CN1222148A - Process for producing epoxides from olefines and hydrogen peroxide or hydroperoxides using zeolithic oxidation catalyst - Google Patents
Process for producing epoxides from olefines and hydrogen peroxide or hydroperoxides using zeolithic oxidation catalyst Download PDFInfo
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- CN1222148A CN1222148A CN 97195499 CN97195499A CN1222148A CN 1222148 A CN1222148 A CN 1222148A CN 97195499 CN97195499 CN 97195499 CN 97195499 A CN97195499 A CN 97195499A CN 1222148 A CN1222148 A CN 1222148A
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- hydrogen peroxide
- titanium
- zeolite
- weight
- hydroperoxide
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000003054 catalyst Substances 0.000 title claims abstract description 9
- 150000002432 hydroperoxides Chemical class 0.000 title abstract description 4
- 230000003647 oxidation Effects 0.000 title abstract description 3
- 238000007254 oxidation reaction Methods 0.000 title abstract description 3
- 150000002118 epoxides Chemical class 0.000 title abstract 2
- 239000011541 reaction mixture Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 239000007791 liquid phase Substances 0.000 claims abstract description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 23
- 239000010457 zeolite Substances 0.000 claims description 23
- 229910021536 Zeolite Inorganic materials 0.000 claims description 21
- 238000006735 epoxidation reaction Methods 0.000 claims description 14
- 150000001336 alkenes Chemical class 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 7
- 150000002924 oxiranes Chemical class 0.000 claims description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 6
- GNKTZDSRQHMHLZ-UHFFFAOYSA-N [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] Chemical compound [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] GNKTZDSRQHMHLZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- SSHPBHBFGZLRRS-UHFFFAOYSA-N [V].[Si](O)(O)(O)O Chemical compound [V].[Si](O)(O)(O)O SSHPBHBFGZLRRS-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 102000004190 Enzymes Human genes 0.000 claims description 2
- 108090000790 Enzymes Proteins 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 235000013372 meat Nutrition 0.000 claims description 2
- 235000014347 soups Nutrition 0.000 claims description 2
- 239000012224 working solution Substances 0.000 claims description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims 1
- 150000004056 anthraquinones Chemical class 0.000 claims 1
- 239000010936 titanium Substances 0.000 abstract description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 19
- 229910052719 titanium Inorganic materials 0.000 abstract description 19
- 229910052720 vanadium Inorganic materials 0.000 abstract description 11
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000011521 glass Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000011435 rock Substances 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- -1 alkali metal salt Chemical class 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 description 1
- VQOXUMQBYILCKR-UHFFFAOYSA-N 1-Tridecene Chemical group CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 101000648997 Homo sapiens Tripartite motif-containing protein 44 Proteins 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 102100028017 Tripartite motif-containing protein 44 Human genes 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical group 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
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical group 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 1
- 239000004913 cyclooctene Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 125000005908 glyceryl ester group Chemical group 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002469 indenes Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229960004232 linoleic acid Drugs 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- RWMKKWXZFRMVPB-UHFFFAOYSA-N silicon(4+) Chemical compound [Si+4] RWMKKWXZFRMVPB-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Epoxy Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A process for producing epoxides from olefines and hydrogen peroxide or hydroperoxides in the liquid phase using an oxidation catalyst based on titanium or vanadium silicalites with a zeolithic structure, in which the concentration of the hydrogen peroxide or hydroperoxides in the reaction mixture is in the range from 0.05 to less than 1 wt.% during the reaction.
Description
The present invention relates to a kind of application makes oxide catalyst and prepares improving one's methods of epoxide by alkene and hydrogen peroxide or hydroperoxide based on having zeolite structured titanium silicate or silicic acid vanadium.
Making epoxidation catalyst about the application titanium silicate is disclosed in the method that alkene and aqueous hydrogen peroxide solution prepare epoxide: (1) EP-A100119 and (2) M.G.Clerici etc., catalysis magazine (J.Catal.) 129, (1991), 159-167 page or leaf.
According to (1), the epoxidation of ethene, propylene, 3-chloro-1-propene, 2-butylene, 1-octene, 1-tridecylene, mesityl oxide, isoprene, cyclooctene and cyclohexene is that general hydrogen peroxide dilute aqueous soln carries out in autoclave in the presence of titanium siliceous rock.In this case, the concentration of hydrogen peroxide in the reaction mixture can be reduced to 10% (weight).
In (2), disclose and to be reduced to 1% to the concentration of hydrogen peroxide in this epoxidation.In (2) narration for the titanium siliceous rock catalysis epoxidation effect that becomes propylene oxide from propylene, the source of its employed hydrogen peroxide is that concentration is the H of 30-35%
2O
2The aqueous solution.
Yet the prior art processes of this epoxidation has shortcoming.Use superoxol (about 10-70% (weight) H
2O
2), in reacting, can produce many major safety problems, because spontaneous decomposition may appear in hydrogen peroxide or its by product (for example hydroperoxide), particularly under the situation that some organic solvent exists, improve for getting rid of considerable expense of these safety problem needs and production cost.Even without the problem of described secure context, because intermediate concentration to the superoxol of high density is the comparison costliness, thereby production cost is original just high.
The purpose of this invention is to provide a kind of simply, effectively and particularly epoxidizing method of the economic alkene that does not have the prior art shortcoming again.
Once found by adopting following method to reach this purpose, this method is used based on the oxide catalyst with zeolite structured titanium siliceous rock or vanadium silicite by alkene and hydrogen peroxide or hydroperoxide with the liquid phase production epoxide, the wherein during reaction hydrogen peroxide in the reaction mixture or concentration 0.05%-＜1% (weight) of hydroperoxide, 0.1%-0.8% (weight), especially 0.2%-0.6% (weight) particularly.
The hydroperoxide that can use are all organic hydroperoxides that are used as the oxygenant of this class epoxidation usually, and its general formula is R-O-O-H, and R normally contains the organic radical of 1-30 carbon atom in the formula.In this connection, particularly advantageous is cumene hydroperoxide and hydroperoxidation diisopropylbenzene(DIPB).
In preferred embodiments, the source of the hydrogen peroxide that epoxidation of the present invention is used is an aqueous hydrogen peroxide solution, particularly industry (promptly not purifying) superoxol, its content of hydrogen peroxide is 0.1-10% (weight), particularly 0.15-5% (weight), especially 0.2-2% (weight) hydrogen peroxide.
The industrial hydrogen peroxide cource of particularly suitable is the extraction solution that contains hydrogen peroxide from the anthraquinone-working solution of preparation hydrogen peroxide.
Another kind of well-adapted industrial hydrogen peroxide cource is logistics that contains hydrogen peroxide or the resistates that distillation produces from hydrogen peroxide, for example steam or still bottom product, and this logistics or resistates improve its H without further concentrating usually
2O content.
The industrial hydrogen peroxide cource that is particularly suitable in addition is from fermentor tank meat soup or comes from the extraction solution that contains hydrogen peroxide that contains enzyme mixture, also can come from source naturally occurring or that can obtain with biotechnology.
Application is that prior art is known based on the oxide catalyst with zeolite structured titanium silicate or silicic acid vanadium.As well-known, zeolite is the crystal aluminosilicate with orderly channel architecture and cage structure, and its perforate is the micropore less than 0.9nm.The reticulated structure of this zeolite is the SiO that connects through the ordinary oxygen bridging
4-and AlO
4-tetrahedron.About this known structure can referring to, for example, W.M.Meier and D.H.Olson " zeolite structure type atlas " (Altas of Zeolite StructureTypes " Butterworth, second edition, London, 1987.
Other known zeolites do not contain aluminium, and titanium exists with the form that Ti (IV) part replaces silicon (IV) in lattice silicate.These titanium zeolites particularly have those of MFI type crystal structure, with and may the preparation method be described in, for example, among EP-A311983 or the EP-A405978.Except silicon and titanium, this class material also can contain such as aluminium, zirconium, tin, iron, cobalt, nickel, gallium, boron or small amount of fluorine element.
In described oxide catalyst, the titanium in the zeolite can partly or entirely be replaced by vanadium.Titanium and/or vanadium are generally 0.01 to the mol ratio that silicon adds titanium and/or vanadium total amount: 1-0.1: 1.
Known titanium zeolite with MFI structure, it can be discerned by the peculiar collection of illustrative plates of x-ray diffraction pattern, and can be by in the infrared region (IR) about 960 centimetres
-1Place's skeletal vibration bands of a spectrum are discerned, and are different from metatitanic acid an alkali metal salt or crystallization and amorphous TiO thus
2Phase.
The general method for making of described titanium zeolite and vanadium zeolite is as follows: make SiO in pressurized vessel
2The source, such as the titanium of titanium dioxide or corresponding vanadium oxide or vanadium source and such as the aqueous mixture of the nitrogenous organic base of tetrapropylammonium hydroxide (" template compound " (Schablonen-Verbindung)), can add alkali metal compound when needing, at high temperature reacted several hours or several days, and obtained crystallized product.Products therefrom is filtered, and organic nitrogen(ous) base is removed in washing, drying and calcination at high temperature.In the gained powder, to the titanium of small part or vanadium in varing proportions four-, five-or the effect of six-reprovision position be present in the zeolite lattice.In order to improve catalysis characteristics, then adopt the washing of vitriolic superoxol several times, titanium zeolite or vanadium zeolite powder drying and calcination more after this; Then, handle with alkali metal compound, so that zeolite is transformed into positively charged ion-type from the H-type.
Preferred titanium zeolite of institute or vanadium zeolite are to have pentasil structure person, particularly have the type that X-ray measuring belongs to BEA, MOR, TON, MTW, FER, MFI, MEL or MFI/MEL mixed structure.Such zeolite is described in, for example, and W.M.Meier and D.H.Olson, " zeolite structure type atlas " Butterworths second edition, London, 1987.For the present invention also may be the titanium-containing zeolite with ZSM-48, ZSM-12, ferrierite or beta-zeolite and mordenite structure.
The present invention makes on the methodological principle of epoxide and can adopt all common reaction methods to carry out in the reactor of all common types, for example adopts suspended pattern or in fixed bed unit.Can carry out operate continuously or periodical operation.
Epoxidation of the present invention is carried out in liquid phase, suitable can be only in water or water and can with the mixture of water-soluble mixed organic solvent in carry out.Shi Yi organic solvent is an alcohols especially, for example methyl alcohol, ethanol, Virahol, the trimethyl carbinol or its mixture.If these organic solvents mix application with water, its content in whole mixture is generally 5-95% (volume), particularly 30-85% (volume) so.
Epoxidation of the present invention in temperature is usually-20-70 ℃, particularly-and 5-50 ℃, pressure is to carry out under the 1-10 crust.
Employed alkene can be any organic compound that contains at least one ethylenical unsaturated double bonds.Can be aliphatic series, aromatics or alicyclic character, can have line style or branched structure.Preferred alkene contains 2-30 carbon atom.Can there be an above ethylenical unsaturated double bonds, for example in diene or triolefin.Alkene also can contain other functional group, for example halogen atom, carboxyl, carboxylicesters functional group, hydroxyl, ether bridge, sulphur bridge, carboxyl functional group, cyano group, nitro or amino.
The representative instance of this class alkene is an ethene, propylene, 1-butylene, suitable-and anti--2-butylene, 1,3-butadiene, amylene, isoprene, hexene, octene, nonene, decene, undecylene, dodecylene, cyclopentenes, tetrahydrobenzene, dicyclopentadiene, the methylene radical cyclopropane, vinyl cyclohexane, vinyl cyclohexene, 3-chloro-1-propene, vinylformic acid, methacrylic acid, butenoic acid, vinylacetic acid, vinyl carbinol, alkyl acrylate, alkyl methacrylate, grease, linolic acid, linolenic acid, the ester of above-mentioned unsaturated fatty acids and glyceryl ester, vinylbenzene, 2-methyl styrene, Vinylstyrene, indenes and stilbene.According to method of the present invention, the mixture of described alkene also can be by epoxidation.
Method of the present invention is specially adapted to make epoxidation of propylene to become propylene oxide.
According to the present invention, use titanium siliceous rock or vanadium silicite, be lower than under the concentration of hydrogen peroxide as known in the art at this, can successfully make alkene epoxidation.Because concentration of hydrogen peroxide is low in the system, no longer there is safety problem.In addition, can use the superoxol that does not contain the interference stability agent under high density, but must contain the interference stability agent.Method of the present invention thus has following advantage: can use low-cost technical grade hydrogen peroxide to make raw material; Make the people surprised be that wherein the impurity of Cun Zaiing does not disturb according to epoxidation of the present invention.
Further set forth method of the present invention with following example, but to be not understood to be a kind of restriction.
Example 1
The 455g tetraethyl orthosilicate is added in the 4 neck flasks (2l capacity), and when stirring (250 rev/mins, paddle stirrer), in 30 minutes, adds the 15g original four-isopropyl titanate and form the water white transparency mixture from dropping funnel.20% (weight) hydroxide tetrapropylammonium solution (alkali content＜10ppm), and mixture stirred 1 hour that adds 800g at last.By separate the alcohol mixture (about 450g) of formation at 90-100 ℃ of following dephlegmate.Replenish volume with the 1.5l deionized water, opaque a little solution is moved in the stainless agitated autoclave that capacity is 2.5l.
The temperature of airtight autoclave (200 rev/mins of anchor stirrers) is risen to 175 ° with 3 °/minute speed.Afterreaction was finished in 92 hours.Centrifugation refrigerative reaction mixture (white suspension body).Wash with water several times until neutrality.With gained solid dry 24 hours (weight 149g) under 110 ℃.
Removed the template compound (weightless 14% (weight) of calcining) that still is present in the zeolite in 5 hours by calcination in 550 ℃ of air at last.
According to the wet chemical analytical method, the Ti content of white pure products is 1.5% (weight), and however, residual base content is below the 100ppm.With SiO
2Be the basis meter, productive rate is 97%.Grain size is the 0.05-0.25 micron, and product shows typical IR bands of a spectrum at about 960 centimetres-1 places.
Example 2
The titanium silicate powder of 45ml methyl alcohol and 0.5g example 1 is added in the 250ml glass autoclave, with magnetic stirrer stirring suspension body.Airtight glass autoclave is cooled to-30 ℃ then, and injects the 20.7g propylene.Glass autoclave is warming up to 0 ℃ then, and is metered into 0.5% (weight) superoxol of 23g.Under autogenous pressure in 0 ℃ of stirred reaction mixture 5 hours.Catalyzer is removed in centrifugation then.Adopt gas Chromatographic Determination propylene oxide content.Propylene oxide content is 0.3% (weight).
Example 3
The titanium siliceous rock of 45ml methyl alcohol and 0.5g example 1 is added in the 250ml glass autoclave, with magnetic stirrer stirring suspension body.Airtight glass autoclave is cooled to-30 ℃ then, and injects the 20.2g propylene.Glass autoclave is warming up to 0 ℃ then, and is metered into 0.5% (weight) superoxol of 23g.Under autogenous pressure in 0 ℃ of stirred reaction mixture 30 minutes.Catalyzer is removed in centrifugation then, adopts gas Chromatographic Determination propylene oxide content.Propylene oxide content is 0.18% (weight).
Claims (6)
1. an application is made oxide catalyst by alkene and hydrogen peroxide or the hydroperoxide method with the liquid phase production epoxide based on having zeolite structured titanium silicate or silicic acid vanadium, it is characterized in that during reaction the concentration of hydrogen peroxide in the reaction mixture or hydroperoxide is 0.05-＜1% (weight).
2. according to the method for claim 1, it is characterized in that the hydrogen peroxide cource that epoxidation is used is the aqueous hydrogen peroxide solution that contains the hydrogen peroxide of 0.1-10% (weight).
3. according to the method for claim 2, it is characterized in that employed hydrogen peroxide cource is the extraction solution that contains hydrogen peroxide from the anthraquinone working solution of preparation hydrogen peroxide.
4. according to the method for claim 2, it is characterized in that employed hydrogen peroxide cource is logistics that contains hydrogen peroxide or the resistates that distillation produces from hydrogen peroxide.
5. according to the method for claim 2, it is characterized in that employed hydrogen peroxide cource is from fermentor tank meat soup or contains the extraction solution that contains hydrogen peroxide of enzyme mixture.
6. according to each is prepared the method for propylene oxide among the claim 1-5 by propylene and hydrogen peroxide or hydroperoxide.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97195499 CN1222148A (en) | 1996-06-13 | 1997-05-30 | Process for producing epoxides from olefines and hydrogen peroxide or hydroperoxides using zeolithic oxidation catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19623608.8 | 1996-06-13 | ||
| CN 97195499 CN1222148A (en) | 1996-06-13 | 1997-05-30 | Process for producing epoxides from olefines and hydrogen peroxide or hydroperoxides using zeolithic oxidation catalyst |
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