JP2000001303A - Catalyst for reforming hydrocarbon with gaseous carbon dioxide and method for reforming hydrocarbon - Google Patents
Catalyst for reforming hydrocarbon with gaseous carbon dioxide and method for reforming hydrocarbonInfo
- Publication number
- JP2000001303A JP2000001303A JP10160219A JP16021998A JP2000001303A JP 2000001303 A JP2000001303 A JP 2000001303A JP 10160219 A JP10160219 A JP 10160219A JP 16021998 A JP16021998 A JP 16021998A JP 2000001303 A JP2000001303 A JP 2000001303A
- Authority
- JP
- Japan
- Prior art keywords
- ruthenium
- catalyst
- hydrocarbon
- carbon dioxide
- zirconium
- 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 129
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 115
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 115
- 238000002407 reforming Methods 0.000 title claims abstract description 78
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 75
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims description 137
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims description 68
- 239000001569 carbon dioxide Substances 0.000 title claims description 68
- 238000000034 method Methods 0.000 title claims description 25
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 65
- 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 43
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000010941 cobalt Substances 0.000 claims abstract description 30
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 30
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011777 magnesium Substances 0.000 claims abstract description 19
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000010304 firing Methods 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 59
- 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 44
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 239000003345 natural gas Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 38
- 239000000203 mixture Substances 0.000 abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 20
- 239000002994 raw material Substances 0.000 description 18
- 238000006057 reforming reaction Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 16
- 239000001257 hydrogen Substances 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- 230000000694 effects Effects 0.000 description 15
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 13
- 229910002091 carbon monoxide Inorganic materials 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 7
- 239000000571 coke Substances 0.000 description 7
- 239000000395 magnesium oxide Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- -1 zirconium halides Chemical class 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000001354 calcination Methods 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
- 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
- 239000000843 powder Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000007800 oxidant agent Substances 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
- 229910002076 stabilized zirconia Inorganic materials 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
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 150000002681 magnesium compounds Chemical class 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
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000000629 steam reforming Methods 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-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
- QUWBSOKSBWAQER-UHFFFAOYSA-N [C].O=C=O Chemical compound [C].O=C=O QUWBSOKSBWAQER-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000001869 cobalt compounds Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 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
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 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
- 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
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 101100321669 Fagopyrum esculentum FA02 gene Proteins 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
- 229910052770 Uranium Inorganic materials 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
- 230000002776 aggregation Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 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
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 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
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 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
- 238000005336 cracking Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 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
- 238000004898 kneading Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 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
- 230000001590 oxidative effect Effects 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
- 238000010979 pH adjustment Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 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
- 238000000926 separation method Methods 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
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 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
- 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
- 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
Landscapes
- Hydrogen, Water And Hydrids (AREA)
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【発明の属する技術分野】本発明は、炭化水素の改質に
用いる触媒関にする。さらに詳しくは、ルテニウム、ジ
ルコニウム系の、炭酸ガスによる炭化水素改質用触媒、
およびこれを用いた炭化水素の改質方法に関する。[0001] The present invention relates to a catalyst used for reforming hydrocarbons. More specifically, ruthenium and zirconium-based catalysts for hydrocarbon reforming with carbon dioxide,
And a method for reforming hydrocarbons using the same.
【０００２】[0002]
【従来の技術】炭化水素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。また、
重質炭化水素たとえば減圧残油を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もすでに実用化されて
いる。2. Description of the Related Art Various techniques for producing a synthesis gas or hydrogen by reforming a hydrocarbon are known. In particular, many technologies have been put to practical use for steam reforming of hydrocarbons using steam. These are mainly used in the production of hydrogen and the production of synthesis gas for methanol using methane, LPG, naphtha and the like as raw materials using a nickel-based catalyst. Also,
A technique for producing a synthesis gas or hydrogen by partially oxidizing a heavy hydrocarbon such as a vacuum residue using oxygen has already been put to practical use.
【０００３】しかし、炭酸ガスを用いて炭化水素を改質
する技術は研究段階である。近年、地球温暖化の原因物
質として炭酸ガスが注目されており、これを固定化し、
原料化するため炭酸ガスを用いて炭化水素を改質し、合
成ガスとしてさらにメタノール、合成ガソリン、エーテ
ル類などへの転換が研究されている。また、炭酸ガスを
含む天然ガス田は多くあり、これを分離除去することな
く有用物質とするためにも炭酸ガスを用いた炭化水素改
質技術は検討されている。しかし、炭酸ガスを用いて炭
化水素を改質する技術は十分に実用化できる段階とはな
っていないのが現状である。[0003] However, the technology for reforming hydrocarbons using carbon dioxide is at the research stage. In recent years, carbon dioxide has been attracting attention as a causative substance of global warming.
Research has been conducted on reforming hydrocarbons using carbon dioxide gas as a raw material, and further converting it to methanol, synthetic gasoline, ethers, etc. as a synthesis gas. In addition, there are many natural gas fields containing carbon dioxide, and a hydrocarbon reforming technique using carbon dioxide is being studied in order to convert the natural gas into a useful substance without separating and removing the natural gas. However, at present, the technology of reforming hydrocarbons using carbon dioxide gas has not yet reached a stage where it can be sufficiently commercialized.
【０００４】研究としては各種あり、たとえばＡ．Ｔ．
Ａｓｃｈｒｏｆｔらはアルミナ担体にＮｉ，Ｐｄ，Ｒ
ｕ，Ｒｈ，Ｉｒを担持した触媒で、炭酸ガスによるメタ
ンの改質を評価している。触媒活性はＩｒが相対的に優
れているが実用化できる段階ではない。また、触媒上へ
のコーク蓄積の問題を指摘している（Ｎａｔｕｒｅ Ｖ
ｏｌ．３５２，１８ Ｊｕｌｙ １９９１）。There are various studies, for example, A. T.
Ascroft et al., Reported that Ni, Pd, R
U, Rh, and Ir supported catalysts are used to evaluate methane reforming by carbon dioxide gas. Although Ir is relatively excellent in catalytic activity, it is not at a stage where it can be put to practical use. They also point out the problem of coke accumulation on the catalyst (Nature V
ol. 352, 18 July 1991).
【０００５】Ｊ．Ｔ．Ｌｉｃｈａｒｄｓｏｎらはアルミ
ナ担体ルテニウム触媒およびアルミナ担体ロジウム触媒
を評価し、アルミナ担体ルテニウム触媒はアルミナ担体
ロジウム触媒よりコーク蓄積が多いとしている（Ａｐｐ
ｌ．Ｃａｔａｌ．６１，２９３（１９９０））。その他
にも、おもにアルミナを担体としてVIII族金属を担持し
た触媒によるメタンの炭酸ガスによる改質等の報告がな
されている（特開平０８−１７５８０５、特開平０８−
２５９２０３、特開平０９−０７５７２８、特開平０８
−２３１２０４）。[0005] T. Richardson et al. Evaluated ruthenium on alumina and rhodium on alumina catalysts and found that ruthenium on alumina catalysts accumulated more coke than rhodium on alumina catalysts (App.
l. Catal. 61, 293 (1990)). In addition, reports have been made on reforming methane with carbon dioxide gas using a catalyst mainly supporting alumina and using a group VIII metal (JP-A-08-175805, JP-A-08-175805).
259203, JP-A-09-075728, JP-A-08-08
-231204).
【０００６】[0006]
【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、炭酸ガスにより炭化水素を有効に改
質する触媒を提供することにある。本発明はまた、上記
炭化水素改質用触媒を簡便に、実用的に製造できる炭酸
ガスによる炭化水素改質用触媒の製造方法を提供するこ
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 catalyst for effectively reforming hydrocarbons with carbon dioxide gas. Another object of the present invention is to provide a method for producing a hydrocarbon reforming catalyst using carbon dioxide, which can easily and practically produce the hydrocarbon reforming catalyst.
【０００７】本発明は、さらに上記炭化水素改質用触媒
を用いた炭酸ガスによる炭化水素の改質方法を提供する
ことをも目的としている。Another object of the present invention is to provide a method for reforming hydrocarbons with carbon dioxide using the above catalyst for hydrocarbon reforming.
【０００８】[0008]
【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
担体触媒が炭酸ガスによる炭化水素改質に好適な触媒で
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 present inventors have found that the catalyst is suitable for hydrocarbon reforming using carbon dioxide gas, and have completed the present invention based on this finding.
【０００９】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、炭酸ガスによる炭化水素改質用触媒。 （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、炭酸ガスによる炭化水素改質用触
媒。That is, the gist of the present invention is as follows. (1) A catalyst for reforming hydrocarbons with carbon dioxide, comprising a zirconia carrier supporting ruthenium. (2) A catalyst for reforming hydrocarbons with carbon dioxide, comprising an inorganic oxide carrier supporting zirconium and ruthenium.
【００１０】（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）に記載の炭化
水素改質用触媒。 （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
炭化水素改質用触媒。 （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）記載の炭化水素
改質用触媒。(3) The ruthenium content is 0.05 to 2
The hydrocarbon reforming catalyst according to (1) or (2), which is in a range of 0% by weight. (4) The hydrocarbon reforming catalyst according to any one of (1) to (3), further comprising cobalt and / or magnesium in the catalyst. (5) The hydrocarbon reforming catalyst according to (4), wherein the cobalt content is in the range of 0.01 to 30 in an atomic ratio of cobalt / ruthenium.
【００１１】（６） マグネシウム含有量がＭｇＯに換
算して０．５〜２０重量％の範囲にある請求項４または
５に記載の炭化水素改質用触媒。 （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炭化水素改質用触媒。 （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）記載の炭化水素改質用触媒。(6) The hydrocarbon reforming catalyst according to claim 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 hydrocarbon reforming catalyst according to any of (6). (8) The alumina as a carrier component is α-alumina or γ
The hydrocarbon reforming catalyst according to (7), which is alumina.
【００１２】（９） ジルコニウムの含有量が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炭化水素改質用触媒。 （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、焼成する請求項１または（３）〜（６）の
いずれかに記載の炭化水素改質用触媒の製造方法。(9) The content of zirconium is ZrO 2
Is in the range of 0.05 to 20% by weight (2) to
(8) The hydrocarbon reforming catalyst according to any of (8). (10) a solution containing ruthenium in a zirconia carrier,
The catalyst for hydrocarbon reforming according to any one of claims 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. Method.
【００１３】（１１） 無機酸化物担体に、ジルコニウ
ムを含む溶液、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）〜（９）のいずれかに記載の炭化水素改質用触
媒の製造方法。(11) A solution containing zirconium, a solution containing zirconium and ruthenium, a solution containing zirconium, ruthenium and cobalt, or a solution containing zirconium, ruthenium, cobalt and magnesium is deposited on the inorganic oxide carrier and then dried. The method for producing a hydrocarbon reforming catalyst according to any one of (2) to (9), which is calcined.
【００１４】（１２） （１）〜（９）のいずれかに記
載の炭化水素改質用触媒を用いた、炭酸ガスによる炭化
水素の改質方法。 （１３） 炭化水素がメタンである（１２）に記載の炭
酸ガスによる炭化水素の改質方法。 （１４） （１）〜（９）のいずれかに記載の炭化水素
改質用触媒を用いた、天然ガスの改質方法。(12) A method for reforming hydrocarbons with carbon dioxide using the hydrocarbon reforming catalyst according to any one of (1) to (9). (13) The method according to (12), wherein the hydrocarbon is methane. (14) A method for reforming natural gas, using the hydrocarbon reforming catalyst according to any one of (1) to (9).
【００１５】（１５） （１）〜（９）のいずれかに記
載の炭化水素改質用触媒を用いた、炭酸ガスおよびスチ
ームの混合ガスによる炭化水素または天然ガスの改質方
法。(15) A method for reforming a hydrocarbon or natural gas with a mixed gas of carbon dioxide and steam, using the hydrocarbon reforming catalyst according to any one of (1) to (9).
【００１６】[0016]
ＣＨ4 ＋ ＣＯ2 ＝ ２Ｈ2 ＋ ２ＣＯ 〔スチームによる炭化水素改質〕 ＣＨ4 ＋ Ｈ2 Ｏ ＝ ３Ｈ2 ＋ ＣＯ すなわち、炭酸ガスによる炭化水素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である
が、スチームによる炭化水素改質の場合は合成ガス中の
水素と一酸化炭素の比は３対１である。一方、合成ガス
から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。また、ジメチルエーテル製造では化学量論的に必要
な水素と一酸化炭素の比は１対１である。CH 4 + CO 2 = 2H 2 + 2CO [Hydrocarbon reforming by steam] CH 4 + H 2 O = 3H 2 + CO That is, in the case of hydrocarbon reforming by carbon dioxide gas, the amount of hydrogen is one with hydrogen in the generated synthesis gas. The ratio of carbon oxide is 1: 1, but in the case of hydrocarbon reforming with steam, the ratio of hydrogen to carbon monoxide in the synthesis gas is 3: 1. On the other hand, when producing methanol, synthetic light oil, or synthetic gasoline (by Fischer-Tropsch reaction) from synthesis gas, the stoichiometrically necessary ratio of hydrogen to carbon monoxide is approximately 2: 1. In the production of dimethyl ether, the stoichiometrically required ratio of hydrogen to carbon monoxide is 1: 1.
【００１７】それゆえ、上記のような目的の合成ガスを
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、炭酸ガスによる炭化水素改質、ま
たは炭酸ガスによる炭化水素改質を主体とし一部スチー
ムによる炭化水素改質を含む方法を選択することが望ま
しい。本発明では、こ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。Therefore, when synthesizing the target gas as described above, instead of the conventional hydrocarbon reforming by steam, hydrocarbon reforming by carbon dioxide or hydrocarbon reforming by carbon dioxide is performed. It is desirable to select a method based on quality and involving hydrocarbon reforming with some steam. According to the present invention, such a synthesis gas having a relatively high carbon monoxide content and a low hydrogen content can be produced.
【００１８】本発明の一つの形態（請求項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Ｚ
ｒＯ2 ）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。A zirconia carrier according to one embodiment of the present invention (corresponding to claim 1) is a single zirconia carrier (chemical formula Z).
It may be a stabilized zirconia containing a stabilizing component such as rO 2 ) or magnesia, or a zirconia carrier or a stabilized zirconia carrier containing simply other components. 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.
【００１９】上記の実施形態（請求項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、炭酸ガ
スによる炭化水素の改質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。As the supported metal of the present invention in the above embodiment (corresponding to claim 1), ruthenium is essential. 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 favorable results for reforming hydrocarbons with carbon dioxide. It is considered that the combination of zirconia and ruthenium, which are carriers, is one of the factors for achieving the effect.
【００２０】本発明の別の一つの形態（請求項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（請求項２
に対応）の無機酸化物担体には、ジルコニア担体および
ジルコニア系担体は含まれない。Another embodiment of the present invention (corresponding to claim 2) is one in which zirconium and ruthenium are supported on an inorganic oxide carrier. 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. It should be noted that an embodiment of the present invention (claim 2)
The zirconia carrier and the zirconia-based carrier are not included in the inorganic oxide carrier described in (1).
【００２１】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、本発明における炭酸ガスによる炭化
水素の改質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, alumina carriers are 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 a catalyst for reforming hydrocarbons with carbon dioxide in the present invention. In particular, when catalyst strength is required, it is a suitable catalyst carrier.
【００２２】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もでき
る。なお、γアルミナ担体としては、他の結晶形と混在
し完全に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, but is similar to 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. Note that the γ-alumina carrier does not have to be made of only γ-alumina crystals in a mixture with other crystal forms.
【００２３】上記形態（請求項２に対応する本発明の形
態）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からと
考えられるからである。The catalyst of the above embodiment (the embodiment of the present invention corresponding to claim 2) requires zirconium and ruthenium to be 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 because it is considered that the catalytic activity is expressed by the interaction between zirconium and ruthenium.
【００２４】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、炭酸ガスによる炭化水素の改質反応に対
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おり、炭酸ガスによる炭
化水素の改質反応への使用前及び使用中は還元状態にあ
るのが普通である。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. Further, one of the objects of the present invention, the activity for the reforming reaction of hydrocarbons by carbon dioxide gas is essentially dependent on the interaction between zirconium and ruthenium, so that even a zirconia support, a ruthenium-supported catalyst, an inorganic oxide support, zirconium support, The same effect can be achieved with a ruthenium-supported catalyst. Incidentally, when the supported metal in the present invention is usually produced by firing,
It is carried on a carrier as an oxide, and is usually in a reduced state before and during use in a hydrocarbon reforming reaction with carbon dioxide gas.
【００２５】さらに、好ましい本発明の形態として、上
記触媒中（請求項１および２に対応する形態の触媒）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、ルテニウムと同属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えれる。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 preferable embodiment of the present invention, there is a catalyst containing cobalt or cobalt and magnesium in the above-mentioned catalyst (a catalyst of the form corresponding to claims 1 and 2). Cobalt belongs to Group VIII metals of the periodic table, and is considered to be the same as ruthenium and contributes 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.
【００２６】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、炭酸ガスによる炭化水素の改
質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 hydrocarbon reforming reaction with carbon dioxide 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.
【００２７】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.
【００２８】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.
【００２９】本発明の無機酸化物担体を用いる形態（請
求項２〜８に対応する形態）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０．５〜２０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。In the embodiment using the inorganic oxide carrier of the present invention (the embodiment corresponding to claims 2 to 8), it is preferable to specify the content of zirconium to be supported. 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 in the range of 0.5 to 20% by weight in terms of ZrO 2, preferably in the range of 0.5 to 15 wt%, more preferably desirably in the range of 1-15 wt%.
【００３０】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（請求項９に対応する形態）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 (an embodiment corresponding to claim 9) 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.
【００３１】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.
【００３２】（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 carrier 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.
【００３３】つぎに、本発明の無機酸化物担体ジルコニ
ア、ルテニウム担持触媒の製造方法（請求項１０に対応
する形態）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ア、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０．０５〜５０μm 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℃〜１４００℃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、例えば焼
結すればよい。Next, a method for producing a catalyst supporting zirconia and ruthenium on an inorganic oxide carrier of the present invention (an embodiment corresponding to claim 10) will be described. As a typical embodiment, a method for producing an alumina-supported zirconia 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 in the range of 0.05 to 50 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 1400 ° C. If the raw alumina powder is α-alumina, it may be molded, for example, sintered, so as to maintain its shape as a catalyst.
【００３４】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℃〜７００℃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 preparing a γ-alumina carrier, an aluminate solution such as an aqueous sodium aluminate solution and an acid aluminum salt solution such as an aqueous aluminum sulfate solution are usually 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 700 ° C, preferably 400 ° C to
The treatment may be performed in the air at a temperature of 600 ° C. for 1 hour to 5 hours.
【００３５】（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 solution containing zirconium and a solution containing ruthenium may be 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.
【００３６】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.
【００３７】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.
【００３８】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 and 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.
【００３９】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, the magnesium component and the like may be individually attached to the carrier, but 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 at the same time. 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.
【００４０】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℃〜７００℃の範囲、好ましくは４
００℃〜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。The drying may be carried out in 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. The firing conditions usually used are in the range of 300 ° C. to 700 ° C., preferably 4 ° C.
Heat treatment may be performed in the range of 00 ° C. to 600 ° C. for 1 hour to 5 hours in the air or in an air stream.
【００４１】本発明の炭酸ガスによる炭化水素の改質方
法は、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。以下に代表的な炭酸ガスによる炭化水素の改質方
法の態様について説明する。 （１）原料（炭化水素） この反応に用いられる原料炭化水素としては、とくに制
限はない。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。The method for reforming hydrocarbons with carbon dioxide of the present invention can be carried out in the same manner as the ordinary method for reforming hydrocarbons with steam or the ordinary method for reforming hydrocarbons with carbon dioxide. Hereinafter, embodiments of a typical method for reforming hydrocarbons with carbon dioxide will be described. (1) Raw material (hydrocarbon) The raw material hydrocarbon used in this reaction is not particularly limited. 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.
【００４２】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、ナフサなどは工
業的に現実的な原料である。さらに、炭酸ガスを酸化剤
として使用し、炭化水素を改質するので、炭酸ガスを含
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、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。Also, these mixtures can be effectively used. For example, methane, ethane,
Natural gas including propane, LPG, naphtha and the like are industrially realistic raw materials. Furthermore, since carbon dioxide is used as an oxidizing agent to reform hydrocarbons, hydrocarbons containing carbon dioxide can naturally be used as raw materials. Natural gas contains carbon dioxide gas, water vapor, nitrogen gas, other impurity gases, and the like, which may be used as a raw material hydrocarbon without separation or removal.
【００４３】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、１０重量ｐｐｍ
以下、好ましくは１重量ｐｐｍ以下であることが望まし
い。また、反応生成物としての一酸化炭素、水素ガス
（合成ガス）の純度を高めるためには、原料中炭化水素
には、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。However, sulfur compounds such as hydrogen sulfide and mercaptan in the raw material hydrocarbons have a poisoning effect on the catalyst, and a large amount thereof is not preferable for long-term use of the catalyst. 10 wt ppm as sulfur in the raw hydrocarbon
Or less, preferably 1 ppm by weight or less. Further, in order to increase the purity of carbon monoxide and hydrogen gas (synthesis gas) as reaction products, the hydrocarbons in the raw materials include carbon dioxide, water vapor, carbon monoxide gas, hydrogen and oxygen, and the like. It is desirable to use one made of only the element of O. Others, such as nitrogen, ammonia,
Less helium is desirable.
【００４４】炭化水素と炭酸ガスの供給量の比は所望の
合成ガスの組成、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、現実的には炭化水素を完全に改
質するためには炭酸ガス分子の数と炭化水素中のＣ元素
の数の比率が１（炭酸ガスカーボン比と言い、炭酸ガス
分子の数／炭化水素中のカーボン元素の数の比率で表
す。）未満では化学量論的に酸化剤が不足し、未反応炭
化水素が製品中に残る。また、炭酸ガスカーボン比が２
０を超える場合は合成ガス中に炭酸ガスが多すぎて実用
的でない。The ratio of the supply amounts of hydrocarbon and carbon dioxide may be appropriately selected in consideration of the desired composition of the synthesis gas, the target reaction rate, and the like. However, in reality, in order to completely reform hydrocarbons, the ratio of the number of carbon dioxide molecules to the number of carbon atoms in the hydrocarbon is 1 (referred to as carbon dioxide carbon ratio, the number of carbon dioxide molecules / carbon number). If the ratio is less than the ratio of the number of carbon elements in hydrogen), the oxidizing agent becomes insufficient stoichiometrically, and unreacted hydrocarbon remains in the product. In addition, the carbon dioxide carbon ratio is 2
If it exceeds 0, the synthesis gas contains too much carbon dioxide and is not practical.
【００４５】炭酸ガスは純粋の炭酸ガスでもよいが、水
蒸気、一酸化炭素および酸素など炭化水素の改質に酸化
剤として作用するガスなどを含んでいてもよい。とく
に、水蒸気は炭酸ガスと同じように炭化水素を改質でき
る。水蒸気による炭化水素の改質では、炭酸ガスによる
炭化水素の改質とは一酸化炭素／水素ガス比が異なる合
成ガスが得られる。それゆえ、水蒸気と炭酸ガスの混合
比を調整した混合ガスを酸化剤として用いることによ
り、所望の一酸化炭素／水素ガス比の合成ガスを得るこ
とができる。また、水蒸気を混合することにより触媒上
へのコークの蓄積を抑える効果もある。The carbon dioxide gas may be pure carbon dioxide gas, but may also contain a gas acting as an oxidizing agent for reforming hydrocarbons such as steam, carbon monoxide and oxygen. In particular, steam can reform hydrocarbons in the same way as carbon dioxide. In the reforming of hydrocarbons with steam, a synthesis gas having a different carbon monoxide / hydrogen gas ratio than the reforming of hydrocarbons with carbon dioxide is obtained. Therefore, by using a mixed gas in which the mixing ratio of steam and carbon dioxide gas is adjusted as the oxidizing agent, a synthesis gas having a desired carbon monoxide / hydrogen gas ratio can be obtained. Mixing steam also has the effect of suppressing the accumulation of coke on the catalyst.
【００４６】合成ガスの一酸化炭素／水素ガス比を調整
したり、触媒へのコーク蓄積を抑制するために水蒸気を
加える場合は、炭化水素と炭酸ガス、水蒸気の３者の比
率を調整することが望ましい。触媒へのコーク蓄積を抑
制するために水蒸気を加えるためには、水蒸気の量を多
くする方がよいが、水蒸気が多すぎると水性ガス反応が
進行し生成ガスの水素／一酸化炭素の比率が大きくな
り、水蒸気改質反応に近づいてしまう。水蒸気の量は水
蒸気／炭化水素中のカーボンの比率で１０以下が望まし
い。なお、炭酸ガスと水蒸気による炭化水素の改質では
炭酸ガス／カーボン比は、２０／８０〜７０／３０が好
適な結果が得られる。When adjusting the ratio of carbon monoxide / hydrogen gas in the synthesis gas or adding steam to suppress the accumulation of coke in the catalyst, the ratio of hydrocarbon, carbon dioxide and steam should be adjusted. Is desirable. In order to add steam to suppress coke accumulation in the catalyst, it is better to increase the amount of steam. However, if the amount of steam is too large, the water gas reaction proceeds and the ratio of hydrogen / carbon monoxide in the product gas decreases. It becomes large and approaches a steam reforming reaction. The amount of water vapor is desirably 10 or less in a ratio of water vapor / carbon in hydrocarbon. In the reforming of hydrocarbons with carbon dioxide and water vapor, a preferable result is obtained when the carbon dioxide / carbon ratio is 20/80 to 70/30.
【００４７】（２）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。(2) Reaction Conditions The catalyst of the present invention is desirably 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.
【００４８】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
式管型反応器が用いられる。反応温度は２００℃〜１，
２００℃の範囲、好ましくは４００℃〜１，１００℃の
範囲、さらに好ましくは５００℃〜９００℃の範囲が望
ましい。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２０
ｋｇ／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／ｃｍ
2 Ｇ〜５０ｋｇ／ｃｍ2 Ｇの範囲、さらに好ましくは０
ｋｇ／ｃｍ2 Ｇ〜３０ｋｇ／ｃｍ2 Ｇの範囲が望まし
い。The type of reaction is not particularly limited, and includes a fixed bed type, a moving bed type, a fluidized bed type, and the like. In general, a fixed bed type tubular reactor is used. The reaction temperature is 200 ° C ~ 1,
A range of 200 ° C., preferably a range of 400 ° C. to 1,100 ° C., and more preferably a range of 500 ° C. to 900 ° C. is desirable. 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. (20kg / cm 2 G~100kg / cm about 2 G). For the production of high-purity hydrogen (purity 97%), 20
About kg / cm 2 G is appropriate. 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. Usually, the reaction pressure is from 0 kg / cm 2 G to
In the range of 100 kg / cm 2 G, preferably 0 kg / cm
2 G to 50 kg / cm 2 G, more preferably 0
range kg / cm 2 G~30kg / cm 2 G is preferable.
【００４９】固定床流通式反応の場合の流通原料（炭化
水素＋炭酸ガス）の空間速度（ＧＨＳＶ）は、１，００
０ｈ-1〜１００，０００ｈ-1の範囲、好ましくは１，０
００ｈ-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、水蒸気を含む混合ガスを原料とするときは、水蒸
気も原料として計算する。しかし、窒素、ヘリウムなど
炭化水素の改質反応に直接関与しないガスは原料ガスと
は考えない。The space velocity (GHSV) of the feedstock (hydrocarbon + carbon dioxide) in the fixed bed flow reaction is 1,00
Range 0h -1 ~100,000h -1, preferably 1,0
Range of 00h -1 ~50,000h -1, more preferably is preferably in the range of 1,500h -1 ~40,000h -1.
When a mixed gas containing water vapor is used as a raw material, the calculation is performed using water vapor as a raw material. However, gases that do not directly participate in the hydrocarbon reforming reaction, such as nitrogen and helium, are not considered as source gases.
【００５０】[0050]
（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。 （２）炭酸ガスによる炭化水素の改質 固定床流通式反応器に触媒Ｉを充填し、メタンと炭酸ガ
スの１：１混合ガスを原料ガスとして、炭酸ガスによる
炭化水素の改質反応を行った。改質反応の反応条件を表
４に、反応結果を表５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. (2) Reforming of hydrocarbons by carbon dioxide gas A fixed-bed flow reactor is filled with the catalyst I, and a reforming reaction of hydrocarbons by carbon dioxide gas is performed using a 1: 1 mixed gas of methane and carbon dioxide as a raw material gas. Was. Table 4 shows the reaction conditions for the reforming reaction, and Table 5 shows the reaction results.
【００５１】〔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炭酸ガスによる
炭化水素の改質反応を行った。触媒ＩＩの組成を表１
に、反応結果を表５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 solution of ruthenium chloride and cobalt nitrate instead of the aqueous solution of ruthenium chloride.
Was prepared, and a hydrocarbon reforming reaction with carbon dioxide gas was performed under the same reaction conditions as in Example 1. Table 1 shows the composition of Catalyst II.
Table 5 shows the reaction results.
【００５２】〔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
条件で炭酸ガスによる炭化水素の改質反応を行った。触
媒ＩＩＩの組成を表１に、反応結果を表５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. Under the same reaction conditions as described above, a hydrocarbon reforming reaction with carbon dioxide was performed. Table 1 shows the composition of Catalyst III and Table 5 shows the reaction results.
【００５３】〔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
炭を得た。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 coal 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.
【００５４】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。 （２）炭酸ガスによる炭化水素の改質 触媒ＩＶを用いて、実施例１と同様の炭化水素の改質反
応を行った。触媒ＩＶによる反応結果を表５に示す。The 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. (2) Reforming of Hydrocarbon with Carbon Dioxide The same hydrocarbon reforming reaction as in Example 1 was performed using Catalyst IV. Table 5 shows the results of the reaction using the catalyst IV.
【００５５】〔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（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、硝酸コバルト（Ｃｏ（ＮＯ3 ）3 ６
Ｈ2 Ｏ）２．４７ｇ、および硝酸マグネシウム（Ｍｇ
（ＮＯ3 ）2６Ｈ2 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炭酸ガスによる炭化水
素の改質反応を行った。触媒Ｖの組成、物性を表２に、
反応結果を表５に示す。Example 5 The carrier IV was replaced with the impregnating solution of Example 4 and 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%
Containing) 0.66 g, cobalt nitrate (Co (NO 3) 3 6
H 2 O) 2.47g, and magnesium nitrate (Mg
(NO 3) using 2 6H 2 O) 6.36g, Example 4
10 cc of the impregnating liquid was prepared in the same manner as described above. After the impregnation, a catalyst V was prepared in the same manner as in Example 4. A hydrocarbon reforming reaction with carbon dioxide gas was performed under the same reaction conditions as in Example 1. Table 2 shows the composition and physical properties of Catalyst V.
Table 5 shows the reaction results.
【００５６】〔実施例６〕実施例５で得られた触媒Ｖを
用い、実施例１の反応条件での炭酸ガスによる炭化水素
の改質反応のうち、メタンと炭酸ガスの１：１混合ガス
を原料ガスとする替わりに、メタン、炭酸ガス、水蒸気
の１：１：１混合ガスを原料ガスとして用いて炭化水素
の改質反応を行った。改質反応の反応条件を表４に、反
応結果を表５に示す。Example 6 Using the catalyst V obtained in Example 5, a 1: 1 mixed gas of methane and carbon dioxide was used in the hydrocarbon reforming reaction with carbon dioxide under the reaction conditions of Example 1. Was used as the raw material gas, and a hydrocarbon reforming reaction was performed using a 1: 1: 1 mixed gas of methane, carbon dioxide gas, and steam as the raw material gas. Table 4 shows the reaction conditions for the reforming reaction, and Table 5 shows the reaction results.
【００５７】〔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。Example 7 A commercially available γ-alumina carrier VII was used instead of the carrier IV of Example 4, and the impregnating liquid was 30
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.
【００５８】〔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３０
ｃｃ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ＶＩＩＩの組成を表３に示す。Example 8 A commercially available γ-alumina carrier VII was used instead of the carrier V of Example 5, and the impregnating liquid was 30
Metal loading, drying and calcining were carried out in the same manner as in Example 5 except that the amount of water added was adjusted so as to obtain cc, whereby Catalyst VIII was obtained. Table 3 shows the composition of Catalyst VIII.
【００５９】〔実施例９〕実施例５で得られた触媒Ｖを
用い、実施例６の反応条件での炭酸ガスによる炭化水素
の改質反応のうち、メタン、炭酸ガス、水蒸気の１：
１：１混合ガスを原料ガスとする替わりに、メタン、炭
酸ガス、水蒸気の３：３：４混合ガスを原料ガスとして
用い、反応圧力を５ｋｇ／ｃｍ2 Ｇにあげて炭化水素の
改質反応を行った。改質反応の反応条件を表４に、反応
結果を表５に示す。Example 9 Using the catalyst V obtained in Example 5, in the reaction of reforming hydrocarbons with carbon dioxide under the reaction conditions of Example 6, the ratio of methane, carbon dioxide and steam was as follows:
Instead of using a 1: 1 mixed gas as a raw material gas, a 3: 3: 4 mixed gas of methane, carbon dioxide, and steam is used as a raw material gas, and the reaction pressure is increased to 5 kg / cm 2 G to reform hydrocarbon. Was done. Table 4 shows the reaction conditions for the reforming reaction, and Table 5 shows the reaction results.
【００６０】〔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
反応条件で炭酸ガスによる炭化水素の改質反応を行っ
た。触媒Ｘの性状等を表３に、反応結果を表５に示す。[0060] 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, a hydrocarbon reforming reaction with carbon dioxide 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 5 shows the reaction results.
【００６１】〔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
炭酸ガスによる炭化水素の改質反応を行った。触媒Ｘの
性状等を表３に、反応結果を表５に示す。Comparative Example 2 Ruthenium trichloride (RuCl 3 / nH 2 ) was used instead of the impregnating liquid 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, a hydrocarbon reforming reaction with carbon dioxide 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 5 shows the reaction results.
【００６２】[0062]
【表１】 [Table 1]
【００６３】[0063]
【表２】 [Table 2]
【００６４】[0064]
【表３】 [Table 3]
【００６５】[0065]
【表４】 [Table 4]
【００６６】[0066]
【表５】 [Table 5]
【００６７】[0067]
【発明の効果】通常のニッケル担持アルミナ担体触媒や
ルテニウム担体触媒に較べ、本発明の触媒は炭酸ガスに
よる炭化水素の改質反応において高い一酸化炭素収率を
示す。また、長時間経過した後の反応においても本発明
の触媒は上記改質反応一酸化炭素収率の低下は少なく、
コーク蓄積の少ないことを示す。The catalyst of the present invention has a higher carbon monoxide yield in the hydrocarbon reforming reaction with carbon dioxide gas than the conventional nickel-supported alumina support catalyst or ruthenium support catalyst. Further, even in the reaction after a long time has passed, the catalyst of the present invention has a small decrease in the reforming reaction carbon monoxide yield,
Indicates low coke accumulation.
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Claims (15)
らなる、炭酸ガスによる炭化水素改質用触媒。1. A catalyst for reforming hydrocarbons with carbon dioxide, comprising a zirconia carrier supporting ruthenium.
た無機酸化物担体からなる、炭酸ガスによる炭化水素改
質用触媒。2. A catalyst for reforming hydrocarbons with carbon dioxide, comprising an inorganic oxide carrier supporting zirconium and ruthenium.
％の範囲にある請求項１または２記載の炭化水素改質用
触媒。3. The hydrocarbon 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
載の炭化水素改質用触媒。4. The hydrocarbon reforming catalyst according to claim 1, further comprising cobalt and / or magnesium in the catalyst.
の原子比で０．０１〜３０の範囲にある請求項４記載の
炭化水素改質用触媒。5. The hydrocarbon 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に記
載の炭化水素改質用触媒。6. The hydrocarbon 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炭化水素改質用触媒。7. The hydrocarbon 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記載の炭化水素改質用触
媒。8. The hydrocarbon reforming catalyst according to claim 7, wherein the alumina as the 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
ずれかに記載の炭化水素改質用触媒。9. The hydrocarbon 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炭化水素改質用触媒の製造方法。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 a hydrocarbon reforming catalyst according to any one of 6.
む溶液、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、焼成する請求
項２〜９のいずれかに記載の炭化水素改質用触媒の製造
方法。11. A method comprising applying a solution containing zirconium, a solution containing zirconium and ruthenium, a solution containing zirconium, ruthenium and cobalt, or a solution containing zirconium, ruthenium, cobalt and magnesium to an inorganic oxide carrier, followed by drying, The method for producing a hydrocarbon reforming catalyst according to claim 2, wherein the catalyst is calcined.
水素改質用触媒を用いた、炭酸ガスによる炭化水素の改
質方法。12. A method for reforming hydrocarbons with carbon dioxide using the hydrocarbon reforming catalyst according to claim 1. Description:
記載の炭酸ガスによる炭化水素の改質方法。13. The method according to claim 12, wherein the hydrocarbon is methane.
水素改質用触媒を用いた、炭酸ガスによる天然ガスの改
質方法。14. A method for reforming natural gas with carbon dioxide using the catalyst for hydrocarbon reforming according to claim 1. Description:
水素改質用触媒を用いた、炭酸ガスおよびスチームの混
合ガスによる炭化水素または天然ガスの改質方法。15. A method for reforming a hydrocarbon or natural gas with a mixed gas of carbon dioxide gas and steam, using the hydrocarbon reforming catalyst according to claim 1. Description:
Priority Applications (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10160219A JP2000001303A (en) | 1998-06-09 | 1998-06-09 | Catalyst for reforming hydrocarbon with gaseous carbon dioxide and method for reforming hydrocarbon |
| DE69932869T DE69932869T2 (en) | 1998-06-09 | 1999-06-04 | Process for the autothermal steam reforming of a hydrocarbon feed |
| KR1020067003113A KR100596286B1 (en) | 1998-06-09 | 1999-06-04 | Catalyst and process for reforming hydrocarbon |
| DE69927032T DE69927032T2 (en) | 1998-06-09 | 1999-06-04 | METHOD FOR AUTOTHERMIC REFORMATION OF A HYDROCARBON INGREDIENT |
| EP04016297A EP1481729B1 (en) | 1998-06-09 | 1999-06-04 | Process for the autothermal reforming of a hydrocarbon feedstock |
| US09/701,585 US6749828B1 (en) | 1998-06-09 | 1999-06-04 | Process for reforming hydrocarbon |
| EP99923913A EP1093852B1 (en) | 1998-06-09 | 1999-06-04 | Process for the autothermal reforming of hydrocarbon feedstock |
| AU40597/99A AU740872B2 (en) | 1998-06-09 | 1999-06-04 | Catalyst and process for reforming hydrocarbon |
| KR1020007013887A KR100600218B1 (en) | 1998-06-09 | 1999-06-04 | Catalyst and process for reforming hydrocarbon |
| PCT/JP1999/003002 WO1999064150A1 (en) | 1998-06-09 | 1999-06-04 | Catalyst and process for reforming hydrocarbon |
| CA002332964A CA2332964C (en) | 1998-06-09 | 1999-06-04 | Ruthenium-containing catalyst and process for reforming organic feedstock using the catalyst |
| MYPI99002306A MY128928A (en) | 1998-06-09 | 1999-06-07 | Hydrocarbon reforming catalyst and method for reforming hydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10160219A JP2000001303A (en) | 1998-06-09 | 1998-06-09 | Catalyst for reforming hydrocarbon with gaseous carbon dioxide and method for reforming hydrocarbon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000001303A true JP2000001303A (en) | 2000-01-07 |
Family
ID=15710310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10160219A Pending JP2000001303A (en) | 1998-06-09 | 1998-06-09 | Catalyst for reforming hydrocarbon with gaseous carbon dioxide and method for reforming hydrocarbon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000001303A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002078840A1 (en) * | 2001-03-29 | 2002-10-10 | Idemitsu Kosan Co., Ltd. | Catalyst for reforming hydrocarbon and method for preparation thereof, and process for reforming hydrocarbon using said catalyst |
| JP2008207186A (en) * | 2000-11-08 | 2008-09-11 | Idemitsu Kosan Co Ltd | Catalyst for hydrocarbon reforming and method of reforming hydrocarbon with the same |
-
1998
- 1998-06-09 JP JP10160219A patent/JP2000001303A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008207186A (en) * | 2000-11-08 | 2008-09-11 | Idemitsu Kosan Co Ltd | Catalyst for hydrocarbon reforming and method of reforming hydrocarbon with the same |
| WO2002078840A1 (en) * | 2001-03-29 | 2002-10-10 | Idemitsu Kosan Co., Ltd. | Catalyst for reforming hydrocarbon and method for preparation thereof, and process for reforming hydrocarbon using said catalyst |
| US7378368B2 (en) | 2001-03-29 | 2008-05-27 | Idemitsu Kosan, Co., Ltd. | Catalyst for reforming hydrocarbon and method for preparation thereof, and process for reforming hydrocarbon using said catalyst |
| US7892417B2 (en) | 2001-03-29 | 2011-02-22 | Idemitsu Kosan, Co., Ltd. | Catalyst for reforming hydrocarbon and method for preparation thereof, and process for reforming hydrocarbon using said catalyst |
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