WO2012009056A1 - Process for producing olefin oxide - Google Patents
Process for producing olefin oxide Download PDFInfo
- Publication number
- WO2012009056A1 WO2012009056A1 PCT/US2011/038542 US2011038542W WO2012009056A1 WO 2012009056 A1 WO2012009056 A1 WO 2012009056A1 US 2011038542 W US2011038542 W US 2011038542W WO 2012009056 A1 WO2012009056 A1 WO 2012009056A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- oxide
- catalyst
- alkaline
- alkaline earth
- earth metal
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 48
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 44
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000002184 metal Substances 0.000 claims abstract description 91
- 239000003054 catalyst Substances 0.000 claims abstract description 85
- 229910052751 metal Inorganic materials 0.000 claims abstract description 79
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 59
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 39
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000005751 Copper oxide Substances 0.000 claims abstract description 26
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 26
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 23
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- -1 halogen ion Chemical class 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 24
- 229910052736 halogen Inorganic materials 0.000 claims description 24
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000010949 copper Substances 0.000 claims description 17
- 150000002367 halogens Chemical class 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 15
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 14
- 239000010941 cobalt Substances 0.000 claims description 14
- 229910017052 cobalt Inorganic materials 0.000 claims description 14
- 229910052681 coesite Inorganic materials 0.000 claims description 14
- 229910052906 cristobalite Inorganic materials 0.000 claims description 14
- 229910021645 metal ion Inorganic materials 0.000 claims description 14
- 229910052682 stishovite Inorganic materials 0.000 claims description 14
- 229910052905 tridymite Inorganic materials 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 12
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 11
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 11
- 229910001431 copper ion Inorganic materials 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 29
- 239000007789 gas Substances 0.000 description 26
- 150000003839 salts Chemical class 0.000 description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 18
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 229960004424 carbon dioxide Drugs 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- 229910001507 metal halide Inorganic materials 0.000 description 4
- 150000005309 metal halides Chemical class 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 229910001960 metal nitrate Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000007405 data analysis Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- 239000001272 nitrous oxide Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- WHNBDXQTMPYBAT-UHFFFAOYSA-N 2-butyloxirane Chemical compound CCCCC1CO1 WHNBDXQTMPYBAT-UHFFFAOYSA-N 0.000 description 1
- NJWSNNWLBMSXQR-UHFFFAOYSA-N 2-hexyloxirane Chemical compound CCCCCCC1CO1 NJWSNNWLBMSXQR-UHFFFAOYSA-N 0.000 description 1
- NMOFYYYCFRVWBK-UHFFFAOYSA-N 2-pentyloxirane Chemical compound CCCCCC1CO1 NMOFYYYCFRVWBK-UHFFFAOYSA-N 0.000 description 1
- SYURNNNQIFDVCA-UHFFFAOYSA-N 2-propyloxirane Chemical compound CCCC1CO1 SYURNNNQIFDVCA-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical compound C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910021223 NaCoC Inorganic materials 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical class CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910001964 alkaline earth metal nitrate Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 150000004648 butanoic acid derivatives Chemical class 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- AVWLPUQJODERGA-UHFFFAOYSA-L cobalt(2+);diiodide Chemical compound [Co+2].[I-].[I-] AVWLPUQJODERGA-UHFFFAOYSA-L 0.000 description 1
- BSUSEPIPTZNHMN-UHFFFAOYSA-L cobalt(2+);diperchlorate Chemical compound [Co+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O BSUSEPIPTZNHMN-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- KOKFUFYHQQCNNJ-UHFFFAOYSA-L copper;2-methylpropanoate Chemical compound [Cu+2].CC(C)C([O-])=O.CC(C)C([O-])=O KOKFUFYHQQCNNJ-UHFFFAOYSA-L 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- CRCKGIUJMFFISH-UHFFFAOYSA-N copper;ethanolate Chemical compound [Cu+2].CC[O-].CC[O-] CRCKGIUJMFFISH-UHFFFAOYSA-N 0.000 description 1
- VNGORJHUDAPOQZ-UHFFFAOYSA-N copper;propan-2-olate Chemical compound [Cu+2].CC(C)[O-].CC(C)[O-] VNGORJHUDAPOQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 235000003084 food emulsifier Nutrition 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 239000002316 fumigant Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical class Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 150000003892 tartrate salts Chemical class 0.000 description 1
- LVBXEMGDVWVTGY-UHFFFAOYSA-N trans-2-octenal Natural products CCCCCC=CC=O LVBXEMGDVWVTGY-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B01J35/615—
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
Abstract
A process for producing an olefin oxide which comprises reacting an olefin with oxygen in the presence of a catalyst comprising (a) copper oxide, (b) cobalt oxide and (c) alkaline metal component or alkaline earth metal component.
Description
DESCRIPTION
PROCESS FOR PRODUCING OLEFIN OXIDE
Cross-Reference to Related Applications
This application claims priority to and the benefit of U.S. Provisional Application No. 61/363,224, filed July 10, 2010, incorporated by reference here in its entirely.
Technical Field
The present invention relates to a process for producing an olefin oxide.
Background Art
Olefin oxides, such as propylene oxide, are important and versatile intermediates used in the production of a large variety of valuable consumer products such as polyurethane foams, polymers, alkylene glycol, cosmetics, food emulsifiers and as fumigants and insecticides.
Previous research on olefin epoxidation involved the use of Ag-based catalysts (Appl . Catal . A. Gen. 2001, 221, 73.), as well as silica supported Cu (J. Catal. 2005, 236, 401), various metal oxides (Appl. Catal. A. Gen. 2007, 316, 142), Au-based catalysts with H2 as a co-reactant (Ind. & Eng. Chem. Res. 1995, 34, 2298, J. Catal. 1998, 178, 566; Appl. Catal. A. Gen. 2000, 190, 43; Angew. Chem. Int. Ed. 2004, 43, 1546 ),
titania based catalysts that deactivated quickly (Catal. Commun 2001, 1356; Catal. Commun. 2003, 4, 385), molten salts of metal nitrates (Appl . Catal. A. Gen. 2000, 196, 217), the use of 03 (Appl . Catal. A. Gen. 2000, 196, 217) and nitrous oxide (Ind. & Eng. Chem. Res. 1995, 34, 2298) as reactants. Although these developments are scientifically interesting, they have serious drawbacks, such as low PO selectivities and/or low propylene conversions, short catalyst lifetimes, the use of higher pressures or the use of costly co-reactants (Appl . Catal . A. Gen . 2007, 316, 142) .
Summary of Invention
The present invention provides:
[1] A process for producing an olefin oxide which comprises reacting an olefin with oxygen in the presence of a catalyst comprising (a) copper oxide, (b) cobalt oxide and (c) alkaline metal component or alkaline earth metal component.
[2] The process according to [1], wherein the catalyst comprises (d) halogen component.
[3] The process according to [1] or [2], wherein the catalyst comprises (e) composite oxide.
[4] The process according to [1], wherein (a) copper oxide, (b) cobalt oxide and (c) alkaline metal component or alkaline earth metal component are supported on a porous support.
[5] The process according to [2], wherein (a) copper oxide,
(b) cobalt oxide, (c) alkaline metal component or alkaline earth metal component and (d) halogen component are supported on a porous support.
[6] The process according to [4] or [5], wherein the porous support comprises AI2O3, S1O2, T1O2 or ZrC>2.
[7] The process according to [4] or [5], wherein the porous support comprises Si02.
[8] The process according to any one of [1] to [7], wherein the total amount of (a) copper oxide, (b) cobalt oxide and (c) alkaline metal component or alkaline earth metal component is 0.01 to 80% by weight of the amount of the catalyst.
[9] The process according to any one of [1] to [8], wherein the copper/cobalt metal molar ratio in the catalyst is 1/99 to 99/1.
[10] The process according to any one of [1] to [9], wherein the copper/ (c) component metal molar ratio in the catalyst is 1/99 to 99/1.
[11] The process according to any one of [1] to [10], wherein
(a) copper oxide is CuO.
[12] The process according to any one of [1] to [11], wherein
(b) cobalt oxide is C03O4.
[13] The process according to any one of [1] to [12], wherein
(c) alkaline metal component or alkaline earth metal component is an alkaline metal-containing compound or an alkaline earth metal-containing compound.
[14] The process according to any one of [1] to [13], wherein (c) alkaline metal component or alkaline earth metal component is a sodium-containing compound.
[15] The process according to [4], wherein the catalyst is obtained by impregnating a porous support with a solution containing a copper ion, a cobalt ion and an alkaline metal or alkaline earth metal ion to prepare a composition, followed by calcining the composition.
[16] The process according to [5], wherein the catalyst is obtained by impregnating a porous support with a solution containing a copper ion, a cobalt ion, an alkaline metal or alkaline earth metal ion and a halogen ion to prepare a composition, followed by calcining the composition.
[17] The process according to any one of [1] to [16], wherein the olefin is propylene and the olefin oxide is propylene oxide.
[18] The process according to any one of [1] to [17], which comprises reacting an olefin with oxygen at a temperature of 100 to 350°C.
[19] A catalyst for production of an olefin oxide which comprises (a) copper oxide, (b) cobalt oxide and (c) alkaline metal component or alkaline earth metal component.
[20] The catalyst according to [19] which comprises (d) halogen component .
[21] The catalyst according to [19] or [20] which comprises (e) composite oxide.
[22] The catalyst according to [19], wherein (a) copper oxide, (b) cobalt oxide and (c) alkaline metal component or alkaline earth metal component are supported on a porous support.
[23] The catalyst according to [20], wherein (a) copper oxide,
(b) cobalt oxide, (c) alkaline metal component or alkaline earth metal component and (d) halogen component are supported on a porous support.
[24] The catalyst according to [22] which is obtained by impregnating a porous support with a solution containing a copper ion, a cobalt ion and an alkaline metal or alkaline earth metal ion to prepare a composition, followed by calcining the composition .
[25] The catalyst according to [23] which is obtained by impregnating a porous support with a solution containing a copper ion, a cobalt ion, an alkaline metal or alkaline earth metal ion and a halogen ion to prepare a composition, followed by calcining the composition.
[26] The catalyst according to any one of [19] to [25] , wherein
(c) alkaline metal component or alkaline earth metal component is an alkaline metal-containing compound or an alkaline earth metal-containing compound.
[27] The catalyst according to any one of [22] to [26] , wherein the porous support comprises A1203, Si02, Ti02 or Zr02.
[28] The catalyst according to any one of [22] to [27] , wherein the porous support comprises Si02.
[29] The catalyst according to any one of [19] to [28] , wherein the olefin oxide is propylene oxide.
[30] Use of a catalyst for producing an olefin oxide, said catalyst comprising (a) copper oxide, (b) cobalt oxide and (c) alkaline metal component or alkaline earth metal component.
[31] The use of a catalyst according to [30] , wherein the olefin oxide is propylene oxide.
Description of Embodiment
The process of the present invention comprises reacting an olefin with oxygen in the presence of a catalyst comprising (a) copper oxide, (b) cobalt oxide and (c) alkaline metal component or alkaline earth metal component.
The components (a) , (b) and (c) may be supported on a porous support or a non-porous support. Examples of the non-porous support include a non-porous support comprising S1O2 such as CAB-O-SIL (registered trademark) .
In the catalyst, the components (a) , (b) and (c) are preferably supported on a porous support. This catalyst is valuable for production of olefin oxides, which is one aspect of the present invention.
The porous support has pores capable of supporting the components (a) , (b) and (c) . The porous support comprises preferably AI2O3, S1O2, T1O2 or Zr02, more preferably Si02. Examples of the porous support comprising S1O2 include
mesoporous silica. Such a porous support may also comprise zeolites .
If the catalyst comprises S1O2 as a support, olefin oxides can be prepared with good yield and good selectivity.
The catalyst may comprise one or more kinds of (a) copper oxide. The (a) copper oxide is usually composed of copper and oxygen. Examples of the copper oxide include CU2O and CuO. The copper oxide is preferably CuO.
The catalyst may comprise one or more kinds of (b) cobalt oxide .
The component (b) is usually composed of cobalt and oxygen . Examples of the component (b) oxide include CoO, C03O4 and C02O3 , preferably Co304.
The catalyst may comprise one or more kinds of (c) alkaline metal component or alkaline earth metal component.
The component (c) may be an alkaline metal-containing compound, an alkaline earth metal-containing compound, an alkaline metal ion or an alkaline earth metal ion.
Examples of the alkaline metal-containing compound include compounds containing an alkaline metal such as Na, K, Rb and Cs . Examples of the alkaline earth metal-containing compound include compounds containing an alkaline earth metal such as Ca, Mg, Sr and Ba. Examples of the alkaline metal ion include Na+, K+, Rb+ and Cs+. Examples of the alkaline earth metal ion include Ca2+, Mg2+, Sr2+ and Ba2+.
The alkaline metal component may be an alkaline metal oxide . Examples of the alkaline metal oxide include Na20, Na202, K20, K02, K202, Rb20, Rb202, Cs20, Cs202, Cs02, Cs03, Cs203, Csu03, CS4O and CS7O. The alkaline earth metal component may be alkaline metal earth oxide. Examples of the alkaline earth metal oxide include CaO, Ca02, MgO, Mg02, SrO, Sr02, BaO and Ba02.
The alkaline metal-containing compound is preferably an alkaline metal salt. The alkaline earth metal-containing compound is preferably an alkaline earth metal salt. The alkaline metal salt comprises the alkaline metal ion as mentioned above with an anion. The alkaline earth metal salt comprises the alkaline earth metal ion as mentioned above with an anion. Examples of anions in such salts include F~, Cl~, Br~, I", OH", N03 ", S04 2", CO32", HCO3" and S03 2". Such salts are preferably an alkaline metal salt with a halogen, such as an alkaline metal halide, or an alkaline earth metal-containing salt with a halogen, such as an alkaline earth metal halide, more preferably an alkaline metal salt with a halogen, still more preferably an alkaline metal chloride.
The component (c) is preferably an alkaline
metal-containing compound or an alkaline earth
metal-containing compound, more preferably a
sodium-containing compound.
Particularly if the catalyst comprises NaCl as the (c) component, it can show excellent olefin oxide selectivity.
The copper/cobalt metal molar ratio in the catalyst is preferably 1/99 to 99/1. When the metal molar ratio falls within such a range, the olefin oxide yield and selectivity can be further improved. The lower limit of the molar ratio is more preferably 2/98 , still more preferably 3/ 97 , further preferably 10/90, particularly preferably 20/80. The upper limit of the molar ratio is more preferably 98/2, still more preferably 97/3, further preferably 90/10, particularly preferably 80/20.
The copper/ (c) component molar ratio in the catalyst is preferably 1/99 to 99/1. When the molar ratio falls within such a range, the olefin oxide yield and selectivity can be further improved. The lower limit of the molar ratio is more preferably 2/98, still more preferably 3/97. The upper limit of the molar ratio is more preferably 98/2, still more preferably 97/3. The " (c) component" of the molar ratio represents the alkaline metal or alkaline earth metal existing in the (c) component and the alkaline metal or alkaline earth metal ion existing in the (c) component .
When the components (a) , (b) and (c) are supported on a porous support in the catalyst, the total content of the components (a) , (b) and (c) is preferably 0.01 to 80% by weight of the amount of the catalyst. When the total content falls within such a range, the olefin oxide yield and selectivity can be further improved. The lower limit of the total content is more preferably 0.05% by weight, still more preferably 0.1% by
weight of the amount of the catalyst. The upper limit of the total content is more preferably 50% by weight, still more preferably 30% by weight of the amount of the catalyst.
The catalyst may comprise (d) halogen component besides the components (a) , (b) and (c) . The component (d) is generally a halogen-containing compound. Examples of the halogen include chlorine, fluorine, iodine and bromine.
Examples of such a halogen-containing compound include copper halides such as CuCl and CuCl2, cobalt halides such as C0CI2, cupper oxyhalides such as CUOCI2, CUCIO4, CIO2CU (CIO4) 3 and Cu20(C104)2 and cobalt oxyhalides such as Co(C104)2 and CIO2C0 (CIO4) 3. The component (d) may be supported on any of the components (a), (b) and (c) or the porous support.
The catalyst may further comprise (e) composite oxides including those composed of copper, cobalt and oxygen, such as CuxCo3-x04 and CuCo02 those composed of sodium, cobalt and oxygen, such as a4Co04 , NaCoC>2, Na4CoC>4 and NaCo2<04, and those composed of sodium, copper and oxygen, such as NaCuC>2, Na2CuC>2, NaCuO and Na6Cu2<06.
If the catalyst comprises the component (d) or (e) , the component may be supported on the porous support as mentioned above .
Production of the catalyst is not restricted to a specific process, examples of which include the conventional methods.
When the components (a) , (b) and (c) are supported on a
porous support in the catalyst, the catalyst can be obtained by impregnating a porous support with a solution containing a copper ion, a cobalt ion and an alkaline metal or alkaline earth metal ion to prepare a composition, followed by calcining the composition. The support can be in form of powder, or shaped to a desired structure as necessary. If the catalyst comprises the component (c) which is an alkaline metal salt with a halogen or alkaline earth metal salt with a halogen, and the component (d) supported on the porous support, the catalyst can be obtained in the same procedure as mentioned above except that the solution contains a copper ion, a cobalt ion, an alkaline metal or alkaline earth metal-containing ion and a halogen ion.
The solution containing a copper ion, a cobalt ion and an alkaline metal or alkaline earth metal ion can be prepared by dissolving a copper metal salt or a copper oxide, a cobalt metal salt or a cobalt oxide, and an alkaline metal or alkaline earth metal salt or an alkaline metal or alkaline earth metal oxide in a solvent. The solution is preferably prepared by dissolving a copper metal salt, a cobalt metal salt and an alkaline metal or alkaline earth metal salt in a solvent. Examples of the copper metal salt include copper acetate, copper ethoxide, copper isobutyrate, copper isopropoxide, copper hydroxide, copper nitrate, copper sulfate, copper chloride, copper diammonium chloride, copper bromide and copper iodide. Examples of the cobalt metal salt include cobalt sulfate, cobalt
nitrate, cobalt bromide, cobalt chloride, cobalt iodide, cobalt perchlorate, cobalt acetylacetonate, cobalt acetate, cobalt carbonate, cobalt carbonyl, and cobalt hydroxide. The alkaline metal or alkaline earth metal salt for the solution may be the same as or different from the salt of the (c) component in the catalyst. Examples of the alkaline metal or alkaline earth metal salt include alkaline metal nitrates, alkaline earth metal nitrates, alkaline metal halides, alkaline earth metal halides, alkaline metal acetates, alkaline earth metal acetates, alkaline metal butyrates, alkaline earth metal butyrates, alkaline metal benzoates, alkaline earth metal benzoates, alkaline metal alkoxides, alkaline earth metal alkoxides, alkaline metal carbonates, alkaline earth metal carbonates, alkaline metal citrates, alkaline earth metal citrates, alkaline metal formates, alkaline earth metal formates, alkaline metal hydrogen carbonates, alkaline earth metal hydrogen carbonates, alkaline metal hydroxides, alkaline earth metal hydroxides , alkaline metal hypochlorites, alkaline earth metal hypochlorites, alkaline metal halates, alkaline earth metal halates, alkaline metal nitrites, alkaline earth metal nitrites, alkaline metal oxalates, alkaline earth metal oxalates, alkaline metal perhalates, alkaline earth metal perhalates, alkaline metal propionates, alkaline earth metal propionates, alkaline metal tartrates and alkaline earth metal tartrates, preferably alkaline metal halides and alkaline metal
nitrates, more preferably NaNC>3 and NaCl . At least one of the metal salts for the solvent contains preferably a halogen ion, more preferably a chloride ion. Such a halogen ion may form the (c) components such as alkaline metal halides or alkaline earth metal halides, or (d) components such as cobalt halides, cobalt oxyhalides, copper halides and copper oxyhalides. The solution may contain acidic or basic compounds in order to control its pH.
Examples of the solvent for the solution include water and alcohols such as methanol or ethanol.
The total amount of porous support is preferably 20 to 99.99% by weight, more preferably 50 to 99.95% by weight, still preferably 70 to 99.9% by weight of the catalyst as obtained.
The composition as prepared by the impregnation is usually dried, and the drying method thereof is not limited.
The composition as prepared by the impregnation is preferably dried at a temperature of approximately 40°C to approximately 200°C before calcining the composition. Drying is preferably performed under an atmosphere of air or also under an inert gas atmosphere (for example, Ar, N2, He) at standard pressure or reduced pressure . A drying time is preferably in the range from 0.5 to 24 hours. After drying, the composition can be shaped to a desired structure as necessary.
The method of calcining the composition is not limited, and calcining the composition is preferably performed under a
gas atmosphere containing oxygen. Examples of such a gas stream include air, oxygen, nitrous oxide and other oxidizing gases. The gas may be used after being mixed at an appropriate ratio with a diluting gas such as nitrogen, helium, argon, and water vapor. An optimal temperature for calcination varies depending on the kind of the gas and the composition, however, a too high temperature may cause agglomeration of cobalt oxide and copper oxide. Accordingly, the calcination temperature is typically 200 to 800°C, preferably at 400 to 600°C.
The catalyst can be used as powder, but it is usual to shape desired structures such as spheres, pellets, cylinders, rings, hollow cylinders, or stars. The catalyst can be shaped by a known procedure such as extrusion, ram extrusion, tableting The calcination is normally performed after shaping desired structures, but it can also be performed before shaping them.
Next, the following explains a reaction of an olefin with oxygen in the presence of the catalyst as described above.
In the present invention, the olefin may have a linear or branched structure and contains usually 2 to 10, preferably 2 to 8 carbon atoms. Examples of the olefin include preferably ethylene, propylene, butene, pentene, hexene, heptene, octene, and butadiene, more preferably ethylene, propylene and butene, still more preferably propylene.
The reaction is generally performed in the gas phase. In the reaction, the olefin and oxygen may be fed respectively in
the form of gas. Olefin and oxygen gases can be fed in the form of their mixed gas. Olefin and oxygen gases may be fed with diluent gases. Examples of diluent gases include nitrogen, rare gases such as argon and helium, carbon dioxide, water vapor, methane, ethane and propane. Preferable diluent gases are nitrogen, carbon dioxide and the both thereof.
As the oxygen source, pure oxygen may be used, or a mixed gas containing pure oxygen and a gas inactive to the reaction, such as air, may be used. Examples of the gas inactive to the reaction include nitrogen, rare gases such as argon and helium, carbon dioxide, water vapor, methane, ethane and propane. Preferable gases inactive to the reaction are nitrogen, carbon dioxide and the both thereof. The amount of oxygen used varies depending on the reaction type, the catalyst, the reaction temperature or the like. The amount of oxygen is typically 0.01 to 100 mol, and preferably 0.03 to 30 mol, more preferably 0.05 to 10 mol and especially preferably 0.25 to 10 mol, with respect to 1 mol of the olefin.
The reaction is performed at a temperature generally of 100 to 350°C, preferably of 120 to 330°C, more preferably of 170 to 310°C.
The present reaction is carried out under reaction pressure in the range of reduced pressure to increased pressure .
By carrying out the reaction under such a reaction pressure condition, the productivity and selectivity of olefin oxides
can be improved. Reduced pressure means a pressure lower than atmospheric pressure. Increased pressure means a pressure higher than atmospheric pressure. The reaction pressure is typically in the range of 0.01 to 3 MPa, and preferably in the range of 0.02 to 2 MPa, in the absolute pressure.
The reaction of the present invention may be carried out as a batch reaction or a continuous reaction, preferably as a continuous reaction for industrial application. The reaction of the present invention may be carried out by mixing an olefin and oxygen and then contacting the mixture with the catalyst under reduced pressure to increased pressure.
The reactor type is not limited. Examples of the reactor types are fluid bed reactor, fixed bed reactor, moving bed reactor, and the like, preferably fixed bed reactor. In the case of using fixed bed reactor, single tube reactor or multi tube reactor can be employed. More than one reactors can be used. If the number of reactors is large, small reactors as for example microreactors , can be used, which can have multiple channels. Adiabatic type or heat exchange type may be also used.
In the present invention, the olefin oxide may have a linear or branched structure and contains usually 2 to 10, preferably 2 to 8 carbon atoms. Examples of the olefin oxides include preferably ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, heptene oxide, octene oxide, and 3, 4-epoxy-l-butene, more preferably ethylene oxide,
propylene oxide and butene oxide, still more preferably propylene oxide.
The olefin oxide as obtained can be collected by a method known in the art such as separation by distillation.
Examples
In Example 1, data analysis was performed according to the following method:
A reaction gas was mixed with ethane (10 Nml/min) as an external standard, and then directly introduced in the TCD-GC equipped with a column of Gaskuropack 54 (2 m) . All products in the reaction gas were collected for 1 hour with double methanol traps connected in series and cooled with a dry-ice/methanol bath. The two methanol solutions were mixed together and added to anisole as an external standard, and then analyzed with two FID-GCs equipped with different columns, PoraBOND U (25 m) and PoraBOND Q (25 m) .
The detected products were propylene oxide (PO) , acetone (AT), COx (C02 and CO), propanal (PaL) , acrolein (AC) .
The propylene conversion, product selectivity, and yield (calculated as selectivity of product χ propylene conversion) of products were calculated on the basis of carbon balance.
Propylene conversions (XPR) were determined from the following :
XPR = { [PO+AC+AT+PaL +C02/3 ] out/ [ C3H6 ] in } χ 100%;
and PO selectivity (SP0) was then calculated using the following expression :
Spo = { [PO] / [PO+AC+AT+PaL +C02/3] } 100% Each metal weight was determined from the amounts of the metal salts used for preparation of the catalyst.
Example 1
A catalyst was prepared by a co-impregnation method. A predetermined weight (2.7 g) of amorphous silica powder (Si02, Japan Aerosil , 380 m2/g) was added to an aqueous solution mixture containing 0.48 g of CoCl2 (Wako), 0.41 g of Cu(N03)2 (Wako) and 0.20 g of NaN03 (Wako) , followed by stirring the mixture for 24 hours in air to impregnate the support with the metal salts. The resulting material was then heated at 100°C until dried, and calcined at 500°C for 12 hours in air to give the catalyst.
The catalyst was evaluated by using a fixed-bed reactor. Filling a 1/2-inch OD reaction tube made of stainless steel with 1 mL of the thus obtained catalyst, the reaction tube was supplied with 450 NmL/h of propylene, 900 NmL/h of the air, and 990 NmL/h of a nitrogen gas to carry out the reaction at the reaction temperature of 200, 250 and 270 °C under increased pressure (equivalent to 0.3 MPa in the absolute pressure) .
The result is shown in Table 1.
Table 1
Example 2
The catalyst obtained in Example 1 (5.0 mg) was placed in a well of a reactor as mentioned in Angew. Chem. Int. Ed. 38 (1999) 2794, equipped with array microreactors, wells along each reactor channel and a passivated 200 micron ID capillary sampling probe within the reactor channel. The mixture gas consisting of 1 vol% propylene (C3H6) , 4 vol% 02, and 95 vol% He was fed to the well containing the catalyst, at a gas hourly space velocity (GHSV) of 20,000 h_1, at a reactor temperature of 250°C.
Gas sampling was accomplished by withdrawing reactor exit gases using the passivated 200 micron ID capillary sampling probe .
Data analysis for sample gases was conducted by an on-line Micro-Gas Chromatograph (Varian, CP-4900) equipped with a thermal conductivity detector (TCD) , PoraPLOT U (10M) and
Molecular sieve 13X (10M) .
The detected products were propylene oxide (PO) , acetone (AT) , acetaldehyde (AD) , COx (C02 and CO) , and propanal + acrolein (PaL+AC) .
The propylene conversion, product selectivity, and yield (calculated as selectivity of product χ propylene conversion) of products were calculated on the basis of carbon balance.
Propylene conversions (XPR) were determined from the following :
XPR = { [PO+AC+AT+2AD/3+C02/3] 0ut / [C3H6]in} x 100%; and PO selectivities (SP0) were then calculated using the following expression:
Spo = { [PO] / [PO+AC+AT+2AD/3+C02/3] } 100% Note: PaL+AC are reported together since the two compounds appear at the same retention time, although the PaL is typically only found in trace amounts.
The result is shown in Table 2.
Table 2
Claims
1. A process for producing an olefin oxide which comprises reacting an olefin with oxygen in the presence of a catalyst comprising (a) copper oxide, (b) cobalt oxide and (c) alkaline metal component or alkaline earth metal component.
2. The process according to claim 1, wherein the catalyst comprises (d) halogen component.
3. The process according to claim 1 or 2, wherein the catalyst comprises (e) composite oxide.
4. The process according to claim 1, wherein (a) copper oxide, (b) cobalt oxide and (c) alkaline metal component or alkaline earth metal component are supported on a porous support .
5. The process according to claim 2, wherein (a) copper oxide, (b) cobalt oxide, (c) alkaline metal component or alkaline earth metal component and (d) halogen component are supported on a porous support.
6. The process according to claim 4 or 5, wherein the porous support comprises A1203, Si02, Ti02 or Zr02.
7. The process according to claim 4 or 5, wherein the porous support comprises Si02.
8. The process according to claim 1 or 2, wherein the total amount of (a) copper oxide, (b) cobalt oxide and (c) alkaline metal component or alkaline earth metal component is 0.01 to 80% by weight of the amount of the catalyst.
9. The process according to claim 1 or 2, wherein the copper/ cobalt metal molar ratio in the catalyst is 1/99 to 99/1.
10. The process according to claim 1 or 2, wherein the copper/ (c) component metal molar ratio in the catalyst is 1/99 to 99/1.
11. The process according to claim 1 or 2, wherein (a) copper oxide is CuO.
12. The process according to claim 1 or 2, wherein (b) cobalt oxide is C03O4.
13. The process according to claim 1 or 2, wherein (c) alkaline metal component or alkaline earth metal component is an alkaline metal-containing compound or an alkaline earth metal-containing compound.
14. The process according to claim 1 or 2, wherein (c) alkaline metal component or alkaline earth metal component is a sodium-containing compound.
15. The process according to claim 4, wherein the catalyst is obtained by impregnating a porous support with a solution containing a copper ion, a cobalt ion and an alkaline metal or alkaline earth metal ion to prepare a composition, followed by calcining the composition.
16. The process according to claim 5, wherein the catalyst is obtained by impregnating a porous support with a solution containing a copper ion, a cobalt ion, an alkaline metal or alkaline earth metal ion and a halogen ion to prepare a composition, followed by calcining the composition.
17. The process according to claim 1 or 2, wherein the olefin is propylene and the olefin oxide is propylene oxide.
18. The process according to claim 1 or 2, which comprises reacting an olefin with oxygen at a temperature of 100 to 350°C.
19. A catalyst for production of an olefin oxide which comprises (a) copper oxide, (b) cobalt oxide and (c) alkaline metal component or alkaline earth metal component.
20. The catalyst according to claim 19 which comprises (d) halogen component.
21. The catalyst according to claim 19 or 20 which comprises (e) composite oxide.
22. The catalyst according to claim 19, wherein (a) copper oxide, (b) cobalt oxide and (c) alkaline metal component or alkaline earth metal component are supported on a porous support .
23. The catalyst according to claim 20, wherein (a) copper oxide, (b) cobalt oxide, (c) alkaline metal component or alkaline earth metal component and (d) halogen component are supported on a porous support.
24. The catalyst according to claim 22 which is obtained by impregnating a porous support with a solution containing a copper ion, a cobalt ion and an alkaline metal or alkaline earth metal ion to prepare a composition, followed by calcining the composition .
25. The catalyst according to claim 23, which is obtained by impregnating a porous support with a solution containing a copper ion, a cobalt ion, an alkaline metal or alkaline earth metal ion and a halogen ion to prepare a composition, followed by calcining the composition.
26. The catalyst according to claim 19 or 20, wherein the (c) alkaline metal component or alkaline earth metal component is an alkaline metal-containing compound or an alkaline earth metal-containing compound.
27. The catalyst according to claim 22 or 23, wherein the porous support comprises AI2O3, S1O2, T1O2 or ZrC>2.
28. The catalyst according to claim 22 or 23, wherein the porous support comprises Si02.
29. The catalyst according to claim 19 or 20, wherein the olefin oxide is propylene oxide.
30. Use of a catalyst for producing an olefin oxide, said catalyst comprising (a) copper oxide, (b) cobalt oxide and (c) alkaline metal component or alkaline earth metal component.
31. The use of a catalyst according to claim 30, wherein the olefin oxide is propylene oxide.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112823882A (en) * | 2019-11-20 | 2021-05-21 | Sk新技术株式会社 | Shaped dehydrogenation catalyst and process for converting paraffins to corresponding olefins using same |
| CN112996596A (en) * | 2018-10-31 | 2021-06-18 | Sk新技术株式会社 | Cobalt-based monatomic dehydrogenation catalyst and method for producing corresponding olefin from paraffin using same |
| CN115282968A (en) * | 2022-09-02 | 2022-11-04 | 宁夏大学 | Metal-doped self-assembly catalyst |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107855127B (en) * | 2017-11-09 | 2020-06-19 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation of high-temperature stable supported cobaltosic oxide catalyst based on strong interaction of metal and carrier, product and application |
| EP3928864A1 (en) | 2020-06-25 | 2021-12-29 | SK Innovation Co., Ltd. | Cobalt-based single-atom dehydrogenation catalysts having improved thermal stability and method for producing olefins from corresponding paraffins by using the same |
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| EP0480537A1 (en) * | 1990-10-12 | 1992-04-15 | Union Carbide Chemicals And Plastics Company, Inc. | Stable alkylene oxide catalysts |
| US5112795A (en) * | 1990-10-12 | 1992-05-12 | Union Carbide Chemicals & Plastics Technology Corporation | Supported silver catalyst, and processes for making and using same |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112996596A (en) * | 2018-10-31 | 2021-06-18 | Sk新技术株式会社 | Cobalt-based monatomic dehydrogenation catalyst and method for producing corresponding olefin from paraffin using same |
| CN112996596B (en) * | 2018-10-31 | 2023-10-03 | Sk新技术株式会社 | Cobalt-based monoatomic dehydrogenation catalyst and method for preparing corresponding olefin from alkane by using catalyst |
| CN112823882A (en) * | 2019-11-20 | 2021-05-21 | Sk新技术株式会社 | Shaped dehydrogenation catalyst and process for converting paraffins to corresponding olefins using same |
| CN115282968A (en) * | 2022-09-02 | 2022-11-04 | 宁夏大学 | Metal-doped self-assembly catalyst |
| CN115282968B (en) * | 2022-09-02 | 2023-11-14 | 宁夏大学 | Metal doped self-assembled catalyst |
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| Publication number | Publication date |
|---|---|
| JP2013505996A (en) | 2013-02-21 |
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