JP2000084410A - Preparation of autothermal reforming catalyst and production of hydrogen or synthesis gas - Google Patents
Preparation of autothermal reforming catalyst and production of hydrogen or synthesis gasInfo
- Publication number
- JP2000084410A JP2000084410A JP11181145A JP18114599A JP2000084410A JP 2000084410 A JP2000084410 A JP 2000084410A JP 11181145 A JP11181145 A JP 11181145A JP 18114599 A JP18114599 A JP 18114599A JP 2000084410 A JP2000084410 A JP 2000084410A
- Authority
- JP
- Japan
- Prior art keywords
- ruthenium
- catalyst
- autothermal reforming
- reaction
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 143
- 238000002453 autothermal reforming Methods 0.000 title claims abstract description 80
- 239000007789 gas Substances 0.000 title claims description 110
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 61
- 239000001257 hydrogen Substances 0.000 title claims description 60
- 230000015572 biosynthetic process Effects 0.000 title claims description 54
- 238000003786 synthesis reaction Methods 0.000 title claims description 54
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 52
- 238000004519 manufacturing process Methods 0.000 title claims description 35
- 238000002360 preparation method Methods 0.000 title description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 65
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 64
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 42
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000010941 cobalt Substances 0.000 claims abstract description 28
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 28
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 19
- 239000011777 magnesium Substances 0.000 claims abstract description 18
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 70
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 56
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 52
- 239000002994 raw material Substances 0.000 claims description 50
- 229930195733 hydrocarbon Natural products 0.000 claims description 40
- 150000002430 hydrocarbons Chemical class 0.000 claims description 40
- 229910052760 oxygen Inorganic materials 0.000 claims description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 36
- 239000001301 oxygen Substances 0.000 claims description 36
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 35
- 239000001569 carbon dioxide Substances 0.000 claims description 35
- 238000002407 reforming Methods 0.000 claims description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 25
- 239000004215 Carbon black (E152) Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- -1 naphtha Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 8
- 239000003915 liquefied petroleum gas Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 238000010304 firing Methods 0.000 claims description 6
- 239000003350 kerosene Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 99
- 239000000243 solution Substances 0.000 description 30
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 14
- 238000007254 oxidation reaction Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000000629 steam reforming Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 11
- 239000003345 natural gas Substances 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 239000000571 coke Substances 0.000 description 9
- 150000002431 hydrogen Chemical class 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 7
- 238000006477 desulfuration reaction Methods 0.000 description 7
- 230000023556 desulfurization Effects 0.000 description 7
- 239000000395 magnesium oxide Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 6
- 150000003304 ruthenium compounds Chemical class 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 150000003755 zirconium compounds Chemical class 0.000 description 6
- 238000009825 accumulation Methods 0.000 description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000006057 reforming reaction Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 150000002681 magnesium compounds Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
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- 238000011084 recovery Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
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- 150000001869 cobalt compounds Chemical class 0.000 description 2
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- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
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- 230000001590 oxidative effect Effects 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910018590 Ni(NO3)2-6H2O Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
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- 150000004645 aluminates Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 235000012216 bentonite Nutrition 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
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- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
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- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229940045032 cobaltous nitrate Drugs 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
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- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
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- 239000011261 inert gas Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- LYTNHSCLZRMKON-UHFFFAOYSA-L oxygen(2-);zirconium(4+);diacetate Chemical compound [O-2].[Zr+4].CC([O-])=O.CC([O-])=O LYTNHSCLZRMKON-UHFFFAOYSA-L 0.000 description 1
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- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 description 1
- QLHCBKPNNDKZOJ-UHFFFAOYSA-N ruthenium zirconium Chemical compound [Zr].[Ru] QLHCBKPNNDKZOJ-UHFFFAOYSA-N 0.000 description 1
- VDRDGQXTSLSKKY-UHFFFAOYSA-K ruthenium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ru+3] VDRDGQXTSLSKKY-UHFFFAOYSA-K 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
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- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- 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
【０００１】[0001]
【発明の属する技術分野】本発明は、オートサーマルリ
フォーミングに用いる触媒に関する。さらに詳しくは、
ルテニウム、ジルコニウム系のオートサーマルリフォー
ミング触媒とその製造方法、およびこれを用いた水素ま
たは合成ガスの製造方法に関する。[0001] The present invention relates to a catalyst used for autothermal reforming. For more information,
The present invention relates to a ruthenium or zirconium-based autothermal reforming catalyst and a method for producing the same, and a method for producing hydrogen or a synthesis gas using the same.
【０００２】[0002]
【従来の技術】炭化水素等の有機化合物を改質して合成
ガスや水素を製造する技術は各種知られている。とくに
スチームを用いた炭化水素のスチームリフォーミングは
多くの技術が実用化されている。これらは、ニッケル系
の触媒を用いメタン、ＬＰＧ、ナフサ等を原料として、
主に水素製造やメタノール用の合成ガス製造に用いられ
ている。2. Description of the Related Art Various techniques for producing a synthesis gas or hydrogen by reforming an organic compound such as a hydrocarbon are known. In particular, many technologies have been put to practical use for steam reforming of hydrocarbons using steam. These are produced using methane, LPG, naphtha, etc. as raw materials using a nickel-based catalyst.
It is mainly used for producing hydrogen and syngas for methanol.
【０００３】アルミナ担体にジルコニウム、ルテニウム
等の金属を担持した触媒を用いた炭化水素のスチームリ
フォーミングについても研究がなされている（特開平０
８−１９６９０７，特開平０９−０２９０９７，特開平
０９−０２９０９８）。通常のスチームリフォーミング
による炭化水素の改質は、大きな吸熱反応を伴い工業的
に実施する場合は外部からの熱の供給が技術的に問題で
あった。とくに工業的に用いられているニッケル系の触
媒を用いた炭化水素のスチームリフォーミングにおいて
は、６００℃〜９００℃の高温での反応である。たとえ
ばメタンのスチームリフォーミングにおいては７００℃
前後の高温で４９．３ｋｃａｌ／ｍｏｌの吸熱反応を行
わねばならない。このために、反応器や熱回収システム
に各種の工夫がなされている。しかし、熱回収や設備の
簡素化という点からは本質的な解決にはなっていない。[0003] Studies have also been made on steam reforming of hydrocarbons using a catalyst in which a metal such as zirconium or ruthenium is supported on an alumina carrier (Japanese Patent Application Laid-Open No. Hei 0 (1999) -107).
8-196907, JP-A-09-022907, JP-A-09-022908). Hydrocarbon reforming by ordinary steam reforming involves a large endothermic reaction, and when industrially performed, supply of external heat is a technical problem. In particular, in the steam reforming of hydrocarbons using a nickel-based catalyst that is industrially used, the reaction is performed at a high temperature of 600 ° C to 900 ° C. For example, 700 ° C in steam reforming of methane
An endothermic reaction of 49.3 kcal / mol must be performed at high and low temperatures. For this reason, various devices have been devised for the reactor and the heat recovery system. However, it has not been an essential solution in terms of heat recovery and equipment simplification.
【０００４】一方、炭化水素の部分酸化により合成ガス
や水素を製造する技術がある。重質炭化水素、たとえば
減圧残油を高温で酸素により部分酸化して合成ガスや水
素を製造する技術がすでに実用化されている。スチーム
リフォーミング並の温度で反応を進める技術として、研
究レベルではジルコニア、ルテニウム系触媒を用いたメ
タンの部分酸化による合成ガスの製造方法が知られてい
る（特開平０５−２２１６０２）。これらの部分酸化法
による炭化水素の改質は逆に酸化熱の除去が問題とな
る。反応の安定性および省エネルギーの観点からの検討
が必要である。On the other hand, there is a technique for producing synthesis gas and hydrogen by partial oxidation of hydrocarbons. A technique for producing a synthesis gas or hydrogen by partially oxidizing a heavy hydrocarbon, for example, a vacuum residue at a high temperature with oxygen has already been put to practical use. As a technology for promoting the reaction at a temperature similar to that of steam reforming, a method for producing a synthesis gas by partial oxidation of methane using a zirconia- or ruthenium-based catalyst is known at the research level (Japanese Patent Application Laid-Open No. 05-221602). On the other hand, in the reforming of hydrocarbons by these partial oxidation methods, removal of oxidation heat becomes a problem. It is necessary to study from the viewpoint of reaction stability and energy saving.
【０００５】そこで、炭化水素等の合成ガス製造原料
を、酸素で部分酸化すると同時にスチーム等のリフォー
ミングガスでリフォーミングすることにより、反応熱の
バランスを取りながら合成ガスを製造する方法（オート
サーマルリフォーミング）が検討されている。触媒とし
てニッケル系が主として検討されており、白金、パラジ
ウムなども実験室的には実施されているが、触媒上への
コーク蓄積の問題等が指摘されている（Ｉｎｔ．Ｊ．Ｈ
ｙｄｒｏｇｅｎ Ｅｎｅｒｇｙ Ｖｏｌ．８，ｐ５３９
−５４８，Ｈｙｄｒｏｇｅｎ Ｅｎｅｒｇｙ Ｐｒｏｇ
ｒｅｓｓ ４，ｖｏｌ．１，ｐ３３−４５）。[0005] Therefore, a method for producing a synthesis gas while balancing the heat of reaction by partially oxidizing a synthesis gas production material such as a hydrocarbon with oxygen and reforming the material with a reforming gas such as steam at the same time (autothermal method). Reforming) is being considered. Nickel-based catalysts have been mainly studied, and platinum, palladium and the like have been used in laboratories, but problems such as coke accumulation on the catalyst have been pointed out (Int. JH).
ydogen Energy Vol. 8, p539
-548, Hydrogen Energy Prog
res 4, vol. 1, p33-45).
【０００６】それ故、触媒上へのコーク蓄積の問題が比
較的少ない原料であるメタンを対象とした研究が主に行
われている。反応そのもの以外に、熱のバランスを考え
て反応器システム等の検討も進められている（Ｊｏｕｒ
ｎａｌ ｏｆ ＰｏｗｅｒＳｏｕｒｃｅｓ ６１（１９
９６）ｐ１１３−１２４，ＨｙｄｒｏｃａｒｂｏｎＰｒ
ｏｃｅｓｓｉｎｇ，Ｍａｒｃｈ １９９４，ｐ３９−４
６，特開平０７−０５７７５６）。[0006] Therefore, research has been mainly conducted on methane, which is a raw material having a relatively small problem of coke accumulation on the catalyst. In addition to the reaction itself, studies on a reactor system and the like are also being conducted in consideration of heat balance (Jour.
nal of PowerSources 61 (19
96) p113-124, HydrocarbonPr
processing, March 1994, p39-4
6, JP-A-07-057756).
【０００７】また、類似技術としては銅系触媒等を用い
てメタノールを酸素およびスチームにより改質し、合成
ガスを製造する研究も進められている（特開平０６−２
５６００１，特開平０６−２７９００１）。[0007] As a similar technique, researches on reforming methanol with oxygen and steam using a copper-based catalyst or the like to produce a synthesis gas have been conducted (Japanese Patent Laid-Open No. 06-2).
56001, JP-A-06-279001).
【０００８】[0008]
【発明が解決しようとする課題】本発明は、上記観点か
らなされたもので、下記の三つを目的としている。本発
明の第一の目的は、オートサーマルリフォーミング用の
高性能の触媒を提供することにある。本発明はまた、上
記オートサーマルリフォーミング用の触媒を簡便に、実
用的に製造する方法を提供することにある。SUMMARY OF THE INVENTION The present invention has been made in view of the above, and has the following three objects. A first object of the present invention is to provide a high-performance catalyst for auto thermal reforming. Another object of the present invention is to provide a method for simply and practically producing the above-mentioned catalyst for autothermal reforming.
【０００９】本発明は、さらに上記触媒を用いてオート
サーマルリフォーミングを行い水素または合成ガスを製
造する方法を提供することをも目的とする。Another object of the present invention is to provide a method for producing hydrogen or synthesis gas by performing autothermal reforming using the above catalyst.
【００１０】[0010]
【課題を解決するための手段】本発明者は、上記の課題
を解決すべく鋭意研究を重ねた結果、ルテニウムージル
コニウム系の触媒、すなわちルテニウム担持ジルコニア
担体触媒またはルテニウムージルコニウム担持アルミナ
担体触媒がオートサーマルリフォーミングに好適な触媒
であることを見出し、この知見に基づき本発明を完成す
るに至った。The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, a ruthenium-zirconium-based catalyst, that is, a ruthenium-supported zirconia-supported catalyst or a ruthenium-zirconium-supported alumina-supported catalyst has been developed. The inventors have found that the catalyst is suitable for autothermal reforming, and have completed the present invention based on this finding.
【００１１】すなわち、本発明の要旨は以下のとおりで
ある。 〔１〕 ルテニウムを担持したジルコニア担体からなる
オートサーマルリフォーミング触媒。 〔２〕 ジルコニウムおよびルテニウムを担持した無機
酸化物担体からなるオートサーマルリフォーミング触
媒。That is, the gist of the present invention is as follows. [1] An autothermal reforming catalyst comprising a zirconia support supporting ruthenium. [2] An autothermal reforming catalyst comprising an inorganic oxide carrier supporting zirconium and ruthenium.
【００１２】〔３〕 ルテニウム含有量が０．０５〜２
０重量％の範囲にある〔１〕または〔２〕記載のオート
サーマルリフォーミング触媒。 〔４〕 触媒中にさらに、コバルトおよび／またはマグ
ネシウムを含有する〔１〕〜〔３〕のいずれかに記載の
オートサーマルリフォーミング触媒。 〔５〕 コバルト含有量がコバルト／ルテニウムの原子
比で０．０１〜３０の範囲にある〔４〕記載のオートサ
ーマルリフォーミング触媒。[3] Ruthenium content of 0.05 to 2
The autothermal reforming catalyst according to [1] or [2], which is in a range of 0% by weight. [4] The autothermal reforming catalyst according to any one of [1] to [3], further comprising cobalt and / or magnesium in the catalyst. [5] The autothermal reforming catalyst according to [4], wherein the cobalt content is in a range of 0.01 to 30 in an atomic ratio of cobalt / ruthenium.
【００１３】〔６〕 マグネシウム含有量がＭｇＯに換
算して０．５〜２０重量％の範囲にある〔４〕または
〔５〕記載のオートサーマルリフォーミング触媒。 〔７〕 無機酸化物担体がアルミナである〔２〕〜
〔６〕のいずれかに記載のオートサーマルリフォーミン
グ触媒。 〔８〕 担体成分であるアルミナがαアルミナまたはγ
アルミナである〔７〕記載のオートサーマルリフォーミ
ング触媒。[6] The autothermal reforming catalyst according to [4] or [5], wherein the magnesium content is in the range of 0.5 to 20% by weight in terms of MgO. [7] The inorganic oxide carrier is alumina [2]-
The autothermal reforming catalyst according to any one of [6]. [8] The alumina as a carrier component is α-alumina or γ
The autothermal reforming catalyst according to [7], which is alumina.
【００１４】[0014]
〔９〕 ジルコニウム含有量がＺｒＯ2 に
換算して０．０５〜２０重量％の範囲である〔２〕〜
〔８〕のいずれかに記載のオートサーマルリフォーミン
グ触媒。 〔１０〕 ジルコニア担体に、ルテニウムを含む溶液、
ルテニウムおよびコバルトを含む溶液、またはルテニウ
ム、コバルトおよびマグネシウムを含む溶液を付着させ
たのち乾燥、焼成する〔１〕または〔３〕〜〔６〕のい
ずれかに記載のオートサーマルリフォーミング触媒の製
造方法。[9] The zirconium content is in the range of 0.05 to 20% by weight in terms of ZrO 2 [2] to
The autothermal reforming catalyst according to any one of [8]. [10] a solution containing ruthenium in a zirconia carrier,
The method for producing an autothermal reforming catalyst according to any one of [1] or [3] to [6], wherein a solution containing ruthenium and cobalt or a solution containing ruthenium, cobalt and magnesium is applied, and then dried and calcined. .
【００１５】〔１１〕 無機酸化物担体に、ジルコニウ
ムおよびルテニウムを含む溶液、ジルコニウム、ルテニ
ウムおよびコバルトを含む溶液、またはジルコニウム、
ルテニウム、コバルトおよびマグネシウムを含む溶液を
付着させたのち乾燥、焼成する〔２〕〜[11] A solution containing zirconium and ruthenium, a solution containing zirconium, ruthenium and cobalt, or zirconium, on an inorganic oxide carrier.
After attaching a solution containing ruthenium, cobalt and magnesium, drying and baking [2]-
〔９〕のいずれ
かに記載のオートサーマルリフォーミング触媒の製造方
法。[9] The method for producing an autothermal reforming catalyst according to any one of [9].
【００１６】〔１２〕 〔１〕〜[12] [1]-
〔９〕のいずれかに記
載のオートサーマルリフォーミング触媒を用いた水素ま
たは合成ガスの製造方法。 〔１３〕 水素または合成ガスの製造原料が炭化水素で
ある〔１２〕に記載の水素または合成ガスの製造方法。 〔１４〕 炭化水素がメタン、液化石油ガス、ナフサ、
灯油または軽油である〔１３〕に記載の水素または合成
ガスの製造方法。[9] A method for producing hydrogen or a synthesis gas using the autothermal reforming catalyst according to any one of [9]. [13] The method for producing hydrogen or synthesis gas according to [12], wherein the raw material for producing hydrogen or synthesis gas is a hydrocarbon. [14] The hydrocarbon is methane, liquefied petroleum gas, naphtha,
The method for producing hydrogen or synthesis gas according to [13], which is kerosene or light oil.
【００１７】〔１５〕 水素または合成ガスの製造原料
がメタノール、エタノールまたはジメチルエーテルであ
る〔１２〕に記載の水素または合成ガスの製造方法。 〔１６〕 リフォーミングガスが酸素、スチームおよび
炭酸ガスの混合ガスである〔１２〕〜〔１５〕のいずれ
かに記載の合成ガスの製造方法。[15] The method for producing hydrogen or synthesis gas according to [12], wherein the raw material for producing hydrogen or synthesis gas is methanol, ethanol or dimethyl ether. [16] The method for producing a synthesis gas according to any one of [12] to [15], wherein the reforming gas is a mixed gas of oxygen, steam and carbon dioxide.
【００１８】[0018]
【発明の実施の形態】以下に本発明の実施の形態を説明
する。本発明におけるオートサーマルリフォーミングと
は、炭化水素、アルコールやエーテル類等の有機化合物
を酸素およびスチームのリフォーミングガスを用い、水
素または合成ガスを製造する反応のことを言う。酸素お
よびスチームは反応帯域に原料有機化合物（通常はメタ
ン、ＬＰＧ、ナフサ等）と同時に導入してもよいし、別
々にあるいは一部づつ導入してもよい。模式的には次の
ような酸素による酸化反応（発熱反応）と、スチームに
よるリフォーミング反応（吸熱反応）が組合わさり、全
体としてあまり大きな吸熱または発熱反応とならない反
応である。Embodiments of the present invention will be described below. Autothermal reforming in the present invention refers to a reaction in which an organic compound such as a hydrocarbon, an alcohol or an ether is used to produce hydrogen or a synthesis gas using a reforming gas of oxygen and steam. Oxygen and steam may be introduced into the reaction zone at the same time as the starting organic compounds (usually methane, LPG, naphtha, etc.) or separately or partly. Schematically, the following oxidation reaction (exothermic reaction) by oxygen and reforming reaction (endothermic reaction) by steam are combined, and as a whole, the reaction does not become too large endothermic or exothermic reaction.
【００１９】〔酸素によるメタンの酸化〕 ＣＨ4 ＋ ２Ｏ2 ＝ ２Ｈ2 Ｏ ＋ ＣＯ2 ΔＨ＝−１９２ kcal/mol ＣＨ4 ＋１．５Ｏ2 ＝ ２Ｈ2 Ｏ ＋ ＣＯ ΔＨ＝−１２４ kcal/mol ＣＨ4 ＋ Ｏ2 ＝ ２Ｈ2 ＋ ＣＯ2 ΔＨ＝−７８ kcal/mol ＣＨ4 ＋０．５Ｏ2 ＝ ２Ｈ2 ＋ ＣＯ ΔＨ＝−８．５ kcal/mol 〔スチームによるメタンの改質〕 ＣＨ4 ＋ Ｈ2 Ｏ ＝ ３Ｈ2 ＋ ＣＯ ΔＨ＝４９．３ kcal/mol ＣＨ4 ＋２Ｈ2 Ｏ ＝ ４Ｈ2 ＋ ＣＯ2 ΔＨ＝３９．２ kcal/mol （ＣＨＥＭＴＥＣ ＤＥＣ．１９９５ Ｐ４３より） これらと並行して、メタンとＣＯ2 の反応、ＣＯとスチ
ームの反応等が起こり、水素、ＣＯ、スチーム、Ｃ
Ｏ2 、メタンが熱力学的に平衡状態の合成ガスが生成す
る場合が多い。[Oxidation of methane with oxygen] CH 4 + 2O 2 = 2H 2 O + CO 2 ΔH = −192 kcal / mol CH 4 + 1.5O 2 = 2H 2 O + CO ΔH = −124 kcal / mol CH 4 + O 2 = 2H 2 + CO 2 ΔH = −78 kcal / mol CH 4 + 0.5O 2 = 2H 2 + CO ΔH = −8.5 kcal / mol [Reforming of methane by steam] CH 4 + H 2 O = 3H 2 + CO ΔH = 49.3 kcal / mol CH 4 + 2H 2 O = 4H 2 + CO 2 ΔH = 39.2 kcal / mol (from CHEMTEC DEC. 1995 P43) In parallel with these, methane and CO 2 Reaction, reaction between CO and steam, etc., and hydrogen, CO, steam, C
In many cases, synthesis gas in which O 2 and methane are in a thermodynamic equilibrium state is generated.
【００２０】工業的な方法としては、通常は、熱バラン
スが取れる程度の酸素を含むスチームをリフォーミング
ガスとする炭化水素のオートサーマルリフォーミングが
適している。水素を製造する場合は、比較的高温でスチ
ームを過剰にして反応させることが化学平衡的に有利で
ある。一方、合成ガスを製造する場合は、生成する合成
ガスの目標組成に合わせて酸素の導入量を変えたり、炭
酸ガスをリフォーミングガスの一部として使用して平衡
をずらす方法がある。As an industrial method, usually, autothermal reforming of hydrocarbons using steam containing oxygen to a degree capable of achieving a thermal balance as a reforming gas is suitable. When producing hydrogen, it is advantageous in terms of chemical equilibrium to carry out the reaction with excess steam at a relatively high temperature. On the other hand, in the case of producing a synthesis gas, there are methods of changing the introduction amount of oxygen in accordance with the target composition of the synthesis gas to be generated, and shifting the equilibrium by using carbon dioxide gas as a part of the reforming gas.
【００２１】最もわかり易い例の一つとして炭化水素が
メタンである場合で説明すると、それぞれの反応は以下
のようになる。すなわち、スチームリフォーミング反応
は合成ガス中の水素と一酸化炭素の比は３対１となる。
炭酸ガスによる改質の場合は生成した合成ガス中の水素
と一酸化炭素の比は１対１となる。水素を製造する場合
は一酸化炭素の比は小さいほうがよいが、生成ガス中の
一酸化炭素をスチームにより水素と炭酸ガスに転換（水
性ガス反応）してやれば容易に水素リッチのガスとな
る。このガスは炭酸ガスを除去して高純度水素として使
用できる。また、燃料電池用のガスとしても好適に使用
することができる。とくに、最近は炭酸ガスを除去しな
くてもよいシステムの開発も進んでいる。In the case where the hydrocarbon is methane as one of the most obvious examples, the respective reactions are as follows. That is, in the steam reforming reaction, the ratio of hydrogen to carbon monoxide in the synthesis gas is 3: 1.
In the case of reforming with carbon dioxide, the ratio of hydrogen to carbon monoxide in the generated synthesis gas is 1: 1. In the case of producing hydrogen, the smaller the ratio of carbon monoxide, the better. However, if carbon monoxide in the produced gas is converted into hydrogen and carbon dioxide by steam (water gas reaction), a hydrogen-rich gas can be easily obtained. This gas can be used as high-purity hydrogen by removing carbon dioxide gas. Further, it can be suitably used as a gas for a fuel cell. In particular, recently, the development of a system that does not require removal of carbon dioxide has been progressing.
【００２２】一方、メタノール製造や合成軽油、合成ガ
ソリン製造（フィッシャートロプシュ反応による）を行
う場合は化学量論的に必要な水素と一酸化炭素の比はお
よそ２対１である。それゆえ、合成ガスを製造する場合
には、従来行われていたスチームによる炭化水素改質に
かわり、オートサーマルリフォーミングによる炭化水素
改質を選択し、水素と一酸化炭素の比はおよそ２対１に
合わせることが望ましい。On the other hand, when producing methanol, synthetic gas oil, or synthetic gasoline (by Fischer-Tropsch reaction), the stoichiometrically necessary ratio of hydrogen to carbon monoxide is about 2: 1. Therefore, when producing synthesis gas, instead of the conventional steam reforming by steam, hydrocarbon reforming by auto thermal reforming is selected, and the ratio of hydrogen to carbon monoxide is about 2 to 2. It is desirable to adjust to 1.
【００２３】本発明を含むオートサーマルリフォーミン
グでは、リフォーミング反応時の熱バランスを酸素供給
量で調整できるため、反応開始時に触媒を迅速に所要の
温度まで上げることが容易であり、反応の停止、開始の
頻度の高い燃料電池用の水素製造などに適している。一
方では、上記のような比較的一酸化炭素含有量が多く水
素含有量の少ない合成ガスを製造することができる。と
くに、本発明は、高い転化率で水素または合成ガスを得
ることができ、また、触媒上へのコーク蓄積を抑えるこ
とができ有用な方法である。In the autothermal reforming including the present invention, the heat balance at the time of the reforming reaction can be adjusted by the supply amount of oxygen, so that it is easy to quickly raise the temperature of the catalyst to the required temperature at the start of the reaction, and to stop the reaction. It is suitable for producing hydrogen for a fuel cell, which is frequently started. On the other hand, it is possible to produce a synthesis gas having a relatively high carbon monoxide content and a low hydrogen content as described above. In particular, the present invention is a useful method capable of obtaining hydrogen or synthesis gas at a high conversion rate and suppressing coke accumulation on the catalyst.
【００２４】本発明の一つの形態（前記課題を解決する
ための手段の〔１〕に対応）としてのジルコニア担体
は、単体のジルコニア（化学式ＺｒＯ2 ）またはマグネ
シアのような安定化成分を含む安定化ジルコニア、ある
いは単に他の成分を含むジルコニア担体または安定化ジ
ルコニア担体でもよい。安定化ジルコニアとしては、マ
グネシア、イットリア、セリアなどを含むものが好適で
ある。とくに、マグネシアを含有する安定化ジルコニア
は担体の安定性、反応活性やその持続性の面からいって
も好適な触媒担体となる。The zirconia carrier as one mode of the present invention (corresponding to the means for solving the above problems [1]) is a stable zirconia carrier containing a stabilizing component such as simple zirconia (chemical formula ZrO 2 ) or magnesia. Zirconia carrier, or a zirconia carrier or a stabilized zirconia carrier simply containing other components may be used. As the stabilized zirconia, those containing magnesia, yttria, ceria, and the like are preferable. In particular, stabilized zirconia containing magnesia is a suitable catalyst carrier in terms of the stability of the carrier, the reaction activity, and its sustainability.
【００２５】上記の実施形態（前記課題を解決するため
の手段の〔１〕に対応）の本発明の担持金属としては、
ルテニウムが必須である。ルテニウムは周期律表VIII族
金属に属し、ＮｉやＰｄと類似の触媒活性を示すことが
多く、これらはすべてスチームによる炭化水素の改質に
は好適である。しかし、オートサーマルリフォーミング
にはルテニウムのみが好適な結果を示す。担体であるジ
ルコニアとルテニウムの組合せが、効果発現の要因のひ
とつであると考えられる。In the above embodiment (corresponding to the means for solving the problem [1]), the supported metal of the present invention includes:
Ruthenium is required. Ruthenium belongs to the Group VIII metals of the periodic table, and often exhibits catalytic activity similar to that of Ni or Pd, all of which are suitable for reforming hydrocarbons with steam. However, ruthenium alone shows good results for autothermal reforming. It is considered that the combination of zirconia and ruthenium, which are carriers, is one of the factors for achieving the effect.
【００２６】本発明の別の一つの形態（前記課題を解決
するための手段の〔２〕に対応）として、無機酸化物担
体にジルコニウムおよびルテニウムを担持したものがあ
る。無機酸化物担体としては、通常の炭化水素の反応等
に用いられる触媒用の無機酸化物担体を使用することが
できる。たとえば、スチームによる炭化水素改質用触媒
等に用いられる無機酸化物担体を好適に用いることがで
きる。具体的には、アルミナ、シリカ、チタニア、シリ
カアルミナ、りん含有アルミナなどが挙げられる。な
お、本発明の形態（前記課題を解決するための手段の
〔２〕に対応）の無機酸化物担体には、前記説明した形
態（前記課題を解決するための手段の〔１〕に対応）の
担体（ジルコニア担体およびジルコニア系担体）は含ま
れない。As another embodiment of the present invention (corresponding to [2] of the means for solving the above problems), there is an inorganic oxide carrier having zirconium and ruthenium supported thereon. As the inorganic oxide carrier, an inorganic oxide carrier for a catalyst used for a normal reaction of hydrocarbons or the like can be used. For example, an inorganic oxide carrier used for a catalyst for reforming hydrocarbons by steam can be suitably used. Specific examples include alumina, silica, titania, silica alumina, and phosphorus-containing alumina. The inorganic oxide carrier of the embodiment of the present invention (corresponding to [2] of the means for solving the problem) includes the above-described embodiment (corresponding to [1] of the means for solving the problem). (Zirconia carrier and zirconia-based carrier) are not included.
【００２７】上記無機酸化物担体のうちでも、アルミナ
担体が好適に用いられる。さらに、アルミナ担体のうち
でも、αアルミナ担体またはγアルミナ担体がとくに好
適である。αアルミナ担体は比表面積があまり大きく作
れないので、通常触媒担体としては使用されていない
が、特開平１０−５２６３９に示すようにスチームによ
る炭化水素改質用触媒として高活性を表わす触媒担体と
なり得る。同様に、本発明におけるオートサーマルリフ
ォーミング用触媒の担体としても望ましく、とくに触媒
強度が必要な場合には好適な触媒担体となる。Among the above inorganic oxide carriers, an alumina carrier is preferably used. Further, among the alumina carriers, an α-alumina carrier and a γ-alumina carrier are particularly suitable. The α-alumina carrier is not usually used as a catalyst carrier because the specific surface area cannot be made so large. However, as shown in JP-A-10-52639, it can be a catalyst carrier exhibiting high activity as a hydrocarbon reforming catalyst by steam. . Similarly, it is also desirable as a carrier for the catalyst for autothermal reforming in the present invention, and particularly when catalyst strength is required, it is a suitable catalyst carrier.
【００２８】γアルミナ担体はどのようなものでもよい
が、他の触媒用に用いられている、たとえば炭化水素の
水素化、改質、分解、異性化等に用いられているγアル
ミナ担体と同様のものを使用してもよい。また炭化水素
の水蒸気改質用触媒の担体としてもγアルミナ担体が用
いられており、これと同様のものも使用することができ
る。なお、アルミナ担体としては、他の結晶形や非晶質
と混在し、完全にαアルミナまたはγアルミナの結晶の
みからできていなくともよい。The γ-alumina carrier may be of any type, and is the same as the γ-alumina carrier used for other catalysts, for example, for hydrogenation, reforming, cracking, isomerization, etc. of hydrocarbons. May be used. Also, a γ-alumina carrier is used as a carrier for a catalyst for steam reforming of hydrocarbons, and the same carrier can also be used. The alumina carrier may be mixed with another crystal form or amorphous, and may not be completely made of only α-alumina or γ-alumina crystals.
【００２９】上記形態（前記課題を解決するための手段
の〔２〕に対応）の触媒には、無機酸化物担体にジルコ
ニウムおよびルテニウムが担持されている必要がある。
ジルコニウムおよびルテニウムは同時に担持してもよ
く、別々に担持してもよい。触媒としてジルコニウムお
よびルテニウムが担持されていればよいが、一方だけが
担持されていても本発明の触媒とはならない。これは、
ジルコニウムとルテニウムの相互作用で触媒活性を発現
していると考えられるからである。The catalyst of the above embodiment (corresponding to [2] of the means for solving the above-mentioned problems) requires that zirconium and ruthenium are supported on an inorganic oxide carrier.
Zirconium and ruthenium may be supported simultaneously or separately. It is sufficient that zirconium and ruthenium are supported as a catalyst, but even if only one is supported, the catalyst of the present invention is not obtained. this is,
This is because it is considered that the catalytic activity is expressed by the interaction between zirconium and ruthenium.
【００３０】アルミナ等の無機酸化物担体は、通常ジル
コニア担体よりも比表面積が大きく、強度があり、製造
においても容易なものが多い。さらに、本発明の目的の
ひとつである、オートサーマルリフォーミング反応に対
する活性は本質的にはジルコニウムとルテニウムの相互
関係によっているのでジルコニア担体、ルテニウム担持
触媒でも、無機酸化物担体、ジルコニウム、ルテニウム
担持触媒でも同様の効果を発揮できる。なお、本発明に
おける担持金属は通常焼成により製造されたときには、
酸化物として担体に担持されているが、通常はオートサ
ーマルリフォーミング反応を行う前に、触媒の還元操作
を行ってから使用するとよい。An inorganic oxide carrier such as alumina usually has a larger specific surface area than a zirconia carrier, has strength, and is easily manufactured in many cases. Furthermore, one of the objects of the present invention is that the activity for the autothermal reforming reaction is essentially dependent on the interaction between zirconium and ruthenium, so that the zirconia support, ruthenium-supported catalyst, inorganic oxide support, zirconium, ruthenium-supported catalyst are also used. However, the same effect can be achieved. Incidentally, when the supported metal in the present invention is usually produced by firing,
The oxide is supported on the carrier as an oxide, but it is usually preferable to use the catalyst after performing a reduction operation of the catalyst before performing the autothermal reforming reaction.
【００３１】さらに、好ましい本発明の形態として、上
記触媒（前記課題を解決するための手段の〔１〕および
〔２〕に対応する触媒）中にコバルト、またはコバルト
およびマグネシウムを含有するものがある。コバルトは
周期律表のVIII族金属に属し、ルテニウムと同族であり
ルテニウムの活性向上に寄与しているものと考えられ
る。また、マグネシウムはジルコニアに添加するとジル
コニア結晶の熱安定性等を向上させる働きがある。この
効果はジルコニア担体の場合だけでなく、無機酸化物担
体にジルコニウムを担持したものに対しても発揮でき
る。Further, as a preferred embodiment of the present invention, there is a catalyst containing cobalt or cobalt and magnesium in the above-mentioned catalyst (a catalyst corresponding to the above-mentioned means [1] and [2]). . Cobalt belongs to the Group VIII metal of the periodic table, and is considered to be the same as ruthenium and contribute to the improvement of the activity of ruthenium. Further, when magnesium is added to zirconia, it has a function of improving the thermal stability and the like of the zirconia crystal. This effect can be exerted not only in the case of a zirconia support but also in a case where zirconium is supported on an inorganic oxide support.
【００３２】ルテニウムは、本発明においては最重要の
要素のひとつであるが、ルテニウム含有量には好適な範
囲がある。ルテニウム含有量が少なすぎる、とくに０．
０５重量％より少ないと、オートサーマルリフォーミン
グ反応を十分進めることができなくなる。また、ルテニ
ウム含有量が多すぎる場合、とくに２０重量％を超える
場合には、担体表面でのルテニウムの凝集が多くなり、
活性点は増加しなくなる。ときには、比表面積が小さく
なり有効な活性点は減少してしまうこともある。あるい
は強度、耐摩耗性など実用触媒としての機能を失ってし
なうこともある。触媒中のルテニウム含有量は０．０５
〜２０重量％の範囲、好ましくは０．０５〜３重量％の
範囲、さらに好ましくは０．１〜２重量％の範囲である
ことが望ましい。Ruthenium is one of the most important factors in the present invention, but there is a suitable range for the ruthenium content. Ruthenium content is too low, especially 0.
If the amount is less than 05% by weight, the autothermal reforming reaction cannot be sufficiently advanced. Further, when the ruthenium content is too large, particularly when it exceeds 20% by weight, the aggregation of ruthenium on the carrier surface increases,
Active points no longer increase. Occasionally, the specific surface area is reduced and the effective active sites are reduced. Alternatively, the function as a practical catalyst such as strength and abrasion resistance may be lost. Ruthenium content in the catalyst is 0.05
It is desirably in the range of 20 to 20% by weight, preferably in the range of 0.05 to 3% by weight, and more preferably in the range of 0.1 to 2% by weight.
【００３３】本発明の好ましい形態として、触媒中への
コバルトの添加がある。通常はルテニウム等と同じよう
に担持するのであるが、コバルトはルテニウムの活性向
上の効果を担っているのでルテニウムの含有量との関係
で添加されていることが必要である。コバルトの含有量
は、コバルト／ルテニウムの原子比で表わすと、０．０
１〜３０の範囲、好ましくは０．１〜３０の範囲、さら
に好ましくは０．１〜１０の範囲であることが望まし
い。コバルト／ルテニウムの原子比が小さすぎると、と
くに０．０１より小さいとルテニウムの活性向上効果が
十分に発揮できない。また、コバルト／ルテニウムの原
子比が大きすぎる、とくに３０より大きいとルテニウム
自体の活性が十分発揮できなくなってしまうことがあ
る。A preferred embodiment of the present invention is the addition of cobalt into the catalyst. Usually, it is carried in the same manner as ruthenium or the like. However, since cobalt plays a role in improving the activity of ruthenium, it must be added in relation to the content of ruthenium. The cobalt content is expressed as an atomic ratio of cobalt / ruthenium of 0.0
It is desirably in the range of 1 to 30, preferably in the range of 0.1 to 30, and more preferably in the range of 0.1 to 10. If the atomic ratio of cobalt / ruthenium is too small, especially if it is smaller than 0.01, the effect of improving the activity of ruthenium cannot be sufficiently exhibited. On the other hand, if the atomic ratio of cobalt / ruthenium is too large, especially if it is larger than 30, the activity of ruthenium itself may not be sufficiently exhibited.
【００３４】さらに、コバルトに加えてマグネシウムの
添加が望ましい。マグネシウムはジルコニアまたはジル
コニウムの安定化に寄与していると考えられるが、その
含有量は多すぎても少なすぎても効果が十分に発揮でき
ない。マグネシウムの含有量は、マグネシア換算で０．
５〜２０重量％の範囲、好ましくは０．５〜１５重量％
の範囲、さらに好ましくは１〜１５重量％の範囲である
ことが望ましい。なお、本発明におけるマグネシアの含
有量はＭｇＯに換算した重量％で表わす。Further, it is desirable to add magnesium in addition to cobalt. Although magnesium is considered to contribute to stabilization of zirconia or zirconium, the effect cannot be sufficiently exhibited if the content is too large or too small. The content of magnesium is 0.1 in terms of magnesia.
5-20% by weight, preferably 0.5-15% by weight
And more preferably in the range of 1 to 15% by weight. In the present invention, the content of magnesia is expressed in terms of% by weight in terms of MgO.
【００３５】本発明の無機酸化物担体を用いる形態（前
記課題を解決するための手段の〔２〕〜The form using the inorganic oxide carrier of the present invention (the means for solving the above problems [2] to
〔９〕に対応）
においては、担持するジルコニウムの含有量を特定する
ことが好ましい。ジルコニウムが少なすぎれば、とくに
０．０５重量％より少ないと、ジルコニウム、ルテニウ
ム触媒としての活性が十分には発揮できなくなる。ま
た、ジルコニウムが多すぎると、とくに２０重量％超え
ると、触媒強度、比表面積などに影響し実用性に問題が
生ずることがある。ジルコニウムの含有量は、ＺｒＯ2
に換算して０．０５〜２０重量％の範囲、好ましくは
０．５〜１５重量％の範囲、さらに好ましくは１〜１５
重量％の範囲であることが望ましい。(Corresponds to [9])
In the above, it is preferable to specify the content of the supported zirconium. If the amount of zirconium is too small, especially if it is less than 0.05% by weight, the activity as a zirconium or ruthenium catalyst cannot be sufficiently exhibited. On the other hand, if the amount of zirconium is too large, especially if it exceeds 20% by weight, the strength of the catalyst, the specific surface area and the like may be affected, which may cause a problem in practicality. The content of zirconium is ZrO 2
In the range of 0.05 to 20% by weight, preferably in the range of 0.5 to 15% by weight, more preferably 1 to 15%.
It is desirably in the range of weight%.
【００３６】つぎに、本発明の触媒の製造方法の形態に
ついて説明する。まず、本発明のジルコニア担体ルテニ
ウム担持触媒の製造方法（前記課題を解決するための手
段の〔１０〕に対応する方法）について説明する。 （１）ジルコニア担体の製造 ジルコニアは市販のジルコニアまたは酸化ジルコニウム
でもよい。製造する場合は通常は、水溶液中に溶解させ
たジルコニウム化合物をｐＨ調製等により水酸化ジルコ
ニウムの沈殿として、水溶液から分離し、これを乾燥、
焼成してジルコニアとすればよい。たとえば、４塩化ジ
ルコニウムのようなハロゲン化ジルコニウムや塩化ジル
コニルのようなオキシハロゲン化物、硫酸ジルコニル、
硝酸ジルコニウム等の各種のジルコニウムまたはジコニ
ルと酸との塩類が好適に用いられる。あるいは、ジルコ
ニウム酸塩、ジルコニウムアルコキシド、錯塩などが挙
げられる。なお、ジルコニアの安定化のためにマグネシ
ウム化合物を水溶液中に添加しておくこともできる。ま
た、水溶液には本発明の目的の担体が得られる範囲で他
の物質を加えてもよい。Next, an embodiment of the method for producing a catalyst of the present invention will be described. First, a method for producing a zirconia-supported ruthenium-supported catalyst of the present invention (a method corresponding to [10] of the means for solving the above problems) will be described. (1) Production of zirconia carrier Zirconia may be commercially available zirconia or zirconium oxide. In the case of production, usually, the zirconium compound dissolved in the aqueous solution is separated from the aqueous solution as a precipitate of zirconium hydroxide by pH adjustment or the like, and dried,
It may be fired to obtain zirconia. For example, zirconium halides such as zirconium tetrachloride, oxyhalides such as zirconyl chloride, zirconyl sulfate,
Various salts of zirconium or ziconyl such as zirconium nitrate and an acid are preferably used. Alternatively, zirconate, zirconium alkoxide, complex salts and the like can be mentioned. In addition, a magnesium compound may be added to the aqueous solution for stabilizing zirconia. Further, other substances may be added to the aqueous solution as long as the carrier of the present invention can be obtained.
【００３７】ジルコニウム塩類の溶解性を高めるために
は酸類を加え加温することもよい。ジルコニウム化合物
が完全に溶解したら、アンモニア水等のアルカリ性物質
を加えｐＨを高めて水酸化ジルコニウムを沈殿させる。
これを濾過し、乾燥、焼成すればジルコニア担体が得ら
れる。焼成は大気中で３００℃以上好ましくは４００℃
以上で１〜５時間加熱すればよい。In order to increase the solubility of the zirconium salts, an acid may be added and the mixture may be heated. When the zirconium compound is completely dissolved, an alkaline substance such as aqueous ammonia is added to raise the pH to precipitate zirconium hydroxide.
This is filtered, dried and calcined to obtain a zirconia carrier. Baking in air at 300 ° C or higher, preferably 400 ° C
Heating may be performed for 1 to 5 hours as described above.
【００３８】（２）ルテニウム担持触媒の製造 上記で得られたジルコニア担体にルテニウム、必要に応
じてコバルト、マグネシウムあるいはその他の物質を担
持させれば触媒ができあがる。担持方法は、ルテニウム
化合物を水溶液として必要に応じこれにコバルト、マグ
ネシウム等の化合物を溶解させる。ルテニウム化合物と
してはどのようなものでもよいが、たとえば３塩化ルテ
ニウムのようなハロゲン化ルテニウムがあげられる。こ
の溶液をジルコニア担体に付着させたのち、乾燥、焼成
すればジルコニア担体ルテニウム担持触媒がえられる。
付着のさせかたはとくに限定されないが、含浸、浸漬、
スプレー塗布などが好適である。また、ルテニウム化合
物の溶液でなくとも、ルテニウム化合物をスラリー化し
てジルコニア担体と混練したのち、乾燥、焼成すれば好
適なジルコニア担体ルテニウム担持触媒が得られる。担
持量については溶液等の濃度、量あるいは付着操作の回
数等を適宜調節することで所望のものが得られる。焼成
は通常は、３００℃〜７００℃の範囲、好ましくは４０
０℃〜６００℃の範囲で１時間〜５時間大気中で処理す
ればよい。(2) Production of Ruthenium-Supported Catalyst The zirconia support obtained above is supported with ruthenium and, if necessary, cobalt, magnesium or other substances to complete the catalyst. In the loading method, a compound such as cobalt or magnesium is dissolved in a ruthenium compound as an aqueous solution if necessary. As the ruthenium compound, any compound may be used. For example, a ruthenium halide such as ruthenium trichloride may be used. This solution is applied to a zirconia support, dried and calcined to obtain a ruthenium-supported zirconia support catalyst.
The method of adhesion is not particularly limited, but impregnation, dipping,
Spray coating and the like are preferred. Even if it is not a ruthenium compound solution, a suitable zirconia-supported ruthenium-supported catalyst can be obtained by forming a slurry of the ruthenium compound, kneading the slurry with the zirconia support, and then drying and calcining. A desired amount can be obtained by appropriately adjusting the concentration and amount of the solution or the like, the number of times of the adhesion operation, and the like. The calcination is usually in the range of 300C to 700C, preferably 40C.
The treatment may be performed in the atmosphere at 0 ° C. to 600 ° C. for 1 hour to 5 hours.
【００３９】つぎに、本発明の無機酸化物担体ジルコニ
ウム、ルテニウム担持触媒の製造方法（前記課題を解決
するための手段の〔１１〕に対応する方法）について説
明する。その代表的な形態として、アルミナ担体ジルコ
ニウム、ルテニウム担持触媒の製造方法について説明す
る。 （１）アルミナ担体の製造 アルミナ担体は市販のαアルミナまたはγアルミナでも
よい。αアルミナ担体を製造する場合は通常は、市販の
原料アルミナ粉末を成形、焼結して得られる。αアルミ
ナ担体の場合は多孔質にすることが触媒として好適であ
る。それゆえ、原料αアルミナ粉末の平均粒子径を０．
０１〜１００μm の範囲、好ましくは０．０５〜５０μ
m の範囲、さらに好ましくは０．０５〜３０μm の範囲
にすることが望ましい。また、成形、焼結、多孔質化を
助けるため、原料αアルミナ粉末に添加物を添加しても
よい。添加物としては、澱粉、ワックス、ポリエチレン
グリコール、メチルセルロース、カルボキシメチルセル
ロース、グリセリンなどがある。また、カオリン、ベン
トナイトなどの粘土鉱物や水ガラスなどが好適である。
焼成は、αアルミナが形成される温度にする必要があ
る。通常は、１，０００℃〜１，４００℃で焼成するこ
とで達成できる。なお、原料アルミナ粉末がαアルミナ
であれば、触媒として形状を保てるように成形してから
焼結すればよい。Next, a method for producing a catalyst supporting zirconium and ruthenium on an inorganic oxide carrier of the present invention (a method corresponding to the means [11] for solving the above problems) will be described. As a typical embodiment, a method for producing an alumina-supported zirconium- and ruthenium-supported catalyst will be described. (1) Production of alumina carrier The alumina carrier may be commercially available α-alumina or γ-alumina. When producing an α-alumina carrier, it is usually obtained by molding and sintering a commercially available raw alumina powder. In the case of an α-alumina carrier, it is preferable to make the carrier porous, as a catalyst. Therefore, the average particle diameter of the raw material α-alumina powder is set to 0.1.
01-100 μm, preferably 0.05-50 μm
m, more preferably 0.05 to 30 μm. Further, an additive may be added to the raw material α-alumina powder in order to assist molding, sintering, and making the material porous. Additives include starch, wax, polyethylene glycol, methylcellulose, carboxymethylcellulose, glycerin and the like. Also, clay minerals such as kaolin and bentonite, and water glass are suitable.
Firing must be at a temperature at which alpha alumina is formed. Usually, it can be achieved by firing at 1,000 to 1,400 ° C. If the raw alumina powder is α-alumina, it may be molded and sintered so as to maintain its shape as a catalyst.
【００４０】γアルミナ担体を製造する場合は、通常ア
ルミン酸ナトリウム水溶液のようなアルミン酸塩溶液と
硫酸アルミニウム水溶液のような酸アルミニウム塩溶液
を混合し、ｐＨ調製することにより水酸化アルミニウム
を沈殿させる。この際、無機酸や有機酸を添加してｐＨ
を調整すると好適に水酸化アルミニウムを沈殿させるこ
とができる。この沈殿を濾過し、洗浄水およびアンモニ
ア水等で洗浄し所望の水酸化アルミニウムのスラリーが
得られる。このスラリーを成形、乾燥、焼成すればγア
ルミナ担体が得られる。成形にはとくに制限はないが、
通常は押出成形が用いられる。また、焼成はγアルミナ
が形成する温度であればよく、またγアルミナが消滅し
てしまう高温に長時間曝さない程度であればよい。通常
は、３００℃〜１０００℃の範囲、好ましくは４００℃
〜６００℃の範囲で１時間〜５時間大気中で処理すれば
よい。When a γ-alumina carrier is produced, an aluminate solution such as an aqueous solution of sodium aluminate and an aluminum acid salt solution such as an aqueous solution of aluminum sulfate are mixed, and the pH is adjusted to precipitate aluminum hydroxide. . At this time, an inorganic or organic acid is added to adjust the pH.
Is adjusted, aluminum hydroxide can be suitably precipitated. The precipitate is filtered and washed with washing water and aqueous ammonia to obtain a desired slurry of aluminum hydroxide. If this slurry is formed, dried and fired, a γ-alumina carrier can be obtained. There are no particular restrictions on molding,
Usually, extrusion is used. The sintering may be performed at a temperature at which γ-alumina is formed, or at a temperature at which the γ-alumina is not exposed to a high temperature at which γ-alumina disappears for a long time. Usually, in the range of 300 ° C. to 1000 ° C., preferably 400 ° C.
The treatment may be performed in the air at a temperature in the range of 600 to 600 ° C. for 1 hour to 5 hours.
【００４１】（２）ジルコニウム、ルテニウム担持アル
ミナ担体触媒の製造 ジルコニウムおよびルテニウムをアルミナ担体に担持さ
せるには、ジルコニウムを含む溶液およびルテニウムを
含む溶液をそれぞれ単独で、または両者を含む溶液を、
上記で得られたアルミナ担体に付着させればよい。この
ジルコニウムおよびルテニウムの付着したアルミナ担体
を乾燥、焼成すればジルコニウム、ルテニウム担持アル
ミナ担体触媒が得られる。(2) Preparation of Zirconium and Ruthenium-Supported Alumina Support Catalyst In order to support zirconium and ruthenium on an alumina support, a zirconium-containing solution and a ruthenium-containing solution are used alone or in combination.
What is necessary is just to make it adhere to the alumina support obtained above. By drying and calcining the alumina carrier to which zirconium and ruthenium are adhered, an alumina carrier catalyst supporting zirconium and ruthenium can be obtained.
【００４２】ジルコニウムを含む溶液には、水等の溶媒
に可溶性のジルコニウム化合物を溶解したものでよい。
たとえば、４塩化ジルコニウムのようなハロゲン化ジル
コニウム、またはその部分加水分解物、塩化ジルコニル
等のオキシハロゲン化物、硫酸ジルコニル、硝酸ジルコ
ニウム、硝酸ジルコニルなどの酸素酸塩類、酢酸ジルコ
ニウム、酢酸ジルコニルなどの有機酸塩類などの水溶液
を用いることができる。ジルコニウムを溶解させる場
合、溶液に酸等を加えてｐＨを３以下，好ましくは１．
５以下とすることが望ましい。これは、ジルコニウム化
合物の加水分解によるゾル化やゲル化を防ぐためであ
る。The solution containing zirconium may be a solution in which a soluble zirconium compound is dissolved in a solvent such as water.
For example, zirconium halides such as zirconium tetrachloride, or partial hydrolysates thereof, oxyhalides such as zirconyl chloride, oxyacids such as zirconyl sulfate, zirconium nitrate and zirconyl nitrate, and organic acids such as zirconium acetate and zirconyl acetate An aqueous solution of salts or the like can be used. When dissolving zirconium, an acid or the like is added to the solution to adjust the pH to 3 or less, preferably 1.
It is desirably 5 or less. This is to prevent sol or gelation due to hydrolysis of the zirconium compound.
【００４３】ルテニウムを含む溶液には、ジルコニウム
を含む溶液と同様に水等の溶媒に可溶性のルテニウム化
合物を溶解したものでよい。たとえば、３塩化ルテニウ
ムのようなハロゲン化ルテニウム、またはヘキサアミン
ルテニウム酸塩化物等のアミン錯塩、４酸化ルテニウム
などの水溶液を用いることができる。また、酸化ルテニ
ウムや水酸化ルテニウムのように溶解度の低い化合物で
も、酸を共存させることによりｐＨを調整して溶解させ
ればよい。The ruthenium-containing solution may be a solution in which a soluble ruthenium compound is dissolved in a solvent such as water, like the zirconium-containing solution. For example, an aqueous solution of ruthenium halide such as ruthenium trichloride, or an amine complex salt such as hexaamine ruthenium chloride or ruthenium tetroxide can be used. Further, even a compound having low solubility such as ruthenium oxide or ruthenium hydroxide may be dissolved by adjusting the pH by coexisting an acid.
【００４４】ジルコニウムとルテニウムを同一溶液に溶
解して担体に付着させる場合は、溶液に酸等を加えてｐ
Ｈを３以下，好ましくは１．５以下とすることが望まし
い。これは、ジルコニウム化合物の加水分解によるゾル
化やゲル化を防ぎ、ジルコニウム化合物とルテニウム化
合物とがお互いに反応し錯体様の化合物を作り易くする
ためである。この錯体様化合物は担体上に付着して、焼
成されたのちに触媒活性を示す要因と考えられるジルコ
ニア、ルテニウムの担持状態を好適なものとしている。When zirconium and ruthenium are dissolved in the same solution and adhered to a carrier, an acid or the like is added to the solution to add p
It is desirable that H is 3 or less, preferably 1.5 or less. This is because the zirconium compound is prevented from being solified or gelled by hydrolysis, and the zirconium compound and the ruthenium compound react with each other to easily form a complex-like compound. The complex-like compound adheres to the support and, after being calcined, renders the zirconia and ruthenium supported states, which are considered to be factors that exhibit catalytic activity, suitable.
【００４５】コバルト成分やマグネシウム成分などはそ
れぞれ単独で担体に付着させてもよいが、通常はジルコ
ニウム、ルテニウム溶液に同時にコバルト化合物、マグ
ネシウム化合物を溶解させて同時に付着させることが便
利である。コバルト化合物、マグネシウム化合物はそれ
ぞれ溶液、通常は水溶液に溶解する化合物であり、焼成
したのちには酸化物となる化合物であればよい。たとえ
ば、硝酸第一コバルト、塩基性硝酸コバルト、２塩化コ
バルトや硝酸マグネシウム、塩化マグネシウムなどがあ
げられる。The cobalt component and the magnesium component may be individually attached to the carrier. However, it is usually convenient to dissolve the cobalt compound and the magnesium compound in a zirconium and ruthenium solution at the same time and attach them simultaneously. Each of the cobalt compound and the magnesium compound is a compound that is dissolved in a solution, usually an aqueous solution, and may be any compound that becomes an oxide after firing. Examples include cobaltous nitrate, basic cobalt nitrate, cobalt dichloride, magnesium nitrate, magnesium chloride and the like.
【００４６】乾燥は、通常の乾燥方法たとえば大気中放
置、または５０℃〜１５０℃で空気中または窒素ガス気
流中などで実施する方法がある。焼成は、触媒上の担持
金属が酸化物の状態になる条件で行う。また、担持金属
が変化して活性を示さない化合物になったり、担体の結
晶構造が破壊、変化してしまうような高温に長時間曝さ
ない程度で実施する必要がある。通常用いられる焼成条
件としては、３００℃〜１０００℃の範囲、好ましくは
４００℃〜６００℃の範囲で１時間〜５時間、大気中ま
たは空気気流中で加熱処理すればよい。Drying may be carried out by a usual drying method, for example, by leaving it in the air, or at 50 ° C. to 150 ° C. in air or in a stream of nitrogen gas. The calcination is performed under the condition that the supported metal on the catalyst is in an oxide state. In addition, it is necessary to carry out the method without exposing the compound to a compound having no activity due to a change in the supported metal, or a high temperature at which the crystal structure of the carrier is destroyed or changed for a long time. As a generally used firing condition, heat treatment may be performed in the range of 300 ° C. to 1000 ° C., preferably in the range of 400 ° C. to 600 ° C. for 1 hour to 5 hours in the air or in the air stream.
【００４７】本発明のオートサーマルリフォーミング
は、通常の炭化水素の水蒸気改質方法や通常の炭酸ガス
による炭化水素の改質方法と同様に実施することができ
る。以下に、本発明の代表的なオートサーマルリフォー
ミングの態様について説明する。 （１）原料 この反応に用いられる原料は有機化合物であればとくに
制限はないが、炭化水素類が好適に使用できる。たとえ
ば、メタン、エタン、プロパン、ブタン、ペンタン、ヘ
キサン、シクロペンタン、シクロヘキサンなどの飽和脂
肪族炭化水素、エチレン、プロピレン、ブテン等の不飽
和脂肪族炭化水素、あるいは、ベンゼン、トルエン、キ
シレンなどの芳香族炭化水素を用いることができる。ま
た、メタノール、エタノールのようなアルコール類やジ
メチルエーテルのようなエーテル類も有効である。これ
らの含酸素化合物を原料とする場合は反応温度が低く出
来、触媒寿命、熱回収等の面で有利な場合がある。The autothermal reforming of the present invention can be carried out in the same manner as a normal hydrocarbon steam reforming method or a normal hydrocarbon reforming method using carbon dioxide. Hereinafter, typical aspects of the autothermal reforming of the present invention will be described. (1) Raw Material The raw material used in this reaction is not particularly limited as long as it is an organic compound, but hydrocarbons can be suitably used. For example, saturated aliphatic hydrocarbons such as methane, ethane, propane, butane, pentane, hexane, cyclopentane, and cyclohexane; unsaturated aliphatic hydrocarbons such as ethylene, propylene, and butene; and aromatic compounds such as benzene, toluene, and xylene Group hydrocarbons can be used. Also, alcohols such as methanol and ethanol and ethers such as dimethyl ether are effective. When these oxygen-containing compounds are used as raw materials, the reaction temperature can be lowered, which may be advantageous in terms of catalyst life, heat recovery, and the like.
【００４８】また、これらの混合物も有効に使用するこ
とができる。たとえば、メタン、を主成分としエタン、
プロパンなどを含む天然ガスやＬＰＧ、ナフサ、灯油、
軽油などは工業的に現実的な原料である。さらに、酸
素、スチーム、炭酸ガスをリフォーミングガスとして使
用し、炭化水素を改質するので、これらのガスを含む炭
化水素は当然原料として使用できる。天然ガス中には炭
酸ガス、水蒸気、酸素、窒素ガスや他の不純物ガス等が
混在しているが、これらは分離、除去することなく原料
炭化水素として使用してもよい。また、下記するように
原料炭化水素は脱硫して使用することが多いが、そのと
きに未反応で残った水素が原料中に存在しても差し支え
はない。Also, these mixtures can be used effectively. For example, methane, ethane,
Natural gas including propane, LPG, naphtha, kerosene,
Diesel oil and the like are industrially realistic raw materials. Further, oxygen, steam, and carbon dioxide are used as reforming gases to reform hydrocarbons, so that hydrocarbons containing these gases can be used as raw materials. Natural gas contains carbon dioxide gas, water vapor, oxygen, nitrogen gas, other impurity gases, and the like, which may be used as a raw material hydrocarbon without separation or removal. Further, as described below, the raw material hydrocarbon is often used after desulfurization, but hydrogen remaining unreacted at that time may be present in the raw material.
【００４９】しかし、原料炭化水素中の硫化水素やメル
カプタンなどの硫黄化合物は触媒の被毒作用があり、こ
れらが多いと触媒を長時間使用するには好ましくはな
い。原料炭化水素中の硫黄分としては、５０重量ｐｐｍ
以下、好ましくは１重量ｐｐｍ以下、さらに好ましくは
１００重量ｐｐｂ以下であることが望ましい。また、反
応生成物としての水素ガスまたは合成ガスの純度を高め
るためには、原料炭化水素中の不純物は炭酸ガス、水蒸
気、一酸化炭素ガス、水素および酸素などＣ、Ｈ、Ｏの
元素のみからできているものであることが望ましい。そ
れ以外のもの、たとえば窒素、アンモニア、ヘリウムな
どは少ない方が望ましい。ただし、アンモニア製造原料
としての水素製造や、燃料電池用水素製造の場合には窒
素ガスはとくに除去する必要はない。However, sulfur compounds such as hydrogen sulfide and mercaptan in the starting hydrocarbons have a poisoning effect on the catalyst, and if they are large, it is not preferable to use the catalyst for a long time. 50 wt ppm as sulfur in the raw hydrocarbon
Or less, preferably 1 ppm by weight or less, more preferably 100 ppm by weight or less. Further, in order to increase the purity of hydrogen gas or synthesis gas as a reaction product, impurities in the raw material hydrocarbon include only C, H, and O elements such as carbon dioxide gas, water vapor, carbon monoxide gas, hydrogen, and oxygen. It is desirable that it is made. It is desirable that the amount of other substances, such as nitrogen, ammonia, and helium, be small. However, in the case of producing hydrogen as a raw material for producing ammonia or producing hydrogen for a fuel cell, nitrogen gas does not need to be particularly removed.
【００５０】本発明におけるオートサーマルリフォーミ
ングでは、メタン、液化石油ガス（ＬＰＧ）、ナフサ、
灯油または軽油を原料とする場合に特に好適である。現
状ではこれらの比較的分子量の大きい炭化水素のオート
サーマルリフォーミングに使用されている触媒はニッケ
ル系が多く、これらは前述したようにコークの蓄積が起
こりやすく長期間使用しにくい欠点がある。しかし、本
発明の触媒は、とくにコーク蓄積が少なく上記炭化水素
類を原料としても好適に水素または合成ガスを製造でき
る。ただし、硫黄含有量の多い炭化水素類は原料として
は好ましくない。それ故、重油のような硫黄分の多い原
料は好ましい原料とは言えない。原料中の硫黄分が多い
場合は、オートサーマルリフォーミング反応の前に脱硫
操作を行い前述の濃度まで硫黄分を除去してやればよ
い。また、含酸素化合物も本発明の原料として適してい
るが、メタノール、エタノールおよびジメチルエーテル
が特に好適な原料として使用できる。In the automatic thermal reforming of the present invention, methane, liquefied petroleum gas (LPG), naphtha,
Particularly suitable when kerosene or light oil is used as a raw material. At present, most of the catalysts used for autothermal reforming of these hydrocarbons having a relatively high molecular weight are nickel-based catalysts, and as described above, they have a drawback that coke tends to accumulate and is difficult to use for a long period of time. However, the catalyst of the present invention has low coke accumulation, and can suitably produce hydrogen or synthesis gas even using the above hydrocarbons as a raw material. However, hydrocarbons having a high sulfur content are not preferred as raw materials. Therefore, a raw material having a high sulfur content such as heavy oil is not a preferable raw material. When the sulfur content in the raw material is large, desulfurization operation may be performed before the autothermal reforming reaction to remove the sulfur content to the above-mentioned concentration. Oxygen-containing compounds are also suitable as the raw material of the present invention, but methanol, ethanol and dimethyl ether can be used as particularly preferable raw materials.
【００５１】（２）リフォーミングガス リフォーミングガスとは、原料と反応して水素または合
成ガスを生成するガス、すなわち酸素、スチームあるい
は炭酸ガスをいう。炭化水素とスチーム、酸素あるいは
炭酸ガスの供給量の割合は反応システムの熱バランス、
生成合成ガスの所望の組成比、目標とする反応率等を勘
案し適宜選択すればよい。しかし、現実的には原料を完
全に改質することが好ましく、そのためには化学量論比
より過剰のリフォーミングガスを導入することが望まし
い。とくに、スチームは過剰に供給する場合がおおい。(2) Reforming gas Reforming gas is a gas that reacts with a raw material to generate hydrogen or a synthesis gas, that is, oxygen, steam or carbon dioxide gas. The proportions of hydrocarbon and steam, oxygen or carbon dioxide supply are based on the heat balance of the reaction system,
It may be appropriately selected in consideration of a desired composition ratio of the produced synthesis gas, a target reaction rate, and the like. However, in practice, it is preferable to completely reform the raw material, and for that purpose, it is desirable to introduce a reforming gas in excess of the stoichiometric ratio. In particular, steam is often oversupplied.
【００５２】通常、反応系に導入するスチームと原料の
比、スチーム／カーボン比（水分子の数／原料（（１）
で説明した原料で不純物やリフォーミングガスの炭酸ガ
ス等は含まない。以下同じ）中のカーボン原子の数の比
率）が０．１〜１０、好ましくは０．４〜４であること
が望ましい。これが上記範囲より小さすぎると触媒上に
コークが蓄積し易く、また、水素の多い合成ガスは製造
できない。スチーム／カーボン比が上記範囲より大きい
と改質反応は十分進むが、過剰の未反応スチームが生成
ガス中に残り、無駄となる。Usually, the ratio of steam to the raw material introduced into the reaction system, the steam / carbon ratio (the number of water molecules / the raw material ((1)
It does not include impurities, carbon dioxide gas of reforming gas, and the like. The same applies to the following), it is desirable that the ratio of the number of carbon atoms) is 0.1 to 10, preferably 0.4 to 4. If it is smaller than the above range, coke tends to accumulate on the catalyst, and a synthesis gas containing much hydrogen cannot be produced. If the steam / carbon ratio is larger than the above range, the reforming reaction proceeds sufficiently, but excess unreacted steam remains in the generated gas and is wasted.
【００５３】同様に、反応系に導入する酸素と原料の
比、酸素／カーボン比（酸素分子の数／原料中のカーボ
ン原子の数の比率）は０．１〜１、好ましくは０．２〜
０．８であることが望ましい。これが上記範囲より小さ
いと発熱反応が少なく、外部から多量の熱を供給せねば
ならなく、スチームリフォーミング反応と変わらないも
のとなる。酸素／カーボン比が上記範囲より大きいと改
質反応は十分進むが、過剰の発熱があり熱バランス的に
無駄となる場合が多い。また、完全酸化が進み、対原料
の水素得率または合成ガス得率が下がってしまう。Similarly, the ratio of oxygen to the raw material to be introduced into the reaction system and the oxygen / carbon ratio (the ratio of the number of oxygen molecules / the number of carbon atoms in the raw material) are 0.1 to 1, preferably 0.2 to 1.
0.8 is desirable. When this value is smaller than the above range, the exothermic reaction is small, a large amount of heat must be supplied from the outside, and it is not different from the steam reforming reaction. If the oxygen / carbon ratio is larger than the above range, the reforming reaction proceeds sufficiently, but excessive heat is generated and the heat balance is often wasted. Further, complete oxidation proceeds, and the hydrogen yield or the synthesis gas yield of the raw material decreases.
【００５４】また、炭酸ガスをリフォーミングガスに混
合する場合は、炭酸ガス／カーボン比（炭酸ガス分子の
数／原料中のカーボン原子の数の比率）は０．１〜５、
好ましくは０．１〜３であることが望ましい。炭酸ガス
の導入は酸素の導入量が少ない場合でもＣＯガスの多い
合成ガスの製造に好適である。熱バランス的に酸素の導
入量を制限したい時に特に有効となる。しかし、炭酸ガ
ス／カーボン比が上記範囲より大きいと、触媒上にコー
クが蓄積し易く、また、水素の多い合成ガスは製造でき
ない。水素製造を目的とする場合は炭酸ガスは含まれて
いない方がよいが、含まれていても本発明は実施でき
る。炭酸ガスを事前に除去するより経済的に有利な場合
は、炭酸ガスを含んだままオートサーマルリフォーミン
グ反応を進めればよい。When the carbon dioxide gas is mixed with the reforming gas, the carbon dioxide / carbon ratio (ratio of the number of carbon dioxide molecules / the number of carbon atoms in the raw material) is 0.1 to 5;
Preferably, it is 0.1 to 3. The introduction of carbon dioxide gas is suitable for producing a synthesis gas containing a large amount of CO gas even when the amount of introduced oxygen is small. This is particularly effective when it is desired to limit the amount of oxygen introduced in terms of heat balance. However, if the carbon dioxide / carbon ratio is larger than the above range, coke tends to accumulate on the catalyst, and a synthesis gas containing much hydrogen cannot be produced. For the purpose of producing hydrogen, it is preferable that carbon dioxide gas is not contained, but even if it is contained, the present invention can be carried out. When it is more economically advantageous to remove the carbon dioxide gas in advance, the autothermal reforming reaction may be performed while the carbon dioxide gas is still contained.
【００５５】酸素は純粋の酸素でもよいが、水蒸気、一
酸化炭素および炭酸ガスなどを含んでいてもよい。ま
た、窒素等のオートサーマルリフォーミングには不活性
なガスをふくんでいても良い。現実的には、純粋の酸素
の替わりに空気を用いてオートサーマルリフォーミング
を行い、燃料電池用、アンモニア製造用、フィシャート
ロプシュ反応用あるいはメタノール合成用の原料ガスな
どに使用することもできる。The oxygen may be pure oxygen, but may include water vapor, carbon monoxide, carbon dioxide, and the like. In addition, an inert gas may be included in the autothermal reforming such as nitrogen. In practice, autothermal reforming is performed by using air instead of pure oxygen, and can be used as a raw material gas for fuel cells, ammonia production, Fischer-Tropsch reaction, or methanol synthesis.
【００５６】（３）反応形式および水素または合成ガス
製造プロセス 反応形式は、とくに制限はなく、固定床式、移動床式、
流動床式などがあるが、通常は、固定床式反応器が用い
られる。図１に固定床式反応器を用いた天然ガスのオー
トサーマルリフォーミングのプロセスの例を示す。ナフ
サ、ＬＰＧ等でも同様のプロセスでよい。天然ガスは、
まず脱硫部１０で脱硫され、硫黄分を除去される。この
脱硫部１０では通常水素化脱硫および硫化水素の洗浄除
去を行うが、触媒層下層に酸化亜鉛のような硫化水素を
吸着する触媒を充填しておき、硫化水素を洗浄除去しな
いでもよい方法もある。つぎに脱硫天然ガス６（水素を
分離していない場合が多い）はスチームおよび酸素と混
合し混合ガス７（必要に応じ炭酸ガスを加えてもよ
い）、オートサーマルリフォーミング反応部１１に導入
される。ここで、天然ガスの部分酸化、改質等のオート
サーマルリフォーミング反応が起こり粗合成ガス８が得
られる。この粗合成ガス８から炭酸ガス分離部１６、お
よび過剰水素分離部１７にて処理され、所望の水素／一
酸化炭素の比を持つ合成ガスを得る。分離された炭酸ガ
ス４の一部はオートサーマルリフォーミング反応部１１
に再度導入され使用することができる。水素５は原料天
然ガスの脱硫用に使用してもよい。また、酸素、スチー
ム、炭酸ガスの量を調整することにより、炭酸ガス分離
部１６および水素分離部１７を省略することもできる。(3) Reaction type and hydrogen or synthesis gas production process The reaction type is not particularly limited, and may be a fixed bed type, a moving bed type,
There are fluidized bed reactors and the like, but usually a fixed bed reactor is used. FIG. 1 shows an example of a process for autothermal reforming of natural gas using a fixed-bed reactor. The same process may be applied to naphtha, LPG and the like. Natural gas is
First, desulfurization is performed in the desulfurization unit 10 to remove sulfur components. The desulfurization unit 10 normally performs hydrodesulfurization and washing and removal of hydrogen sulfide. However, a method may be employed in which a catalyst that adsorbs hydrogen sulfide such as zinc oxide is filled in the lower layer of the catalyst layer and the washing and removal of hydrogen sulfide may not be performed. is there. Next, the desulfurized natural gas 6 (often not separating hydrogen) is mixed with steam and oxygen, and introduced into the mixed gas 7 (carbon dioxide may be added if necessary), and introduced into the autothermal reforming reaction section 11. You. Here, an autothermal reforming reaction such as partial oxidation and reforming of natural gas occurs, and a crude synthesis gas 8 is obtained. The crude synthesis gas 8 is treated in the carbon dioxide gas separation section 16 and the excess hydrogen separation section 17 to obtain a synthesis gas having a desired ratio of hydrogen / carbon monoxide. A part of the separated carbon dioxide 4 is supplied to the auto thermal reforming reaction section 11.
Can be re-introduced and used. Hydrogen 5 may be used for desulfurization of raw natural gas. Further, by adjusting the amounts of oxygen, steam and carbon dioxide, the carbon dioxide separator 16 and the hydrogen separator 17 can be omitted.
【００５７】オートサーマルリフォーミング反応部１１
の形態としては、図２から図５に示すようなものが好適
に用いられる。図２は反応器前段１２は無触媒で反応さ
せ、部分酸化を主体とした反応で流体の温度を上げ、触
媒反応に適した温度にして後段部１３で本発明の触媒を
用いてオートサーマルリフォーミング反応を完結させ
る。この場合前段の反応部１２と後段の反応部１３の熱
のバランスをとれるよう、リフォーミングガス導入方法
や反応器１１を工夫することが望ましい。Auto thermal reforming reaction section 11
2 to 5 are preferably used. FIG. 2 shows that the first stage of the reactor is reacted without a catalyst, the temperature of the fluid is increased by a reaction mainly based on partial oxidation, and the temperature is adjusted to a temperature suitable for the catalytic reaction. Complete the forming reaction. In this case, it is desirable to devise a reforming gas introduction method and the reactor 11 so as to balance the heat of the former reaction part 12 and the latter reaction part 13.
【００５８】図３はスチーム導入量が比較的多い場合の
例で、前段部１４にまず混合ガス７を導入し酸化反応主
体の反応を酸化触媒、例えば白金パラジウム触媒を用い
て進め、反応物の温度を上げ、後段部１５では本発明の
触媒を用いてさらにスチームを導入してスチームリフォ
ーミング反応主体のオートサーマルリフォーミング反応
を進める。図４も同様であるが前段部１４でとくに酸化
触媒を用いず、本発明の触媒を用いた例である。FIG. 3 shows an example in which the amount of introduced steam is relatively large. First, the mixed gas 7 is introduced into the former stage 14, and the reaction mainly comprising the oxidation reaction is advanced using an oxidation catalyst, for example, a platinum-palladium catalyst. The temperature is increased, and steam is further introduced into the latter part 15 using the catalyst of the present invention to advance an autothermal reforming reaction mainly comprising a steam reforming reaction. FIG. 4 is also similar, but shows an example in which the catalyst of the present invention is used without using an oxidation catalyst particularly in the former part 14.
【００５９】図５は通常のオートサーマルリフォーミン
グ反応用の混合ガス７は反応器上部から導入するが、酸
素２の一部は分割して触媒層の１以上の部分に導入する
方法である。オートサーマルリフォーミング反応におい
ては、酸素による酸化反応が先に進み、スチームによる
リフォーミング反応が遅れる傾向にある。このため、触
媒層の上流部で酸化反応による発熱が起こり、下流部で
はスチームリフォーミング反応による吸熱が激しくなる
ことがある。このような場合は酸素を触媒層の各部に分
散して導入することにより、発熱と吸熱のバランスを取
り全体としてのオートサーマルリフォーミング反応を好
適に行わせることができる。FIG. 5 shows a method in which the normal mixed gas 7 for the autothermal reforming reaction is introduced from the upper part of the reactor, but a part of the oxygen 2 is divided and introduced into one or more parts of the catalyst layer. In the autothermal reforming reaction, the oxidation reaction by oxygen proceeds first, and the reforming reaction by steam tends to be delayed. For this reason, heat generation due to the oxidation reaction may occur in the upstream part of the catalyst layer, and heat absorption due to the steam reforming reaction may become severe in the downstream part. In such a case, by dispersing and introducing oxygen to each part of the catalyst layer, the balance between heat generation and heat absorption can be balanced, and the autothermal reforming reaction as a whole can be suitably performed.
【００６０】なお、上記のようにスチームや酸素を分割
して導入する場合の導入スチーム量等は反応部入口の混
合ガス中の量のみではなく、反応器へ導入した全スチー
ム量等をいうものである。 （４）反応条件 本発明の触媒は反応開始前に、還元処理をしておくこと
が望ましい。還元処理は４００℃〜９００℃で水素気流
中１〜１０時間処理すればよい。通常は触媒を反応温度
まで昇温している間に水素または水素を含むガスを触媒
層中に流通させて実施する。When the steam or oxygen is divided and introduced as described above, the introduced steam amount and the like refer not only to the amount in the mixed gas at the inlet of the reaction section but also to the total steam amount introduced to the reactor. It is. (4) Reaction Conditions The catalyst of the present invention is preferably subjected to a reduction treatment before the start of the reaction. The reduction treatment may be performed at 400 ° C. to 900 ° C. in a hydrogen stream for 1 to 10 hours. Usually, hydrogen or a gas containing hydrogen is passed through the catalyst layer while the temperature of the catalyst is raised to the reaction temperature.
【００６１】オートサーマルリフォーミング反応の反応
温度は、酸素とスチームのみで反応させる場合は２００
℃〜１，２００℃の範囲、好ましくは４００℃〜１，１
００℃の範囲、さらに好ましくは４００℃〜９００℃の
範囲が望ましい。アルコール類、エーテル類を原料とす
る場合は比較的低温でよいが、炭化水素を原料とする場
合は５００℃〜９００℃の範囲が望ましい。さらに、炭
酸ガスを加えて反応させる場合の反応温度は２００℃〜
１，３００℃の範囲、好ましくは４００℃〜１，２００
℃の範囲、さらに好ましくは６００℃〜１，１００℃の
範囲が望ましい。上記範囲のなかでも、アルコール類、
エーテル類を原料とする場合は比較的低温でよいが、炭
化水素を原料とする場合は比較的高温が望ましい。The reaction temperature of the autothermal reforming reaction is 200 when the reaction is carried out only with oxygen and steam.
C. to 1,200.degree. C., preferably 400.degree.
A range of 00 ° C, more preferably a range of 400 ° C to 900 ° C, is desirable. When alcohols and ethers are used as raw materials, the temperature may be relatively low, but when hydrocarbons are used as raw materials, the temperature is preferably in the range of 500 ° C to 900 ° C. Furthermore, the reaction temperature when reacting by adding carbon dioxide gas is 200 ° C.
1,300 ° C. range, preferably 400 ° C. to 1,200
C., more preferably in the range of 600C to 1,100C. Alcohols,
When ethers are used as the starting material, a relatively low temperature may be used, but when hydrocarbons are used as the starting material, a relatively high temperature is desirable.
【００６２】反応圧力は、とくに限定されない。通常は
合成ガスの用途に応じて設定すればよい。合成ガソリ
ン、合成軽油やメタノール合成に使用する場合は高圧が
望ましい。（２０ｋｇ／ｃｍ2 Ｇ〜１００ｋｇ／ｃｍ2
Ｇ程度）。また、高純度水素（純度９７％）の製造には
２０ｋｇ／ｃｍ2 Ｇ程度が適当である。しかし、反応圧
力が高いと化学平衡的にはメタンが多くなること、およ
びコーク析出が多くなることなどから、適当な圧力が現
実的である。さらに、燃料電池や燃料ガス原料とすると
きは、０ｋｇ／ｃｍ2 Ｇ〜１０ｋｇ／ｃｍ2 Ｇの範囲が
好ましい。通常実施する反応圧力は、０ｋｇ／ｃｍ2 Ｇ
〜１００ｋｇ／ｃｍ2 Ｇの範囲、好ましくは０ｋｇ／ｃ
ｍ2 Ｇ〜５０ｋｇ／ｃｍ2 Ｇの範囲、さらに好ましくは
０ｋｇ／ｃｍ2 Ｇ〜３０ｋｇ／ｃｍ2 Ｇの範囲が望まし
い。The reaction pressure is not particularly limited. Usually, it may be set according to the use of the synthesis gas. When used for synthetic gasoline, synthetic light oil or methanol synthesis, high pressure is desirable. (20 kg / cm 2 G to 100 kg / cm 2
G). Further, about 20 kg / cm 2 G is appropriate for the production of high-purity hydrogen (purity 97%). However, if the reaction pressure is high, methane increases in chemical equilibrium, and coke precipitation increases, and so an appropriate pressure is realistic. Further, when the fuel cell and the fuel gas feed is in the range of 0kg / cm 2 G~10kg / cm 2 G are preferred. The reaction pressure usually used is 0 kg / cm 2 G
-100 kg / cm 2 G, preferably 0 kg / c
m 2 G~50kg / cm 2 G range, more preferably is preferably in the range of 0kg / cm 2 G~30kg / cm 2 G.
【００６３】固定床流通式反応でガス状原料をオートサ
ーマルリフォーミング反応させる場合の流通原料（原料
＋リフォーミングガス）の空間速度（ＧＨＳＶ）は、
１，０００ｈ-1〜１００，０００ｈ-1の範囲、好ましく
は１，０００ｈ-1〜５０，０００ｈ-1の範囲、さらに好
ましくは１，５００ｈ-1〜４０，０００ｈ-1の範囲が望
ましい。なお、炭酸ガスを含む混合ガスを原料とすると
きは、炭酸ガスも流通原料として計算する。しかし、窒
素、ヘリウムなどオートサーマルリフォーミング反応に
直接関与しないガスは、流通原料とは考えない。When the gaseous raw material is subjected to an autothermal reforming reaction in a fixed bed flow reaction, the space velocity (GHSV) of the flowing raw material (raw material + reforming gas) is as follows:
Range of 1,000h -1 ~100,000h -1, preferably in the range of 1,000h -1 ~50,000h -1, more preferably is preferably in the range of 1,500h -1 ~40,000h -1. When a mixed gas containing carbon dioxide is used as a raw material, carbon dioxide is also calculated as a distribution raw material. However, gases that are not directly involved in the autothermal reforming reaction, such as nitrogen and helium, are not considered as raw materials for distribution.
【００６４】液状原料は通常、質量空間速度（ＷＨＳ
Ｖ）で原料供給量を特定する場合が多いが、質量空間速
度で言えば０．０５〜１００ｈ-1、好ましくは０．１〜
１０とすることが望ましい。なお、上記質量空間速度で
特定した数値は原料のみ（リフォーミングガスを含まな
い）の供給量である。The liquid raw material usually has a mass hourly space velocity (WHS).
In many cases, the raw material supply amount is specified in V), but in terms of mass space velocity, 0.05 to 100 h -1 , preferably 0.1 to 100 h -1 .
It is desirable to set to 10. The numerical value specified by the mass space velocity is the supply amount of only the raw material (not including the reforming gas).
【００６５】[0065]
（１）触媒調製 水酸化ジルコニウム２００ｇを５００℃で１時間焼成
し、ジルコニア担体Ｉを得た。この担体Ｉを塩化ルテニ
ウム水溶液に浸漬させたのち、８０℃に加熱しながら１
時間攪拌し水分を蒸発させた。さらに、１２０℃で６時
間乾燥させた。その後、得られた乾燥物を５００℃で１
時間焼成した。これを１６〜３２メッシュに粒径を整え
触媒Ｉとした。触媒Ｉのルテニウム含有量は０．５重量
％であった。触媒Ｉの組成を表１に示す。(1) Preparation of Catalyst 200 g of zirconium hydroxide was calcined at 500 ° C. for 1 hour to obtain a zirconia support I. The carrier I was immersed in an aqueous ruthenium chloride solution, and heated at 80 ° C. for 1 hour.
After stirring for an hour, water was evaporated. Furthermore, it dried at 120 degreeC for 6 hours. Thereafter, the obtained dried product was heated at 500 ° C. for 1 hour.
Fired for hours. This was adjusted to a particle size of 16 to 32 mesh to obtain a catalyst I. The ruthenium content of catalyst I was 0.5% by weight. Table 1 shows the composition of Catalyst I.
【００６６】（２）水素の製造 固定床流通式反応器に触媒Ｉを充填し、脱硫ナフサ、ス
チーム、酸素の混合ガスを原料ガスとして、水素製造の
ためのオートサーマルリフォーミング反応を行った。使
用した脱硫ナフサの組成を表４に、反応条件を表５に、
反応結果を表６に示す。(2) Production of Hydrogen A fixed-bed flow reactor was charged with the catalyst I, and an autothermal reforming reaction for producing hydrogen was performed using a mixed gas of desulfurized naphtha, steam and oxygen as a raw material gas. Table 4 shows the composition of the desulfurized naphtha used, and Table 5 shows the reaction conditions.
Table 6 shows the reaction results.
【００６７】〔実施例２〕担体Ｉを塩化ルテニウム水溶
液の替わりに、塩化ルテニウム、硝酸コバルト水溶液に
浸漬させた以外は実施例１と同じ操作により、触媒ＩＩ
を調製し、実施例１と同様の反応条件でオートサーマル
リフォーミング反応を行った。触媒ＩＩの組成を表１
に、反応結果を表６に示す。Example 2 A catalyst II was prepared in the same manner as in Example 1 except that the carrier I was immersed in an aqueous ruthenium chloride or cobalt nitrate solution instead of the aqueous ruthenium chloride solution.
Was prepared, and an autothermal reforming reaction was performed under the same reaction conditions as in Example 1. Table 1 shows the composition of Catalyst II.
Table 6 shows the reaction results.
【００６８】〔実施例３〕担体Ｉを塩化ルテニウム水溶
液の替わりに、塩化ルテニウム、硝酸コバルト、硝酸マ
グネシウム水溶液に浸漬させた以外は実施例１と同じ操
作により、触媒ＩＩＩを調製し、実施例１と同様の反応
条件でオートサーマルリフォーミング反応を行った。触
媒ＩＩＩの組成を表１に、反応結果を表６に示す。Example 3 A catalyst III was prepared in the same manner as in Example 1 except that the carrier I was immersed in an aqueous solution of ruthenium chloride, cobalt nitrate and magnesium nitrate instead of the aqueous solution of ruthenium chloride. The autothermal reforming reaction was performed under the same reaction conditions as described above. Table 1 shows the composition of Catalyst III, and Table 6 shows the reaction results.
【００６９】〔実施例４〕 （１）触媒調製 αアルミナ粉末に水２０重量％を加えニーダーで混合し
た後、圧縮成形し直径５ｍｍ、長さ５ｍｍの円柱状成形
体を得た。これを、１００℃〜３００℃の燃焼炉排ガス
で乾燥した後、１２８０℃で２６時間焼成し、アルミナ
担体ＩＶを得た。Example 4 (1) Preparation of Catalyst 20% by weight of water was added to α-alumina powder, mixed with a kneader, and compression-molded to obtain a columnar molded body having a diameter of 5 mm and a length of 5 mm. This was dried with a combustion furnace exhaust gas at 100 ° C. to 300 ° C., and then calcined at 1280 ° C. for 26 hours to obtain an alumina carrier IV.
【００７０】ジルコニウムのオキシ塩化物（ＺｒＯ（Ｏ
Ｈ）Ｃｌ）の水溶液（ＺｒＯ2 に換算して２．５ｇ）に
３塩化ルテニウム（ＲｕＣｌ3 ／ｎＨ2 Ｏ：Ｒｕ３８％
含有）０．６６ｇ、および硝酸コバルト（Ｃｏ（Ｎ
Ｏ3 ）3 ６Ｈ2 Ｏ）２．４７ｇを溶解するまで１時間以
上攪拌した。溶液の総量は１０ｃｃとなりこれを含浸液
とした。この含浸液を、上記担体ＩＶ５０ｇにポアフィ
リング法により含浸させた。これを１２０℃、５時間乾
燥した。さらに、５００℃で２時間焼成したのち、１６
〜３２メッシュに粒径を調整し、触媒ＩＶとした。触媒
ＩＶの組成、物性を表２に示す。Zirconium oxychloride (ZrO (O
H) Cl) in an aqueous solution (2.5 g in terms of ZrO 2 ) in ruthenium trichloride (RuCl 3 / nH 2 O: Ru 38%
0.66 g) and cobalt nitrate (Co (N
O 3) 3 and stirred for 1 hour or more until dissolved 6H 2 O) 2.47g. The total amount of the solution was 10 cc, which was used as the impregnating liquid. This impregnating liquid was impregnated with 50 g of the above-mentioned carrier IV by a pore filling method. This was dried at 120 ° C. for 5 hours. Furthermore, after baking at 500 ° C. for 2 hours, 16
The particle size was adjusted to ~ 32 mesh to obtain catalyst IV. Table 2 shows the composition and physical properties of Catalyst IV.
【００７１】（２）水素の製造 触媒ＩＶを用いて、実施例１と同様のオートサーマルリ
フォーミング反応を行った。触媒ＩＶによる反応結果を
表６に示す。 〔実施例５〕担体ＩＶを実施例４の含浸液の替わりに、
ジルコニウムのオキシ塩化物（ＺｒＯ（ＯＨ）Ｃｌ）の
水溶液（ＺｒＯ2 に換算して２．５ｇ）に３塩化ルテニ
ウム（ＲｕＣｌ3 ／ｎＨ2 Ｏ：Ｒｕ３８％含有）０．６
６ｇ、硝酸コバルト（Ｃｏ（ＮＯ3 ）3 ６Ｈ2 Ｏ）２．
４７ｇ、および硝酸マグネシウム（Ｍｇ（ＮＯ3 ）2６
Ｈ2 Ｏ）６．３６ｇを用いて、実施例４と同じようにし
て、１０ｃｃの含浸液を調製した。含浸以降は実施例４
と同様の操作により、触媒Ｖを調製した。実施例１と同
様の反応条件でオートサーマルリフォーミング反応を行
った。触媒Ｖの組成、物性を表２に、反応結果を表６に
示す。(2) Production of Hydrogen The same autothermal reforming reaction as in Example 1 was performed using Catalyst IV. Table 6 shows the results of the reaction using the catalyst IV. Example 5 The carrier IV was replaced with the impregnating liquid of Example 4,
Ruthenium trichloride (RuCl 3 / nH 2 O: containing 38% of Ru) 0.6 in an aqueous solution (2.5 g in terms of ZrO 2 ) of zirconium oxychloride (ZrO (OH) Cl)
6 g, cobalt nitrate (Co (NO 3) 3 6H 2 O) 2.
47 g, and magnesium nitrate (Mg (NO 3) 2 6
In the same manner as in Example 4, 10 cc of the impregnating liquid was prepared using 6.36 g of H 2 O). Example 4 after impregnation
Catalyst V was prepared in the same manner as described above. An autothermal reforming reaction was performed under the same reaction conditions as in Example 1. Table 2 shows the composition and physical properties of Catalyst V, and Table 6 shows the reaction results.
【００７２】〔実施例６〕 （１）合成ガスの製造 実施例５で得られた触媒Ｖを用い、水素／一酸化炭素の
比が２／１である合成ガスの製造を行った。原料として
メタンを用い、酸素、スチームおよび炭酸ガスの混合ガ
スによりオートサーマルリフォーミング反応を行った。
反応条件を表５に、反応結果を表６に示す。Example 6 (1) Production of synthesis gas Using the catalyst V obtained in Example 5, a synthesis gas having a hydrogen / carbon monoxide ratio of 2/1 was produced. Autothermal reforming reaction was performed using methane as a raw material and a mixed gas of oxygen, steam and carbon dioxide.
The reaction conditions are shown in Table 5, and the reaction results are shown in Table 6.
【００７３】〔実施例７〕実施例４の担体ＩＶのかわり
に、市販のγアルミナ担体ＶＩＩを用い、含浸液を３０
ｃｃとなるよう添加水を調整した以外は実施例４と同様
の操作で金属担持、乾燥、焼成を行い、触媒ＶＩＩを得
た。触媒ＶＩＩの組成を表２に示す。 〔実施例８〕実施例５の担体Ｖのかわりに、市販のγア
ルミナ担体ＶＩＩを用い、含浸液を３０ｃｃとなるよう
添加水を調整した以外は実施例５と同様の操作で金属担
持、乾燥、焼成を行い、触媒ＶＩＩＩを得た。触媒ＶＩ
ＩＩの組成を表３に示す。Example 7 Instead of the carrier IV in Example 4, a commercially available γ-alumina carrier VII was used,
Metal loading, drying and calcination were carried out in the same manner as in Example 4 except that the added water was adjusted so as to obtain cc to obtain Catalyst VII. Table 2 shows the composition of Catalyst VII. [Example 8] Instead of the carrier V of Example 5, a commercially available γ-alumina carrier VII was used, and the amount of impregnating solution was adjusted to 30 cc by adding water. Then, calcination was performed to obtain a catalyst VIII. Catalyst VI
Table 3 shows the composition of II.
【００７４】〔比較例１〕実施例４において用いた含浸
液の替わりに、硝酸ニッケル（Ｎｉ（ＮＯ3 ）2６Ｈ2
Ｏ）５．０ｇを水に溶かし、１０ｃｃの含浸液を調製
し、この含浸液をαアルミナ担体ＩＶに含浸させた後、
実施例４と同様の方法で乾燥した。この含浸、乾燥を５
回繰り返した。これ以外は実施例４と同様の操作で触媒
ＩＸを調製した。触媒ＩＸを用いて、実施例１と同様の
反応条件でオートサーマルリフォーミング反応を行っ
た。触媒ＩＸの性状等を表３に、反応結果を表６に示
す。[0074] The impregnation solution instead of using in Comparative Example 1 Example 4, nickel nitrate (Ni (NO 3) 2 6H 2
O) 5.0 g is dissolved in water to prepare a 10 cc impregnating liquid, and the impregnating liquid is impregnated into the α-alumina carrier IV.
Drying was performed in the same manner as in Example 4. This impregnation and drying
Repeated times. Except for this, the catalyst IX was prepared in the same manner as in Example 4. Using the catalyst IX, an autothermal reforming reaction was performed under the same reaction conditions as in Example 1. Table 3 shows the properties and the like of the catalyst IX, and Table 6 shows the reaction results.
【００７５】〔比較例２〕実施例４において用いた含浸
液の替わりに、３塩化ルテニウム（ＲｕＣｌ3 ／ｎＨ2
Ｏ：Ｒｕ３８％含有）０．６６ｇを水に溶かし、１０ｃ
ｃの含浸液を調製し、この含浸液をαアルミナ担体ＩＶ
に含浸させた以外は実施例４と同様の操作で触媒Ｘを調
製した。触媒Ｘを用いて、実施例１と同様の反応条件で
オートサーマルリフォーミング反応を行った。触媒Ｘの
性状等を表３に、反応結果を表６に示す。Comparative Example 2 Ruthenium trichloride (RuCl 3 / nH 2 ) was used instead of the impregnating solution used in Example 4.
0.66 g was dissolved in water, and 10 c
c was prepared, and this impregnating liquid was used as an α-alumina carrier IV.
Was prepared in the same manner as in Example 4 except that the catalyst X was impregnated. Using the catalyst X, an autothermal reforming reaction was performed under the same reaction conditions as in Example 1. Table 3 shows the properties and the like of the catalyst X, and Table 6 shows the reaction results.
【００７６】[0076]
【表１】 [Table 1]
【００７７】[0077]
【表２】 [Table 2]
【００７８】[0078]
【表３】 [Table 3]
【００７９】[0079]
【表４】 [Table 4]
【００８０】[0080]
【表５】 [Table 5]
【００８１】[0081]
【表６】 [Table 6]
【００８２】[0082]
【発明の効果】通常のニッケル担持アルミナ担体触媒や
ルテニウム担持触媒に較べ、本発明の触媒は脱硫ナフサ
のオートサーマルリフォーミング反応において高い転化
率を示す。また、１０時間反応を継続した後において
も、本発明の触媒はコーク蓄積の少ないことを示す。さ
らに、本発明の触媒は炭酸ガスを含むリフォーミングガ
スを用いたメタンからの合成ガス製造にも適しているこ
とがわかる。The catalyst of the present invention has a higher conversion in the autothermal reforming reaction of desulfurized naphtha than the conventional nickel-supported alumina-supported catalyst or ruthenium-supported catalyst. In addition, even after the reaction was continued for 10 hours, the catalyst of the present invention showed little coke accumulation. Further, it can be seen that the catalyst of the present invention is suitable for producing synthesis gas from methane using a reforming gas containing carbon dioxide.
【図１】オートサーマルリフォーミングプロセスの概念
的フロー図FIG. 1 is a conceptual flow chart of an auto thermal reforming process.
【図２】オートサーマルリフォーミング反応器部の例１FIG. 2 Example 1 of an autothermal reforming reactor section
【図３】オートサーマルリフォーミング反応器部の例２FIG. 3 is an example 2 of an auto thermal reforming reactor.
【図４】オートサーマルリフォーミング反応器部の例３FIG. 4 is an example 3 of an autothermal reforming reactor.
【図５】オートサーマルリフォーミング反応器部の例４FIG. 5: Example 4 of an autothermal reforming reactor section
１：原料（天然ガス） ２：スチーム ３：酸素 ４：炭酸ガス ５：水素 ６：脱硫天然ガス ７：混合ガス ８：粗合成ガス ９：精製合成ガス １０：原料（天然ガス）脱硫部 １１：オートサーマルリフォーミング反応部全体 １２：オートサーマルリフォーミング反応部の前段側無
触媒反応部 １３：オートサーマルリフォーミング反応部の後段側触
媒反応部 １４：オートサーマルリフォーミング反応部の前段側触
媒反応部 １５：オートサーマルリフォーミング反応部の後段側触
媒反応部 １６：粗合成ガス中の炭酸ガス分離部 １７：粗合成ガス中の過剰水素分離部1: Raw material (natural gas) 2: Steam 3: Oxygen 4: Carbon dioxide gas 5: Hydrogen 6: Desulfurized natural gas 7: Mixed gas 8: Crude synthesis gas 9: Purified synthesis gas 10: Raw material (natural gas) desulfurization unit 11: The entirety of the autothermal reforming reaction section 12: The non-catalytic reaction section on the upstream side of the autothermal reforming reaction section 13: The downstream catalyst reaction section of the autothermal reforming reaction section 14: The upstream catalyst reaction section of the autothermal reforming reaction section 15: Catalytic reaction section on the downstream side of the autothermal reforming reaction section 16: Separation section of carbon dioxide gas in crude synthesis gas 17: Separation section of excess hydrogen in crude synthesis gas
Claims (16)
らなるオートサーマルリフォーミング触媒。1. An autothermal reforming catalyst comprising a zirconia support supporting ruthenium.
た無機酸化物担体からなるオートサーマルリフォーミン
グ触媒。2. An autothermal reforming catalyst comprising an inorganic oxide carrier supporting zirconium and ruthenium.
％の範囲にある請求項１または２記載のオートサーマル
リフォーミング触媒。3. The autothermal reforming catalyst according to claim 1, wherein the ruthenium content is in the range of 0.05 to 20% by weight.
はマグネシウムを含有する請求項１〜３のいずれかに記
載のオートサーマルリフォーミング触媒。4. The autothermal reforming catalyst according to claim 1, wherein the catalyst further contains cobalt and / or magnesium.
の原子比で０．０１〜３０の範囲にある請求項４記載の
オートサーマルリフォーミング触媒。5. The autothermal reforming catalyst according to claim 4, wherein the cobalt content is in the range of 0.01 to 30 in an atomic ratio of cobalt / ruthenium.
０．５〜２０重量％の範囲にある請求項４または５記載
のオートサーマルリフォーミング触媒。6. The autothermal reforming catalyst according to claim 4, wherein the magnesium content is in the range of 0.5 to 20% by weight in terms of MgO.
２〜６のいずれかに記載のオートサーマルリフォーミン
グ触媒。7. The autothermal reforming catalyst according to claim 2, wherein the inorganic oxide carrier is alumina.
たはγアルミナである請求項７記載のオートサーマルリ
フォーミング触媒。8. The autothermal reforming catalyst according to claim 7, wherein the alumina as a carrier component is α alumina or γ alumina.
て０．０５〜２０重量％の範囲である請求項２〜８のい
ずれかに記載のオートサーマルリフォーミング触媒。9. The autothermal reforming catalyst according to claim 2 , wherein the zirconium content is in the range of 0.05 to 20% by weight in terms of ZrO 2 .
溶液、ルテニウムおよびコバルトを含む溶液、またはル
テニウム、コバルトおよびマグネシウムを含む溶液を付
着させたのち乾燥、焼成する請求項１または請求項３〜
６のいずれかに記載のオートサーマルリフォーミング触
媒の製造方法。10. The method according to claim 1, wherein a solution containing ruthenium, a solution containing ruthenium and cobalt, or a solution containing ruthenium, cobalt and magnesium is applied to the zirconia support, followed by drying and firing.
7. The method for producing an autothermal reforming catalyst according to any one of 6.
びルテニウムを含む溶液、ジルコニウム、ルテニウムお
よびコバルトを含む溶液、またはジルコニウム、ルテニ
ウム、コバルトおよびマグネシウムを含む溶液を付着さ
せたのち乾燥、焼成する請求項２〜９のいずれかに記載
のオートサーマルリフォーミング触媒の製造方法。11. A method for drying and calcining a solution containing zirconium and ruthenium, a solution containing zirconium, ruthenium and cobalt, or a solution containing zirconium, ruthenium, cobalt and magnesium on an inorganic oxide carrier. 10. The method for producing an autothermal reforming catalyst according to any one of claims 9 to 9.
トサーマルリフォーミング触媒を用いた水素または合成
ガスの製造方法。12. A method for producing hydrogen or synthesis gas using the autothermal reforming catalyst according to claim 1.
水素である請求項１２に記載の水素または合成ガスの製
造方法。13. The method for producing hydrogen or synthesis gas according to claim 12, wherein the raw material for producing hydrogen or synthesis gas is a hydrocarbon.
フサ、灯油または軽油である請求項１３に記載の水素ま
たは合成ガスの製造方法。14. The method for producing hydrogen or synthesis gas according to claim 13, wherein the hydrocarbon is methane, liquefied petroleum gas, naphtha, kerosene or light oil.
ノール、エタノールまたはジメチルエーテルである請求
項１２に記載の水素または合成ガスの製造方法。15. The method for producing hydrogen or synthesis gas according to claim 12, wherein the raw material for producing hydrogen or synthesis gas is methanol, ethanol or dimethyl ether.
および炭酸ガスの混合ガスである請求項１２〜１５のい
ずれかに記載の合成ガスの製造方法。16. The method according to claim 12, wherein the reforming gas is a mixed gas of oxygen, steam, and carbon dioxide.
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| JP2010103084A (en) * | 2008-10-27 | 2010-05-06 | Korea Advanced Inst Of Science & Technol | Fuel reforming method for solid oxide fuel cell system |
| WO2019244546A1 (en) | 2018-06-20 | 2019-12-26 | 住友電気工業株式会社 | Steam reforming catalyst, and fuel cell system using same |
| US11883801B2 (en) | 2018-06-20 | 2024-01-30 | Sumitomo Electric Industries, Ltd. | Steam reforming catalyst and fuel cell system using the same |
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