WO2011075459A1 - Process for producing olefin oxide - Google Patents
Process for producing olefin oxide Download PDFInfo
- Publication number
- WO2011075459A1 WO2011075459A1 PCT/US2010/060188 US2010060188W WO2011075459A1 WO 2011075459 A1 WO2011075459 A1 WO 2011075459A1 US 2010060188 W US2010060188 W US 2010060188W WO 2011075459 A1 WO2011075459 A1 WO 2011075459A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- oxide
- ruthenium
- alkaline
- metal component
- Prior art date
Links
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000003054 catalyst Substances 0.000 claims abstract description 106
- 239000002184 metal Substances 0.000 claims abstract description 80
- 229910052751 metal Inorganic materials 0.000 claims abstract description 70
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 45
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 43
- 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 34
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000005751 Copper oxide Substances 0.000 claims abstract description 25
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 25
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 51
- 150000001875 compounds Chemical class 0.000 claims description 34
- 229910052681 coesite Inorganic materials 0.000 claims description 31
- 229910052906 cristobalite Inorganic materials 0.000 claims description 31
- 229910052682 stishovite Inorganic materials 0.000 claims description 31
- 229910052905 tridymite Inorganic materials 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 29
- -1 halogen ion Chemical class 0.000 claims description 25
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 24
- 229910052736 halogen Inorganic materials 0.000 claims description 24
- 239000010949 copper Substances 0.000 claims description 18
- 150000002367 halogens Chemical class 0.000 claims description 17
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 14
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 13
- 229910021645 metal ion Inorganic materials 0.000 claims description 13
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 13
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 11
- 229910001431 copper ion Inorganic materials 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 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 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 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 2
- 238000006243 chemical reaction Methods 0.000 description 41
- 239000007789 gas Substances 0.000 description 23
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 16
- 150000003839 salts Chemical class 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 229910002012 Aerosil® Inorganic materials 0.000 description 8
- 239000011780 sodium chloride Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical class [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- 229910001960 metal nitrate Inorganic materials 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 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
- 239000002904 solvent Substances 0.000 description 3
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical compound C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 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
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 229960004424 carbon dioxide Drugs 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000007405 data analysis Methods 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000011049 filling Methods 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
- 150000002429 hydrazines Chemical class 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 150000005673 monoalkenes Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- WHNBDXQTMPYBAT-UHFFFAOYSA-N 2-butyloxirane Chemical compound CCCCC1CO1 WHNBDXQTMPYBAT-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 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
- 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
- 239000005752 Copper oxychloride Substances 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical group O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910021603 Ruthenium iodide Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 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
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 229910001964 alkaline earth metal nitrate Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- FDFGHPKPHFUHBP-UHFFFAOYSA-N anthracene-9,10-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=C(C=CC=C3)C3=C(C(O)=O)C2=C1 FDFGHPKPHFUHBP-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- SUWCFTLKWQKEFZ-UHFFFAOYSA-M azane;ruthenium(3+);chloride Chemical compound N.N.N.N.N.[Cl-].[Ru+3] SUWCFTLKWQKEFZ-UHFFFAOYSA-M 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzenetricarboxylic Acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 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
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 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
- 239000001569 carbon dioxide Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- HKMOPYJWSFRURD-UHFFFAOYSA-N chloro hypochlorite;copper Chemical compound [Cu].ClOCl HKMOPYJWSFRURD-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical class Cl[Cu]Cl ORTQZVOHEJQUHG-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
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-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
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 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
- 229960002887 deanol Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 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
- 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
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000002316 fumigant Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-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
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- PQSDBPCEDVVCRA-UHFFFAOYSA-N nitrosyl chloride;ruthenium Chemical compound [Ru].ClN=O PQSDBPCEDVVCRA-UHFFFAOYSA-N 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-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
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 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 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- WYRXRHOISWEUST-UHFFFAOYSA-K ruthenium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Ru+3] WYRXRHOISWEUST-UHFFFAOYSA-K 0.000 description 1
- LJZVDOUZSMHXJH-UHFFFAOYSA-K ruthenium(3+);triiodide Chemical compound [Ru+3].[I-].[I-].[I-] LJZVDOUZSMHXJH-UHFFFAOYSA-K 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 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
- 229910052712 strontium Inorganic materials 0.000 description 1
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Inorganic materials [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 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
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides 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
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
- C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present invention relates to a process for producing an olefin oxide.
- Olefin oxides such as propylene oxide
- the present invention provides:
- 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) ruthenium metal or ruthenium oxide and (c) alkaline metal component or alkaline earth metal component .
- alkaline metal component or alkaline earth metal component is an alkaline metal-containing compound.
- a catalyst for production of an olefin oxide which comprises (a) copper oxide, (b) ruthenium metal or ruthenium oxide and (c) alkaline metal component or alkaline earth metal component.
- alkaline metal component or alkaline earth metal component is an alkaline metal-containing compound.
- a catalyst for producing an olefin oxide comprising (a) copper oxide, (b) ruthenium metal or ruthenium oxide and (c) alkaline metal component or alkaline earth metal component.
- Fig. 1 is a graph showing the result of Example 1.
- Fig. 2 is a graph showing the result of Example 2.
- Fig. 3 is a graph showing the result of Example 3.
- Fig. 4 is a graph showing the result of Example 4.
- Fig. 5 is a graph showing the result of Example 5.
- Fig. 6 is a graph showing the XRD patterns of Example 6.
- the process of the present invention comprises reacting an olefin with oxygen in the presence of a catalyst comprising (a) copper oxide, (b) ruthenium metal or ruthenium oxide and (c) alkaline metal component or alkaline earth metal component.
- a catalyst comprising (a) copper oxide, (b) ruthenium metal or ruthenium oxide and (c) alkaline metal component or alkaline earth metal component.
- 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 ZrC>2, more preferably Si0 2 .
- Examples of the porous support comprising S1O 2 include mesoporous silica.
- Such a porous support may also comprise zeolites.
- 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 CU 2 O and CuO.
- the copper oxide is preferably CuO.
- the catalyst may comprise one or more kinds of (b) ruthenium metal or ruthenium oxide .
- the (b) ruthenium oxide is usually composed of ruthenium and oxygen. Examples of the ruthenium oxide include RUO 4 , and RUO 2 .
- the component (b) is preferably RuC> 2 .
- 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 such as Ca 2+ , Mg 2+ , Sr 2+ and Ba 2+ .
- the component (c) is preferably an alkaline
- metal-containing compound an alkaline metal or both of them, more preferably an alkaline metal-containing compound, still more preferably a sodium-containing compound or a
- the olefin oxide selectivity is excellent at reaction temperature not more than 270 ° C.
- the alkaline metal-containing compound and alkaline earth metal-containing compound are preferably an alkaline metal salt and 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 Cl ⁇ , Br ⁇ , I ⁇ , 0 3 ⁇ , SO 4 ⁇ and CO 3 ⁇ .
- 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 catalyst comprises preferably CuO, RUO 2 and an alkaline metal- containing compound, still more preferably CuO, RUO 2 and a sodium-containing compound, because the olefin oxide yield and selectivity can be improved by adopting such combination to the production of an olefin oxide.
- the catalyst comprises NaCl, as the (c) component, it can show excellent olefin oxide selectivity and yield.
- the copper/ruthenium 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.
- the upper limit of the molar ratio is more preferably 98/2, still more preferably 97/3.
- the ruthenium/ (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.
- the total content of the components (a) , (b) and (c) is preferably 0.01 to 80% by weight of the amount of the catalyst.
- 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.
- halogen-containing compound examples include halides of copper or ruthenium and oxyhalides of copper or ruthenium. If the catalyst comprises the component (d) , 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 .
- the catalyst can be obtained by impregnating a porous support with a solution containing a copper ion, a ruthenium ion and an alkaline metal or alkaline earth metal-containing ion to prepare a composition, followed by calcining the composition.
- the support can be in form of powder, or shaped to a desired stucture as necessary.
- the catalyst comprises 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 solution contains copper ion, a ruthenium ion, an alkaline metal or alkaline earth metal-containing ion and a halogen ion.
- the solution containing a copper ion, a ruthenium ion and an alkaline metal or alkaline earth metal ion can be prepared by dissolving a copper metal salt, a ruthenium metal salt and an alkaline metal or alkaline earth metal salt in a solvent.
- the copper metal salt include copper acetate, copper ammonium chloride, copper bromide, copper carbonate, copper ethoxide, copper hydroxide, copper iodide, copper isobutyrate, copper isopropoxide, copper oxalate, copper oxychloride, copper nitrates, and copper chlorides.
- ruthenium metal salt examples include, for example, a halide such as ruthenium bromide, ruthenium chloride, ruthenium iodide, an oxyhalide such as RU 2 OCI 4 , RU 2 OCI 5 and RU 2 OC 16 , a halogeno complex such as [RUCI 2 (H 2 0) 4 ] CI , an ammine complex such as
- the alkaline metal or alkaline earth metal salt for the solution may be the same as or different from the (c) component.
- the alkaline metal or alkaline earth metal salt include alkaline metal nitrates, alkaline earth metal nitrates, alkaline metal halides and alkaline earth metal halides, preferably alkaline metal halides and alkaline metal nitrates, more preferably NaN03, NaCl, KC1 and KNO3.
- At least one of the metal salts for the solvent contains preferably a halogen ion, more preferably a chloride ion.
- a halogen ion may form the (c) component such as NaCl and the (d) component such as halides and oxyhalides of Cu or Ru .
- the solution may contain acidic or basic compounds in order to control its pH.
- the acid compound may be any of an inorganic acid and an organic acid.
- the inorganic acid include hydrochloric acid, nitric acid, nitrous acid and perchloric acid etc.
- the organic acid include aliphatic carboxylic acids such as acetic acid, oxalic acid, propionic acid, butyric acid, citric acid, maleic acid, fumaric acid and tartaric acid etc.; and aromatic carboxylic acids such as benzoic acid, dicarboxybenzene, tricarboxybenzene,
- Examples of the base compound include alkaline metal hydroxides, amine compounds, imine compounds, hydrazine or hydrazine compounds, ammonia, hydroxylamine, hydroxyamine and ammonium hydroxides.
- alkaline metal hydroxides include sodium hydroxide, potassium hydroxide etc.
- amine compounds include aliphatic amines having a carbon number of 1 to 20 and aromatic amines having a carbon number of 6 to 20, such as methylamine, ethylamine, propylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, decylamine, dodecylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, trimethylamine, triethylamine, ethanolamine, dimethylethanolamine, diethylethanolamine, triethanolamine, ethylenediamine, tetramethylenediamine, pentamethylenediamine, diethylenetriamine, aniline,
- Examples of the imine compounds include ethyleneimine, pyrrolidine, piperidine and piperazine etc.
- Examples of the amide compounds include acetamide and benzamide etc.
- Examples of the hydrazine compounds include methylhydrazine and phenylhydrazine etc.
- Examples of the quaternary ammonium salts include quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide etc.; quaternary ammonium halides such as tetramethylammonium chloride,
- Examples of the solvent for the solution include water and alcohols such as methanol or ethanol.
- the total amount of the porous support is preferably 20 to 99.99% by weight, more preferably 50 to 99.5% by weight, still preferably 70 to 99.9% by weight of the catalyst as obtained.
- 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 may be performed under an atmosphere of air or also under an inert gas atmosphere (for example, Ar, N 2 , 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 stucture as necessary.
- Calcining the composition is not limited, but preferably may be performed under a gas atmosphere containing oxygen.
- a gas atmosphere containing oxygen examples include air and an oxygen gas.
- 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 ruthenium oxide and copper oxide. Accordingly, the calcination temperature is typically 200 to 800 ° C, preferably 400 to 600 ° C.
- the catalyst can be used as powder, but it is usual to shape it into 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 into the desired structures, but it can also be performed before shaping them.
- the olefin may have a linear or branched structure and contains usually 2 to 10, preferably 2 to 8 carbon atoms .
- the olefin may be amonoolefin or a diolefin .
- Examples of the monoolefin include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, and decene.
- the diene include butadiene such as 1 , 3-butadiene or 1 , 2-butadiene .
- the olefin examples include preferably monoolefin, more preferably ethylene, propylene, butene, pentene, hexene, heptene and octene, still more preferably ethylene, propylene and butene, most preferably propylene.
- the reaction is generally performed in the gas phase.
- the olefin and oxygen may be fed respectively in the form of a 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, methane, ethane, propane, carbon dioxide, or rare gases, such as argon and helium.
- oxygen source pure oxygen may be used, or a mixed gas containing a gas inactive to the reaction, such as air, may be used.
- 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, and more 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, still more preferably of 200 to 270 ° C.
- the reaction temperature is most preferably 240 to 270 ° C for the reaction in a microreactor .
- the reaction is usually carried out under reaction pressure in the range of reduced pressure to increased pressure .
- Reduced pressure means a pressure lower than atmospheric pressure.
- Increased pressure means a pressure higher than atmospheric pressure.
- the pressure is typically in the range of 0.01 to 3 MPa, and preferably in the range of
- the reaction 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 the increased pressure.
- the reactor type is not limited. Examples of the reactor type 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 reactor can be used.
- reactors as for example microreactors , can be used, which can have multiple channels .
- Adiabatic type or heat exchange type may also be used.
- the olefin oxide may have a linear or branched structure and contains usually 2 to 10, preferably 2 to 8 carbon atoms.
- the olefin oxide may have one carbon-carbon double bond when the diolefin is applied for the reaction.
- Examples of the olefin oxide having one carbon-carbon double bond include 3, 4-epoxy-l-butene .
- Examples of the olefin oxides include preferably ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, heptene oxide and octene oxide, 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.
- the detected products were propylene oxide (PO) , acetone
- AT acetaldehyde
- AD acetaldehyde
- CO x C0 2 and CO
- PaL+AC propanal + acrolein
- the metal salt solution was then allowed to impregnate the support for 24 hours in air.
- the resulting material was then heated at 150°C until dried, and calcined at 500°C for 12 hours in air.
- the catalyst (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 (C 3 H 6 ) , 4 vol% O 2 , 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 190, 210, 230, 250, 260, 270, 290 or 310°C.
- GHSV gas hourly space velocity
- Gas sampling was accomplished by withdrawing reactor exit gases using the passivated 200 micron ID capillary sampling probe .
- the catalysts were prepared in the same manner as Example 1, except that the total metal content in the catalyst was 8 ⁇ 6 by weight.
- Propylene oxide was prepared in the same manner as Example 1 except that the catalysts of the present example were used, the reactor temperature was 250 °C, and GHSV was changed.
- the catalysts were prepared in the same manner as Example 1, except that the total metal content in each of the catalysts was 5, 7, 10 or 12.5% by weight.
- Propylene oxide was prepared in the same manner as Example 1 except that the catalysts of the present example were used and the reactor temperature was 250°C.
- the catalysts were prepared in the same manner as Example 3, except that the total metal content in the catalysts was 12.5% by weight.
- Propylene oxide was prepared in the same manner as Example 3 except that the oxygen/propylene (volume ratio) was changed .
- the powder x-ray diffraction pattern of the catalyst obtained in Example 1 was determined with PANalytical X' Pert PRO fitted with a Ni filter and a Soller slit collimator.
- the C -K a radiation at 45 kV and 40 mA was used to identify the active catalyst phase.
- the XRD patterns are shown in Fig. 6.
- the XRD pattern of the catalyst shows that the catalyst comprises CuO, RUO 2 and NaCl without forming any crystalline mixed metal oxides or alloys .
- a catalyst is prepared in the same manner as Example 1, except that T1O 2 is used instead of Si0 2 .
- Production of propylene oxide is carried out in the same manner as Example 1 except that the catalyst of the present example is used.
- a reaction gas was mixed with ethane (10 Nml/min) as an external standard, and then directly introduced into 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 metal compostion was prepared by a co-impregnation method.
- a predetermined weight (1.9 g) of an amorphous silica powder (Si0 2 , Japan Aerosil, 380 m 2 /g) was added to an aqueous solution mixture containing 0.54 g of (NIHU ⁇ RuCle (Aldrich) , 0.30 g of Cu(N0 3 ) 2 of (Wako) and 0.10 g NaN0 3 (Wako) , followed by stirring for 24 hours in the 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 the air to give a catalyst .
- the catalyst was evaluated by using a fixed-bed reactor. Filling a 1/2-inch reaction tube made of stainless steel with 1 mL of the thus obtained catalyst, the following gases were fed to the reaction tube to carry out the reaction: 450 NmL/h of propylene, 900 NmL/h of the air, 990 NmL/h of a nitrogen gas. Such a reaction was carried out at the reaction temperature of 200°C under the increased pressure (equivalent to 0.3 MPa in the absolute pressure) .
- the preparation and the reaction were conducted in the same manner as Example 8, except that the preparation was conducted using 0.64 g of (NH 4 ) 2 RuCl 6 (Aldrich) , 0.35 g of Cu(N0 3 ) 2 (Wako) , 0.08 g of Rb(N0 3 ) (Wako) and 2.3 g of an amorphous silica powder (S1O2, Japan Aerosil , 380 m 2 /g) as raw materials .
- the preparation and the reaction were conducted in the same manner as Example 8, except that the preparation was conducted using 0.76 g of (NH 4 ) 2 RuCl 6 (Aldrich), 0.42 g of Cu(N0 3 ) 2 (Wako), 0.08 g of Cs(N0 3 ) (Wako) and 2.7 g of an amorphous silica powder (Si0 2 , Japan Aerosil , 380 m 2 /g) as raw materials .
- the preparation and the reaction were conducted in the same manner as Example 8, except that the preparation was conducted using 0.23 g of (NIHU ⁇ RuCle (Aldrich), 0.13 g of Cu(N0 3 ) 2 (Wako), 0.1 g of Mg(N0 3 ) 2 (Wako) and 0.8 g of an amorphous silica powder (Si0 2 , Japan Aerosil, 380 m 2 /g) as raw materials .
- the preparation and the reaction were conducted in the same manner as Example 8, except that the preparation was conducted using 1.0 g of (NH 4 ) 2 RuCl 6 (Aldrich) , 0.58 g of Cu (N0 3 ) 2 (Wako), 0.08 g of Ca (N0 3 ) 2 (Wako) and 3.7 g of an amorphous silica powder (SiC>2, Japan Aerosil, 380 m 2 /g) as raw materials.
- amorphous silica powder SiC>2, Japan Aerosil, 380 m 2 /g
- the preparation and the reaction were conducted in the same manner as Example 8, except that the preparation was conducted using 0.86 g of (NH 4 ) 2 RuCl 6 (Aldrich), 0.47 g of Cu(N0 3 ) 2 (Wako), 0.15 g of Sr(N0 3 ) 2 (Wako) and 3.0 g of an amorphous silica powder (Si0 2 , Japan Aerosil, 380 m 2 /g) as raw materials .
- the preparation and the reaction were conducted in the same manner as Example 8, except that the preparation was conducted using 0.73 g of (NH 4 ) 2 RuCl 6 (Aldrich), 0.40 g of Cu (N0 3 ) 2 (Wako) , 0.10 g of Ba (N0 3 ) 2 (Wako) and 2.6 g of amorphous silica powder (Si0 2 , Japan Aerosil , 380 m 2 /g) as raw materials .
- a catalyst is prepared in the same manner as Example 8, except that Ti0 2 is used instead of Si0 2 .
- Production of propylene oxide is carried out in the same manner as Example 8 except that the catalyst of the present example is used. Examples 16-18
- the metal composition was prepared by a co-impregnation method.
- a predetermined weight (1.9 g) of an amorphous silica powder (Si0 2 , Japan Aerosil, 380 m 2 /g) was added to an aqueous solution mixture containing 0.54 g of (NH 4 ) 2 RuCl6 (Aldrich) , 0.30 g of Cu(N0 3 ) 2 (Wako) and 0.10 g of KN0 3 (Wako) , followed by stirring for 24 hours in the 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 the air to give a catalyst.
- the catalyst was evaluated by using a fixed-bed reactor, Filling a 1/2-inch reaction tube made of stainless steel with 1 mL of the thus obtained catalyst, the following gases were fed to the reaction tube to carry out the reaction: 450 NmL/h of propylene, 900 NmL/h of the air, 990 NmL/h of a nitrogen gas, Such a reaction was carried out at the reaction temperature of
- *STY i.e., space time yield, represents "(The amount of propylene oxide ( ⁇ ) / ⁇ the amount of catalyst (ml ) *hour ⁇ " .
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Epoxy Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201080057749XA CN102652130A (en) | 2009-12-17 | 2010-12-14 | Process for producing olefin oxide |
JP2012532152A JP2013505985A (en) | 2009-12-17 | 2010-12-14 | Process for producing olefin oxide |
BR112012017167A BR112012017167A2 (en) | 2009-12-17 | 2010-12-14 | process for the production of olefin oxide |
US13/516,222 US20120283454A1 (en) | 2009-12-17 | 2010-12-14 | Process for producing olefin oxide |
EP10838193.0A EP2513074A4 (en) | 2009-12-17 | 2010-12-14 | Process for producing olefin oxide |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US28432409P | 2009-12-17 | 2009-12-17 | |
US61/284,324 | 2009-12-17 | ||
US12/826,458 US20110152547A1 (en) | 2009-12-17 | 2010-06-29 | Process for producing olefin oxide |
US12/826,458 | 2010-06-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011075459A1 true WO2011075459A1 (en) | 2011-06-23 |
Family
ID=44152003
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2010/060188 WO2011075459A1 (en) | 2009-12-17 | 2010-12-14 | Process for producing olefin oxide |
PCT/US2010/060185 WO2011075458A1 (en) | 2009-12-17 | 2010-12-14 | Process for producing olefin oxide |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2010/060185 WO2011075458A1 (en) | 2009-12-17 | 2010-12-14 | Process for producing olefin oxide |
Country Status (7)
Country | Link |
---|---|
US (4) | US20110152546A1 (en) |
EP (2) | EP2513074A4 (en) |
JP (2) | JP2013505985A (en) |
KR (2) | KR101763966B1 (en) |
CN (2) | CN102652130A (en) |
BR (2) | BR112012017167A2 (en) |
WO (2) | WO2011075459A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2513073A1 (en) * | 2009-12-17 | 2012-10-24 | Sumitomo Chemical Company, Limited | Process for producing olefin oxide |
EP2668170A1 (en) * | 2011-01-24 | 2013-12-04 | Sumitomo Chemical Company Limited | Direct conversion of olefin to olefin oxide by molecular oxygen |
WO2014003209A1 (en) * | 2012-06-29 | 2014-01-03 | Sumitomo Chemical Company, Limited | Process for producing olefin oxide |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012094118A1 (en) | 2011-01-05 | 2012-07-12 | Sumitomo Chemical Company, Limited | Process for producing olefin oxide |
WO2013025315A1 (en) * | 2011-08-17 | 2013-02-21 | Sumitomo Chemical Company, Limited | Process for producing olefin oxide |
WO2013025316A1 (en) * | 2011-08-17 | 2013-02-21 | Sumitomo Chemical Company, Limited | Process for producing olefin oxide |
WO2013062791A1 (en) * | 2011-10-24 | 2013-05-02 | Sumitomo Chemical Company, Limited | Process for producing olefin oxide |
WO2016153969A1 (en) | 2015-03-20 | 2016-09-29 | Northwestern University | Catalysts and related methods for photocatalytc production of h2o2 and thermocatalytic reactant oxidation |
EP3117898A1 (en) * | 2015-07-15 | 2017-01-18 | i2 Gesellschaft für Innovation mbH | Preparation of a mixed catalyst |
CN106732593B (en) * | 2016-12-30 | 2019-11-22 | 天津市长芦化工新材料有限公司 | Copper-based solid-phase catalyst and its preparation method and application |
CN110785392A (en) | 2017-06-23 | 2020-02-11 | 托普索公司 | Process for the oxidation of lower alkanes at low temperatures in ammonia-containing gas mixtures |
WO2018234045A1 (en) * | 2017-06-23 | 2018-12-27 | Haldor Topsøe A/S | A process for oxidation of a lower alkene at low temperatures in ammonia-containing gas mixtures |
US10800981B2 (en) | 2019-02-13 | 2020-10-13 | Saudi Arabian Oil Company | Process for producing diesel fuel from olefinic refinery feedstreams |
WO2021126947A1 (en) * | 2019-12-16 | 2021-06-24 | Calera Corporation | Electrochemical, bromination, and oxybromination systems and methods to form propylene oxide or ethylene oxide |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4497908A (en) * | 1984-03-23 | 1985-02-05 | Shell Oil Company | Copper-alkali metal-ruthenium/silica catalyst for converting syngas to linear alpha-olefins |
US6362349B1 (en) * | 1998-04-15 | 2002-03-26 | The Dow Chemical Company | Process for the direct oxidation of olefins to olefin oxides |
US6765101B1 (en) * | 2001-05-01 | 2004-07-20 | Union Carbide Chemicals & Plastics Technology Corporation | Synthesis of lower alkylene oxides and lower alkylene glycols from lower alkanes and/or lower alkenes |
US20060016722A1 (en) * | 2004-07-08 | 2006-01-26 | Conocophillips Company | Synthetic hydrocarbon products |
US20060166809A1 (en) * | 2002-11-20 | 2006-07-27 | Andrzej Malek | Methods for preparing catalysts |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5957221A (en) | 1996-02-28 | 1999-09-28 | Baker Hughes Incorporated | Downhole core sampling and testing apparatus |
DE10024096A1 (en) * | 2000-05-18 | 2001-11-22 | Bayer Ag | Hydrocarbon epoxidation is catalysed by a mixture of two or more metals on a support so as to allow direct oxygen or air oxidation of propylene to propylene oxide |
JP2002371074A (en) * | 2001-04-13 | 2002-12-26 | Mitsubishi Chemicals Corp | Method for producing oxysilane compound |
US6472572B1 (en) * | 2001-06-20 | 2002-10-29 | Grt, Inc. | Integrated process for synthesizing alcohols and ethers from alkanes |
DE10208254A1 (en) * | 2002-02-26 | 2003-09-04 | Bayer Ag | catalyst |
US7348444B2 (en) | 2003-04-07 | 2008-03-25 | Shell Oil Company | Process for the production of an olefin oxide |
US20110152546A1 (en) * | 2009-12-17 | 2011-06-23 | Sumitomo Chemical Company, Limited | Process for producing olefin oxide |
-
2010
- 2010-06-29 US US12/826,445 patent/US20110152546A1/en not_active Abandoned
- 2010-06-29 US US12/826,458 patent/US20110152547A1/en not_active Abandoned
- 2010-12-14 US US13/516,226 patent/US8822372B2/en not_active Expired - Fee Related
- 2010-12-14 JP JP2012532152A patent/JP2013505985A/en active Pending
- 2010-12-14 EP EP10838193.0A patent/EP2513074A4/en not_active Withdrawn
- 2010-12-14 CN CN201080057749XA patent/CN102652130A/en active Pending
- 2010-12-14 JP JP2012532151A patent/JP2013505984A/en active Pending
- 2010-12-14 BR BR112012017167A patent/BR112012017167A2/en not_active IP Right Cessation
- 2010-12-14 CN CN201080057846.9A patent/CN102933566B/en not_active Expired - Fee Related
- 2010-12-14 US US13/516,222 patent/US20120283454A1/en not_active Abandoned
- 2010-12-14 BR BR112012014674A patent/BR112012014674B1/en not_active IP Right Cessation
- 2010-12-14 KR KR1020127015627A patent/KR101763966B1/en active IP Right Grant
- 2010-12-14 WO PCT/US2010/060188 patent/WO2011075459A1/en active Application Filing
- 2010-12-14 KR KR1020127015445A patent/KR20120115269A/en not_active Application Discontinuation
- 2010-12-14 WO PCT/US2010/060185 patent/WO2011075458A1/en active Application Filing
- 2010-12-14 EP EP10838192.2A patent/EP2513073B1/en not_active Not-in-force
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4497908A (en) * | 1984-03-23 | 1985-02-05 | Shell Oil Company | Copper-alkali metal-ruthenium/silica catalyst for converting syngas to linear alpha-olefins |
US6362349B1 (en) * | 1998-04-15 | 2002-03-26 | The Dow Chemical Company | Process for the direct oxidation of olefins to olefin oxides |
US6765101B1 (en) * | 2001-05-01 | 2004-07-20 | Union Carbide Chemicals & Plastics Technology Corporation | Synthesis of lower alkylene oxides and lower alkylene glycols from lower alkanes and/or lower alkenes |
US20060166809A1 (en) * | 2002-11-20 | 2006-07-27 | Andrzej Malek | Methods for preparing catalysts |
US20060016722A1 (en) * | 2004-07-08 | 2006-01-26 | Conocophillips Company | Synthetic hydrocarbon products |
Non-Patent Citations (1)
Title |
---|
See also references of EP2513074A4 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2513073A1 (en) * | 2009-12-17 | 2012-10-24 | Sumitomo Chemical Company, Limited | Process for producing olefin oxide |
EP2513073A4 (en) * | 2009-12-17 | 2014-02-12 | Sumitomo Chemical Co | Process for producing olefin oxide |
US8822372B2 (en) | 2009-12-17 | 2014-09-02 | Sumitomo Chemical Company, Limited | Process for producing olefin oxide |
EP2668170A1 (en) * | 2011-01-24 | 2013-12-04 | Sumitomo Chemical Company Limited | Direct conversion of olefin to olefin oxide by molecular oxygen |
EP2668170A4 (en) * | 2011-01-24 | 2014-07-02 | Sumitomo Chemical Co | Direct conversion of olefin to olefin oxide by molecular oxygen |
US8829211B2 (en) | 2011-01-24 | 2014-09-09 | Sumitomo Chemical Company, Limited | Direct conversion of olefin to olefin oxide by molecular oxygen |
WO2014003209A1 (en) * | 2012-06-29 | 2014-01-03 | Sumitomo Chemical Company, Limited | Process for producing olefin oxide |
Also Published As
Publication number | Publication date |
---|---|
KR20120104253A (en) | 2012-09-20 |
CN102933566A (en) | 2013-02-13 |
EP2513073A4 (en) | 2014-02-12 |
US8822372B2 (en) | 2014-09-02 |
KR101763966B1 (en) | 2017-08-01 |
JP2013505985A (en) | 2013-02-21 |
US20120283455A1 (en) | 2012-11-08 |
EP2513073A1 (en) | 2012-10-24 |
EP2513074A1 (en) | 2012-10-24 |
BR112012014674A8 (en) | 2016-05-03 |
US20110152547A1 (en) | 2011-06-23 |
EP2513074A4 (en) | 2013-11-20 |
CN102652130A (en) | 2012-08-29 |
CN102933566B (en) | 2015-07-29 |
BR112012014674A2 (en) | 2015-09-15 |
US20120283454A1 (en) | 2012-11-08 |
WO2011075458A1 (en) | 2011-06-23 |
KR20120115269A (en) | 2012-10-17 |
JP2013505984A (en) | 2013-02-21 |
EP2513073B1 (en) | 2015-08-05 |
US20110152546A1 (en) | 2011-06-23 |
BR112012014674B1 (en) | 2017-06-20 |
BR112012017167A2 (en) | 2019-09-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20120283454A1 (en) | Process for producing olefin oxide | |
WO2012009056A1 (en) | Process for producing olefin oxide | |
US8765981B2 (en) | Process for producing olefin oxide | |
US8889892B2 (en) | Process for producing olefin oxide | |
WO2012009052A1 (en) | Process for producing olefin oxide | |
WO2012009058A2 (en) | Process for producing olefin oxide | |
WO2012009054A1 (en) | Process for producing olefin oxide | |
WO2012009055A1 (en) | Process for producing olefin oxide | |
WO2012005831A1 (en) | Process for producing olefin oxide | |
WO2012005825A1 (en) | Process for producing olefin oxide | |
WO2012009059A1 (en) | Process for producing olefin oxide | |
WO2012009057A1 (en) | Process for producing olefin oxide | |
WO2012005823A1 (en) | Process for producing olefin oxide | |
WO2012005832A1 (en) | Process for producing olefin oxide | |
WO2012009053A1 (en) | Process for producing olefin oxide | |
WO2012094122A1 (en) | Process for producing olefin oxide | |
WO2012094121A1 (en) | Process for producing olefin oxide | |
WO2012005824A1 (en) | Process for producing olefin oxide | |
WO2012005835A1 (en) | Process for producing olefin oxide | |
WO2012005837A1 (en) | Process for producing olefin oxide |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201080057749.X Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10838193 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012532152 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 5182/CHENP/2012 Country of ref document: IN |
|
ENP | Entry into the national phase |
Ref document number: 20127015445 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1201002894 Country of ref document: TH |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010838193 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13516222 Country of ref document: US |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112012017167 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: 112012017167 Country of ref document: BR Kind code of ref document: A2 Effective date: 20120618 |