%
Example 8
Example 8 is substantially the same as example 1 except that: in the step (2), hexanol, hydrogen peroxide and ethylene are fed into a reactor according to the mol ratio of 5:1:1.5 for continuous reaction, and the reaction is carried out at the temperature of 100 ℃ and the pressure of 2.5MPa, and the reaction space velocity is 4h -1. The other conditions and the step conditions were the same as in example 1. The results show that: the conversion of the olefin was 99.8%, and the selectivity of the alcohol ether compound ethylene glycol hexyl ether and ethylene glycol was 43.5% and 54.2%, respectively.
Wherein the olefin conversion and propylene glycol selectivity are calculated as in step (3) of example 1.
Propylene glycol hexyl ether selectivity = total moles of propylene glycol hexyl ether/(moles of olefin feedstock-moles of olefin in reaction product) ×100% of the total moles of propylene glycol hexyl ether
Comparative example 1
Example 7 is substantially the same as example 4 except that: in step (1), an unmodified titanium silicalite molecular sieve TS-1 is provided. The other conditions and the step conditions were the same as in example 4.
The results show that: the conversion of olefin was 99.5%, and the selectivity of the alcohol ether compound propylene glycol monomethyl ether and propylene glycol was 57.7% and 33.3%, respectively. Further, the gas chromatography result shows that the mole ratio of the two isomers of propylene glycol monomethyl ether, namely 1-methoxy-2-propanol and 2-methoxy-1-propanol, is 35.9:21.8.
The foregoing examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (4)
1. The preparation method of the alcohol ether compound is characterized by comprising the following steps:
(1) Placing the modified titanium silicon aluminum molecular sieve in a fixed bed tubular reactor with the diameter of 2cm and the length of 60cm, wherein the volume of a catalyst bed layer is 13cm 2, and then purging the device with nitrogen;
the preparation process of the modified titanium-silicon-aluminum molecular sieve comprises the following steps:
At normal temperature of 25 ℃ and normal pressure, firstly, the mass ratio of the MFI structure titanium-silicon molecular sieve to the sulfonic acid is 0.2:1, mixing and pulping, carrying out heat treatment on the obtained slurry for 20 hours at 80 ℃, and carrying out solid-liquid separation to obtain a first solid with the relative crystallinity of 80%;
mixing the first solid with 20wt% of aluminum sol, titanium source n-propyl titanate, silicon source methyl orthosilicate, acid source fluoboric acid and water according to the mass ratio of 100:3:5:5:20:500 is put into a stainless steel sealed reaction kettle, is subjected to second heat treatment for 15 hours at 150 ℃, is discharged, is dried for 2 hours at 200 ℃, and is finally baked for 6 hours at 500 ℃ to obtain the acid modified titanium-silicon-aluminum molecular sieve;
(2) Feeding methanol, hydrogen peroxide and propylene into a reactor according to the molar ratio of the methanol, the hydrogen peroxide and the propylene of 4:1:2 for continuous reaction, and reacting at the temperature of 60 ℃ and the pressure of 2.5MPa with the reaction space velocity of 3h -1; after the reaction is finished, a reaction product is obtained; the hydrogen peroxide is provided as a 30wt% aqueous hydrogen peroxide solution;
In the preparation method, the olefin conversion rate is 98.8%, the selectivity of the alcohol ether compound propylene glycol monomethyl ether and propylene glycol is 69.6% and 28.8%, respectively, and the molar ratio of the two isomers of propylene glycol methyl ether 1-methoxy-2-propanol to 2-methoxy-1-propanol is 66:3.6.
2. The preparation method of the alcohol ether compound is characterized by comprising the following steps:
(1) Placing the modified titanium silicon aluminum molecular sieve in a fixed bed tubular reactor with the diameter of 2cm and the length of 60cm, wherein the volume of a catalyst bed layer is 13cm 2, and then purging the device with nitrogen;
the preparation process of the modified titanium-silicon-aluminum molecular sieve comprises the following steps:
At normal temperature of 25 ℃ and normal pressure, firstly, the mass ratio of the MFI structure titanium-silicon molecular sieve to the sulfonic acid is 0.2:1, mixing and pulping, carrying out heat treatment on the obtained slurry for 20 hours at 80 ℃, and carrying out solid-liquid separation to obtain a first solid with the relative crystallinity of 80%;
mixing the first solid with 20wt% of aluminum sol, titanium source n-propyl titanate, silicon source methyl orthosilicate, acid source fluoboric acid and water according to the mass ratio of 100:3:5:5:20:500 is put into a stainless steel sealed reaction kettle, is subjected to second heat treatment for 15 hours at 150 ℃, is discharged, is dried for 2 hours at 200 ℃, and is finally baked for 6 hours at 500 ℃ to obtain the acid modified titanium-silicon-aluminum molecular sieve;
(2) Feeding methanol, hydrogen peroxide and propylene into a reactor according to the molar ratio of the methanol, the hydrogen peroxide and the propylene of 4:1:2 for continuous reaction, and reacting at the temperature of 80 ℃ and the pressure of 3MPa with the reaction space velocity of 3h -1; after the reaction is finished, a reaction product is obtained; the hydrogen peroxide is provided as a 30wt% aqueous hydrogen peroxide solution;
In the preparation method, the conversion rate of olefin is 99.5%, the selectivity of alcohol ether compound propylene glycol monomethyl ether and propylene glycol is 58.6% and 38.8%, respectively, and the molar ratio of the two isomers of propylene glycol methyl ether 1-methoxy-2-propanol to 2-methoxy-1-propanol is 55.1:3.5.
3. The preparation method of the alcohol ether compound is characterized by comprising the following steps:
(1) Placing the modified titanium silicon aluminum molecular sieve in a fixed bed tubular reactor with the diameter of 2cm and the length of 60cm, wherein the volume of a catalyst bed layer is 13cm 2, and then purging the device with nitrogen;
the preparation process of the modified titanium-silicon-aluminum molecular sieve comprises the following steps:
At normal temperature of 25 ℃ and normal pressure, firstly, the mass ratio of the MFI structure titanium-silicon molecular sieve to the sulfonic acid is 0.2:1, mixing and pulping, carrying out heat treatment on the obtained slurry for 20 hours at 80 ℃, and carrying out solid-liquid separation to obtain a first solid with the relative crystallinity of 80%;
mixing the first solid with 20wt% of aluminum sol, titanium source n-propyl titanate, silicon source methyl orthosilicate, acid source fluoboric acid and water according to the mass ratio of 100:3:5:5:20:500 is put into a stainless steel sealed reaction kettle, is subjected to second heat treatment for 15 hours at 150 ℃, is discharged, is dried for 2 hours at 200 ℃, and is finally baked for 6 hours at 500 ℃ to obtain the acid modified titanium-silicon-aluminum molecular sieve;
(2) Feeding methanol, hydrogen peroxide and propylene into a reactor according to the molar ratio of the methanol, the hydrogen peroxide and the propylene of 4:1:1.5 for continuous reaction, and reacting at the temperature of 80 ℃ and the pressure of 3MPa with the reaction space velocity of 3h -1; after the reaction is finished, a reaction product is obtained; the hydrogen peroxide is provided as a 30wt% aqueous hydrogen peroxide solution;
In the preparation method, the conversion rate of olefin is 99.4%, the selectivity of alcohol ether compounds propylene glycol methyl ether and propylene glycol is 58.6% and 41.8%, respectively, and the molar ratio of the two isomers of propylene glycol methyl ether, namely 1-methoxy-2-propanol to 2-methoxy-1-propanol is 55:3.6.
4. The preparation method of the alcohol ether compound is characterized by comprising the following steps:
(1) Placing the modified titanium silicon aluminum molecular sieve in a fixed bed tubular reactor with the diameter of 2cm and the length of 60cm, wherein the volume of a catalyst bed layer is 13cm 2, and then purging the device with nitrogen;
the preparation process of the modified titanium-silicon-aluminum molecular sieve comprises the following steps:
At normal temperature of 25 ℃ and normal pressure, firstly, the mass ratio of the MFI structure titanium-silicon molecular sieve to the sulfonic acid is 0.2:1, mixing and pulping, carrying out heat treatment on the obtained slurry for 20 hours at 80 ℃, and carrying out solid-liquid separation to obtain a first solid with the relative crystallinity of 80%;
mixing the first solid with 20wt% of aluminum sol, titanium source n-propyl titanate, silicon source methyl orthosilicate, acid source fluoboric acid and water according to the mass ratio of 100:3:5:5:20:500 is put into a stainless steel sealed reaction kettle, is subjected to second heat treatment for 15 hours at 150 ℃, is discharged, is dried for 2 hours at 200 ℃, and is finally baked for 6 hours at 500 ℃ to obtain the acid modified titanium-silicon-aluminum molecular sieve;
(2) Feeding butanol, hydrogen peroxide and propylene into a reactor according to the molar ratio of butanol, hydrogen peroxide and propylene of 4:1:1.5 for continuous reaction, and reacting at 80 ℃ and 3MPa with the reaction space velocity of 3h -1; after the reaction is finished, a reaction product is obtained; the hydrogen peroxide is provided as a 30wt% aqueous hydrogen peroxide solution;
In the preparation method, the conversion rate of olefin is 99.4%, the selectivity of alcohol ether compound propylene glycol butyl ether and propylene glycol is 54.6% and 41.8%, respectively, and the mole ratio of 1-butoxy-2-propanol to 2-butoxy-1-propanol of two isomers of propylene glycol butyl ether is 53:1.6.
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