JP2011219466A - Gold catalyst for ethanol oxidation and method for producing acetaldehyde and acetic acid using the same - Google Patents
Gold catalyst for ethanol oxidation and method for producing acetaldehyde and acetic acid using the same Download PDFInfo
- Publication number
- JP2011219466A JP2011219466A JP2011059461A JP2011059461A JP2011219466A JP 2011219466 A JP2011219466 A JP 2011219466A JP 2011059461 A JP2011059461 A JP 2011059461A JP 2011059461 A JP2011059461 A JP 2011059461A JP 2011219466 A JP2011219466 A JP 2011219466A
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- Japan
- Prior art keywords
- catalyst
- ethanol
- gold
- acetaldehyde
- base metal
- Prior art date
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- Granted
Links
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 195
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 153
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 239000003054 catalyst Substances 0.000 title claims abstract description 120
- 239000010931 gold Substances 0.000 title claims abstract description 95
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 77
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 48
- 230000003647 oxidation Effects 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 62
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 50
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 50
- 239000010953 base metal Substances 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000010419 fine particle Substances 0.000 claims abstract description 30
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 29
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 29
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims description 66
- 239000012071 phase Substances 0.000 claims description 40
- 239000001301 oxygen Substances 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 23
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 20
- 239000010936 titanium Substances 0.000 claims description 20
- 229910052719 titanium Inorganic materials 0.000 claims description 20
- 239000002105 nanoparticle Substances 0.000 claims description 16
- 239000012808 vapor phase Substances 0.000 claims description 12
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 7
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 6
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims description 6
- 150000002343 gold Chemical class 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 11
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 239000002245 particle Substances 0.000 description 42
- 238000006243 chemical reaction Methods 0.000 description 37
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 30
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 20
- 239000002994 raw material Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 12
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 12
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 11
- 239000011787 zinc oxide Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000000446 fuel Substances 0.000 description 9
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 229910001882 dioxygen Inorganic materials 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000010304 firing Methods 0.000 description 7
- 239000000395 magnesium oxide Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000004408 titanium dioxide Substances 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 150000002344 gold compounds Chemical class 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000012495 reaction gas Substances 0.000 description 5
- 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 4
- -1 V 2 O 5 Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 238000004108 freeze drying Methods 0.000 description 4
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 description 4
- WDZVNNYQBQRJRX-UHFFFAOYSA-K gold(iii) hydroxide Chemical compound O[Au](O)O WDZVNNYQBQRJRX-UHFFFAOYSA-K 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 3
- 238000004887 air purification Methods 0.000 description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- AUFHQOUHGKXFEM-UHFFFAOYSA-N C[Au]C Chemical compound C[Au]C AUFHQOUHGKXFEM-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 2
- 150000004685 tetrahydrates Chemical class 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001619348 Idris Species 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- XSTRYINNFZBYIU-UHFFFAOYSA-N [O-2].[Fe+2].[N+](=O)([O-])[O-].[Cu+2] Chemical compound [O-2].[Fe+2].[N+](=O)([O-])[O-].[Cu+2] XSTRYINNFZBYIU-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
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- 230000005540 biological transmission Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
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- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- MIQUYXUHGQNVDN-UHFFFAOYSA-N ethane-1,2-diamine;gold Chemical compound [Au].NCCN MIQUYXUHGQNVDN-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- IZLAVFWQHMDDGK-UHFFFAOYSA-N gold(1+);cyanide Chemical compound [Au+].N#[C-] IZLAVFWQHMDDGK-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- HVDZMISZAKTZFP-UHFFFAOYSA-N indium(3+) trinitrate trihydrate Chemical compound O.O.O.[In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HVDZMISZAKTZFP-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- GKYQBMNOFTZZSX-UHFFFAOYSA-K n-ethylethanamine;trichlorogold Chemical compound Cl[Au](Cl)Cl.CCNCC GKYQBMNOFTZZSX-UHFFFAOYSA-K 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 description 1
- MHHDXUNFNAZUGB-UHFFFAOYSA-N oxidovanadium(2+) Chemical compound [V+2]=O MHHDXUNFNAZUGB-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- XTFKWYDMKGAZKK-UHFFFAOYSA-N potassium;gold(1+);dicyanide Chemical compound [K+].[Au+].N#[C-].N#[C-] XTFKWYDMKGAZKK-UHFFFAOYSA-N 0.000 description 1
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- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
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- 229940071240 tetrachloroaurate Drugs 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- QBAZWXKSCUESGU-UHFFFAOYSA-N yttrium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QBAZWXKSCUESGU-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- 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
Abstract
Description
本発明は、金触媒を用いてエタノールからアセトアルデヒドや酢酸あるいはアセトアルデヒドを選択的に製造する方法およびエタノールを二酸化炭素と水に分解する方法並びに、これらに用いられるエタノール酸化用金触媒に関する。 The present invention relates to a method for selectively producing acetaldehyde, acetic acid or acetaldehyde from ethanol using a gold catalyst, a method for decomposing ethanol into carbon dioxide and water, and a gold catalyst for ethanol oxidation used in these.
アセトアルデヒドおよび酢酸は工業用原料として重要な化学薬品である。現在、アセトアルデヒドおよび酢酸は、工業的には石油から得られる不飽和炭化水素であるエチレンや、天然ガスから製造されるメタノールを原料として用いて製造されている。例えば、アセトアルデヒドの製造においては、ＰｄＣｌ2−ＣｕＣｌ2触媒によりエチレンを酸化してアセトアルデヒドを製造するワッカー法が主として採用されている。しかし、この方法は触媒の酸性が強いので、反応容器の材質や腐食に課題がある。一方、酢酸の現行製造プロセスとしては、Ｐｄ／ヘテロポリ酸触媒を用いエチレンから製造する方法と、Ｒｈ触媒を用いメタノールから製造する方法の２種類の方法があるが、これらの方法においては３ＭＰａという高い酸素圧を必要とする。 Acetaldehyde and acetic acid are important chemicals as industrial raw materials. At present, acetaldehyde and acetic acid are industrially produced using ethylene, which is an unsaturated hydrocarbon obtained from petroleum, and methanol produced from natural gas as raw materials. For example, in the production of acetaldehyde, a Wacker method in which acetaldehyde is produced by oxidizing ethylene with a PdCl 2 —CuCl 2 catalyst is mainly employed. However, this method has a problem in the material and corrosion of the reaction vessel because the acidity of the catalyst is strong. On the other hand, there are two types of acetic acid production processes, a method of producing from ethylene using a Pd / heteropolyacid catalyst and a method of producing from methanol using an Rh catalyst. In these methods, the method is as high as 3 MPa. Requires oxygen pressure.
一方、２１世紀に入って、地球温暖化を防止する観点から、ガソリンなどの燃料を始めとして、化学産業、ガソリンなどの燃料などあらゆる産業において化石資源から再生可能資源へと原料の転換が進められつつある。アセトアルデヒドや酢酸を製造するプロセスにおいても、石油などの化石資源から得られるエチレンのような不飽和炭化水素などから、エタノールなどのバイオマス由来の化合物に原料がシフトして行く技術潮流が見られる。このようなプロセスが実現すれば、石油資源に依らず、バイオマスを原料としてアセトアルデヒドと酢酸を製造することができるので、持続可能な化学プロセスの開拓を図ることができ、その工業的価値は大きい。 On the other hand, from the viewpoint of preventing global warming in the 21st century, conversion of raw materials from fossil resources to renewable resources has been promoted in various industries including fuels such as gasoline, chemical industries, and fuels such as gasoline. It's getting on. In the process of producing acetaldehyde and acetic acid, there is a technological trend in which the raw material shifts from unsaturated hydrocarbons such as ethylene obtained from fossil resources such as petroleum to biomass-derived compounds such as ethanol. If such a process is realized, it is possible to produce acetaldehyde and acetic acid using biomass as a raw material regardless of petroleum resources, so that a sustainable chemical process can be developed, and its industrial value is great.
さらに、エタノールを二酸化炭素と水まで完全酸化する技術は、居住空間や工場等の空気浄化やエタノールを燃料とする燃料電池にとって非常に重要であり、これに適した触媒の開発も必要とされている。 Furthermore, the technology that completely oxidizes ethanol to carbon dioxide and water is very important for air purification in living spaces and factories and fuel cells using ethanol as fuel, and the development of a catalyst suitable for this is also required. Yes.
これまで、エタノールを金触媒を用いて酸化する方法として、水溶液相でエタノールを酸素酸化する方法が報告されている（例えば、非特許文献１参照）。しかし、水溶液相での製造は生産効率がそれほど高いものではないことから、工業的に行うにはさらに反応時間の短縮、反応効率の改善により、高速流量においても高収量でアセトアルデヒドあるいは酢酸を製造することが必要とされる。すなわち、上記のエチレンあるいはメタノールを用いる現行プロセスに置き換わりうる経済性を有する、エタノールを原料としてのアセトアルデヒドあるいは酢酸の製造プロセスを開発するには、液相による酸化ではなく、生産性の高い気相（気相反応においては反応ガス全体の触媒との接触時間は１秒前後であるのに対し、液相では分単位以上である）でのエタノール酸化反応を行うことが必要である。またエタノールの除去や燃料電池に応用するためには、できるだけ低温において気相でエタノールを効率よく分解できることが重要となってくる。 So far, as a method of oxidizing ethanol using a gold catalyst, a method of oxygen-oxidizing ethanol in an aqueous phase has been reported (for example, see Non-Patent Document 1). However, since the production in the aqueous phase is not so high in production efficiency, acetaldehyde or acetic acid can be produced in a high yield even at a high flow rate by shortening the reaction time and improving the reaction efficiency for industrial production. Is needed. That is, in order to develop a process for producing acetaldehyde or acetic acid using ethanol as a raw material, which has economic efficiency that can replace the above-described current process using ethylene or methanol, gas phase with high productivity (rather than oxidation by liquid phase) In the gas phase reaction, it is necessary to carry out an ethanol oxidation reaction in which the contact time of the entire reaction gas with the catalyst is about 1 second, whereas in the liquid phase it is a minute unit or more. In addition, it is important to be able to efficiently decompose ethanol in the gas phase at as low a temperature as possible in order to remove ethanol and apply it to fuel cells.
しかし、気相でのエタノールの酸素酸化については、これまで報告はあまりみられない。そのような数少ない報告例の一つとして、Ａｕ／ＣｅＯ2によるエタノール気相酸化が挙げられる（非特許文献２）。この報告においては、アセトアルデヒドの生成は確認されているものの、反応条件として選定された４７３Ｋ〜１０７３Ｋの温度においては、酢酸の生成は確認されていないし、エタノールの転化率を上げるべく反応温度を高温とすると、そのほとんどは炭酸ガスや一酸化炭素、メタンなどに分解されてしまう。また、他の報告例（非特許文献３）においては、Ｖ2Ｏ5／ＴｉＯ2（ａｎａｔａｓｅ）による気相エタノール酸化が挙げられる。この反応においては、原料ガスの供給量を少なくすると、酢酸が選択的に生成されることが記載されているものの、反応収量が少ないという問題がある。 However, there have been few reports on oxygen oxidation of ethanol in the gas phase. One of such few reported examples is ethanol vapor phase oxidation with Au / CeO 2 (Non-patent Document 2). In this report, although the formation of acetaldehyde has been confirmed, the formation of acetic acid has not been confirmed at temperatures of 473K to 1073K selected as the reaction conditions, and the reaction temperature was increased to increase the ethanol conversion. Then, most of them are decomposed into carbon dioxide, carbon monoxide, methane and the like. In the other reported cases (Non-Patent Document 3), and a vapor phase ethanol oxidation by V 2 O 5 / TiO 2 ( anatase). In this reaction, it is described that acetic acid is selectively produced when the supply amount of the raw material gas is reduced, but there is a problem that the reaction yield is low.
一方、本発明者は触媒としての活性が極めて乏しいとされていた金でも、直径１０ｎｍ以下の半球状ナノ粒子として種々の金属酸化物担体上に分散・固定化することにより、低温ＣＯ酸化、プロピレンの気相一段エポキシ化、低温水性ガスシフト反応、酸素と水素からの直接過酸化水素合成など多くの反応に対して、他の貴金属より優れた触媒特性を発現することを見出している（例えば、特許文献１、非特許文献４参照）。また、本発明者らは、金の粒子径が２ｎｍ以下、原子数で３００個以内のクラスターになると、触媒特性がさらに激変する場合があることも見出している（例えば、非特許文献５参照）。
On the other hand, the present inventor is able to disperse and immobilize gold, which has been considered to be extremely poor in activity as a catalyst, on various metal oxide supports as hemispherical nanoparticles having a diameter of 10 nm or less, thereby allowing low temperature CO oxidation, It has been found that it exhibits catalytic properties superior to other noble metals for many reactions such as gas-phase single-stage epoxidation, low-temperature water gas shift reaction, and direct hydrogen peroxide synthesis from oxygen and hydrogen (for example, patents)
本発明は、このような状況下になされたもので、本発明の目的は、エタノールを酸素により気相で反応させることにより、高収量で選択的にアセトアルデヒドあるいはアセトアルデヒドと酢酸を製造する方法を提供することである。 The present invention has been made under such circumstances, and an object of the present invention is to provide a method for selectively producing acetaldehyde or acetaldehyde and acetic acid in high yield by reacting ethanol in a gas phase with oxygen. It is to be.
また、本発明の目的は、エタノールを酸素と気相でかつ低温で反応させることにより、エタノールを二酸化炭素と水に分解する方法を提供することである。 Another object of the present invention is to provide a method for decomposing ethanol into carbon dioxide and water by reacting ethanol with oxygen in a gas phase at a low temperature.
さらに、本発明の目的は、これらの方法に適したエタノール酸化用金触媒を提供することである。 Furthermore, an object of the present invention is to provide a gold catalyst for ethanol oxidation suitable for these methods.
本発明者は、鋭意研究の結果、触媒として用いられる金ナノ粒子の担体を選択することにより、気相でエタノールからアセトアルデヒドあるいはアセトアルデヒドと酢酸を選択的に得ることができること、さらにエタノールを低温で二酸化炭素と水まで完全酸化できることを見出して、本発明を成したものである。 As a result of diligent research, the present inventor has been able to selectively obtain acetaldehyde or acetaldehyde and acetic acid from ethanol in the gas phase by selecting a gold nanoparticle carrier to be used as a catalyst. The present invention has been made by finding that carbon and water can be completely oxidized.
すなわち、本発明は、酸素分子の存在下に、金微粒子を分散・固定した、Ｌａ2Ｏ3、ＭｏＯ3、Ｂｉ2Ｏ3、ＳｒＯ、Ｙ2Ｏ３、ＭｇＯ、ＢａＯ、ＷＯ3、ＣｕＯおよびそれらを１種類以上含む複合酸化物から選ばれた卑金属酸化物を触媒として用いて、エタノールからアセトアルデヒドを気相で選択的に製造する方法に関する。 That is, the present invention relates to La 2 O 3 , MoO 3 , Bi 2 O 3 , SrO, Y 2 O 3 , MgO, BaO, WO 3 , CuO and gold fine particles dispersed and fixed in the presence of oxygen molecules. The present invention relates to a method for selectively producing acetaldehyde from ethanol in a gas phase using a base metal oxide selected from complex oxides containing one or more of them as a catalyst.
また、本発明は、酸素分子の存在下に、金微粒子を分散・固定した、ＺｎＯ、Ｉｎ2Ｏ3、ＳｉＯ2、Ａｌ2Ｏ３、ＺｒＯ2、ＴｉＯ2、ＳｎＯ2、Ｖ2Ｏ5およびそれらを１種類以上含む複合酸化物から選ばれた卑金属酸化物を触媒として用いて、エタノールからアセトアルデヒドと酢酸を気相で選択的に製造する方法に関する。 Further, the present invention relates to ZnO, In 2 O 3 , SiO 2 , Al 2 O 3 , ZrO 2 , TiO 2 , SnO 2 , V 2 O 5, and gold particles dispersed and fixed in the presence of oxygen molecules. The present invention relates to a method for selectively producing acetaldehyde and acetic acid from ethanol in a gas phase using a base metal oxide selected from a complex oxide containing one or more of them as a catalyst.
また、本発明は、酸素分子の存在下に、金微粒子を分散・固定した、ＭｎＯ2、ＣｅＯ2、ＣｕＯ、Ｃｏ3Ｏ4、ＮｉＯ、Ｆｅ2Ｏ3およびそれらを１種類以上含む複合酸化物から選ばれた卑金属酸化物を触媒として用いて、エタノールを二酸化炭素と水にまで完全酸化する方法に関する。 The present invention also provides a composite oxide comprising MnO 2 , CeO 2 , CuO, Co 3 O 4 , NiO, Fe 2 O 3 and one or more of them, in which gold fine particles are dispersed and fixed in the presence of oxygen molecules. The present invention relates to a method for completely oxidizing ethanol to carbon dioxide and water using a base metal oxide selected from the above as a catalyst.
また、本発明は、上記エタノールからアセトアルデヒドを気相で選択的に製造する方法に用いられる、金微粒子を分散・固定した、Ｌａ2Ｏ3、ＭｏＯ3、Ｂｉ2Ｏ3、ＳｒＯ、Ｙ2Ｏ３、ＭｇＯ、ＢａＯ、ＷＯ3、ＣｕＯおよびそれらを１種類以上含む複合酸化物から選ばれた卑金属酸化物触媒に関する。 The present invention is also used in the method for selectively producing acetaldehyde from ethanol in the gas phase, in which gold fine particles are dispersed and fixed, La 2 O 3 , MoO 3 , Bi 2 O 3 , SrO, Y 2 O. 3 , relates to a base metal oxide catalyst selected from MgO, BaO, WO 3 , CuO and composite oxides containing one or more thereof.
また、本発明は、上記エタノールからアセトアルデヒドと酢酸を気相で選択的に製造する方法に用いられる、金微粒子を分散・固定した、ＺｎＯ、Ｉｎ2Ｏ3、ＳｉＯ2、Ａｌ2Ｏ３、ＺｒＯ2、ＴｉＯ2、ＳｎＯ2、Ｖ2Ｏ5およびそれらを１種類以上含む複合酸化物から選ばれた卑金属酸化物触媒に関する。 The present invention also provides ZnO, In 2 O 3 , SiO 2 , Al 2 O 3 , ZrO in which gold fine particles are dispersed and fixed, which is used in the method for selectively producing acetaldehyde and acetic acid from ethanol in the gas phase. 2 , TiO 2 , SnO 2 , V 2 O 5 and a base metal oxide catalyst selected from composite oxides containing one or more thereof.
また、本発明は、上記エタノールを二酸化炭素と水にまで完全酸化する方法に用いられる、金微粒子を分散・固定した、ＭｎＯ2、ＣｅＯ2、ＣｕＯ、Ｃｏ3Ｏ4、ＮｉＯ、Ｆｅ2Ｏ3およびそれらを１種類含む以上含む複合酸化物から選ばれた卑金属酸化物触媒に関する。 The present invention is also used in the above-described method for completely oxidizing ethanol to carbon dioxide and water, in which gold fine particles are dispersed and fixed, MnO 2 , CeO 2 , CuO, Co 3 O 4 , NiO, Fe 2 O 3. And a base metal oxide catalyst selected from composite oxides containing one or more of them.
本発明の好ましい態様においては、上記各触媒において、卑金属酸化物担体上に分散・固定される金微粒子は、直径１０ｎｍ以下の金ナノ粒子または金クラスターである。 In a preferred embodiment of the present invention, in each of the above catalysts, the gold fine particles dispersed and fixed on the base metal oxide support are gold nanoparticles or gold clusters having a diameter of 10 nm or less.
本発明の別の好適態様によれば、チタンを含む酸化物からなる担体と、前記担体に分散・固定されたＶ2Ｏ5とを有する、エタノールの気相酸化触媒が提供される。さらに、本発明は、エタノールの気相酸化触媒の存在下で、エタノールを酸素分子により気相分解して、（Ａ）アセトアルデヒド及び／又は酢酸を選択的に製造するか、あるいは、（Ｂ）二酸化炭素と水にまで完全酸化する、エタノールの酸化方法も提供する。 According to another preferred embodiment of the present invention, there is provided a gas phase oxidation catalyst for ethanol comprising a support made of an oxide containing titanium and V 2 O 5 dispersed and fixed on the support. Furthermore, the present invention provides (A) selective production of acetaldehyde and / or acetic acid by vapor-decomposing ethanol with molecular oxygen in the presence of a gas-phase oxidation catalyst for ethanol, or (B) carbon dioxide. Also provided is a method for the oxidation of ethanol that completely oxidizes to carbon and water.
本発明によれば、金ナノ粒子を分散・固定した卑金属酸化物担体、あるいは酸化バナジウムを分散・固定したチタン含有酸化物担体の種類を選ぶことによって、エタノールの完全酸化、酢酸とアセトアルデヒドの混合物の選択合成、アセトアルデヒドの選択合成のいずれかが可能であるので、バイオエタノールの有効利用に役立つ。また、本発明の方法は、居住空間や工場等の空気浄化やエタノールを燃料とする燃料電池の開発に重要な役割を果たすことができる。さらに、本発明の触媒は、気相でのアルコール、炭化水素の酸素酸化、空気浄化、燃料電池、化学センサなどの用途への適用も期待できる。 According to the present invention, by selecting a base metal oxide carrier in which gold nanoparticles are dispersed and fixed, or a titanium-containing oxide carrier in which vanadium oxide is dispersed and fixed, a complete oxidation of ethanol, a mixture of acetic acid and acetaldehyde Since either selective synthesis or selective synthesis of acetaldehyde is possible, it is useful for effective utilization of bioethanol. Further, the method of the present invention can play an important role in the purification of air in living spaces and factories and the development of fuel cells using ethanol as fuel. Furthermore, the catalyst of the present invention can be expected to be applied to uses such as alcohol in the gas phase, oxygen oxidation of hydrocarbons, air purification, fuel cells, and chemical sensors.
本発明は、気相でエタノールを酸素分子の存在下に酸化してアセトアルデヒドあるいはアセトアルデヒドと酢酸を選択的に製造する方法および気相でエタノールを二酸化炭素と水にまで完全酸化する方法に関するものである。本発明のアセトアルデヒドあるいはアセトアルデヒドと酢酸を選択的に製造する方法は、エチレンまたはメタノールから出発する現行の化学プロセスに比べ、新しい反応となるので、この反応に適した新規な固体触媒の開発が必要不可欠となる。なぜならば、エタノールと酸素との反応を気相で行うと、エタノールの転化率が高いとき（例えば、工業的に必要な１０％以上）は二酸化炭素と水までの完全酸化反応が進行し、アセトアルデヒドや酢酸のところで反応を止めることが通常難しいからである。一方、エタノールを酸素分子または空気で酸化して二酸化炭素と水までに完全酸化する触媒は、２００℃以下の低温で使えるものについては例が少ないが、空気浄化、燃料電池、化学センサの開発にとって低温でのエタノールの完全分解は有用な技術である。 The present invention relates to a method for selectively producing acetaldehyde or acetaldehyde and acetic acid by oxidizing ethanol in the presence of oxygen molecules in the gas phase and a method for completely oxidizing ethanol to carbon dioxide and water in the gas phase. . Since the method for selectively producing acetaldehyde or acetaldehyde and acetic acid according to the present invention is a new reaction compared to the current chemical process starting from ethylene or methanol, the development of a new solid catalyst suitable for this reaction is indispensable. It becomes. This is because when the reaction between ethanol and oxygen is carried out in the gas phase, when the conversion rate of ethanol is high (for example, 10% or more industrially necessary), a complete oxidation reaction to carbon dioxide and water proceeds, and acetaldehyde This is because it is usually difficult to stop the reaction at acetic acid. On the other hand, there are few examples of catalysts that oxidize ethanol with oxygen molecules or air to completely oxidize to carbon dioxide and water, but those that can be used at a low temperature of 200 ° C or less are few, but for the development of air purification, fuel cells, and chemical sensors. Complete decomposition of ethanol at low temperatures is a useful technique.
本発明は、気相でエタノールを酸素分子の存在下で酸化して、アセトアルデヒドあるいはアセトアルデヒドと酢酸を選択的に製造する、あるいは二酸化炭素と水にまで完全酸化する際に、金担持触媒の担体として、特定の卑金属酸化物を用いることにより、高効率あるいは高収率、かつ低圧でアセトアルデヒドや酢酸を製造することができる、あるいは従来に比べ低温、低圧でエタノールを二酸化炭素と水にまで完全酸化することを見出したものである。本発明で用いられる金担持触媒の金微粒子としては、金ナノ粒子あるいは金クラスターが挙げられる（なお、以下では、金クラスターを含め「金ナノ粒子」という。）。金ナノ粒子の平均粒子径は、０．８ｎｍから１００ｎｍ、さらには１ｎｍから１０ｎｍであることが好ましく、特に好ましくは２ｎｍから５ｎｍである。一方、卑金属酸化物の平均粒子径は１０ｎｍから１，０００ｎｍであることが好ましい。上記の金ナノ粒子の担持量としては、卑金属酸化物に対して０．１〜５．０質量％とするのが好ましく、０．５〜２．０質量％とするのがさらに好ましい。 The present invention oxidizes ethanol in the gas phase in the presence of oxygen molecules to selectively produce acetaldehyde or acetaldehyde and acetic acid, or to completely oxidize to carbon dioxide and water as a carrier for a gold-supported catalyst. By using specific base metal oxides, acetaldehyde and acetic acid can be produced with high efficiency or high yield and low pressure, or ethanol can be completely oxidized to carbon dioxide and water at low temperature and low pressure compared to conventional methods. This is what we found. Examples of the gold fine particles of the gold-supported catalyst used in the present invention include gold nanoparticles and gold clusters (hereinafter referred to as “gold nanoparticles” including gold clusters). The average particle diameter of the gold nanoparticles is preferably 0.8 nm to 100 nm, more preferably 1 nm to 10 nm, and particularly preferably 2 nm to 5 nm. On the other hand, the average particle diameter of the base metal oxide is preferably 10 nm to 1,000 nm. The supported amount of the gold nanoparticles is preferably 0.1 to 5.0% by mass, and more preferably 0.5 to 2.0% by mass with respect to the base metal oxide.
また、本発明のエタノール酸化触媒に用いられる卑金属酸化物担体は、前記の通り各方法により異なるものが使用され、大きく３つのグループに分けられる。まず第一のグループは、担体となる卑金属酸化物が、ＭｎＯ2、ＣｅＯ2、ＣｕＯ、Ｃｏ3Ｏ4、ＮｉＯ、Ｆｅ2Ｏ3およびそれらを１種類含む以上含む複合酸化物からなり、エタノールの完全酸化に有効なものである。すなわち、第一のグループの担体は、卑金属酸化物が、半導体性（主としてｐ型）を持つ３ｄ遷移金属酸化物とＣｅＯ2のように酸素の吸放出能を有する金属酸化物である場合である。第二のグループは、卑金属酸化物がＺｎＯ、Ｉｎ2Ｏ3、ＳｉＯ2、Ａｌ2Ｏ3、ＺｒＯ2、ＴｉＯ2、ＳｎＯ２、Ｖ2Ｏ5およびそれらを１種類含む以上含む複合酸化物からなり、酢酸とアセトアルデヒドの合成に選択的である。すなわち、第二のグループの担体は、卑金属酸化物が、ＺｎＯ、ＴｉＯ2、ＳｎＯ2、Ｖ2Ｏ5などのｎ型半導体性金属酸化物、ＳｉＯ2、Ａｌ2Ｏ3、Ｉｎ2Ｏ3などの共有結合性の高い絶縁性金属酸化物、ＺｒＯ2などのその他の金属酸化物である場合である。第三のグループは、卑金属酸化物がＬａ2Ｏ3、ＭｏＯ3、Ｂｉ2Ｏ3、ＳｒＯ、Ｙ2Ｏ３、ＭｇＯ、ＢａＯ、ＷＯ3、ＣｕＯおよびそれらを１種類含む以上含む複合酸化物からなり、アセトアルデヒドの合成に選択的である。すなわち、第三のグループの担体は、卑金属酸化物が、Ｌａ2Ｏ3、ＭｇＯ、ＢａＯなどのイオン結合性が高く塩基性の金属酸化物、ＭｏＯ3とＷＯ3などの酸性の強い金属酸化物、Ｂｉ2Ｏ3、ＳｒＯ、Ｙ2Ｏ3などの酸素イオン導電性金属酸化物およびＣｕＯなどである場合である。 Further, as described above, different base metal oxide carriers used in the ethanol oxidation catalyst of the present invention are used depending on the method, and are roughly divided into three groups. In the first group, the base metal oxide serving as a carrier is composed of MnO 2 , CeO 2 , CuO, Co 3 O 4 , NiO, Fe 2 O 3 and a composite oxide containing one or more of them, It is effective for complete oxidation. That is, the carrier of the first group is a case where the base metal oxide is a 3d transition metal oxide having semiconducting properties (mainly p-type) and a metal oxide having oxygen absorbing / releasing ability such as CeO 2. . The second group consists of complex oxides in which the base metal oxide includes ZnO, In 2 O 3 , SiO 2 , Al 2 O 3 , ZrO 2 , TiO 2 , SnO 2 , V 2 O 5 and one or more of them. It is selective for the synthesis of acetic acid and acetaldehyde. That is, the carrier of the second group is such that the base metal oxide is an n-type semiconductor metal oxide such as ZnO, TiO 2 , SnO 2 , V 2 O 5 , SiO 2 , Al 2 O 3 , In 2 O 3, etc. This is the case of an insulating metal oxide having a high covalent bond and other metal oxides such as ZrO 2 . The third group consists of complex oxides in which the base metal oxide contains La 2 O 3 , MoO 3 , Bi 2 O 3 , SrO, Y 2 O 3 , MgO, BaO, WO 3 , CuO and one or more of them. It is selective for the synthesis of acetaldehyde. That is, the third group of carriers is a base metal oxide such as La 2 O 3 , MgO, or BaO that has a high ion binding property and a basic metal oxide, or a highly acidic metal oxide such as MoO 3 and WO 3 . , Bi 2 O 3 , SrO, Y 2 O 3 and other oxygen ion conductive metal oxides and CuO.
本発明の卑金属酸化物表面に金ナノ粒子を分散・固定させた触媒は、従来知られた卑金属酸化物表面に金ナノ粒子を分散・固定させる方法のいずれを用いて作製されてもよい。このような方法としては、析出沈殿法の他、共沈法、析出還元法、気相グラフティング、固相混合法などが例示される。例えば、その一例として、析出沈殿法により金担持卑金属酸化物触媒を製造する方法を示すと、卑金属酸化物粒子粉末またはそれらを球状、円筒状、蜂の巣状などの支持体に担持させた成形体を金化合物の水溶液に懸濁または浸漬し、アルカリを加えてｐＨを７〜１０の範囲のある点で調整し、金水酸化物を卑金属酸化物表面上に析出沈殿させる。よく攪拌を行い、水溶液の濃度（金化合物および還元剤等）や、ｐＨおよび温度を調整して、攪拌を１時間以上（通常は１時間程度）続けることにより金水酸化物を卑金属酸化物表面に分散・固定化できる。これを水洗し、乾燥後、３００℃以上で空気焼成することによって、金ナノ粒子触媒が得られる。このとき、卑金属酸化物は、エタノールの完全酸化、酢酸とアセトアルデヒドの選択合成、アセトアルデヒドの選択合成と、目的に応じて選択される。 The catalyst in which gold nanoparticles are dispersed and fixed on the surface of the base metal oxide according to the present invention may be prepared using any of the conventionally known methods for dispersing and fixing gold nanoparticles on the surface of a base metal oxide. Examples of such a method include a precipitation method, a coprecipitation method, a precipitation reduction method, a gas phase grafting method, and a solid phase mixing method. For example, as an example, a method for producing a gold-supported base metal oxide catalyst by a precipitation method is shown. A base metal oxide particle powder or a molded body in which they are supported on a spherical, cylindrical, or honeycomb support. It is suspended or immersed in an aqueous solution of a gold compound, an alkali is added to adjust the pH at a certain point in the range of 7 to 10, and gold hydroxide is precipitated and precipitated on the surface of the base metal oxide. Stir well, adjust the concentration of the aqueous solution (gold compound and reducing agent, etc.), pH and temperature, and continue stirring for 1 hour or more (usually about 1 hour) to bring the gold hydroxide to the base metal oxide surface. Can be distributed and fixed. This is washed with water, dried, and then air calcined at 300 ° C. or higher to obtain a gold nanoparticle catalyst. At this time, the base metal oxide is selected according to the purpose of complete oxidation of ethanol, selective synthesis of acetic acid and acetaldehyde, selective synthesis of acetaldehyde.
本発明の方法に用いられる金担持卑金属酸化物触媒を製造する際に用いられる金化合物としては、従来金ナノ粒子担持金属酸化物触媒を製造する際に用いられた金化合物の何れをも用いることができる。本発明において用いることのできる金化合物の例を挙げると、例えば、四塩化金酸（ＨＡｕＣｌ4）、四塩化金酸塩（例えばＮａＡｕＣｌ4）、シアン化金（ＡｕＣＮ）、シアン化金カリウム｛Ｋ［Ａｕ（ＣＮ）2］｝、三塩化ジエチルアミン金酸［（Ｃ2Ｈ5）2ＮＨ・ＡｕＣｌ3］、エチレンジアミン金錯体（例えば、塩化物錯体｛Ａｕ［Ｃ2Ｈ4（ＮＨ2）2］2Ｃｌ3｝）、ジメチル金β‐ジケトン誘導体錯体（例えば、ジメチル金アセチルアセトナート｛（ＣＨ3）2Ａｕ［ＣＨ3ＣＯＣＨＣＯＣＨ3］｝）や、その他、水や有機溶媒に溶解できる金の塩や錯体などが挙げられる。 As the gold compound used in producing the gold-supported base metal oxide catalyst used in the method of the present invention, any of the gold compounds conventionally used in producing the gold nanoparticle-supported metal oxide catalyst should be used. Can do. Examples of gold compounds that can be used in the present invention include, for example, tetrachloroauric acid (HAuCl 4 ), tetrachloroaurate (eg, NaAuCl 4 ), gold cyanide (AuCN), potassium gold cyanide {K [Au (CN) 2 ]}, diethylamine trichloride gold acid [(C 2 H 5 ) 2 NH · AuCl 3 ], ethylenediamine gold complex (for example, chloride complex {Au [C 2 H 4 (NH 2 ) 2 ]) 2 Cl 3 }), dimethylgold β-diketone derivative complexes (for example, dimethylgold acetylacetonate {(CH 3 ) 2 Au [CH 3 COCHCOCH 3 ]}), and other gold salts that can be dissolved in water or organic solvents And complexes.
金化合物の水溶液中の濃度としては、希薄すぎると金が卑金属酸化物上に水酸化物として析出できなくなり、濃厚すぎると卑金属酸化物上だけでなく溶液中でも金水酸化物の沈殿が起こってしまうので、０．１ｍｍｏｌ／Ｌから１０ｍｍｏｌ／Ｌまでの範囲が望ましく、０．５ｍｍｏｌ／Ｌから２ｍｍｏｌ／Ｌまでの範囲がより望ましい。 If the concentration of the gold compound in the aqueous solution is too dilute, gold cannot be deposited as a hydroxide on the base metal oxide, and if it is too thick, the gold hydroxide precipitates not only on the base metal oxide but also in the solution. The range from 0.1 mmol / L to 10 mmol / L is desirable, and the range from 0.5 mmol / L to 2 mmol / L is more desirable.
卑金属酸化物に分散・固定する金の担持量は、水溶液の濃度と量によって０．０１質量％から５０質量％までの範囲で調整することができる。 The amount of gold to be dispersed and fixed in the base metal oxide can be adjusted in the range from 0.01% by mass to 50% by mass depending on the concentration and amount of the aqueous solution.
ｐＨ調整用のアルカリとしては、アルカリ金属の水酸化物や炭酸塩、アルカリ土類金属の水酸化物や炭酸塩、アンモニア、尿素などを使うことができる。 As the alkali for pH adjustment, alkali metal hydroxide or carbonate, alkaline earth metal hydroxide or carbonate, ammonia, urea or the like can be used.
溶液のｐＨは、５〜１３、好ましくは６〜１０であり、金の水酸化物の溶解度が相対的に低い範囲を選ぶことが肝要である。温度は、０℃から９０℃までの範囲が好ましく、特に好ましくは３０℃から７０℃までの範囲である。 The pH of the solution is 5 to 13, preferably 6 to 10, and it is important to select a range in which the solubility of the gold hydroxide is relatively low. The temperature is preferably in the range of 0 ° C. to 90 ° C., particularly preferably in the range of 30 ° C. to 70 ° C.
このようにして得られる表面に金微粒子を分散・固定させた卑金属酸化物における金ナノ粒子の平均粒子径は１ｎｍから５０ｎｍであり、目的・用途によって異なるが、触媒として用いるときは、１０ｎｍ以下、さらには５ｎｍ以下であることが好ましい。このときの平均粒子径は、球状粒子の場合は直径、楕円形粒子の場合は長径であり、走査型電子顕微鏡（ＳＥＭ）観察あるいは透過型電子顕微鏡（ＴＥＭ）観察から、粒子径分布を作り、平均値を求めたものである。 The average particle diameter of the gold nanoparticles in the base metal oxide in which the gold fine particles are dispersed and fixed on the surface thus obtained is 1 nm to 50 nm, and varies depending on the purpose and use, but when used as a catalyst, 10 nm or less, Furthermore, it is preferable that it is 5 nm or less. The average particle size at this time is a diameter in the case of a spherical particle, and a long diameter in the case of an elliptical particle. From the observation with a scanning electron microscope (SEM) or transmission electron microscope (TEM), The average value is obtained.
また、上記製造方法により、担持される金ナノ粒子の粒子分布が比較的狭い、粒子径の揃った触媒を製造することができる。粒子径分布の狭い金ナノ粒子を卑金属酸化物の表面に分散・固定させることによって、ナノオーダーの金微粒子を用いる触媒用途においては、性能の向上を図ることができる。 In addition, the above production method can produce a catalyst having a uniform particle size with a relatively narrow particle distribution of supported gold nanoparticles. By dispersing and fixing gold nanoparticles having a narrow particle size distribution on the surface of the base metal oxide, it is possible to improve performance in a catalyst application using nano-order gold fine particles.
本発明の別の態様によれば、チタンを含む酸化物からなる担体と、前記担体に分散・固定されたＶ2Ｏ5とを有する組成物も、エタノールの気相酸化触媒として優れている。チタンを含む酸化物は、チタンを含む複合酸化物であるかあるいはＴｉＯ２であり、好ましくはＴｉＯ２である。ＴｉＯ２はルチル型であってもよいし、アナターゼ型であってもよい。 According to another aspect of the present invention, a composition comprising a support composed of an oxide containing titanium and V 2 O 5 dispersed and fixed on the support is also excellent as a gas phase oxidation catalyst for ethanol. The oxide containing titanium is a composite oxide containing titanium or TiO 2 , preferably TiO 2 . TiO 2 may be a rutile type or an anatase type.
この態様において、Ｖ２Ｏ５の平均粒子径は、好ましくは５〜２００ｎｍであり、より好ましくは１０〜５０ｎｍである。Ｖ２Ｏ５の平均粒子径を小さくするためには焼成温度を低くするなどの手法があり、大きくするためにはその逆の手法をとればよい。チタンを含む酸化物の平均粒子径は５〜５００ｎｍであり、より好ましくは１０〜１００ｎｍである。チタンを含む酸化物１００重量部に対するＶ２Ｏ５の担持量は好ましくは１〜５０重量部であり、より好ましくは５〜４０重量部である。 In this embodiment, the average particle diameter of V 2 O 5 is preferably 5 to 200 nm, more preferably 10 to 50 nm. In order to reduce the average particle diameter of V 2 O 5 , there is a technique such as lowering the firing temperature, and in order to increase it, the opposite technique may be taken. The average particle diameter of the oxide containing titanium is 5 to 500 nm, more preferably 10 to 100 nm. The supported amount of V 2 O 5 with respect to 100 parts by weight of the oxide containing titanium is preferably 1 to 50 parts by weight, and more preferably 5 to 40 parts by weight.
チタンを含む酸化物に対してＶ２Ｏ５を分散・固定（担持）させる方法は特に限定は無い。非限定的な例示として、水溶性のバナジウム含有化合物を水に溶かし、そこに、チタンを含む酸化物粒子を加え、超音波攪拌を行って、凍結乾燥に供し、しかる後に、焼成するという方法が挙げられる。 A method for dispersing and fixing (supporting) V 2 O 5 with respect to an oxide containing titanium is not particularly limited. As a non-limiting example, there is a method in which a water-soluble vanadium-containing compound is dissolved in water, oxide particles containing titanium are added thereto, subjected to ultrasonic agitation, subjected to freeze-drying, and then fired. Can be mentioned.
水溶性のバナジウム含有化合物は特に限定はなく、例えば、バナジン酸塩その他の化合物などが挙げられ、具体例としては、バナジン（Ｖ）酸アンモニウム、オキシ三塩化バナジウム、シュウ酸バナジル、ビス(アセチルアセトナト)オキソバナジウム（ＩＶ）などが挙げられる。バナジウム含有化合物に対する水の量は後述する超音波攪拌ができる範囲でなるべく少量であることが好ましい。 The water-soluble vanadium-containing compound is not particularly limited, and examples thereof include vanadate and other compounds. Specific examples include ammonium vanadate (V), vanadium oxytrichloride, vanadyl oxalate, bis (acetylacetate). Nato) oxovanadium (IV) and the like. The amount of water relative to the vanadium-containing compound is preferably as small as possible within a range where ultrasonic stirring described later can be performed.
バナジン酸塩の水溶液にチタンを含む酸化物粒子を加えた後の超音波攪拌の条件は特に限定はなく、酸化物粒子をなるべくよく分散させることが好ましい。超音波攪拌に代えて、棒状あるいはプロペラ状の撹拌子を混合スラリー中で回転させるなどの方法による攪拌でもよい。 The conditions for ultrasonic stirring after adding oxide particles containing titanium to an aqueous solution of vanadate are not particularly limited, and it is preferable to disperse the oxide particles as well as possible. Instead of ultrasonic stirring, stirring by a method such as rotating a rod-like or propeller-like stirring bar in the mixed slurry may be used.
凍結乾燥については、例えば液体窒素などの冷媒を用いる凍結が挙げられ、ひとたび凍結したら、真空下において乾燥処理をすればよい。例えば、凍結後、真空下におき室温にて一晩放置することなどが挙げられる。 As for freeze-drying, for example, freezing using a refrigerant such as liquid nitrogen can be mentioned. Once frozen, it may be dried under vacuum. For example, after freezing, it may be left under vacuum at room temperature overnight.
凍結乾燥の後に、焼成する。焼成は、好ましくは空気中で所定時間の間、所定温度に保たれる。本発明者らの新知見では、焼成温度により、エタノール酸化触媒として異なる性質のものを作り分けることができることがわかった。例えば、担体としてルチル型の二酸化チタンを用いる場合には、好ましくは２６０〜３４０℃、より好ましくは２８０〜３２０℃で、好ましくは２〜６時間、より好ましくは３〜５時間焼成することにより、エタノールを好ましくは１５０〜１７０℃で酸化してアセトアルデヒドを選択的に生成する触媒を得ることができる。他方、担体としてアナターゼ型の二酸化チタンを用いる場合には、好ましくは２６０〜４４０℃、より好ましくは２８０〜４２０℃で、好ましくは２〜６時間、より好ましくは３〜５時間焼成することにより、エタノールを酸化するときの温度に応じてしてアセトアルデヒド、酢酸を選択的に生成するか、あるいは二酸化炭素にまで酸化させることができる触媒を得ることができる。具体的には、好ましくは１７０〜１９０℃でエタノールを気相酸化することにより選択的に酢酸を得ることができ、好ましくは２３０〜２７０℃でエタノールを気相酸化することにより二酸化炭素と水にまで完全参加させることができる。別の好適態様として、担体としてアナターゼ型の二酸化チタンを用い、好ましくは４６０〜５４０℃、より好ましくは４８０〜５２０℃で、好ましくは２〜６時間、より好ましくは３〜５時間焼成することにより、エタノールを酸化するときの温度に応じてしてアセトアルデヒドを選択的に生成するか、あるいは、酢酸を選択的に生成することができる触媒を得ることができる。具体的には、好ましくは１３０〜１５０℃でエタノールを気相酸化することにより選択的にアセトアルデヒドを得ることができ、好ましくは２１０〜２３０℃でエタノールを気相酸化することにより選択的に酢酸を得ることができる。 Baking after freeze-drying. Firing is preferably maintained at a predetermined temperature for a predetermined time in air. According to the new knowledge of the present inventors, it was found that different properties of the ethanol oxidation catalyst can be made depending on the firing temperature. For example, when rutile type titanium dioxide is used as a carrier, it is preferably 260 to 340 ° C, more preferably 280 to 320 ° C, preferably 2 to 6 hours, more preferably 3 to 5 hours. A catalyst for selectively producing acetaldehyde can be obtained by oxidizing ethanol preferably at 150 to 170 ° C. On the other hand, when anatase type titanium dioxide is used as a carrier, it is preferably 260 to 440 ° C, more preferably 280 to 420 ° C, preferably 2 to 6 hours, more preferably 3 to 5 hours. Depending on the temperature at which ethanol is oxidized, a catalyst capable of selectively producing acetaldehyde and acetic acid or oxidizing it to carbon dioxide can be obtained. Specifically, preferably, acetic acid can be selectively obtained by vapor-phase oxidation of ethanol at 170 to 190 ° C., and preferably carbon dioxide and water by vapor-phase oxidation of ethanol at 230 to 270 ° C. Until complete participation. In another preferred embodiment, anatase-type titanium dioxide is used as a carrier, and it is preferably calcined at 460 to 540 ° C., more preferably 480 to 520 ° C., preferably 2 to 6 hours, more preferably 3 to 5 hours. Depending on the temperature when ethanol is oxidized, a catalyst capable of selectively producing acetaldehyde or selectively producing acetic acid can be obtained. Specifically, preferably, acetaldehyde can be selectively obtained by vapor-phase oxidation of ethanol at 130 to 150 ° C, and preferably acetic acid is selectively obtained by vapor-phase oxidation of ethanol at 210 to 230 ° C. Obtainable.
さらに、本発明は、チタンを含む酸化物からなる担体と、前記担体に分散・固定されたＶ2Ｏ5とを有する、エタノールの気相酸化触媒の存在下で、エタノールを酸素分子により気相分解して、（Ａ）アセトアルデヒド及び／又は酢酸を選択的に製造するか、あるいは、（Ｂ）二酸化炭素と水にまで完全酸化する、エタノールの酸化方法も提供する。
したがって、チタンを含む酸化物にＶ2Ｏ5を担持させてなるエタノールの気相酸化触媒については、例えば、以下の発明を包含すると評価することもできる。
（イ）チタンを含む酸化物からなる担体と、前記担体に分散・固定されたＶ2Ｏ5とを有する、エタノールの気相酸化触媒。
（ロ）チタンを含む酸化物がＴｉＯ２である（イ）の気相酸化触媒。
（ハ）バナジウム酸塩の水溶液にチタンを含む酸化物を分散させて、次いで、凍結乾燥し、その後、焼成して得られる、（イ）又は（ロ）の気相酸化触媒。
（ニ）チタンを含む酸化物がルチル型のＴｉＯ２であり、焼成温度が２６０〜３４０℃である（ハ）の気相酸化触媒。
（ホ）チタンを含む酸化物がアナターゼ型のＴｉＯ２であり、焼成温度が２６０〜４４０℃である（ハ）の気相酸化触媒。
（へ）チタンを含む酸化物がアナターゼ型のＴｉＯ２であり、焼成温度が４６０〜５４０℃である（ハ）の気相酸化触媒。
（ト）（ホ）の気相酸化触媒の存在下、エタノールを１７０〜１９０℃度で気相酸化することによる、選択的な酢酸の製造方法。
（チ）（ホ）の気相酸化触媒の存在下、エタノールを２３０〜２７０℃度で気相酸化することによる、二酸化炭素と水へ完全酸化する方法。
（リ）（ヘ）の気相酸化触媒の存在下、エタノールを１３０〜１５０℃度で気相酸化することによる、選択的なアセトアルデヒドの製造方法。
（ヌ）（ヘ）の気相酸化触媒の存在下、エタノールを２１０〜２３０℃度で気相酸化することによる、選択的なアセトアルデヒドの製造方法。
Furthermore, the present invention provides ethanol in a gas phase with oxygen molecules in the presence of a gas phase oxidation catalyst of ethanol having a carrier made of an oxide containing titanium and V 2 O 5 dispersed and fixed on the carrier. Also provided is a method for the oxidation of ethanol that decomposes to (A) selectively produce acetaldehyde and / or acetic acid, or (B) complete oxidation to carbon dioxide and water.
Therefore, it can be evaluated that the gas phase oxidation catalyst of ethanol in which V 2 O 5 is supported on an oxide containing titanium includes the following invention, for example.
(A) A gas phase oxidation catalyst for ethanol comprising a support made of an oxide containing titanium and V 2 O 5 dispersed and fixed on the support.
(B) The gas phase oxidation catalyst according to (a), wherein the oxide containing titanium is TiO 2 .
(C) A gas phase oxidation catalyst according to (a) or (b) obtained by dispersing an oxide containing titanium in an aqueous solution of vanadate, then freeze-drying, and then calcining.
(D) The gas phase oxidation catalyst according to (c), wherein the oxide containing titanium is rutile TiO 2 and the firing temperature is 260 to 340 ° C.
(E) The gas phase oxidation catalyst according to (c), in which the oxide containing titanium is anatase TiO 2 and the firing temperature is 260 to 440 ° C.
(F) The gas phase oxidation catalyst according to (c), wherein the oxide containing titanium is anatase TiO 2 and the firing temperature is 460 to 540 ° C.
(G) A selective method for producing acetic acid by subjecting ethanol to vapor phase oxidation at 170 to 190 ° C. in the presence of the gas phase oxidation catalyst of (e).
(H) A method for completely oxidizing ethanol into water dioxide and water by subjecting ethanol to vapor phase oxidation at 230 to 270 ° C. in the presence of the gas phase oxidation catalyst of (e).
(I) A method for selectively producing acetaldehyde by subjecting ethanol to vapor phase oxidation at 130 to 150 ° C. in the presence of the gas phase oxidation catalyst of (f).
(Nu) A method for selectively producing acetaldehyde by subjecting ethanol to vapor phase oxidation at 210 to 230 ° C. in the presence of the vapor phase oxidation catalyst of (f).
本発明においては、エタノールの酸化反応は、エタノールと酸素分子を含有する気体を前記触媒と、例えば１００〜２８０℃で接触させることによって行われる。反応に用いられる酸素分子は、酸素ガスとして供給されてもよいし、空気が用いられてもよい。また前記気体である原料ガスには、必要に応じ希釈ガス（キャリアガス）が含有されてもよい。このとき反応に用いられる装置は、通常気相反応を行う際に利用されている一般的な装置によればよい。例えば、触媒を反応管内に充填し、反応管を所定の温度に加熱した状態で、エタノールおよび酸素ガスあるいは空気を含有する気体を反応管に送り込み、これら原料ガスと触媒とを接触させ、反応ガスを回収することにより行われる。反応圧は、常圧で行われればよく、必要であれば０．５〜５Ｐａ（気圧）程度加圧してもよい。希釈ガスとしては、例えば、窒素、アルゴン、ヘリウム、二酸化炭素などのいわゆる不活性ガスが用いられる。希釈ガスの使用量は、原料ガスの組成、流量、反応熱などを勘案して適宜決定すればよいが、通常エタノールに対し、１〜１００容量倍とされることが好ましい。 In the present invention, the oxidation reaction of ethanol is performed by bringing a gas containing ethanol and oxygen molecules into contact with the catalyst at, for example, 100 to 280 ° C. Oxygen molecules used for the reaction may be supplied as oxygen gas or air may be used. Moreover, the source gas which is the gas may contain a dilution gas (carrier gas) as necessary. The apparatus used for the reaction at this time may be a general apparatus that is normally used when performing a gas phase reaction. For example, a catalyst is filled in a reaction tube, and a gas containing ethanol and oxygen gas or air is sent to the reaction tube in a state where the reaction tube is heated to a predetermined temperature. It is performed by collecting. The reaction pressure should just be performed by a normal pressure, and if necessary, you may pressurize about 0.5-5 Pa (atmospheric pressure). As the dilution gas, for example, a so-called inert gas such as nitrogen, argon, helium, carbon dioxide, or the like is used. The amount of the diluent gas used may be appropriately determined in consideration of the composition of the raw material gas, the flow rate, the heat of reaction, etc., but it is usually preferably 1 to 100 times the volume of ethanol.
反応管に供給されるエタノールと酸素分子（酸素ガス）の割合は、特に限定されるわけではないが、通常エタノール１容量部に対し、酸素ガスあるいは空気中の酸素ガス０．５〜１００容量部であり、好ましくは１〜１０容積部、より好ましくは２〜５容量部である。 The ratio of ethanol and oxygen molecules (oxygen gas) supplied to the reaction tube is not particularly limited, but is usually 0.5 to 100 parts by volume of oxygen gas or oxygen gas in air with respect to 1 part by volume of ethanol. And preferably 1 to 10 parts by volume, more preferably 2 to 5 parts by volume.
触媒の使用量も、特に限定されるものではないが、反応管の内径が６〜１０ｍｍの条件であれば、一般的には０．１〜１．０ｇ程度とされればよい。実用的には、ガス流量との関係で、空間速度（ＳＶ）が１０，０００〜４０，０００ｈｒ-1・ｍｌ・ｇcat -1程度の範囲内となる量を使用することが好ましい。 The amount of the catalyst used is also not particularly limited, but generally it may be about 0.1 to 1.0 g as long as the inner diameter of the reaction tube is 6 to 10 mm. Practically, it is preferable to use an amount in which the space velocity (SV) is in the range of about 10,000 to 40,000 hr −1 · ml · g cat −1 in relation to the gas flow rate.
反応後のガスは冷却され、集められる。アセトアルデヒドあるいはアセトアルデヒドと酢酸を得る場合においては、集められた反応生成物から未反応エタノールや反応生成物であるアセトアルデヒド、酢酸を分離し、エタノールは必要に応じ原料ガスとして再度使用されてもよい。また、アセトアルデヒドは、本発明とは別の反応過程を経る酢酸製造における原料として利用されてもよい。 The gas after the reaction is cooled and collected. In the case of obtaining acetaldehyde or acetaldehyde and acetic acid, unreacted ethanol and acetaldehyde and acetic acid as reaction products are separated from the collected reaction products, and ethanol may be reused as a raw material gas as necessary. Acetaldehyde may be used as a raw material in acetic acid production through a reaction process different from that of the present invention.
さらに具体的に、希釈ガスとして窒素ガスを用いる場合を例に挙げて、反応装置および反応プロセスの一例を、図１を参照して説明する。図１の装置においては、所定量の触媒が詰められた反応管は、使用する触媒の種類に応じ、予め所定の温度に電気炉内で加熱され、この加熱された触媒層に原料ガスが送られる。原料ガスとしては、エタノールと酸素ガスと希釈ガスとしての窒素ガスとの混合物が用いられる。この混合ガスは、エタノール溶液をプランジャーポンプにより所定量、連続的に気化器に送り気体状としたエタノールガスと、それぞれ流量制御器を通して所定量の供給量とされた酸素ガスおよび窒素ガスとを混合することにより作製される。触媒を通過した後の反応ガスは、図１の装置においてはガスクロマトグラフィー（ＧＣ）に送られ、反応ガスの組成が調べられる。この工程は、工業的な方法においては、アセトアルデヒドまたはアセトアルデヒドと酢酸を製造する際には、反応ガスは冷却後集積され、得られた反応物から必要に応じ未反応のエタノール、アセトアルデヒド、酢酸が分離される。 More specifically, an example of a reaction apparatus and a reaction process will be described with reference to FIG. 1, taking as an example the case of using nitrogen gas as the dilution gas. In the apparatus of FIG. 1, a reaction tube packed with a predetermined amount of catalyst is heated in advance in an electric furnace to a predetermined temperature according to the type of catalyst used, and a raw material gas is sent to the heated catalyst layer. It is done. As the source gas, a mixture of ethanol, oxygen gas and nitrogen gas as a dilution gas is used. This mixed gas is composed of ethanol gas that is a predetermined amount of ethanol solution sent to a vaporizer by a plunger pump and gasified, and oxygen gas and nitrogen gas that are supplied in a predetermined amount through a flow controller, respectively. It is produced by mixing. The reaction gas after passing through the catalyst is sent to gas chromatography (GC) in the apparatus of FIG. 1, and the composition of the reaction gas is examined. In the industrial process, when producing acetaldehyde or acetaldehyde and acetic acid, the reaction gas is collected after cooling, and unreacted ethanol, acetaldehyde, and acetic acid are separated from the obtained reaction product as necessary. Is done.
図１においては、反応管として、内径６ないし１０ｍｍの反応管が用いられ、触媒量は１５０ｍｇとされ、ガス流速は５０ｍＬ／ｍｉｎ、ＳＶは２０，０００ｈｒ-1・ｍｌ・ｇcat -1、エタノール：Ｏ2：Ｎ2＝１：３：１２６（０．７７ｖｏｌ％エタノール）とされ、反応温度は１００〜２８０℃の所定の温度とされている。 In FIG. 1, a reaction tube having an inner diameter of 6 to 10 mm is used as the reaction tube, the catalyst amount is 150 mg, the gas flow rate is 50 mL / min, SV is 20,000 hr −1 · ml · g cat −1 , ethanol : O 2 : N 2 = 1: 3: 126 (0.77 vol% ethanol), and the reaction temperature is a predetermined temperature of 100 to 280 ° C.
本発明においては、エタノールからアセトアルデヒドを気相で選択的に製造する、エタノールからアセトアルデヒドと酢酸を気相で選択的に製造する、あるいはエタノールを二酸化炭素と水にまで完全酸化する、の何れの方法であるかによって、前記するように使用される触媒が異なり、また反応時の温度もそれぞれ異なる。エタノールからアセトアルデヒドを気相で選択的に製造するのであれば、金微粒子を分散・固定した、Ｌａ2Ｏ3、ＭｏＯ3、Ｂｉ2Ｏ3、ＳｒＯ、Ｙ2Ｏ３、ＭｇＯ、ＢａＯ、ＷＯ3、ＣｕＯおよびそれらを１種類以上含む複合酸化物から選ばれた卑金属酸化物を触媒とし、その時の反応温度は、使用する担体によっても異なるが、通常１４０〜３００℃とすることが好ましく、より好ましくは１６０〜２８０℃である。また、エタノールからアセトアルデヒドと酢酸を気相で選択的に製造するのであれば、金微粒子を分散・固定した、ＺｎＯ、Ｉｎ2Ｏ3、ＳｉＯ2、Ａｌ2Ｏ３、ＺｒＯ2、ＴｉＯ2、ＳｎＯ2、Ｖ2Ｏ5およびそれらを１種類以上含む複合酸化物から選ばれた卑金属酸化物を触媒とし、その時の反応温度は、使用する触媒担体によっても異なるが、通常１５０〜２５０℃とすることが好ましく、より好ましくは１８０〜２２０℃である。このとき、Ｖ2Ｏ5とＴｉＯ２とを併用することがより好ましい。さらに、エタノールを二酸化炭素と水にまで完全酸化するのであれば、金微粒子を分散・固定した、ＭｎＯ2、ＣｅＯ2、ＣｕＯ、Ｃｏ3Ｏ4、ＮｉＯ、Ｆｅ2Ｏ3およびそれらを１種類以上含む複合酸化物から選ばれた卑金属酸化物を触媒とし、その時の反応温度は、使用する触媒担体によっても異なるが、通常１５０℃以上とすることが好ましく、より好ましくは１８０℃以上である。 In the present invention, any method of selectively producing acetaldehyde from ethanol in the gas phase, selectively producing acetaldehyde and acetic acid from ethanol in the gas phase, or completely oxidizing ethanol to carbon dioxide and water. Depending on whether or not, the catalyst used differs as described above, and the temperature during the reaction also differs. If acetaldehyde is selectively produced in the gas phase from ethanol, La 2 O 3 , MoO 3 , Bi 2 O 3 , SrO, Y 2 O 3 , MgO, BaO, WO 3 with gold fine particles dispersed and fixed. In addition, a base metal oxide selected from CuO and a composite oxide containing one or more of them is used as a catalyst, and the reaction temperature at that time varies depending on the support used, but is usually preferably 140 to 300 ° C., more preferably Is 160-280 ° C. In addition, if acetaldehyde and acetic acid are selectively produced from ethanol in a gas phase, ZnO, In 2 O 3 , SiO 2 , Al 2 O 3 , ZrO 2 , TiO 2 , SnO in which gold fine particles are dispersed and fixed are used. 2 , V 2 O 5 and base metal oxides selected from complex oxides containing one or more of them are used as catalysts, and the reaction temperature at that time is usually 150 to 250 ° C., although it depends on the catalyst carrier used. Is more preferable, and it is 180-220 degreeC. At this time, it is more preferable to use V 2 O 5 and TiO 2 in combination. Further, if ethanol is completely oxidized to carbon dioxide and water, MnO 2 , CeO 2 , CuO, Co 3 O 4 , NiO, Fe 2 O 3 and one or more of them dispersed and fixed with gold fine particles The base metal oxide selected from the complex oxides to be included is used as a catalyst, and the reaction temperature at that time varies depending on the catalyst carrier used, but is usually preferably 150 ° C. or higher, more preferably 180 ° C. or higher.
なお、本発明において、「選択的」とは、反応生成物の主要部分が目的とする化合物であることを意味するもので、アセトアルデヒドのみ、あるいはアセトアルデヒドと酢酸のみが得られることを意味するものではない。また、二酸化炭素と水にまで完全酸化するという場合も、１００％二酸化炭素と水にまで酸化される場合のみならず、アセトアルデヒドや酢酸などが極少量含まれる場合をも含むものである。 In the present invention, “selective” means that the main part of the reaction product is the target compound, and does not mean that only acetaldehyde or only acetaldehyde and acetic acid can be obtained. Absent. The case of complete oxidation to carbon dioxide and water includes not only the case of being oxidized to 100% carbon dioxide and water but also the case of containing a very small amount of acetaldehyde, acetic acid and the like.
以下、実施例を挙げて本発明を具体的に説明するが、本発明はこれによって何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited at all by this.
実施例１
［Ａｕ／ＺｎＯ触媒の調製］
硝酸亜鉛・六水和物（Ｚｎ（ＮＯ3）2・６Ｈ2Ｏ）０．０１９ｍｏｌ（５．６５ｇ）およびテトラクロロ金（III）酸・四水和物（ＨＡｕＣｌ4・４Ｈ2Ｏ）０．００１ｍｏｌ（０．４１２ｇ）を蒸留水２００ｍＬに溶解させて水溶液を得た（水溶液１）。一方、これとは別に２．６７ｇの炭酸ナトリウムを蒸留水２５０ｍＬに溶解し、７０℃に加温した（水溶液２）。次いで、前記水溶液１を水溶液２に一気に加え、７０℃で１時間撹拌した。生成した沈殿物をｐＨが一定となるまで蒸留水にて洗浄を行い、ろ過した生成物を１００℃、空気中で一晩乾燥した後、空気中３００℃で４時間焼成し、酸化亜鉛担体に担持された金触媒（Ａｕ／ＺｎＯ；金微粒子の平均粒径４ｎｍ、担体の平均粒径５０ｎｍ）を得た。
Example 1
[Preparation of Au / ZnO catalyst]
0.019 mol (5.65 g) of zinc nitrate hexahydrate (Zn (NO 3 ) 2 .6H 2 O) and tetrachloroauric (III) acid tetrahydrate (HAuCl 4 .4H 2 O) 001 mol (0.412 g) was dissolved in 200 mL of distilled water to obtain an aqueous solution (aqueous solution 1). Separately, 2.67 g of sodium carbonate was dissolved in 250 mL of distilled water and heated to 70 ° C. (aqueous solution 2). Next, the
［触媒活性評価］
触媒１５０ｍｇをガラス製Ｕ字型反応管（内径６ｍｍ）に充填し、空気ガス（５０ｍＬ／ｍｉｎ）により、２５℃で３０分間処理を行った。その後、図１に示される方法で、原料ガスを作製し、窒素（４８．５ｍＬ／ｍｉｎ）、酸素（１．１５ｍＬ／ｍｉｎ）、エタノール蒸気（０．３８ｍＬ／ｍｉｎ）を流通させ、触媒層の温度を１００℃から２８０℃まで２０℃刻みで変化させて触媒反応を行った。触媒層を通過した反応ガスをガスクロマトグラフィーで分析し、各温度でのアセトアルデヒド、酢酸、二酸化炭素の収率を求めた。結果を表１に示す。
[Catalyst activity evaluation]
150 mg of the catalyst was filled in a glass U-shaped reaction tube (inner diameter 6 mm) and treated with air gas (50 mL / min) at 25 ° C. for 30 minutes. Thereafter, a raw material gas is produced by the method shown in FIG. 1, and nitrogen (48.5 mL / min), oxygen (1.15 mL / min), and ethanol vapor (0.38 mL / min) are circulated to form a catalyst layer. The catalytic reaction was carried out by changing the temperature from 100 ° C. to 280 ° C. in steps of 20 ° C. The reaction gas that passed through the catalyst layer was analyzed by gas chromatography, and the yields of acetaldehyde, acetic acid, and carbon dioxide at each temperature were determined. The results are shown in Table 1.
アセトアルデヒド、酢酸、二酸化炭素の収率は、次式に従って求めた。 The yields of acetaldehyde, acetic acid and carbon dioxide were determined according to the following formula.
アセトアルデヒドの収率＝（触媒層通過後ガス中のアセトアルデヒドの濃度／原料ガス中のエタノールの濃度）×１００（％）
酢酸の収率＝（触媒層通過後ガス中の酢酸の濃度／原料ガス中のエタノールの濃度）×１００（％）
二酸化炭素の収率＝（触媒層通過後ガス中の二酸化炭素の濃度／原料ガス中のエタノールの濃度）×１００（％）
Acetaldehyde yield = (concentration of acetaldehyde in gas after passing through catalyst layer / concentration of ethanol in raw material gas) x 100 (%)
Acetic acid yield = (concentration of acetic acid in gas after passing through catalyst layer / concentration of ethanol in raw material gas) x 100 (%)
Yield of carbon dioxide = (concentration of carbon dioxide in gas after passing through catalyst layer / concentration of ethanol in raw material gas) × 100 (%)
比較例１
テトラクロロ金（III）酸・四水和物を用いないことを除き実施例１と同様にして、酸化亜鉛担体を作製した。得られた担体（担体の平均粒径１００ｎｍ）を用いて、実施例１と同様の触媒活性評価法により触媒の活性を測定した。結果を表２に示す。
Comparative Example 1
A zinc oxide support was produced in the same manner as in Example 1 except that tetrachloroauric (III) acid tetrahydrate was not used. Using the obtained carrier (average particle diameter of the carrier 100 nm), the activity of the catalyst was measured by the same catalytic activity evaluation method as in Example 1. The results are shown in Table 2.
実施例２〜１０
実施例１の硝酸亜鉛・六水和物のかわりに、硝酸鉄・九水和物、硝酸コバルト・六水和物、硝酸ニッケル・六水和物、硝酸マグネシウム・六水和物、硝酸銅・三水和物、硝酸ランタン・六水和物、硝酸セリウム・六水和物、硝酸イットリウム・六水和物、硝酸インジウム・三水和物を用いて、実施例１と同様に、酸化鉄担体に担持された金触媒（Ａｕ／Ｆｅ2Ｏ3；金微粒子の平均粒径５ｎｍ、担体の平均粒径４０ｎｍ）、酸化コバルト担体に担持された金触媒（Ａｕ／Ｃｏ3Ｏ4；金微粒子の平均粒径４ｎｍ、担体の平均粒径２０ｎｍ）、酸化ニッケル担体に担持された金触媒（Ａｕ／ＮｉＯ；金微粒子の平均粒径６ｎｍ、担体の平均粒径３０ｎｍ）、酸化マグネシウム担体に担持された金触媒（Ａｕ／ＭｇＯ；金微粒子の平均粒径５ｎｍ、担体の平均粒径１５ｎｍ）、酸化銅担体に担持された金触媒（Ａｕ／ＣｕＯ；金微粒子の平均粒径７ｎｍ、担体の平均粒径８０ｎｍ）、酸化ランタン担体に担持された金触媒（Ａｕ／Ｌａ2Ｏ3；金微粒子の平均粒径８ｎｍ、担体の平均粒径１００ｎｍ）、酸化セリウム担体に担持された金触媒（Ａｕ／ＣｅＯ2；金微粒子の平均粒径４ｎｍ、担体の平均粒径４０ｎｍ）、酸化イットリウム担体に担持された金触媒（Ａｕ／Ｙ2Ｏ3；金微粒子の平均粒径６ｎｍ、担体の平均粒径４０ｎｍ）、酸化インジウム担体に担持された金触媒（Ａｕ／Ｉｎ2Ｏ3；金微粒子の平均粒径５ｎｍ、担体の平均粒径４０ｎｍ）を作製し、得られた金触媒を用いて、実施例１と同様の触媒活性評価法により触媒の活性を測定した。結果を表３に示す。なお、表３においては、最大のアセトアルデヒド、酢酸、二酸化炭素の収率およびそのときの温度のみを記載する。
Examples 2-10
Instead of the zinc nitrate hexahydrate of Example 1, iron nitrate nonahydrate, cobalt nitrate hexahydrate, nickel nitrate hexahydrate, magnesium nitrate hexahydrate, copper nitrate Iron oxide carrier using trihydrate, lanthanum nitrate hexahydrate, cerium nitrate hexahydrate, yttrium nitrate hexahydrate, indium nitrate trihydrate in the same manner as in Example 1. Gold catalyst (Au / Fe 2 O 3 ; average particle diameter of gold fine particles 5 nm, average particle diameter of support 40 nm) supported on the surface of the catalyst, gold catalyst (Au / Co 3 O 4 ; gold fine particles supported on the cobalt oxide support) (Average particle diameter 4 nm, average particle diameter 20 nm of support), gold catalyst supported on nickel oxide support (Au / NiO; average particle diameter of gold fine particles 6 nm, average particle diameter 30 nm of support), supported on magnesium oxide support Gold catalyst (Au / MgO; average particle size of gold fine particles 5 nm The average particle diameter of the support is 15 nm), the gold catalyst supported on the copper oxide support (Au / CuO; the average particle diameter of gold fine particles is 7 nm, the average particle diameter of the support is 80 nm), the gold catalyst supported on the lanthanum oxide support (Au / Cu / La 2 O 3 ; average particle size of gold fine particles 8 nm, average particle size of support 100 nm, gold catalyst supported on cerium oxide support (Au / CeO 2 ; average particle size of gold fine particles 4 nm, average particle size of support 40 nm ), Gold catalyst supported on yttrium oxide support (Au / Y 2 O 3 ; average particle diameter of gold fine particles 6 nm, average particle diameter of support 40 nm), gold catalyst supported on indium oxide support (Au / In 2 O 3 ; average particle size of gold fine particles 5 nm, average particle size of support 40 nm) was prepared, and the activity of the catalyst was measured by the same catalytic activity evaluation method as in Example 1 using the obtained gold catalyst. The results are shown in Table 3. In Table 3, only the maximum acetaldehyde, acetic acid, carbon dioxide yield and the temperature at that time are listed.
実施例１１〜１３
酸化モリブデン１．０００ｇと金アセチルアセトナート錯体０．０５８０ｍｍｏｌ（０．０１６６ｇ）を乳鉢で混合した後、空気中４００℃で４時間焼成し、酸化モリブデン担体に担持された金触媒（Ａｕ／ＭｏＯ3；金微粒子の平均粒径６ｎｍ、担体の平均粒径４０ｎｍ）を作製し、実施例１と同様の触媒活性評価法により触媒の活性を測定した。結果を表３に示す。
Examples 11-13
After mixing 1.000 g of molybdenum oxide and 0.0580 mmol (0.0166 g) of gold acetylacetonate complex in a mortar, the mixture was calcined in air at 400 ° C. for 4 hours, and a gold catalyst (Au / MoO 3 supported on a molybdenum oxide support). A gold fine particle average particle diameter of 6 nm and a carrier average particle diameter of 40 nm) were prepared, and the activity of the catalyst was measured by the same catalytic activity evaluation method as in Example 1. The results are shown in Table 3.
五酸化バナジウム１．０００ｇと金アセチルアセトナート錯体０．０５８００ｍｍｏｌ（０．０１６６ｇ）を乳鉢で混合した後、空気中４００℃で４時間焼成し、五酸化バナジウム担体に担持された金触媒（Ａｕ／Ｖ２Ｏ５；担体の平均粒径２００ｎｍ）を作製し、実施例１と同様の触媒活性評価法により触媒の活性を測定した。結果を表３に示す。 After mixing 1.000 g of vanadium pentoxide and 0.05800 mmol (0.0166 g) of gold acetylacetonate complex in a mortar, the mixture was calcined in air at 400 ° C. for 4 hours, and the gold catalyst (Au / V 2 O 5 ; average particle diameter of support 200 nm) was prepared, and the activity of the catalyst was measured by the same catalytic activity evaluation method as in Example 1. The results are shown in Table 3.
後述の実施例１５と同じ酸化チタンに担持された五酸化バナジウム（Ｖ２Ｏ５／ＴｉＯ２）１．０００ｇと金アセチルアセトナート錯体０．０５８００ｍｍｏｌ（０．０１６６ｇ）を乳鉢で混合した後、空気中４００℃で４時間焼成し、酸化チタンに担持された五酸化バナジウム担体に担持された金触媒（Ａｕ／Ｖ２Ｏ５／ＴｉＯ２；酸化チタン担体の平均粒径２５ｎｍ）を作製し、実施例１と同様の触媒活性評価法により触媒の活性を測定した。結果を表３に示す。なお、用いる酸化チタンについて、後述の実施例１５のものに代えて、実施例１６および実施例１７のものについても同様に実験したところ、同様の結果を得た。 After mixing 1.000 g of vanadium pentoxide (V 2 O 5 / TiO 2 ) supported on the same titanium oxide as in Example 15 described later and 0.05800 mmol (0.0166 g) of a gold acetylacetonate complex in a mortar, air Baked at 400 ° C. for 4 hours to prepare a gold catalyst (Au / V 2 O 5 / TiO 2 ; average particle diameter of titanium oxide support 25 nm) supported on a vanadium pentoxide support supported on titanium oxide The activity of the catalyst was measured by the same catalytic activity evaluation method as in Example 1. The results are shown in Table 3. In addition, it replaced with the thing of Example 15 mentioned later about the titanium oxide to be used, and when it experimented similarly about the thing of Example 16 and Example 17, the same result was obtained.
表１および表３より、エタノールから酢酸を生成する金触媒の担体は限られており、特に酸化亜鉛、酸化インジウム、五酸化バナジウムが酢酸を高い収率で得ることのできる金触媒の担体として優れたものであることがわかる。また、酸化モリブデンや酸化ランタンはアセトアルデヒドを二酸化炭素の発生なしに高い収率で得ることのできる金触媒の担体として優れたものであることがわかる。 From Tables 1 and 3, the gold catalyst carrier that produces acetic acid from ethanol is limited. In particular, zinc oxide, indium oxide, and vanadium pentoxide are excellent as gold catalyst carriers that can obtain acetic acid in high yield. You can see that Further, it can be seen that molybdenum oxide and lanthanum oxide are excellent as a support for a gold catalyst capable of obtaining acetaldehyde in a high yield without generating carbon dioxide.
実施例１４
水５０ｍＬを０℃に保ち、激しく撹拌しながら四塩化チタン２８．５４ｇを滴下した。この水溶液の濃度を０．３Ｍに希釈して、７０℃で６時間水熱反応を行った。生成した沈殿物を洗浄し、６５℃で一晩乾燥した後、３００℃、４時間空気中で焼成し、ルチル型二酸化チタン（５２ｍ２／ｇ）を得た。バナジン（Ｖ）酸アンモニウムを所定のＶ２Ｏ５となるようにはかりとり、少量の水で溶解した。そこへルチル型二酸化チタンを加えて超音波をかけながら３０分間撹拌した。本実施例では、１００重量部のＴｉＯ２に対して５重量部のＶ２Ｏ５が担持するように添加量を設定した。その後、液体窒素で凍結させ室温で一晩真空乾燥した。乾燥後、３００℃、４時間空気中で焼成し、ルチル型二酸化チタン担体に担持された酸化バナジウム触媒（Ｖ２Ｏ５／ＴｉＯ２；担体の比表面積５２ｍ２／ｇ）を作製し、実施例１と同様の触媒活性評価法により触媒の活性を測定した。結果を表４に示す。
Example 14
Maintaining 50 mL of water at 0 ° C., 28.54 g of titanium tetrachloride was added dropwise with vigorous stirring. The concentration of this aqueous solution was diluted to 0.3 M, and a hydrothermal reaction was performed at 70 ° C. for 6 hours. The produced precipitate was washed, dried at 65 ° C. overnight, and then calcined in air at 300 ° C. for 4 hours to obtain rutile titanium dioxide (52 m 2 / g). Ammonium vanadate (V) was weighed out to a predetermined V 2 O 5 and dissolved with a small amount of water. Rutile titanium dioxide was added thereto and stirred for 30 minutes while applying ultrasonic waves. In this example, the addition amount was set so that 5 parts by weight of V 2 O 5 was supported on 100 parts by weight of TiO 2 . Then, it was frozen with liquid nitrogen and vacuum dried at room temperature overnight. After drying, it was calcined in the air at 300 ° C. for 4 hours to prepare a vanadium oxide catalyst (V 2 O 5 / TiO 2 ; specific surface area of the support 52 m 2 / g) supported on a rutile titanium dioxide support. The activity of the catalyst was measured by the same catalytic activity evaluation method as in 1. The results are shown in Table 4.
実施例１５〜１７
バナジン（Ｖ）酸アンモニウムを担体に対して３４ｗｔ％のＶ２Ｏ５となるようにはかりとり、少量の水で溶解した。そこへアナターゼ型二酸化チタン（チタン工業株式会社、３４０ｍ２／ｇ）を加えて超音波をかけながら３０分間撹拌した。その後、液体窒素で凍結させ室温で一晩真空乾燥した。乾燥後、所定の温度で、４時間空気中で焼成し、アナターゼ型二酸化チタン担体に担持された酸化バナジウム触媒（Ｖ２Ｏ５／ＴｉＯ２；担体の比表面積３４０ｍ２／ｇ）を作製し、実施例１と同様の触媒活性評価法により触媒の活性を測定した。結果を表４に示す。
Examples 15-17
Ammonium vanadate (V) was weighed out to a concentration of 34 wt% V 2 O 5 with respect to the carrier and dissolved in a small amount of water. Anatase type titanium dioxide (Titanium Industry Co., Ltd., 340 m 2 / g) was added thereto and stirred for 30 minutes while applying ultrasonic waves. Then, it was frozen with liquid nitrogen and vacuum dried at room temperature overnight. After drying, calcination in air at a predetermined temperature for 4 hours to produce a vanadium oxide catalyst (V 2 O 5 / TiO 2 ; specific surface area of the support 340 m 2 / g) supported on anatase-type titanium dioxide support, The activity of the catalyst was measured by the same catalytic activity evaluation method as in Example 1. The results are shown in Table 4.
表４より、ルチル型二酸化チタンを担体とした五酸化バナジウム触媒は、アセトアルデヒドを比較的低温できわめて高い収率で得ることのできる触媒であることがわかる。また、アナターゼ型二酸化チタンを担体とした五酸化バナジウム触媒は、焼成温度を５００℃とすることで、触媒層温度の制御によってアセトアルデヒドあるいは酢酸を高い収率で得ることのできる触媒であることがわかる。 From Table 4, it can be seen that the vanadium pentoxide catalyst using rutile-type titanium dioxide as a carrier is a catalyst capable of obtaining acetaldehyde in a very high yield at a relatively low temperature. Further, it can be seen that the vanadium pentoxide catalyst using anatase-type titanium dioxide as a carrier is a catalyst that can obtain acetaldehyde or acetic acid in a high yield by controlling the catalyst layer temperature by setting the firing temperature to 500 ° C. .
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| JP5920750B2 (en) | 2016-05-18 |
| JP5787206B2 (en) | 2015-09-30 |
| JP2015178525A (en) | 2015-10-08 |
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