CN116803967A - Method for preparing o-diol by oxidizing olefin - Google Patents
Method for preparing o-diol by oxidizing olefin Download PDFInfo
- Publication number
- CN116803967A CN116803967A CN202210256397.5A CN202210256397A CN116803967A CN 116803967 A CN116803967 A CN 116803967A CN 202210256397 A CN202210256397 A CN 202210256397A CN 116803967 A CN116803967 A CN 116803967A
- Authority
- CN
- China
- Prior art keywords
- acid
- molecular sieve
- titanium silicalite
- olefin
- tungsten
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 76
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 51
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 23
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 132
- 239000010936 titanium Substances 0.000 claims abstract description 85
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 81
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 239000002253 acid Substances 0.000 claims abstract description 37
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000010937 tungsten Substances 0.000 claims abstract description 29
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 239000007800 oxidant agent Substances 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 150000002009 diols Chemical group 0.000 claims abstract description 18
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 239000002808 molecular sieve Substances 0.000 claims description 132
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 132
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 44
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 28
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 25
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 14
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 14
- -1 nitro, hydroxyl Chemical group 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 239000002149 hierarchical pore Substances 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 150000002148 esters Chemical group 0.000 claims description 7
- 150000001451 organic peroxides Chemical class 0.000 claims description 7
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 6
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 6
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 150000001299 aldehydes Chemical group 0.000 claims description 6
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 6
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 6
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 6
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims description 6
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 6
- 150000002978 peroxides Chemical class 0.000 claims description 6
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 6
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 5
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000005711 Benzoic acid Substances 0.000 claims description 4
- XKGDWZQXVZSXAO-ADYSOMBNSA-N Ricinoleic Acid methyl ester Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(=O)OC XKGDWZQXVZSXAO-ADYSOMBNSA-N 0.000 claims description 4
- XKGDWZQXVZSXAO-SFHVURJKSA-N Ricinolsaeure-methylester Natural products CCCCCC[C@H](O)CC=CCCCCCCCC(=O)OC XKGDWZQXVZSXAO-SFHVURJKSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 235000010233 benzoic acid Nutrition 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 claims description 4
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 claims description 4
- 229940073769 methyl oleate Drugs 0.000 claims description 4
- XKGDWZQXVZSXAO-UHFFFAOYSA-N ricinoleic acid methyl ester Natural products CCCCCCC(O)CC=CCCCCCCCC(=O)OC XKGDWZQXVZSXAO-UHFFFAOYSA-N 0.000 claims description 4
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- GQNOPVSQPBUJKQ-UHFFFAOYSA-N 1-hydroperoxyethylbenzene Chemical compound OOC(C)C1=CC=CC=C1 GQNOPVSQPBUJKQ-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 3
- XRXANEMIFVRKLN-UHFFFAOYSA-N 2-hydroperoxy-2-methylbutane Chemical compound CCC(C)(C)OO XRXANEMIFVRKLN-UHFFFAOYSA-N 0.000 claims description 3
- SGJUFIMCHSLMRJ-UHFFFAOYSA-N 2-hydroperoxypropane Chemical compound CC(C)OO SGJUFIMCHSLMRJ-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000008107 benzenesulfonic acids Chemical class 0.000 claims description 3
- 229940078916 carbamide peroxide Drugs 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 3
- IBAHLNWTOIHLKE-UHFFFAOYSA-N cyano cyanate Chemical group N#COC#N IBAHLNWTOIHLKE-UHFFFAOYSA-N 0.000 claims description 3
- HYPABJGVBDSCIT-UPHRSURJSA-N cyclododecene Chemical compound C1CCCCC\C=C/CCCC1 HYPABJGVBDSCIT-UPHRSURJSA-N 0.000 claims description 3
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 claims description 3
- 239000004913 cyclooctene Substances 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 claims description 3
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 claims description 3
- FGGJBCRKSVGDPO-UHFFFAOYSA-N hydroperoxycyclohexane Chemical compound OOC1CCCCC1 FGGJBCRKSVGDPO-UHFFFAOYSA-N 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- 150000002576 ketones Chemical group 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 229960002969 oleic acid Drugs 0.000 claims description 3
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 claims description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Chemical group 0.000 claims description 3
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 claims description 3
- 229960003656 ricinoleic acid Drugs 0.000 claims description 3
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 claims description 3
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 3
- 229960001922 sodium perborate Drugs 0.000 claims description 3
- 229940045872 sodium percarbonate Drugs 0.000 claims description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 3
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 claims description 3
- 239000011593 sulfur Chemical group 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 3
- NNQDMQVWOWCVEM-UHFFFAOYSA-N 1-bromoprop-1-ene Chemical compound CC=CBr NNQDMQVWOWCVEM-UHFFFAOYSA-N 0.000 claims description 2
- ATQUFXWBVZUTKO-UHFFFAOYSA-N 1-methylcyclopentene Chemical compound CC1=CCCC1 ATQUFXWBVZUTKO-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 claims description 2
- 229940044603 styrene Drugs 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 75
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- 239000002994 raw material Substances 0.000 abstract description 9
- 229960002163 hydrogen peroxide Drugs 0.000 description 58
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 46
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- 230000000052 comparative effect Effects 0.000 description 8
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- 238000004519 manufacturing process Methods 0.000 description 7
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- 238000000926 separation method Methods 0.000 description 6
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 6
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- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
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- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 238000006735 epoxidation reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
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- 150000002367 halogens Chemical group 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000003444 phase transfer catalyst Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 229910052736 halogen Chemical group 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229940051250 hexylene glycol Drugs 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000005673 monoalkenes Chemical class 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000007039 two-step reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 229940083957 1,2-butanediol Drugs 0.000 description 1
- 229940015975 1,2-hexanediol Drugs 0.000 description 1
- UFTUYFPADJIUDL-UHFFFAOYSA-N 2,3-diethylbenzenesulfonic acid Chemical compound CCC1=CC=CC(S(O)(=O)=O)=C1CC UFTUYFPADJIUDL-UHFFFAOYSA-N 0.000 description 1
- ZZXDRXVIRVJQBT-UHFFFAOYSA-N 2,3-dimethylbenzenesulfonic acid Chemical compound CC1=CC=CC(S(O)(=O)=O)=C1C ZZXDRXVIRVJQBT-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- CMGPPGOUOGYCGD-UHFFFAOYSA-N 2-cyclohexylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C1CCCCC1 CMGPPGOUOGYCGD-UHFFFAOYSA-N 0.000 description 1
- UAZLASMTBCLJKO-UHFFFAOYSA-N 2-decylbenzenesulfonic acid Chemical compound CCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O UAZLASMTBCLJKO-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- CTIFKKWVNGEOBU-UHFFFAOYSA-N 2-hexadecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O CTIFKKWVNGEOBU-UHFFFAOYSA-N 0.000 description 1
- AQQPJNOXVZFTGE-UHFFFAOYSA-N 2-octadecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O AQQPJNOXVZFTGE-UHFFFAOYSA-N 0.000 description 1
- VBVVNLPJLRAFAI-UHFFFAOYSA-N 2-pentylbenzenesulfonic acid Chemical compound CCCCCC1=CC=CC=C1S(O)(=O)=O VBVVNLPJLRAFAI-UHFFFAOYSA-N 0.000 description 1
- RIOSJKSGNLGONI-UHFFFAOYSA-N 2-phenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C1=CC=CC=C1 RIOSJKSGNLGONI-UHFFFAOYSA-N 0.000 description 1
- JBVOQKNLGSOPNZ-UHFFFAOYSA-N 2-propan-2-ylbenzenesulfonic acid Chemical compound CC(C)C1=CC=CC=C1S(O)(=O)=O JBVOQKNLGSOPNZ-UHFFFAOYSA-N 0.000 description 1
- UDTHXSLCACXSKA-UHFFFAOYSA-N 3-tetradecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCCCC1=CC=CC(S(O)(=O)=O)=C1 UDTHXSLCACXSKA-UHFFFAOYSA-N 0.000 description 1
- RJWBTWIBUIGANW-UHFFFAOYSA-N 4-chlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(Cl)C=C1 RJWBTWIBUIGANW-UHFFFAOYSA-N 0.000 description 1
- BRIXOPDYGQCZFO-UHFFFAOYSA-N 4-ethylphenylsulfonic acid Chemical compound CCC1=CC=C(S(O)(=O)=O)C=C1 BRIXOPDYGQCZFO-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- YYLLIJHXUHJATK-UHFFFAOYSA-N Cyclohexyl acetate Chemical compound CC(=O)OC1CCCCC1 YYLLIJHXUHJATK-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- LVGKNOAMLMIIKO-UHFFFAOYSA-N Elaidinsaeure-aethylester Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC LVGKNOAMLMIIKO-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005643 Pelargonic acid Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002635 aromatic organic solvent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- PBWZKZYHONABLN-UHFFFAOYSA-N difluoroacetic acid Chemical compound OC(=O)C(F)F PBWZKZYHONABLN-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- LVGKNOAMLMIIKO-QXMHVHEDSA-N ethyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC LVGKNOAMLMIIKO-QXMHVHEDSA-N 0.000 description 1
- 229940093471 ethyl oleate Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- FHKSXSQHXQEMOK-UHFFFAOYSA-N hexane-1,2-diol Chemical compound CCCCC(O)CO FHKSXSQHXQEMOK-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M isovalerate Chemical compound CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- GHDIHPNJQVDFBL-UHFFFAOYSA-N methoxycyclohexane Chemical compound COC1CCCCC1 GHDIHPNJQVDFBL-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 229930015698 phenylpropene Natural products 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- QROGIFZRVHSFLM-UHFFFAOYSA-N prop-1-enylbenzene Chemical compound CC=CC1=CC=CC=C1 QROGIFZRVHSFLM-UHFFFAOYSA-N 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
A process for the preparation of an vicinal diol by oxidation of an olefin, the process comprising contacting the olefin, an oxidant, an acid and a solvent with a composite catalyst comprising a titanium silicalite and a tungsten-containing compound to obtain a product comprising the vicinal diol. The method has the characteristics of mild reaction conditions, simple operation process, high raw material conversion rate, high o-diol selectivity, high hydrogen peroxide utilization rate and the like.
Description
Technical Field
The invention relates to a method for preparing o-diol by oxidizing olefin, in particular to a method for preparing o-diol by oxidizing olefin under the co-catalysis of a titanium silicon molecular sieve and a tungsten-containing compound.
Background
Vicinal diols refer to hydrocarbon organic compounds in which hydroxyl groups are present in each of the adjacent two carbon atoms. Common vicinal diols include 1, 2-ethanediol (hereinafter abbreviated as ethanediol), 1, 2-propanediol (hereinafter abbreviated as propanediol), 1, 2-butanediol (hereinafter abbreviated as butanediol), 1, 2-hexanediol (hereinafter abbreviated as hexanediol), and the like. The vicinal diols have important uses, for example, ethylene glycol can be used as a solvent, an antifreezing agent, synthetic polyester, etc., propylene glycol can be used as an unsaturated polyester resin, as an antifreezing agent, a humectant, etc., and hexylene glycol can be used for the production of high-end cosmetics, etc. The o-glycol has wide market application, and the yield is larger, and the global propylene glycol yield in 2018 reaches 180 ten thousand tons/year by taking propylene glycol as an example.
The main production method of the vicinal diols is obtained by hydrolyzing the upstream epoxy compounds under certain conditions. For example, ethylene oxide is hydrolyzed to obtain ethylene glycol, propylene oxide is hydrolyzed to obtain propylene glycol, and hexane is hydrolyzed to obtain hexylene glycol, etc. In addition, the propylene glycol can also be obtained by a dimethyl carbonate/propylene glycol co-production method. The method for hydrolyzing the epoxy compound must prepare the epoxy compound first, and the whole flow brings the problems of increased process complexity, low raw material utilization rate and three wastes discharge, which directly leads to increased cost. The co-production method also requires the production of the epoxy compound first, and in addition, the price of the co-production product is always affected by market fluctuation.
US10214471 and US20180354878A1 disclose a method for obtaining propylene glycol by reacting propylene and hydrogen peroxide in a reactor under the action of a heteropolyacid and a phase transfer catalyst. In the method, heteropolyacid and hydrogen peroxide form heteropolyacid peroxide salt in a water phase, and organic phase soluble salt is formed by the phase transfer catalyst and the heteropolyacid peroxide salt. In the method, an alkylated aromatic organic solvent having 8-12 carbon atoms increases the proportion of heteropolyacid salt in the organic phase to complete the oxidation of propylene to propylene oxide. The heteropolyacid is dissolved in water to continuously act with hydrogen peroxide, and the generated propylene oxide can enter into a water phase, and the propylene oxide is hydrolyzed under the action of water phase acid to obtain propylene glycol because the pH value of the water phase is maintained within the range of 1-3.5. The method is actually only to carry out two-step reaction of propylene epoxidation to propylene oxide, wherein the propylene oxide is hydrolyzed and ring-opened to propylene glycol under the action of acid in one reactor, a large amount of solvent is needed in the reaction process, the catalyst system is complex, and the operation difficulty is high.
EP1527057A1 discloses a process for the continuous preparation of propylene glycol. Propylene and hydrogen peroxide react to generate propylene oxide, propylene glycol is produced as a byproduct, the generated propylene oxide is reacted at 180-220 ℃ and 15-25bar to generate propylene glycol, and the propylene glycol is obtained after separation. The method is the physical integration of two-step reaction of epoxidation and hydrolysis, and cannot avoid the problems of low reaction efficiency and severe hydrolysis treatment conditions.
WO2019029808A1 discloses a process for preparing terminal 1, 2-alkanediols having from 5 to 12 carbon atoms by mixing the corresponding terminal alkene with formic acid and hydrogen peroxide to give the mono-or di-formate, and decomposing the mono-or di-formate under the action of a decarbonizing catalyst to give the corresponding diols and carbon monoxide. The method has low selectivity and high safety risk of the organic peroxide.
CN103570493a discloses a method for synthesizing 1, 2-o-diol by solid-supported heteropolyacid phase transfer catalytic oxidation, which is characterized in that acid, terminal alkene, hydrogen peroxide and heteropolyacid phase transfer catalyst are mixed and reacted, then separated to obtain an epoxidation mixture, then alkali liquor is added to maintain the pH value of 10-12, and then the o-diol is obtained by extraction with ester and reduced pressure distillation. The method has long operation flow and low product yield.
CN107879893a discloses a method for preparing an ortho-diol compound by catalytic oxidation, which is to prepare ortho-diol under the action of olefin, oxidant and bifunctional catalyst, wherein the bifunctional catalyst contains silicoaluminophosphate molecular sieve, alumina and titanium silicalite molecular sieve. The method uses an aluminum-containing catalyst, and the utilization rate of hydrogen peroxide is low.
CN102452899a discloses a method for preparing propylene glycol from propylene, which is to perform epoxidation ring-opening hydration reaction on titanium-silicon molecular sieve composite catalyst, propylene and hydrogen peroxide to prepare propylene glycol, wherein the titanium-silicon molecular sieve composite catalyst comprises titanium-silicon molecular sieve, acidic molecular sieve and resin. The method has low hydrogen peroxide utilization rate.
CN104447204a discloses a method for preparing glycol, which uses a titanium silicon molecular sieve loaded with rare earth oxide as a catalyst to promote the reaction of olefin and oxidant to generate glycol. The method has low hydrogen peroxide utilization rate.
Disclosure of Invention
The invention aims to provide a method for preparing o-diol by oxidizing olefin, which has the characteristics of mild reaction conditions, simple operation process, high raw material conversion rate, high o-diol selectivity, high effective utilization rate of hydrogen peroxide and the like.
In order to achieve the above object, the present invention provides a process for producing an vicinal diol by oxidizing an olefin, characterized in that the process comprises contacting an olefin with an oxidizing agent in the presence of an acid, a solvent and a composite catalyst to obtain a product containing an vicinal diol, wherein the composite catalyst contains a titanium silicalite and a tungsten-containing compound.
In the method, the olefin is C2-C30 mono-olefin or multi-olefin. The olefin may further contain one or more functional groups selected from alkyl, aryl, ester, nitro, hydroxyl, carboxyl, aldehyde, ketone, cyano, ether, amino, imino, halogen substituents, or further contain oxygen, nitrogen, sulfur, phosphorus, halogen heteroatom groups. Preferably, the olefin is one or more of ethylene, vinyl chloride, propylene, chloropropene, bromopropene, acrylonitrile, acrylic acid, acrolein, allyl alcohol, vinyl acetate, butenoic acid, isobutylene, 1-butene, 2-butene, butadiene, 1-pentene, cyclopentene, methylcyclopentene, 1, 4-pentadiene, cyclopentadiene, isoprene, 1-hexene, cyclohexene, hexadiene, 1-heptene, cycloheptene, 1-octene, cyclooctene, 1-decene, cyclododecene, styrene, oleic acid, methyl oleate, ricinoleic acid, methyl ricinoleate. More preferably, the olefin is one or more of propylene, 1-butene, 1-hexene, cyclohexene and chloropropene.
In the method, the oxidant is at least one selected from inorganic peroxide, organic peroxide and ozone; the inorganic peroxide is at least one selected from hydrogen peroxide, carbamide peroxide, potassium hydrogen peroxymonosulfate, potassium peroxydisulfate, sodium percarbonate, percarbamide and sodium perborate; the organic peroxide is at least one selected from tert-butyl hydroperoxide, cyclohexyl hydroperoxide, cumene hydroperoxide, ethylbenzene hydroperoxide, benzoic acid peroxide, methyl ethyl ketone peroxide, tert-butyl peroxypivalate, isopropyl hydroperoxide, tert-amyl hydroperoxide and di-tert-butyl peroxide; preferably, the oxidizing agent is hydrogen peroxide.
In the method, the acid is one or more of organic carboxylic acid, substituted benzenesulfonic acid, phosphoric acid, nitric acid and sulfuric acid; preferably, the acid is selected from one or more of phosphoric acid, nitric acid and sulfuric acid.
In the method, the solvent is one or more of water, C2-C20 ether, C2-C20 acid, C2-C30 ester and derivatives; preferably, the solvent is water.
In the method, the titanium silicalite molecular sieve is at least one of an MFI type titanium silicalite molecular sieve, an MEL type titanium silicalite molecular sieve, a BEA type titanium silicalite molecular sieve, an MWW type titanium silicalite molecular sieve, a MOR type titanium silicalite molecular sieve, a TON type titanium silicalite molecular sieve, a TUN type titanium silicalite molecular sieve and a hexagonal structure titanium silicalite molecular sieve; preferably, the titanium silicalite molecular sieve is an MFI type titanium silicalite molecular sieve; more preferably, the MFI-type titanium-silicon molecular sieve has a hierarchical pore structure or an intragranular hollow structure.
In the method, the tungsten-containing compound is selected from tungsten-containing oxides, oxy-acids and salts; preferably, the tungsten-containing compound is selected from one or more of tungsten trioxide, blue tungsten, huang Wu, huang Wusuan, white tungstic acid, metatungstic acid, silicotungstic acid, ammonium tungstate, ammonium metatungstate and sodium tungstate; more preferably, the tungsten-containing compound is tungsten trioxide and/or metatungstic acid.
In the method, the weight ratio of the titanium silicon molecular sieve to the oxidant is (0.01-10) to 1. The weight ratio of the tungsten-containing compound to the titanium-silicon molecular sieve is (0.01-0.5) to 1, and the preferable weight ratio is (0.03-0.3): 1, more preferably (0.07-0.2): 1. the acid brings the pH of the reacted solution system to a value of 1 to 4, preferably 1.5 to 3. The molar ratio of the oxidant to the olefin is (0.1-20) to 1, preferably (0.5-10): 1. further preferably (0.8-5): 1. the molar ratio of the oxidant to the solvent is 1: (3-200), preferably 1: (5-80), further preferably 1: (10-40). The contact condition is that the temperature is 5 ℃ to 100 ℃ and the pressure is normal pressure to 5MPa.
The invention provides a method for preparing o-diol by oxidizing olefin, which comprises the step of reacting olefin, oxidant, acid and solvent in one reactor under the action of a composite catalyst containing titanium-silicon molecular sieve and tungsten-containing compound to generate a product containing o-diol. Compared with the prior art, the method does not need the step of preparing the epoxy compound, has simple operation process, mild reaction conditions, high raw material conversion rate, higher o-diol selectivity and safer and more efficient process, and is suitable for large-scale industrial production and application.
Detailed Description
The invention provides a process characterized in that the process comprises contacting an olefin with an oxidizing agent in the presence of an acid, a solvent and a complex catalyst comprising a titanium silicalite and a tungsten-containing compound to obtain a product comprising an ortho-diol.
The present invention is not limited in the kind of the raw olefin, and may be mono-olefin or multi-olefin. The olefin may be aliphatic, alicyclic or aromatic hydrocarbon, and may have a substituent such as alkyl, aryl, ester, nitro, hydroxyl, carboxyl, aldehyde, ketone, cyano, ether, amino, imino or halogen, and may contain oxygen, nitrogen, sulfur, phosphorus or halogen hetero atoms. Preferably, wherein the olefin is a C2-C30 mono-or multiolefin, further preferred is a C2-C18, more preferred is a C3-C8 mono-or multiolefin. For example, the olefin may be ethylene, vinyl chloride, propylene, chloropropene, acrylonitrile, acrylic acid, acrolein, allyl alcohol, butenoic acid, isobutylene, 1-butene, 2-butene, butadiene, 1-pentene, cyclopentene, 1, 4-pentadiene, cyclopentadiene, isoprene, 1-hexene, cyclohexene, 1-heptene, 1-octene, cyclooctene, 1-decene, cyclododecene, styrene, phenylpropene, oleic acid, methyl oleate, ricinoleic acid, methyl ricinoleate, and the like.
According to the present invention, the olefin may be a single component olefin, may be a mixed component olefin, or may be a mixed olefin feed of an olefin with an inert component such as nitrogen, argon, helium, neon, air, oxygen, hydrogen, methane, ethane, propane, butane. The molar content of olefins in the mixed olefin feed is preferably greater than 20%, more preferably greater than 50%, even more preferably greater than 70%, most preferably greater than 90%. For safety reasons, the oxygen content and the hydrogen content in the mixed olefin raw material are controlled, preferably, the oxygen molar content and the hydrogen molar content are respectively lower than 5%, preferably lower than 2%, more preferably lower than 1%.
According to the present invention, the oxidizing agent may be at least one of an inorganic peroxide, an organic peroxide, and ozone; the inorganic peroxide is at least one selected from hydrogen peroxide, carbamide peroxide, potassium hydrogen peroxymonosulfate, potassium peroxydisulfate, sodium percarbonate, percarbamide and sodium perborate; the organic peroxide is at least one selected from tert-butyl hydroperoxide, cyclohexyl hydroperoxide, cumene hydroperoxide, ethylbenzene hydroperoxide, benzoic acid peroxide, methyl ethyl ketone peroxide, tert-butyl peroxypivalate, isopropyl hydroperoxide, tert-amyl hydroperoxide and di-tert-butyl peroxide; the preferred oxidizing agent is hydrogen peroxide. The hydrogen peroxide is usually prepared into an aqueous solution, namely hydrogen peroxide, and the hydrogen peroxide is used, and the mass concentration of the hydrogen peroxide is not particularly required, preferably, the hydrogen peroxide is a solution with the mass concentration of 2% -70%, more preferably 10% -50%, and even more preferably 20% -45%.
According to the invention, the acid comprises an organic acid and/or an inorganic acid. For example, one or more of organic carboxylic acid, substituted benzene sulfonic acid, phosphoric acid, nitric acid, sulfuric acid may be used. The organic acid may be carboxylic acid such as formic acid, acetic acid, trifluoroacetic acid, difluoroacetic acid, monofluoroacetic acid, propionic acid, butyric acid, succinic acid, cyclohexylacid, benzoic acid, derivatives thereof, etc., and may be benzenesulfonic acid such as one or more of benzenesulfonic acid, toluenesulfonic acid, dimethylbenzenesulfonic acid, ethylbenzenesulfonic acid, diethylbenzenesulfonic acid, isopropylbenzenesulfonic acid, pentylbenzenesulfonic acid, cyclohexylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, octadecylbenzenesulfonic acid, phenylbenzenesulfonic acid, p-chlorobenzenesulfonic acid. The inorganic acid can be one or more of phosphoric acid, nitric acid and sulfuric acid. Preferably, the acid is one or more of phosphoric acid, nitric acid and sulfuric acid. In the process provided by the invention, the acid is ionized in a solvent to generate hydrogen protons, preferably so that the pH value of the solution system is 1-4, and more preferably the pH value is 1.5-3.
According to the present invention, the solvent may be selected from one or more of water, C2-C20 ethers, C2-C20 acids, C2-C30 esters and derivatives thereof. For example, the solvent may be an organic solvent such as methyl ether, diethyl ether, methyl tert-butyl ether, methylcyclohexyl ether, anisole, acetic acid, propionic acid, butyric acid, malonic acid, caprylic acid, pelargonic acid, methyl formate, ethyl acetate, ethyl formate, butyl acetate, isopropyl acetate, cyclohexyl acetate, methyl oleate, ethyl oleate, methyl ricinoleate, etc. In view of the fact that the separation, purification and recovery units of the solvent are required to be added under the condition of adding the organic solvent, the complexity of the process and the energy consumption are increased, and the contact reaction is preferably carried out by using only water as the solvent without adding the organic solvent from the viewpoints of optimizing the reaction process, reducing the energy consumption, reducing the three-waste emission and improving the economical efficiency of the device.
It is understood that heterogeneous mass transfer resistance existing in the reaction process can be realized by selecting a proper reactor, adding internal components, adjusting process parameters and other prior art modes, and the description is omitted here. The process provided by the invention is carried out in the presence of a composite catalyst comprising a titanium silicalite molecular sieve and a tungsten-containing compound. The framework titanium species of the titanium-silicon molecular sieve has the excellent performance of activating hydrogen peroxide and catalyzing the oxidation of organic molecules. According to the present invention, the titanium silicalite molecular sieve is a common titanium silicalite molecular sieve, for example, the titanium silicalite molecular sieve may be an MFI-type titanium silicalite molecular sieve (such as a TS-1 molecular sieve), an MEL-type titanium silicalite molecular sieve (such as a TS-2 molecular sieve), a BEA-type titanium silicalite molecular sieve (such as a Ti- β molecular sieve), an MWW-type titanium silicalite molecular sieve (such as a Ti-MCM-22 molecular sieve), a MOR-type titanium silicalite molecular sieve (such as a Ti-MOR molecular sieve), a TUN-type titanium silicalite molecular sieve (such as a Ti-TUN molecular sieve), a hexagonal-structured titanium silicalite molecular sieve (such as a Ti-MCM-41 molecular sieve, a Ti-SBA-15 molecular sieve), and other-structured titanium silicalite molecular sieves (such as a Ti-ZSM-48 molecular sieve). Preferably, the titanium silicalite molecular sieve is at least one selected from MFI type titanium silicalite molecular sieve, MEL type titanium silicalite molecular sieve and BEA type titanium silicalite molecular sieve. Further preferably, the titanium silicalite molecular sieve is an MFI-type titanium silicalite molecular sieve.
According to the invention, the MFI-type titanium silicalite molecular sieve can be TS-1 molecular sieve prepared by conventional methods such as hydrothermal synthesis, post-treatment synthesis and the like, and can be titanium silicalite molecular sieve with a multi-stage pore structure (namely according to N 2 The absorption and desorption curves are subjected to BJH fitting molecular sieve pore distribution curves, and pore distribution in the range of 2-50nm exists in the crystal of the molecular sieve, and the molecular sieve can be a hollow titanium silicon molecular sieve HTS with an intragranular hollow structure (namely, one or more intragranular cavities exist in the crystal of the molecular sieve through TEM characterization), and can be a titanium silicon molecular sieve with a flaky shape, a spherical shape, a hexagonal column shape and an open surface. In order to achieve better technical effects, the MFI type titanium silicalite molecular sieve which is more preferable in the invention is a titanium silicalite molecular sieve with a hierarchical pore structure and/or a hollow titanium silicalite molecular sieve HTS with a hollow structure.
The skeleton titanium in the titanium-silicon molecular sieve is the catalytic active center of the titanium-silicon molecular sieve, the titanium content of the titanium-silicon molecular sieve is not particularly required, and the higher the skeleton titanium content is, the higher the catalytic activity is under the condition of not violating objective rules. According to the invention, the titanium silicon molecular sieve can have a titanium silicon molar ratio of (0.001-0.05): 1, preferably (0.01-0.03): 1.
according to the invention, the titanium silicon molecular sieve can be molecular sieve raw powder which is directly used as a catalyst, or can be formed, for example, the titanium silicon molecular sieve is formed by tabletting, microsphere and small-sphere catalysts are prepared by rolling sphere forming, bar catalysts are prepared by extrusion molding, spherical catalysts are prepared by spray drying and the like, and then the titanium silicon molecular sieve is used; or the titanium silicon molecular sieve, other catalysts, cocatalysts and inert matrix carriers are directly put into the reaction of the invention for use simultaneously or successively without molding, and the invention is not limited in any way. The titanium-silicon molecular sieve-containing catalyst preferably comprises 20-100% by weight of titanium-silicon molecular sieve, more preferably 50-100% by weight of titanium-silicon molecular sieve, even more preferably 80-100% by weight of titanium-silicon molecular sieve, and can contain a binder, a cocatalyst, a pore-expanding agent, an inert matrix carrier and the like besides the titanium-silicon molecular sieve serving as a main catalyst.
The inventors have unexpectedly found that titanium silicalite molecular sieves and tungsten containing compounds have significant promoting effects when applied as a composite catalyst in the reaction of olefin oxidation to make vicinal diols. The tungsten-containing compound comprises tungsten-containing oxide, oxo acid and salt, and the preferable tungsten-containing compound is selected from one or more of tungsten trioxide, blue tungsten, huang Wu, huang Wusuan, white tungstic acid, metatungstic acid, silicotungstic acid, ammonium tungstate, ammonium metatungstate and sodium tungstate. More preferred tungsten-containing compounds are one or more of tungsten trioxide and metatungstic acid. The weight ratio of the tungsten-containing compound to the titanium-silicon molecular sieve is (0.01-0.5): 1, preferably (0.03-0.3): 1, more preferably (0.07-0.2): 1. in the composite catalyst containing the titanium-silicon molecular sieve and the tungsten-containing compound, the titanium-silicon molecular sieve can be mechanically mixed with the tungsten-containing compound for use, or the titanium-silicon molecular sieve and the tungsten-containing compound can be molded for use as a catalyst, and the invention is not limited.
According to the invention, the titanium silicalite molecular sieve (according to SiO 2 Calculated by weight ratio of (0.01-10) to oxidant: 1, preferably (0.05-5): 1, further preferably (0.1-2): 1. the molar ratio of the oxidant to the solvent is 1: (3-200), preferably 1: (5-80), and more preferably 1: (10-40). The molar ratio of the oxidant to the olefin is (0.1-20): 1, preferably (0.5-10): 1, further preferably (0.8-5): 1.
the method for preparing the vicinal diols by oxidizing the olefin provided by the invention is preferably implemented by a method which comprises premixing an oxidant and the composite catalyst and fully contacting for a period of time, wherein the pre-activation of the catalyst is carried out to obtain a mixture of the oxidant and the composite catalyst, and the contact time is preferably 1-30min. After this, the olefin, acid and solvent are contacted with a mixture of an oxidizing agent and a complex catalyst to yield a product containing the vicinal diol.
In the present invention, the contact is preferably carried out under the following conditions: the temperature is 5-100deg.C, preferably 20-80deg.C, and the pressure is normal pressure to 5Mpa (gauge). In the preferable pressure range of the contact, the reaction system can be liquid-solid three-phase reaction, gas-liquid-solid three-phase reaction, liquid-solid two-phase reaction or gas-liquid-solid four-phase reaction.
In the present invention, the pressure may be the autogenous pressure of the reaction raw materials formed under the reaction conditions, or may be the gas components inert to the reaction, including, but not limited to, nitrogen, argon, helium, neon, air, oxygen, methane, ethane, propane, butane, etc. introduced to maintain the reaction pressure, and the contact reaction process of the present invention is performed without violating objective rules. For safety reasons, the oxygen content and the hydrogen content are controlled, preferably the oxygen molar content and the hydrogen molar content are each less than 5%, more preferably less than 2%, and even more preferably less than 1%, respectively.
The present invention may be carried out under batch conditions or under continuous conditions. The invention is preferably carried out under continuous conditions from the viewpoints of reducing labor intensity and improving product quality and feasibility and safety of technology. The contact is preferably carried out for a period of time, i.e.a reaction time, of from 1min to 24h, or a space velocity of the feed mass, calculated as oxide, of from 0.1 to 5h -1 。
The method provided by the invention can realize intermittent or continuous reaction in different forms of reactors such as a kettle type reactor, a fixed bed reactor, a tubular reactor, a fluidized bed reactor, a suspension bed reactor, a micro-channel reactor and the like. The different reactor forms are only used for adapting to the corresponding purpose requirements, so that better effect of directly preparing the o-diol from the olefin by one-step reaction is achieved. The catalyst of the invention is preferably used in a corresponding form in combination with a reactor, for example, a fixed bed reactor and a tubular reactor adopt shaped catalysts, a kettle reactor adopts molecular sieve raw powder, a microchannel reactor adopts molecular sieve raw powder or the catalysts are fixedly supported in a microchannel, and the invention can achieve relatively better reaction effect.
The reaction process of the method mainly generates o-diol, mono-o-diol (i.e. condensation etherification products of 2 o-diol molecules), di-o-diol (i.e. condensation etherification products of 3 o-diol molecules), aldehyde generated by the double bond rupture of raw material olefin, acid obtained by further oxidation of aldehyde, and the like. The process provided by the present invention may further comprise a step of separating the reaction products, such as, but not limited to, unreacted olefins, produced aldehydes, by distillation, separation of produced o-diols, mono-di-o-diols, di-o-diols under reduced pressure or extraction. The step of separating the product in the above manner is less energy consuming.
In the process of the present invention, the separation of the catalyst from the reaction system may be achieved in a variety of ways. For example, but not limited to, when the original powdery titanium silicalite molecular sieve is used as the catalyst, separation of the product and recovery and reuse of the catalyst can be achieved by sedimentation, filtration, centrifugation, evaporation, membrane separation and the like, or the catalyst can be packed in a fixed bed reactor after being molded, and the catalyst is recovered after the reaction is finished, and various methods for separating and recovering the catalyst are generally involved in the prior literature and are not repeated here.
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
The preparation method of the MFI-type titanium silicalite molecular sieve TS-1 adopted in the example is (refer to the method of Zeolite, 1992,12 (8), 943-50): a solution of approximately 3/4 of tetrapropylammonium hydroxide (TPAOH, 20%, available from Aldrich, USA) was added to a solution of tetraethyl orthosilicate (TEOS) to give a liquid mixture having a pH of approximately 13, and then the desired amount of n-butyl titanate [ Ti (OBu) ] was added dropwise to the resulting liquid mixture with vigorous stirring 4 ]Is stirred for 15 minutesObtaining clarified liquid, adding the rest TPAOH into the clarified liquid slowly, stirring for about 3 hr under 348-353K to obtain TiO with chemical composition of 0.03 2 ：SiO 2 ：0.36TPA：35H 2 O sol, then crystallization at 443K temperature for 3 days, then filtering the obtained solid, washing with distilled water, drying at 373K temperature for 5 hours, and roasting at 823K for 10 hours to obtain a TS-1 molecular sieve sample. Wherein, the amount of TEOS is 42g, the amount of TPAOH is 73g, ti (OBu) 4 The amount of (2 g), the amount of anhydrous isopropyl alcohol (10 g) and the amount of water (68 g). In the TS-1 molecular sieve sample, the molar ratio of Ti to Si is 0.03:1.
Preparation of MFI-type titanium silicalite molecular sieve hierarchical pore TS-1 used in the examples (refer to CN112898237a preparation comparative example 2): (1) Mixing tetraethoxysilane, tetrabutyl titanate, tetrapropylammonium hydroxide and water, and treating for 12 hours at 30 ℃ to obtain the mixture with the molar composition of SiO2, tiO2, tetrapropylammonium hydroxide, water=1: 0.03:0.13: 50; (2) Treating the product of step (1) at 90 ℃ for 12 hours; (3) The product of step (2) (in SiO 2 Calculated as) and silylating agent in a molar ratio of 1:0.1 adding N-phenyl-3-aminopropyl trimethoxy silylating agent and treating at 170 ℃ for 48h; (4) And (3) filtering and washing the product obtained in the step (3), drying the filter cake at 90 ℃ for 12h, and roasting at 550 ℃ for 6h to obtain the MFI type titanium-silicon molecular sieve hierarchical pores TS-1 reamed by the silanization reagent. In the hierarchical pore TS-1, the molar ratio of Ti to Si is 0.03:1, and the hierarchical pore TS-1 is prepared through N 2 The absorption and desorption characterization and BJH pore distribution fitting can find that obvious mesopores exist in the range of 5-30nm, and the volume of the mesopores is more than 0.7cm 3 /g。
The MFI type hollow titanium silicon molecular sieve HTS adopted in the example is prepared by referring to the method described in the specification example 1 of Chinese patent CN1301599A, wherein the molar ratio of Ti to Si in the HTS molecular sieve is 0.03:1, and the TEM characterization shows that an obvious hollow structure exists in the crystal of the molecular sieve.
The raw materials used in the examples were all chemically pure reagents unless otherwise specified.
The reaction product was analyzed for its composition by gas chromatography and the analysis was quantified by external standard method. Wherein, the analysis conditions of the chromatograph are: agilent-6890 chromatograph, HP-5 capillary chromatographic column, sample injection amount 0.5 μl, sample inlet temperature 280 ℃. The column temperature was maintained at 100deg.C for 2min, then raised to 250deg.C at 15 ℃/min and maintained for 15min. FID detector, detector temperature 280 ℃.
The content of hydrogen peroxide is measured by adopting an indirect titration method of sodium thiosulfate.
The following criteria are mainly examined in each of the examples and comparative examples:
conversion of olefins = moles of olefin consumed by each species produced in the product/moles of olefin in the feed x 100%
Selectivity of vicinal diols = moles of vicinal diols in product/moles of olefins consumed to form main by-products x 100%
Effective utilization ratio of hydrogen peroxide = mol number of hydrogen peroxide consumed by organic matters generated in the product/(mol number of hydrogen peroxide in raw materials before reaction-mol number of hydrogen peroxide in product after reaction) ×100%
Example 1
HTS molecular sieve, tungsten trioxide, propylene, 30 mass% hydrogen peroxide solution, phosphoric acid and a required amount of water are put into a reaction kettle. Wherein, the weight ratio of tungsten trioxide to titanium silicalite molecular sieve is 0.1:1, the mol ratio of titanium silicalite molecular sieve to hydrogen peroxide is 0.2:1, the pH value of the reaction solution is 2.0, the mol ratio of hydrogen peroxide (calculated by hydrogen peroxide) to propylene is 2:1, and the mol ratio of hydrogen peroxide (calculated by hydrogen peroxide) to water is 1:20. Then, the mixture in the reaction kettle was reacted at 60℃and 2MPa for 3 hours, and after the reaction was completed, the sample was analyzed, and the analysis results are shown in Table 1.
Example 2
HTS molecular sieve, tungsten trioxide, 1-butene, 40 mass% hydrogen peroxide solution, phosphoric acid and a required amount of water are put into a reaction kettle. Wherein, the weight ratio of tungsten trioxide to titanium silicalite molecular sieve is 0.1:1, the mol ratio of titanium silicalite molecular sieve to hydrogen peroxide is 0.2:1, the pH value of the reaction solution is 2.5, the mol ratio of hydrogen peroxide to 1-butene is 2:1, and the mol ratio of hydrogen peroxide to water is 1:15. Then, the mixture in the reaction kettle was reacted at 40℃and 1MPa for 4 hours, and after the reaction was completed, the sample was analyzed, and the analysis results are shown in Table 1.
Example 3
HTS molecular sieve, metatungstic acid, propylene, 27 mass% hydrogen peroxide solution, sulfuric acid and required amount of water are put into a reaction kettle. Wherein the weight ratio of the metatungstic acid to the titanium silicalite molecular sieve is 0.15:1, the mol ratio of the titanium silicalite molecular sieve to the hydrogen peroxide is 0.5:1, the pH value of the reaction solution is 1.5, the mol ratio of the hydrogen peroxide to the propylene is 3:1, and the mol ratio of the hydrogen peroxide to the water is 1:30. Then, the mixture in the reaction kettle was reacted at 80℃and 4MPa for 2 hours, and after the reaction was completed, the sample was analyzed, and the analysis results are shown in Table 1.
Example 4
HTS molecular sieve, tungsten trioxide and 27 mass percent hydrogen peroxide solution are mixed and activated for 10min at 60 ℃, and then propylene, phosphoric acid and required amount of water are added into a reaction kettle. Wherein, the weight ratio of tungsten trioxide to titanium silicalite molecular sieve is 0.2:1, the mol ratio of titanium silicalite molecular sieve to hydrogen peroxide is 0.2:1, the pH value of the reaction solution is 2.0, the mol ratio of hydrogen peroxide to propylene is 2:1, and the mol ratio of hydrogen peroxide to water is 1:20. The mixture in the reaction kettle was reacted at 60℃and 2MPa for 3 hours, and after the completion of the reaction, the sample was analyzed, and the analysis results are shown in Table 1.
Example 5
HTS molecular sieve, tungsten trioxide and 30 mass percent hydrogen peroxide solution are mixed and activated for 20min at 50 ℃, and then 1-hexene, sulfuric acid and required amount of water are added into a reaction kettle. Wherein the weight ratio of tungsten trioxide to titanium silicalite molecular sieve is 0.07:1, the molar ratio of titanium silicalite molecular sieve to hydrogen peroxide is 1:1, the pH value of the reaction solution is 1.5, the molar ratio of hydrogen peroxide to 1-hexene is 1.2:1, and the molar ratio of hydrogen peroxide to water is 1:20. The mixture in the reaction kettle was reacted at 50℃and 0.5MPa for 3 hours, and after the completion of the reaction, the sample was analyzed, and the analysis results are shown in Table 1.
Example 6
HTS molecular sieve, metatungstic acid and 30 mass% hydrogen peroxide solution are mixed and activated for 30min at 30 ℃, and then the mixture is introduced into a microchannel reactor to react with chloropropene, phosphoric acid and required amount of water. Wherein the weight ratio of the metatungstic acid to the titanium silicalite molecular sieve is 0.2:1, the mol ratio of the titanium silicalite molecular sieve to the hydrogen peroxide is 0.3:1, the pH value of the reaction solution is 2.0, the mol ratio of the hydrogen peroxide to the chloropropene is 1.5:1, and the mol ratio of the hydrogen peroxide to the water is 1:15. The mixture in the reaction kettle was reacted at 30℃and 0.2MPa for 5min, and after the completion of the reaction, the sample was analyzed, and the analysis results are shown in Table 1.
Example 7
HTS molecular sieve, metatungstic acid and 30 mass% hydrogen peroxide solution are mixed and activated for 10min at 80 ℃, and then propylene, phosphoric acid and required amount of water are added into a reaction kettle. Wherein the weight ratio of the metatungstic acid to the titanium silicalite molecular sieve is 0.15:1, the mol ratio of the titanium silicalite molecular sieve to the hydrogen peroxide is 0.3:1, the pH value of the reaction solution is 2.5, the mol ratio of the hydrogen peroxide to the propylene is 2:1, and the mol ratio of the hydrogen peroxide to the water is 1:30. The mixture in the reaction kettle was reacted at 80℃and 3MPa for 2 hours, and after the completion of the reaction, the sample was analyzed, and the analysis results are shown in Table 1.
Example 8
HTS molecular sieve, metatungstic acid and 30 mass% hydrogen peroxide solution are mixed and activated for 10min at 60 ℃, and then propylene, sulfuric acid and required amount of water are added into a reaction kettle. Wherein the weight ratio of the metatungstic acid to the titanium silicalite molecular sieve is 0.15:1, the mol ratio of the titanium silicalite molecular sieve to the hydrogen peroxide is 0.2:1, the pH value of the reaction solution is 2.5, the mol ratio of the hydrogen peroxide to the propylene is 3:1, and the mol ratio of the hydrogen peroxide to the water is 1:20. The mixture in the reaction kettle was reacted at 60℃and 2MPa for 3 hours, and after the completion of the reaction, the sample was analyzed, and the analysis results are shown in Table 1.
Example 9
HTS molecular sieve, tungsten trioxide and 30 mass percent hydrogen peroxide solution are mixed and activated for 5min at 60 ℃, and then propylene, nitric acid and required amount of water are added into a reaction kettle. Wherein, the weight ratio of tungsten trioxide to titanium silicalite molecular sieve is 0.2:1, the mol ratio of titanium silicalite molecular sieve to hydrogen peroxide is 0.2:1, the pH value of the reaction solution is 2.0, the mol ratio of hydrogen peroxide to propylene is 1.5:1, and the mol ratio of hydrogen peroxide to water is 1:15. The mixture in the reaction kettle was reacted at 60℃and 2MPa for 4 hours, and after the completion of the reaction, the sample was analyzed, and the analysis results are shown in Table 1.
Example 10
HTS molecular sieve, tungsten trioxide, propylene, 30 mass% hydrogen peroxide solution, phosphoric acid and a required amount of methyl tertiary butyl ether are put into a reaction kettle. Wherein the weight ratio of tungsten trioxide to titanium silicalite molecular sieve is 0.3:1, the molar ratio of titanium silicalite molecular sieve to hydrogen peroxide is 0.4:1, the pH value of the reaction solution is 1.0, the molar ratio of hydrogen peroxide to propylene is 1.5:1, and the molar ratio of hydrogen peroxide to methyl tertiary butyl ether is 1:10. Then, the mixture in the reaction kettle was reacted at 50℃and 1.5MPa for 2 hours, and after the reaction was completed, the sample was analyzed, and the analysis results are shown in Table 1.
Example 11
The difference from example 1 is that TS-1 molecular sieves were used and the results of the analysis are shown in Table 1.
Example 12
The difference from example 1 is that a hierarchical pore TS-1 molecular sieve was used and the analysis results are shown in Table 1.
Comparative example 1
The difference from example 11 is that no tungsten trioxide was added and the analysis results are shown in Table 1.
Comparative example 2
The difference from example 12 is that no tungsten trioxide was added and the analysis results are shown in Table 1.
Comparative example 3
The difference from example 1 is that no tungsten trioxide was added and the analysis results are shown in Table 1.
Comparative example 4
The difference from example 1 is that no HTS molecular sieve was added and the analysis results are shown in table 1.
Comparative example 5
A cerium oxide-supported TS-1 molecular sieve was prepared according to the method of example 1 of Chinese patent CN104447204A, and the reaction was evaluated according to the method of example 1, in which phosphoric acid and tungsten trioxide were not added during the reaction, and CeO was used 2 TS-1 is the catalyst reaction, and the analysis result after the reaction is finished is shown in Table 1.
TABLE 1
As can be seen from the results of examples 1-12 and comparative examples 1-5 shown in Table 1, the method for preparing the vicinal diols has the advantages of simple operation process, mild reaction conditions, high selectivity of the vicinal diols, high effective utilization rate of the oxydol, safety and controllability, and suitability for large-scale industrial production and application.
Claims (16)
1. A process for the preparation of an vicinal diol by oxidation of an olefin, characterized in that the process comprises contacting an olefin with an oxidizing agent in the presence of an acid, a solvent and a complex catalyst to obtain a product comprising an vicinal diol, wherein the complex catalyst comprises a titanium silicalite and a tungsten-containing compound.
2. The process of claim 1 wherein the olefin is a C2-C30 mono-or multiolefin.
3. The method of claim 1, wherein the olefin further comprises one or more functional groups selected from the group consisting of alkyl, aryl, ester, nitro, hydroxyl, carboxyl, aldehyde, ketone, cyano, ether, amino, imino, halogen substituents, or further comprises oxygen, nitrogen, sulfur, phosphorus, halogen heteroatom groups.
4. The process of claim 1 wherein the olefin is one or more of ethylene, vinyl chloride, propylene, chloropropene, bromopropene, acrylonitrile, acrylic acid, acrolein, allyl alcohol, vinyl acetate, butenoic acid, isobutylene, 1-butene, 2-butene, butadiene, 1-pentene, cyclopentene, methylcyclopentene, 1, 4-pentadiene, cyclopentadiene, isoprene, 1-hexene, cyclohexene, hexadiene, 1-heptene, cycloheptene, 1-octene, cyclooctene, 1-decene, cyclododecene, styrene, oleic acid, methyl oleate, ricinoleic acid, methyl ricinoleate.
5. The process of claim 1 wherein the olefin is one or more of propylene, 1-butene, 1-hexene, cyclohexene, chloropropene.
6. The method of claim 1, wherein the oxidizing agent is at least one selected from the group consisting of inorganic peroxides, organic peroxides, and ozone; the inorganic peroxide is at least one selected from hydrogen peroxide, carbamide peroxide, potassium hydrogen peroxymonosulfate, potassium peroxydisulfate, sodium percarbonate, percarbamide and sodium perborate; the organic peroxide is at least one selected from tert-butyl hydroperoxide, cyclohexyl hydroperoxide, cumene hydroperoxide, ethylbenzene hydroperoxide, benzoic acid peroxide, methyl ethyl ketone peroxide, tert-butyl peroxypivalate, isopropyl hydroperoxide, tert-amyl hydroperoxide and di-tert-butyl peroxide; preferably, the oxidizing agent is hydrogen peroxide.
7. The method of claim 1, wherein the acid is one or more of an organic carboxylic acid, a substituted benzenesulfonic acid, phosphoric acid, nitric acid, sulfuric acid; preferably, the acid is selected from one or more of phosphoric acid, nitric acid and sulfuric acid.
8. The method of claim 1, wherein the solvent is one or more of water, a C2-C20 ether, a C2-C20 acid, a C2-C30 ester, and a derivative thereof; preferably, the solvent is water.
9. The method of claim 1, wherein the titanium silicalite is at least one of MFI-type titanium silicalite, MEL-type titanium silicalite, BEA-type titanium silicalite, MWW-type titanium silicalite, MOR-type titanium silicalite, TON-type titanium silicalite, TUN-type titanium silicalite, and hexagonal structure titanium silicalite; preferably, the titanium silicalite molecular sieve is an MFI type titanium silicalite molecular sieve; more preferably, the MFI-type titanium-silicon molecular sieve has a hierarchical pore structure or an intragranular hollow structure.
10. The method of claim 1 wherein the tungsten-containing compound is selected from the group consisting of tungsten-containing oxides, oxy-acids, and salts; preferably, the tungsten-containing compound is selected from one or more of tungsten trioxide, blue tungsten, huang Wu, huang Wusuan, white tungstic acid, metatungstic acid, silicotungstic acid, ammonium tungstate, ammonium metatungstate and sodium tungstate; more preferably, the tungsten-containing compound is tungsten trioxide and/or metatungstic acid.
11. The method of claim 1, wherein the weight ratio of titanium silicalite molecular sieve to oxidant is (0.01-10) to 1.
12. The method of claim 1, wherein the weight ratio of the tungsten-containing compound to the titanium silicalite molecular sieve is (0.01-0.5) to 1, preferably (0.03-0.3): 1, more preferably (0.07-0.2): 1.
13. a process according to claim 1, wherein the acid brings the pH of the reacted solution system to 1-4, preferably 1.5-3.
14. The process according to claim 1, wherein the molar ratio of oxidant to olefin is (0.1-20) to 1, preferably (0.5-10): 1. further preferably (0.8-5): 1.
15. the method according to claim 1, wherein the molar ratio of the oxidizing agent to the solvent is 1: (3-200), preferably 1: (5-80), further preferably 1: (10-40).
16. The process of claim 1, wherein the contacting is at a temperature of 5 ℃ to 100 ℃ and a pressure of from atmospheric to 5MPa.
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