JP2001276623A - Reforming catalyst and reforming method for hydrocarbon - Google Patents
Reforming catalyst and reforming method for hydrocarbonInfo
- Publication number
- JP2001276623A JP2001276623A JP2000093533A JP2000093533A JP2001276623A JP 2001276623 A JP2001276623 A JP 2001276623A JP 2000093533 A JP2000093533 A JP 2000093533A JP 2000093533 A JP2000093533 A JP 2000093533A JP 2001276623 A JP2001276623 A JP 2001276623A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- reforming
- ruthenium
- component
- carrier
- 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 105
- 238000002407 reforming Methods 0.000 title claims abstract description 60
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 40
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 26
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 62
- 238000000629 steam reforming Methods 0.000 claims abstract description 12
- 238000002453 autothermal reforming Methods 0.000 claims abstract description 7
- 238000004453 electron probe microanalysis Methods 0.000 claims abstract description 7
- 238000005259 measurement Methods 0.000 claims abstract description 6
- 238000004458 analytical method Methods 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 21
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000011777 magnesium Substances 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 11
- 229910052749 magnesium Inorganic materials 0.000 claims description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 28
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000010304 firing Methods 0.000 abstract description 6
- 239000000523 sample Substances 0.000 abstract description 2
- 238000004452 microanalysis Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 23
- 239000001257 hydrogen Substances 0.000 description 23
- 229910052739 hydrogen Inorganic materials 0.000 description 23
- 239000000243 solution Substances 0.000 description 20
- 239000007789 gas Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 13
- 239000000446 fuel Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- 238000005470 impregnation Methods 0.000 description 11
- 150000003304 ruthenium compounds Chemical class 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 150000002681 magnesium compounds Chemical class 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 150000003755 zirconium compounds Chemical class 0.000 description 9
- 150000001869 cobalt compounds Chemical class 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- -1 alkaline earth metal aluminate Chemical class 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 6
- 230000000875 corresponding effect Effects 0.000 description 6
- 239000003350 kerosene 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
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000000395 magnesium oxide Substances 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
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 229940045032 cobaltous nitrate Drugs 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000006057 reforming reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 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 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000723368 Conium Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101100321669 Fagopyrum esculentum FA02 gene Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- KFIKNZBXPKXFTA-UHFFFAOYSA-N dipotassium;dioxido(dioxo)ruthenium Chemical compound [K+].[K+].[O-][Ru]([O-])(=O)=O KFIKNZBXPKXFTA-UHFFFAOYSA-N 0.000 description 1
- XOLNQIIEFUNTQC-UHFFFAOYSA-H dipotassium;hexachlororuthenium(2-) Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[K+].[K+].[Ru+4] XOLNQIIEFUNTQC-UHFFFAOYSA-H 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000003949 liquefied natural gas Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical class [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- DAWBXZHBYOYVLB-UHFFFAOYSA-J oxalate;zirconium(4+) Chemical compound [Zr+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O DAWBXZHBYOYVLB-UHFFFAOYSA-J 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 150000002926 oxygen Chemical class 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
- 239000002245 particle Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 description 1
- VDRDGQXTSLSKKY-UHFFFAOYSA-K ruthenium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ru+3] VDRDGQXTSLSKKY-UHFFFAOYSA-K 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000011787 zinc oxide Substances 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
Landscapes
- Hydrogen, Water And Hydrids (AREA)
- Catalysts (AREA)
- Fuel Cell (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、炭化水素の改質用
触媒に関し、さらに詳しくは、ルテニウムを活性成分と
し、炭化水素、特に灯油の改質活性を効率的に向上せし
める改質用触媒、及び該触媒を用いた改質方法に関する
ものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for reforming hydrocarbons, and more particularly, to a reforming catalyst comprising ruthenium as an active component and efficiently improving the activity of reforming hydrocarbons, especially kerosene. And a reforming method using the catalyst.
【０００２】[0002]
【従来の技術】近年、環境問題から新エネルギー技術が
脚光を浴びており、この新エネルギー技術の一つとして
燃料電池が注目されている。この燃料電池は、水素と酸
素を電気化学的に反応させることにより、化学エネルギ
ーを電気エネルギーに変換するものであって、エネルギ
ーの利用効率が高いという特徴を有しており、民生用、
産業用あるいは自動車用などとして、実用化研究が積極
的になされている。この燃料電池には、使用する電解質
の種類に応じて、リン酸型、溶融炭酸塩型、固体酸化物
型、固体高分子型などのタイプが知られている。一方、
水素源としては、メタノール、メタンを主体とする液化
天然ガス、この天然ガスを主成分とする都市ガス、天然
ガスを原料とする合成液体燃料、さらには石油系のＬＰ
Ｇ、ナフサ、灯油などの石油系炭化水素の使用が研究さ
れている。2. Description of the Related Art In recent years, new energy technologies have been spotlighted due to environmental problems, and fuel cells have attracted attention as one of the new energy technologies. This fuel cell converts chemical energy into electric energy by electrochemically reacting hydrogen and oxygen, and has the feature of high energy use efficiency.
Practical research is being actively conducted for industrial or automotive use. As the fuel cell, types such as a phosphoric acid type, a molten carbonate type, a solid oxide type, and a solid polymer type are known according to the type of electrolyte used. on the other hand,
As a hydrogen source, liquefied natural gas mainly composed of methanol and methane, city gas mainly composed of natural gas, synthetic liquid fuel composed of natural gas as raw material, and petroleum LP
The use of petroleum hydrocarbons such as G, naphtha, and kerosene is being studied.
【０００３】燃料電池を民生用や自動車用などに利用す
る場合、上記石油系炭化水素は、保管及び取扱いが容易
である上、ガソリンスタンドや販売店など、供給システ
ムが整備されていることから、水素源として有利であ
る。この石油系炭化水素油を用いて水素を製造する場
合、一般に、該炭化水素油を、改質触媒の存在下に水蒸
気改質又は部分酸化改質処理する方法が用いられる。こ
のような改質処理においては、改質触媒として、担体に
ルテニウムを活性成分として担持したものが研究されて
おり、該ルテニウム系改質触媒は、例えば炭化水素の水
蒸気改質反応に用いた場合、比較的高活性でかつ低スチ
ーム／カーボン比の運転条件下でも炭素の析出を抑制す
るなどの利点を有し、近年、長寿命の改質用触媒を必要
とする燃料電池への適用が期待されている。このような
ルテニウムを活性成分として用いた改質触媒として、例
えば、特開平５−２２０３９７号公報には、アルカリ土
類金属アルミネートを含む酸化アルミニウムにジルコニ
アゾルを前駆体とする酸化ジルコニウムとルテニウム成
分を担持してなる炭化水素の水蒸気改質触媒が開示され
ている。[0003] When a fuel cell is used for consumer or automobile use, the petroleum-based hydrocarbon is easy to store and handle, and in addition, a supply system such as a gas station and a store is provided. It is advantageous as a hydrogen source. When hydrogen is produced using this petroleum-based hydrocarbon oil, a method is generally used in which the hydrocarbon oil is subjected to steam reforming or partial oxidation reforming treatment in the presence of a reforming catalyst. In such a reforming treatment, a catalyst in which ruthenium is supported as an active component on a carrier has been studied as a reforming catalyst, and the ruthenium-based reforming catalyst is, for example, used in a steam reforming reaction of hydrocarbons. Has the advantage of suppressing carbon deposition even under operating conditions of relatively high activity and low steam / carbon ratio, and is expected to be applied to fuel cells that require a long-life reforming catalyst in recent years. Have been. As such a reforming catalyst using ruthenium as an active component, for example, Japanese Patent Application Laid-Open No. H5-220397 discloses a zirconium oxide and ruthenium component using zirconia sol as a precursor to aluminum oxide containing an alkaline earth metal aluminate. Are disclosed.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、ルテニ
ウム系改質触媒に用いるルテニウムは貴金属であるた
め、これを担持成分として用いる触媒は一般的に高価な
ものとなることから、ルテニウム成分を含有する触媒を
工業的に有用なものとするためには、触媒性能のみなら
ず触媒価格を低減させる必要がある。一方で、上記従来
のルテニウム系改質触媒は担持ルテニウム当たりの触媒
活性が実用的に十分でなく、更に高活性の改質触媒が望
まれていた。本発明は、このような状況下でなされたも
のであり、担持ルテニウム当たりの触媒活性が著しく優
れ、かつ焼成や反応時の高温下においてもその高活性を
維持することができる炭化水素の改質触媒、外触媒の製
造方法及び該改質触媒を用い燃料電池用水素を効率よく
得ることのできる炭化水素の水蒸気改質方法、部分酸化
改質方法及びオートサーマルリフォーミング法を提供す
ることを目的とするものである。However, since ruthenium used in a ruthenium-based reforming catalyst is a noble metal, a catalyst using the same as a supporting component is generally expensive, so that a catalyst containing a ruthenium component is expensive. In order to make the catalyst industrially useful, it is necessary to reduce not only the catalyst performance but also the catalyst price. On the other hand, the above-mentioned conventional ruthenium-based reforming catalyst has a practically insufficient catalytic activity per supported ruthenium, and a higher activity reforming catalyst has been desired. The present invention has been made under such a circumstance, and has a remarkably excellent catalytic activity per supported ruthenium, and is capable of maintaining its high activity even at a high temperature during calcination or reaction. It is an object of the present invention to provide a method for producing a catalyst, an outer catalyst, a method for steam reforming hydrocarbons, a method for partial oxidation reforming, and an autothermal reforming method capable of efficiently obtaining hydrogen for a fuel cell using the reforming catalyst. It is assumed that.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、前記目的
を達成するために鋭意研究を重ねた。その結果、従来の
ルテニウム系改質用触媒においては、ルテニウム成分が
担体中に比較的均一に分散されているが、反応時におい
て反応に寄与するルテニウム成分は、担体の外表面近傍
に存在するもののみであり、内部に存在するルテニウム
成分はほとんど反応に寄与しないことを見出した。そし
て、担体中における活性成分であるルテニウムを、担体
の外表面側に多く分布させたものが、同一担持量であっ
てもその触媒活性において著しく優れており改質触媒と
してその目的に適合しうること、更に、この改質触媒を
用い改質処理することにより、燃料電池用水素が効率よ
く得られることを見出した。本発明は、かかる知見に基
づいて完成したものである。すなわち、本発明は、担体
に少なくともルテニウム成分を担持してなる炭化水素の
改質用触媒において、該触媒の断面を、エレクトロンプ
ローブ・マイクロアナリシス（ＥＰＭＡ）装置を用い
て、一方向にルテニウム原子について線分析測定をして
得られる断面幅方向距離ｒ（中心から触媒表面までの距
離）とＸ線強度Ｉとの関係を示す図において、上記ｒが
一方の触媒表面−ｒ0 から他方の触媒表面ｒ0 の間にお
けるＩ（ｒ）の積分値Ｎ0 から、−２／３ｒ0 から２／
３ｒ0 の間におけるＩ（ｒ）の積分値Ｎ1 を減じた値を
Ｎとし、上記Ｎ0 に対するＮの割合Ｓ＝（Ｎ／Ｎ0 ）×
１００の値が５０以上であることを特徴とする炭化水素
の改質用触媒を提供するものである。また、本発明は、
担体に少なくともルテニウム成分を担持してなり、かつ
上記担体の吸水量以下の量の含浸液を、該担体に含浸さ
せることを特徴とする炭化水素の改質用触媒の製造方
法、及び前記改質用触媒を用いた水蒸気改質方法、部分
酸化改質方法及びオートサーマルリフォーミング法をも
提供するものである。Means for Solving the Problems The present inventors have intensively studied to achieve the above object. As a result, in the conventional ruthenium-based reforming catalyst, the ruthenium component is relatively uniformly dispersed in the carrier, but the ruthenium component contributing to the reaction during the reaction is present near the outer surface of the carrier. Only, and found that the ruthenium component present inside hardly contributes to the reaction. The active ingredient in the carrier, ruthenium, which is distributed in large amounts on the outer surface side of the carrier, is remarkably excellent in catalytic activity even with the same amount of support, and can be adapted to the purpose as a reforming catalyst. Further, it has been found that hydrogen for fuel cells can be efficiently obtained by performing a reforming treatment using this reforming catalyst. The present invention has been completed based on such findings. That is, the present invention relates to a hydrocarbon reforming catalyst comprising at least a ruthenium component supported on a carrier, wherein a cross section of the catalyst is converted to ruthenium atoms in one direction using an electron probe microanalysis (EPMA) apparatus. In the graph showing the relationship between the cross-sectional width direction distance r (distance from the center to the catalyst surface) obtained by the line analysis measurement and the X-ray intensity I, r is from one catalyst surface −r 0 to the other catalyst surface. From the integral value N 0 of I (r) during r 0 , −2 / 3r 0 to 2 /
The value obtained by subtracting the integral value N 1 of I (r) during 3r 0 is defined as N, and the ratio of N to N 0 S = (N / N 0 ) ×
It is intended to provide a hydrocarbon reforming catalyst characterized in that the value of 100 is 50 or more. Also, the present invention
A method for producing a catalyst for reforming hydrocarbons, comprising impregnating the carrier with an impregnating liquid having at least a ruthenium component supported on the carrier and having an amount equal to or less than the water absorption of the carrier, and the reforming. The present invention also provides a steam reforming method, a partial oxidation reforming method, and an autothermal reforming method using a catalyst for use.
【０００６】[0006]
【発明の実施の形態】図１に、本発明の触媒の一例の断
面図及びその幅方向距離とＸ線強度の関係を示す。本発
明の炭化水素の改質用触媒は、担体に少なくともルテニ
ウム成分を担持してなる炭化水素の改質用触媒におい
て、該触媒の断面をエレクトロンプローブ・マイクロア
ナリシス（ＥＰＭＡ）装置を用いて、一方向にルテニウ
ム原子について線分析測定をして得られる断面幅方向距
離ｒ（中心から触媒表面までの距離）とＸ線強度Ｉとの
関係を示す図において、上記ｒが一方の触媒表面−ｒ0
から他方の触媒表面ｒ0 の間におけるＩ（ｒ）の積分値
Ｎ0 から、−２／３ｒ0 から２／３ｒ0 の間におけるＩ
（ｒ）の積分値Ｎ1 を減じた値をＮとし、上記Ｎ0 に対
するＮの割合Ｓ＝（Ｎ／Ｎ0 ）×１００の値が５０以
上、好ましくは５５以上、更に好ましくは７０以上であ
るものである。上記のルテニウム分布を有すること、す
なわち、ルテニウム成分を担体の外表面側に多く分布さ
せることにより、担持ルテニウム当たりの触媒活性が著
しく優れ、かつ焼成や反応時の高温下においてもその高
活性を維持することができる改質触媒が得られる。本発
明においては、上記担体が球状あるいは円柱状の形状を
有するものであることが好ましい。従って、本発明にお
けるｒ（中心から触媒表面までの距離）とは、担体が球
状の場合はその半径をいい、円柱状である場合はその底
面に平行に切断した断面の半径をいう。球状及び円柱状
の形状には、厳密にいう球及び円柱のみならず、その一
部の形状が変形してはいるが実質的には球及び円柱とみ
なすことができるものも包含する。また、球状及び円柱
状以外の他の形状の担体においても、上記球状及び円柱
状の場合に準じて触媒を調製することにより本発明のル
テニウム分布を達成することができる。本発明に用いら
れる上記改質用触媒は、球状あるいは円柱状の場合、通
常その直径あるいは上記断面の直径が１〜１０ｍｍ、好
ましくは２〜６ｍｍであることが好ましい。触媒の径が
上記範囲より小さい場合は外表面担持の効果が十分でな
く、また、上記範囲より大きい場合は触媒活性が十分で
なく好ましくない場合がある。FIG. 1 is a cross-sectional view of an example of the catalyst of the present invention and the relationship between the distance in the width direction and the X-ray intensity. The hydrocarbon reforming catalyst of the present invention is a hydrocarbon reforming catalyst comprising at least a ruthenium component supported on a carrier, and a cross section of the catalyst is obtained by using an electron probe microanalysis (EPMA) apparatus. In the figure showing the relationship between the cross-sectional width direction distance r (distance from the center to the catalyst surface) obtained by performing line analysis measurement on ruthenium atoms in the direction and the X-ray intensity I, r is one of the catalyst surfaces −r 0.
Integrated values N 0 of the I (r) between the other catalyst surface r 0 from, I in between -2 / 3r 0 of 2 / 3r 0
When a value obtained by subtracting the integral value N 1 of (r) is N, the ratio of N to N 0 S = (N / N 0 ) × 100 is 50 or more, preferably 55 or more, more preferably 70 or more. There is something. By having the above-mentioned ruthenium distribution, that is, by distributing a large amount of ruthenium components on the outer surface side of the support, the catalytic activity per supported ruthenium is remarkably excellent, and the high activity is maintained even at a high temperature during calcination or reaction. The resulting reforming catalyst is obtained. In the present invention, the carrier preferably has a spherical or columnar shape. Therefore, r (distance from the center to the catalyst surface) in the present invention refers to the radius of the support when it is spherical, and refers to the radius of a cross section cut parallel to the bottom surface when the support is cylindrical. Spherical and cylindrical shapes include not only strictly spherical and cylindrical shapes but also those which can be regarded as substantially spherical and cylindrical although some of the shapes are deformed. The ruthenium distribution of the present invention can also be achieved by preparing a catalyst in a carrier having a shape other than the spherical and cylindrical shapes according to the above-mentioned spherical and cylindrical shapes. When the reforming catalyst used in the present invention has a spherical or columnar shape, the diameter thereof or the diameter of the cross section is preferably 1 to 10 mm, preferably 2 to 6 mm. If the diameter of the catalyst is smaller than the above range, the effect of supporting the outer surface is not sufficient, and if it is larger than the above range, the catalytic activity may be insufficient and not preferable.
【０００７】本発明の炭化水素の改質用触媒に用いられ
る担体としては多孔質担体が好ましく、特に多孔質の無
機酸化物が好ましい。このようなものとしては、例えば
シリカ、アルミナ、シリカ−アルミナ、チタニア、ジル
コニア、マグネシア、酸化亜鉛、白土、粘土及び珪藻土
などを挙げることができる。これらは単独で用いてもよ
く、二種以上を組み合わせて用いてもよい。これらの中
で、特に、触媒の圧壊強度などの点でα−アルミナが好
適である。これらの担体上に担持させる金属成分として
は、ルテニウム成分が必須である。本発明においては、
このルテニウム成分を外表面側に多く存在せしめるが、
全ルテニウム成分としては、担体上に金属ルテニウム換
算で0.０５〜５重量％担持されることが好ましい。ルテ
ニウム成分が0.０５重量％より少ない場合は、活性成分
としての効果が十分でなく、また５重量％を超える場合
は担持量の増加に見合った効果が得られず不経済であ
る。この点から、担体上のルテニウム成分の担持量は、
金属ルテニウム換算で0.０５〜２重量％、特に0.１〜２
重量％であることが更に好ましい。The carrier used in the hydrocarbon reforming catalyst of the present invention is preferably a porous carrier, particularly preferably a porous inorganic oxide. Such materials include, for example, silica, alumina, silica-alumina, titania, zirconia, magnesia, zinc oxide, clay, clay and diatomaceous earth. These may be used alone or in combination of two or more. Among them, α-alumina is particularly preferred in view of the crushing strength of the catalyst. As a metal component supported on these carriers, a ruthenium component is essential. In the present invention,
This ruthenium component is present on the outer surface side, but
As the total ruthenium component, 0.05 to 5% by weight of metal ruthenium is preferably supported on the carrier. If the content of ruthenium is less than 0.05% by weight, the effect as an active ingredient is not sufficient, and if it exceeds 5% by weight, the effect corresponding to the increase in the supported amount cannot be obtained, which is uneconomical. From this point, the supported amount of the ruthenium component on the carrier is:
0.05 to 2% by weight in metal ruthenium conversion, especially 0.1 to 2%
More preferably, it is% by weight.
【０００８】本発明においては、活性を高め、耐熱性を
向上させるなどの点から上記ルテニウム成分に更にジル
コニウム成分を担持成分として含むことが好ましい。ジ
ルコニウム成分は、担体上にＺｒＯ2 換算で0.０５〜２
０重量％担持されることが好ましい。ジルコニウム成分
が0.０５重量％より少ない場合は、活性成分としての効
果が十分でなく、また２０重量％を超える場合は担持量
の増加に見合った効果が得られず不経済である。この点
から、担体上のジルコニウム成分の担持量は、ＺｒＯ2
換算で0.１〜１５重量％、特に1.０〜１５重量％である
ことが好ましい。また、本発明においては、高活性触媒
の実現、耐熱性の向上などの観点から上記ルテニウム成
分とジルコニウム成分に更にマグネシウム成分を担持成
分として含むことが好ましい。マグネシウム成分は、担
体上にＭｇＯ換算で0.５〜２０重量％担持されることが
好ましい。マグネシウム成分が0.５重量％より少ない場
合は、活性成分としての効果が十分でなく、また２０重
量％を超える場合は担持量の増加に見合った効果が得ら
れず不経済である。この点から、担体上のマグネシウム
成分の担持量は、ＭｇＯ換算で0.５〜１５重量％、特に
１〜１０重量％であることが更に好ましい。In the present invention, it is preferred that the above-mentioned ruthenium component further contains a zirconium component as a supporting component from the viewpoint of enhancing the activity and improving the heat resistance. The zirconium component is deposited on the support in an amount of 0.05 to 2 in terms of ZrO 2.
It is preferable that 0% by weight is supported. If the zirconium component is less than 0.05% by weight, the effect as the active ingredient is not sufficient, and if it exceeds 20% by weight, the effect corresponding to the increase in the supported amount cannot be obtained, which is uneconomical. From this point, the loading amount of the zirconium component on the carrier is ZrO 2
It is preferably 0.1 to 15% by weight, particularly preferably 1.0 to 15% by weight. Further, in the present invention, from the viewpoint of realizing a highly active catalyst and improving heat resistance, it is preferable that the ruthenium component and the zirconium component further include a magnesium component as a supporting component. The magnesium component is preferably supported on the carrier in an amount of 0.5 to 20% by weight in terms of MgO. When the magnesium component is less than 0.5% by weight, the effect as an active ingredient is not sufficient, and when it exceeds 20% by weight, the effect corresponding to the increase in the supported amount cannot be obtained, which is uneconomical. From this point, the loading amount of the magnesium component on the carrier is more preferably 0.5 to 15% by weight, particularly preferably 1 to 10% by weight in terms of MgO.
【０００９】改質触媒中に含まれるマグネシウム成分と
ジルコニウム成分の割合は、Ｍｇ／Ｚｒモル比で、通常
0.０１〜１０、好ましくは0.０５〜５、更に好ましくは
0.１〜２である。上記モル比が0.０１より小さい場合
は、担持成分の耐熱性向上効果が不十分となる場合があ
る。またモル比が１０を超える場合は担持量の増加に見
合った効果が得られず不経済である。本発明の改質触媒
においては、上記担持金属成分として、ルテニウム成
分、ジルコニウム成分及びマグネシウム成分に加えて、
触媒活性を高めるためコバルト成分を担持させることが
好ましい。このコバルト成分の担持量は、コバルト原子
（Ｃｏ）とルテニウム原子（Ｒｕ）の原子比（Ｃｏ／Ｒ
ｕ）で0.０１〜３０となる量とすることが好ましい。上
記原子比が0.０１より小さい場合は、活性向上効果が十
分に得られない場合がある。また、この原子比が３０を
こえる場合は、相対的にルテニウムの量が減少し、改質
触媒として高い活性を保持することが困難となる場合が
ある。この点から、上記原子比（Ｃｏ／Ｒｕ）は0.１〜
３０、特に0.１〜１０であることが好ましい。本発明に
おいては、担持金属成分として、更に本発明の目的を阻
害しない範囲でその他の希土類元素成分などを担持する
こともできる。The ratio between the magnesium component and the zirconium component contained in the reforming catalyst is usually expressed by a molar ratio Mg / Zr.
0.01-10, preferably 0.05-5, more preferably
0.1 and 2. If the above molar ratio is less than 0.01, the effect of improving the heat resistance of the loaded component may be insufficient. On the other hand, if the molar ratio exceeds 10, the effect corresponding to the increase in the supported amount cannot be obtained, which is uneconomical. In the reforming catalyst of the present invention, in addition to the ruthenium component, the zirconium component and the magnesium component as the supported metal component,
It is preferable to carry a cobalt component to increase the catalytic activity. The supported amount of the cobalt component is determined by the atomic ratio (Co / R) of the cobalt atom (Co) and the ruthenium atom (Ru).
It is preferable that the amount is 0.01 to 30 in u). If the above atomic ratio is less than 0.01, the activity improving effect may not be sufficiently obtained. When the atomic ratio exceeds 30, the amount of ruthenium relatively decreases, and it may be difficult to maintain high activity as a reforming catalyst. From this point, the atomic ratio (Co / Ru) is 0.1 to
It is preferably 30 and particularly preferably 0.1 to 10. In the present invention, as the supported metal component, other rare earth element components and the like can be further supported as long as the object of the present invention is not impaired.
【００１０】担体への金属成分の担持方法としては、例
えば、担体に、少なくとも１種又は２種以上のルテニウ
ム化合物と、必要に応じ、１種又は２種以上のジルコニ
ウム化合物と、１種又は２種以上のマグネシウム化合物
と、さらに必要に応じ１種又は２種以上のコバルト化合
物とを溶解含有する溶液を接触含浸させることによって
担持させることができる。特に、担体の吸水量以下の量
の含浸液を、該担体に含浸させ、含浸後直ちに乾燥する
ことによって、本発明のルテニウム成分を外表面側に偏
在せしめることができる。このような方法によって、そ
の担体の表面近傍にルテニウム成分と、必要に応じジル
コニウム成分、マグネシウム成分、コバルト成分等を良
好な分散性で、かつむらのない状態で担持することがで
き、また、その後、通常行なわれるような高温での焼成
や還元等の前処理を行なっても、そのルテニウム成分と
酸化ジルコニウム等との高分散状態を十分安定に維持す
ることができ、高性能担持ルテニウム系触媒を容易に得
ることができる。As a method for supporting the metal component on the carrier, for example, at least one or two or more ruthenium compounds, and if necessary, one or more zirconium compounds, The support can be carried out by contacting and impregnating a solution containing at least one kind of magnesium compound and, if necessary, one or more kinds of cobalt compounds. In particular, by impregnating the carrier with an impregnating liquid having an amount equal to or less than the water absorption of the carrier and drying immediately after the impregnation, the ruthenium component of the present invention can be localized on the outer surface side. By such a method, a ruthenium component and, if necessary, a zirconium component, a magnesium component, a cobalt component, and the like can be supported in the vicinity of the surface of the carrier with good dispersibility and in an even state, and thereafter, Even if a pretreatment such as firing or reduction at a high temperature is performed as usual, a highly dispersed state of the ruthenium component and zirconium oxide can be maintained sufficiently stably, and a high-performance supported ruthenium-based catalyst can be obtained. Can be easily obtained.
【００１１】この担持に用いる溶液は、ルテニウム化合
物、必要に応じ、ジルコニウム化合物、マグネシウム化
合物、コバルト化合物を含有しているが、酸性、好まし
くはｐＨが３以下、さらに好ましくはｐＨ１．５以下に
調整することが好ましい。ｐＨが３を超えるとそれぞれ
の化合物が沈殿したり、ゲル状に凝集したりする傾向が
あるため、高分散担持がしにくくなる。ｐＨが３以下で
あると、ルテニウム化合物とジルコニウム化合物等とが
互いに反応し、錯体様の化合物を形成することによって
優れた特性を発揮するものと考えられる。この担持に用
いる溶液の溶媒としては、例えば、水又は水を主成分と
する水系溶媒やアルコール、エーテル等の有機溶媒であ
って、少なくとも、ルテニウム化合物、必要に応じて用
いられるジルコニウム化合物、マグネシウム化合物、コ
バルト化合物が溶解されるようなものであれば特に制限
はない。中でも、溶解性の高い水又は水を主成分とする
水系溶媒を好適に用いることができる。The solution used for the loading contains a ruthenium compound and, if necessary, a zirconium compound, a magnesium compound and a cobalt compound, and is adjusted to acidic, preferably pH 3 or less, more preferably pH 1.5 or less. Is preferred. When the pH exceeds 3, the respective compounds tend to precipitate or agglomerate in a gel state, so that it is difficult to carry out high dispersion loading. If the pH is 3 or less, it is considered that the ruthenium compound and the zirconium compound react with each other to form a complex-like compound, thereby exhibiting excellent properties. As a solvent of the solution used for this support, for example, water or an aqueous solvent containing water as a main component or an alcohol, an organic solvent such as ether, at least a ruthenium compound, a zirconium compound used as necessary, a magnesium compound There is no particular limitation as long as the cobalt compound is dissolved. Among them, highly soluble water or an aqueous solvent containing water as a main component can be preferably used.
【００１２】担持金属源としては、前記溶媒に溶解し得
るものであれば、その種類または形態について特に制限
はないが、たとえば下記のものを挙げることができる。
ルテニウム源として用いるルテニウム化合物としては、
例えば、三塩化ルテニウム等の各種のハロゲン化ルテニ
ウム、硝酸ルテニウム、ヘキサクロロルテニウム酸カリ
ウム等の各種のハロゲン化ルテニウム酸塩、テトラオク
ソルテニウム酸カリウム等の各種のルテニウム酸塩、四
酸化ルテニウム、ヘキサアンミンルテニウム三塩化物等
の各種のアンミン錯塩、ヘキサシアノルテニウム酸カリ
ウム等のシアノ錯塩などを挙げることができるが、これ
らに限定されるものではない。通常、一定の溶媒に溶解
性を示すものだけに限らず、酸や酸性化合物等の添加ま
たは共存によって十分に溶解できるものであれば、各種
のものが使用可能である。従って、例えば、三酸化二ル
テニウム等の酸化ルテニウムや水酸化ルテニウム、また
はオキシハロゲン化物などの、ｐＨが７付近の水には不
溶性または難溶性のものであっても、適宜塩酸等の酸を
添加し溶解して使用することができる。これら各種のル
テニウム化合物の中でも、工業的にも広く利用され、入
手が容易であることから、特に三塩化ルテニウムが好ま
しい。なお、これらのルテニウム化合物は、１種単独で
用いてもよいし、２種以上を併用してもよい。The type or form of the supported metal source is not particularly limited as long as it can be dissolved in the above-mentioned solvent, and examples thereof include the following.
Ruthenium compounds used as ruthenium sources include:
For example, various ruthenium halides such as ruthenium trichloride, various ruthenium halides such as ruthenium nitrate and potassium hexachlororuthenate, various ruthenates such as potassium tetraoxoruthenate, ruthenium tetroxide, ruthenium hexaammine Examples thereof include, but are not limited to, various ammine complex salts such as trichloride, and cyano complex salts such as potassium hexacyanoruthenate. In general, not only those showing solubility in a certain solvent but also various ones can be used as long as they can be sufficiently dissolved by addition or coexistence of an acid or an acidic compound. Therefore, for example, even if it is insoluble or hardly soluble in water having a pH of around 7, such as ruthenium oxide or ruthenium hydroxide such as diruthenium trioxide or an oxyhalide, an acid such as hydrochloric acid is appropriately added. Can be used after dissolution. Among these various ruthenium compounds, ruthenium trichloride is particularly preferable because it is widely used industrially and easily available. These ruthenium compounds may be used alone or in combination of two or more.
【００１３】ジルコニウム源として用いるジルコニウム
化合物についても同様に、一定の溶媒に溶解性を示すも
のや、塩酸等の酸や酸性化合物等を添加することによっ
て酸性とした溶媒中に溶解し、溶液となり得るものを使
用することができる。具体的には、例えば、四塩化ジル
コニウム等の各種のハロゲン化物またはこれらの部分加
水分解生成物，塩化ジルコニル（オキシ塩化ジルコニウ
ム）等の各種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，硝酸ジルコニル等の各種の酸素酸
塩、テトラオクソジルコニウム酸カリウム，ヘキサフル
オロジルコニウム酸ナトリウム等の各種のジルコニウム
酸塩、酢酸ジルコニウム，酢酸ジルコニル，蓚酸ジルコ
ニル，テトラオキサラトジルコニウム酸カリウム等の各
種の有機酸塩または有機系の配位化合物など、さらに
は、ジルコニウムのアルコキシド、水酸化物、各種の錯
塩などを挙げることができる。これら各種のジルコニウ
ム化合物のなかでも、特に、ジルコニウムのオキシ塩化
物が好ましく、例えば、ＺｒＯＣｌ2 ・ｎＨ2 ＯやＺｒ
Ｏ（ＯＨ）Ｃｌ・ｎＨ 2 Ｏで表される水和物や、溶液の
状態で市販されているものなどが、ルテニウムと錯体様
化合物を生成しやすいことから、好適に用いることがで
きる。なお、これらのジルコニウム化合物は、１種単独
で用いてもよいし２種以上を併用してもよい。Zirconium used as zirconium source
Similarly, compounds exhibit solubility in certain solvents.
By adding an acid such as hydrochloric acid or an acidic compound, etc.
Use a solution that can be dissolved in a solvent
Can be used. Specifically, for example,
Various halides such as conium and their partial additions
Water decomposition product, zirconyl chloride (zirconium oxychloride)
Various oxyhalides such as zirconyl sulfate,
Various oxygen acids such as zirconium nitrate and zirconyl nitrate
Salt, potassium tetraoxozirconate, hexaflur
Various zirconium such as sodium odisilconate
Acid salt, zirconium acetate, zirconyl acetate, zirconium oxalate
Nil, potassium tetraoxalatozirconate, etc.
Some organic acid salts or organic coordination compounds,
Are zirconium alkoxides, hydroxides and various complex
Salts and the like can be mentioned. These various zirconium
Oxychlorination of zirconium
Are preferred, for example, ZrOClTwo・ NHTwoO or Zr
O (OH) Cl.nH TwoHydrates represented by O
Such as those that are commercially available in a state like ruthenium and complex
Because it is easy to produce a compound, it can be suitably used.
Wear. In addition, these zirconium compounds may be used alone.
Or two or more of them may be used in combination.
【００１４】マグネシウム源として用いるマグネシウム
化合物についても、同様に、一定の溶媒に溶解性を示す
ものや、塩酸等の酸や酸性化合物等を添加することによ
って溶解し水溶液となりえるものを使用することができ
る。通常は溶解性の高い硝酸塩、塩化物等の化合物を好
適に用いることにができる。例えば、硝酸マグネシウ
ム、塩化マグネシウムなどを挙げることができる。これ
ら各種のマグネシウム化合物の中でも、硝酸マグネシウ
ム及びこれらの各種含水塩を特に好適に用いることがで
きる。なお、これらのマグネシウム化合物は、１種単独
で用いていもよいし２種以上を併用してもよい。コバル
ト源として用いるコバルト化合物としても、同様に、一
定の溶媒に溶解性を示すものや、塩酸等の酸や酸性化合
物等を添加することによってｐＨを調整することで溶解
することができる各種のものを使用することができる。
通常は溶解性の高い硝酸塩，塩化物等の化合物が好適に
用いられる。具体的には、硝酸第一コバルト、塩基性硝
酸コバルト、二塩化コバルト、これらの各種含水塩など
を挙げることができる。中でも、硝酸第一コバルト等が
特に好ましい。なお、これらのコバルト化合物は１種単
独で用いてもよいし２種以上を併用してもよい。Similarly, as for the magnesium compound used as a magnesium source, a magnesium compound which exhibits solubility in a certain solvent or a compound which can be dissolved by adding an acid such as hydrochloric acid or an acidic compound to form an aqueous solution can be used. it can. Usually, compounds such as nitrates and chlorides having high solubility can be suitably used. For example, magnesium nitrate, magnesium chloride and the like can be mentioned. Among these various magnesium compounds, magnesium nitrate and various hydrates thereof can be particularly preferably used. In addition, these magnesium compounds may be used individually by 1 type, and may use 2 or more types together. Similarly, as a cobalt compound used as a cobalt source, similarly, one that shows solubility in a certain solvent, or one that can be dissolved by adjusting the pH by adding an acid such as hydrochloric acid or an acidic compound, etc. Can be used.
Usually, highly soluble compounds such as nitrates and chlorides are preferably used. Specific examples include cobaltous nitrate, basic cobalt nitrate, cobalt dichloride, and various hydrates thereof. Among them, cobaltous nitrate and the like are particularly preferable. These cobalt compounds may be used alone or in combination of two or more.
【００１５】上記溶媒、ルテニウム化合物、ジルコニウ
ム化合物、マグネシウム化合物、コバルト化合物、酸等
の各成分の添加、混合、溶解の順序及び方法については
特に制限はないが、例えば、溶媒又は予め酸を添加して
酸性溶液に所定の成分を同時添加して溶解させてもよい
し、段階的に添加して溶解させてもよい。また、各成分
の溶液を別途に調製し、これらの溶液を混合させてもよ
いし、一部の成分の溶液を調製した後にその溶液に残り
の成分を溶解させてもよい。また、この際液温は室温程
度が望ましいが、溶解を促進させるため、８０℃程度ま
で加温してもよい。なお、溶解性の向上及びｐＨの調整
のために必要に応じて添加する酸としては、例えば、塩
酸，硫酸，硝酸等の無機酸、酢酸，蓚酸等の有機酸など
各種のものを適宜選定して使用すればよい。上記溶液に
おいて、溶解含有させるルテニウム化合物とジルコニウ
ム化合物の割合は、ジルコニウム原子とルテニウム原子
のモル比（Ｚｒ／Ｒｕ）で１〜１００以下、好ましくは
１〜５０、さらに好ましくは２〜２０の範囲から選定す
る。このモル比（Ｚｒ／Ｒｕ）が１未満であるとジルコ
ニウムの割合が少なくなりすぎてルテニウムの一部が、
錯体様化合物になれないため凝集しやすくなり、その分
分散性の向上効果が少なくなり、ルテニウム成分をジル
コニウム成分の近傍に担持できなくなるおそれがある。
一方、このモル比（Ｚｒ／Ｒｕ）が１００を超えると、
それに見合った分散性等のさらなる改善効果が得られに
くく、場合によっては表面に露出するルテニウム成分の
量が低下したり、または多孔性担体本来の特性が大きく
変化し損なわれるなどの支障が生じるおそれがある。There are no particular restrictions on the order and method of addition, mixing and dissolution of the above components such as the above-mentioned solvent, ruthenium compound, zirconium compound, magnesium compound, cobalt compound and acid. A predetermined component may be added to and dissolved in the acidic solution at the same time, or may be added and dissolved step by step. Alternatively, a solution of each component may be separately prepared, and these solutions may be mixed. Alternatively, a solution of some components may be prepared, and then the remaining components may be dissolved in the solution. At this time, the liquid temperature is desirably about room temperature, but may be heated to about 80 ° C. to promote dissolution. Various acids such as inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid, and organic acids such as acetic acid and oxalic acid are appropriately selected as acids to be added as needed for improving solubility and adjusting pH. And use it. In the above solution, the ratio of the ruthenium compound to the zirconium compound to be dissolved and contained is in the range of 1 to 100 or less, preferably 1 to 50, more preferably 2 to 20 in terms of the molar ratio of zirconium atom to ruthenium atom (Zr / Ru). Select. When the molar ratio (Zr / Ru) is less than 1, the proportion of zirconium becomes too small, and a part of ruthenium becomes
Since the compound does not become a complex-like compound, the compound tends to aggregate, the effect of improving dispersibility is reduced, and the ruthenium component may not be supported near the zirconium component.
On the other hand, when this molar ratio (Zr / Ru) exceeds 100,
It is difficult to obtain a further improvement effect such as dispersibility corresponding thereto, and in some cases, a problem may occur such that the amount of the ruthenium component exposed on the surface is reduced, or the original characteristics of the porous carrier are largely changed and damaged. There is.
【００１６】上記溶液に必要に応じて溶解含有させるマ
グネシウム化合物の量は、マグネシウム原子とジルコニ
ウム化合物のジルコニウム原子とのモル比（Ｍｇ／Ｚ
ｒ）で、通常０．０１〜１０、好ましくは０．０５〜
５、さらに好ましくは０．１〜２の範囲から選定する。
このモル比（Ｍｇ／Ｚｒ）が０．０１未満であるとアル
カリ土類金属及び希土類元素の割合が少なくため、担持
成分の表面積低下の抑制効果や、耐熱性の向上効果が不
十分となることがある。一方、このモル比（Ｍｇ／Ｚ
ｒ）が１０を超えると、それに見合った耐熱性の向上効
果を得ることが困難である。上記溶液中に溶解せしめる
各化合物の量（濃度）は、ルテニウム化合物の濃度がル
テニウム原子のモル濃度として、通常、０．００１モル
／リットル以上、好ましくは０．００５〜１００モル／
リットル、さらに好ましくは０．０１〜１０ル／リット
ルとなるように選定する。The amount of the magnesium compound dissolved and contained in the above-mentioned solution as required depends on the molar ratio of the magnesium atom to the zirconium atom of the zirconium compound (Mg / Z
r) is usually 0.01 to 10, preferably 0.05 to
5, more preferably from the range of 0.1 to 2.
When the molar ratio (Mg / Zr) is less than 0.01, the ratio of the alkaline earth metal and the rare earth element is small, so that the effect of suppressing the decrease in the surface area of the supported component and the effect of improving the heat resistance become insufficient. There is. On the other hand, this molar ratio (Mg / Z
When r) exceeds 10, it is difficult to obtain a corresponding effect of improving heat resistance. The amount (concentration) of each compound to be dissolved in the above solution is such that the concentration of the ruthenium compound is usually 0.001 mol / L or more, preferably 0.005 to 100 mol / L, as the molar concentration of ruthenium atoms.
Liter, more preferably 0.01 to 10 l / liter.
【００１７】なお、上記溶液には、本発明の目的を阻害
しない範囲で、必須化合物としてのルテニウム化合物、
また必要に応じて添加されるジルコニウム化合物、マグ
ネシウム化合物、コバルト化合物、溶解性調整用成分お
よびその他の成分を適宜添加してもよい。上記溶液に必
要に応じて溶解含有させるコバルト化合物の量は、コバ
ルト原子とルテニウム原子とのモル比（Ｃｏ／Ｒｕ）
が、通常０．０１〜３０、好ましくは０．１〜３０、さ
らに好ましくは０．１〜１０となるような量である。こ
のモル比（Ｃｏ／Ｒｕ）が０．０１未満であるとコバル
トの割合が少なくなり、それら成分による活性向上の効
果が期待する程に得られないことがある。一方、このモ
ル比（Ｃｏ／Ｒｕ）が３０を超えると相対的にルテニウ
ムの量が少なくなり、ルテニウム含有の炭化水素の水蒸
気改質触媒としての高い活性を保持することが困難であ
る。The above solution contains a ruthenium compound as an essential compound as long as the object of the present invention is not impaired.
Further, a zirconium compound, a magnesium compound, a cobalt compound, a component for adjusting the solubility and other components which are added as necessary may be appropriately added. The amount of the cobalt compound to be dissolved and contained in the above solution as required is determined by the molar ratio of cobalt atom to ruthenium atom (Co / Ru).
Is usually 0.01 to 30, preferably 0.1 to 30, and more preferably 0.1 to 10. If the molar ratio (Co / Ru) is less than 0.01, the proportion of cobalt becomes small, and the effect of improving the activity by these components may not be obtained as expected. On the other hand, if the molar ratio (Co / Ru) exceeds 30, the amount of ruthenium becomes relatively small, and it is difficult to maintain high activity of the ruthenium-containing hydrocarbon as a steam reforming catalyst.
【００１８】上記のように調製した溶液と担体の接触に
よる含浸担持操作は、常法に従って行うことができ、例
えば、各種の含浸法（加熱含浸法、常温含浸法、真空含
浸法、常圧含浸法、含浸乾固法、ポアフィリング法等、
またはこれらの任意の組合せ等）、浸漬法、軽度浸潤
法、湿式吸着法、スプレー法、塗布法など、またはこれ
らの組合せなどを挙げることができ、溶液と担体とを接
触させて担持させる方法であればどのような方式であっ
てもよい。また本発明においては、この含浸担持，乾
燥，焼成の一連の操作を、少なくとも１回は行うことが
必要だが、さらに必要に応じて、これらの操作を複数回
繰り返してもよい。ここで、用いる担体と溶液の量比
は、目標とする活性金属成分の担持率、用いる水溶液中
の金属化合物の濃度、含浸担持操作方法の種類、用いる
α−アルミナ多孔体の細孔容積や比表面積等に応じて、
適宜定めることができる。接触操作の温度は特に制限は
なく、室温または室温付近でも行うことができるし、必
要に応じて加熱または加温し、例えば室温〜８０℃程度
の温度でも好適に行うことができる。上記溶液と担体と
の接触後の乾燥は、特に制限されないが、通常、５０〜
１５０℃、好ましくは１００〜１２０℃の範囲で１時間
以上行う。室温での風乾では、１昼夜（２４時間）程度
行う。ただし、含浸担持方式によっては、多くの水分が
蒸発し、かなりの乾燥状態のものが得られるので、その
ような場合には、必ずしも別途乾燥操作を施さなくても
よい。The impregnation-supporting operation by contacting the solution prepared as described above with a carrier can be carried out according to a conventional method, and includes, for example, various impregnation methods (heating impregnation method, ordinary temperature impregnation method, vacuum impregnation method, ordinary pressure impregnation method). Method, impregnation drying method, pore filling method, etc.
Or any combination thereof), immersion method, mild infiltration method, wet adsorption method, spray method, coating method, and the like, or a combination thereof, and the like. Any method may be used. Further, in the present invention, it is necessary to perform at least once a series of operations of the impregnation-supporting, drying, and firing, but if necessary, these operations may be repeated a plurality of times. Here, the amount ratio of the carrier and the solution to be used is the target loading ratio of the active metal component, the concentration of the metal compound in the aqueous solution to be used, the type of the impregnation and loading operation method, the pore volume and the ratio of the α-alumina porous material to be used. Depending on the surface area, etc.
It can be determined as appropriate. The temperature of the contact operation is not particularly limited, and the contact operation can be performed at room temperature or near room temperature, and can be suitably performed at a temperature of room temperature to about 80 ° C. by heating or heating as necessary. Drying after the contact between the solution and the carrier is not particularly limited, but is usually 50 to 50.
The heating is performed at 150 ° C, preferably 100 to 120 ° C for 1 hour or more. Air-drying at room temperature is performed for about 24 hours a day. However, depending on the impregnation-supporting method, a large amount of water evaporates and a considerably dry state is obtained. In such a case, a separate drying operation is not necessarily required.
【００１９】焼成は特に行わなくてもよいが、行う場合
は、通常は空気中または空気気流中で、４００〜８００
℃、好ましくは４５０〜８００℃、さらに好ましくは４
５０〜６００℃の温度範囲で実施する。なお、空気の他
に、純酸素や酸素富化空気などの酸素含有ガスを代用し
たり併用してもよい。焼成時間は、通常、１〜２４時間
程度で十分である。この焼成によって得られる触媒中の
ルテニウム成分、必要に応じて用いられるジルコニウム
成分、マグネシウム成分、コバルト成分は、通常酸化物
または複合酸化物の形態で各々の成分の近傍に高分散状
態で担持される。こうして得た触媒は、そのまま、所定
の触媒反応の触媒として利用することもできるが、必要
に応じて、種々の適当な前処理を行って活性化してから
触媒反応に用いてもよい。この前処理は、常法に従って
行うことができ、例えば水素等の還元剤によって適度に
還元して、ルテニウム成分を高分散状態の金属状ルテニ
ウムにして反応に供してもよい。なお、この水素還元に
よる分散金属化処理は、例えば、３００〜８５０℃で水
素の消費が認められなくなるまで還元することが好まし
い。The sintering need not be carried out, but when it is carried out, it is usually carried out in the air or in an air stream at 400 to 800.
° C, preferably 450-800 ° C, more preferably 4 ° C
The test is performed in a temperature range of 50 to 600 ° C. In addition, oxygen-containing gas such as pure oxygen or oxygen-enriched air may be used in place of or in combination with air. Usually, a firing time of about 1 to 24 hours is sufficient. The ruthenium component, the zirconium component, the magnesium component, and the cobalt component used as needed in the catalyst obtained by this calcination are usually supported in a highly dispersed state near each component in the form of an oxide or a composite oxide. . The catalyst thus obtained can be used as it is as a catalyst for a predetermined catalytic reaction. However, if necessary, the catalyst may be activated by performing various appropriate pretreatments and then used in the catalytic reaction. This pretreatment can be carried out according to a conventional method. For example, the ruthenium component may be appropriately reduced with a reducing agent such as hydrogen to convert the ruthenium component into a highly dispersed metallic ruthenium, which may be used for the reaction. In the dispersion metallization treatment by hydrogen reduction, for example, reduction is preferably performed at 300 to 850 ° C. until consumption of hydrogen is not recognized.
【００２０】以下、本発明のルテニウム系触媒を用い
て、炭化水素の水蒸気改質反応を行う場合について説明
する。この反応に用いられる原料炭化水素としては、例
えば、メタン，エタン，プロパン，ブタン，ペンタン，
ヘキサン，ヘプタン，オクタン，ノナン，デカン等の炭
素数が１〜１６程度の直鎖状または分岐状の飽和脂肪族
炭化水素、シクロヘキサン，メチルシクロヘキサン，シ
クロオクタン等の脂環族飽和炭化水素、単環及び多環芳
香族炭化水素、沸点範囲が３００℃以下の都市ガス，Ｌ
ＰＧ，ナフサ，灯油等の各種の炭化水素を挙げることが
できる。Hereinafter, a case in which a steam reforming reaction of a hydrocarbon is performed using the ruthenium-based catalyst of the present invention will be described. As the raw material hydrocarbon used in this reaction, for example, methane, ethane, propane, butane, pentane,
Linear or branched saturated aliphatic hydrocarbons having about 1 to 16 carbon atoms, such as hexane, heptane, octane, nonane, and decane; alicyclic saturated hydrocarbons such as cyclohexane, methylcyclohexane, and cyclooctane; And polycyclic aromatic hydrocarbons, city gas having a boiling point range of 300 ° C. or less, L
Various hydrocarbons such as PG, naphtha, kerosene and the like can be mentioned.
【００２１】また一般に、これらの原料炭化水素中に硫
黄分が存在する場合は、脱硫工程を通して、通常、硫黄
分が0.１ｐｐｍ程度以下になるまで脱硫を行うことが好
ましい。原料炭化水素中の硫黄分が0.１ｐｐｍ程度より
多くなると、改質触媒が失活する原因となることがあ
る。脱硫方法は特に限定されないが、水添脱硫，吸着脱
硫などを適宜用いることができる。なお、炭化水素と反
応させる水蒸気としては特に制限はない。炭化水素と水
蒸気とを反応させる場合、通常、スチーム／カーボン比
が１．５〜１０、好ましくは１．５〜５、さらに好まし
くは２〜４となるように炭化水素量と水蒸気量とを決定
することが好ましい。このようなスチーム／カーボン比
とすることにより、水素含有量の多い生成ガスを効率よ
く得ることができる。反応温度は、通常、２００〜９０
０℃、好ましくは２５０〜９００℃、さらに好ましくは
３００〜８００℃である。反応圧力は、通常、０〜３Ｍ
Ｐａ・Ｇ、好ましくは０〜１ＭＰａ・Ｇである。この場
合、水蒸気改質触媒層の入口温度を６３０℃以下、さら
には６００℃以下に保って水蒸気改質を行うのが好まし
い。入口温度が６３０℃を超えると石油系炭化水素の熱
分解が促進され、生成したラジカル経由で触媒あるいは
反応管壁に炭素が析出して、運転が困難になる場合があ
る。なお、触媒層出口温度は特に制限はないが、６５０
〜８００℃の範囲が好ましい。触媒層出口温度が６５０
℃未満では水素の生成量が充分ではないおそれがあり、
８００℃を超えると反応装置は耐熱材料を必要とする場
合があり、経済的に好ましくない。In general, when sulfur is present in these raw hydrocarbons, desulfurization is preferably performed through the desulfurization step until the sulfur content is reduced to about 0.1 ppm or less. When the sulfur content in the raw material hydrocarbon is more than about 0.1 ppm, it may cause the deactivation of the reforming catalyst. Although the desulfurization method is not particularly limited, hydrodesulfurization, adsorption desulfurization and the like can be used as appropriate. The steam to be reacted with the hydrocarbon is not particularly limited. When reacting a hydrocarbon with water vapor, the amount of hydrocarbon and the amount of water vapor are usually determined so that the steam / carbon ratio becomes 1.5 to 10, preferably 1.5 to 5, and more preferably 2 to 4. Is preferred. With such a steam / carbon ratio, a product gas having a high hydrogen content can be efficiently obtained. The reaction temperature is usually 200 to 90
0 ° C, preferably 250-900 ° C, more preferably 300-800 ° C. Reaction pressure is usually 0-3M
Pa · G, preferably 0 to 1 MPa · G. In this case, it is preferable to perform steam reforming while maintaining the inlet temperature of the steam reforming catalyst layer at 630 ° C. or lower, and more preferably at 600 ° C. or lower. If the inlet temperature exceeds 630 ° C., thermal decomposition of petroleum hydrocarbons is promoted, and carbon is deposited on the catalyst or the reaction tube wall via generated radicals, which may make operation difficult. The catalyst layer outlet temperature is not particularly limited, but is 650
The range of -800 ° C is preferred. The catalyst layer outlet temperature is 650
If the temperature is lower than ℃, there is a possibility that the amount of generated hydrogen is not sufficient,
If the temperature exceeds 800 ° C., the reactor may require a heat-resistant material, which is not economically preferable.
【００２２】反応方式としては、連続流通式，回分式等
のいずれの方式であってもよいが、連続流通式が好まし
い。連続流通式を採用する場合、炭化水素及び水蒸気の
混合ガスの空間速度（ＧＨＳＶ）は、通常、１，０００
〜１００，０００ｈ-1、好ましくは２，０００〜５０，
０００ｈ-1、さらに好ましくは２，０００〜４０，００
０ｈ-1である。反応形式としては、特に制限はなく、固
定床式，移動床式，流動床式などを挙げることができ
る。反応器の形式としても特に制限はなく、例えば管型
反応器等を用いることができる。上記のような条件下で
本発明の触媒を用いて炭化水素と水蒸気とを反応させる
ことにより水素を含む混合物を得ることができ、燃料電
池の水素製造プロセスに好適に採用される。The reaction system may be any of a continuous flow system and a batch system, but the continuous flow system is preferred. When a continuous flow system is adopted, the space velocity (GHSV) of a mixed gas of hydrocarbon and steam is usually 1,000
１００100,000 h −1 , preferably 2,000 to 50,
000 h -1 , more preferably 2,000 to 40,00
0h -1 . The reaction system is not particularly limited, and examples thereof include a fixed bed system, a moving bed system, and a fluidized bed system. The type of the reactor is not particularly limited, and for example, a tubular reactor or the like can be used. By reacting a hydrocarbon with steam using the catalyst of the present invention under the above conditions, a mixture containing hydrogen can be obtained, which is suitably employed in a hydrogen production process of a fuel cell.
【００２３】本発明の改質用触媒は、部分酸化により水
素を製造する場合に使用しても効率的に水素を製造する
ことができる。部分酸化反応の反応式は下記のように表
される。 Ｃn Ｈm ＋ｎＯ2 → ｎＣＯ2 ＋（ｍ／２）Ｈ2 （上式中、Ｃn Ｈm は炭化水素の平均構造を示す。）本
発明の改質用触媒下、反応圧力を常圧〜５ＭＰａ，反応
温度を４００〜１，１００℃、酸素（Ｏ2 ）／カ−ボン
比を０．２〜０．８，ＬＨＳＶを０．１〜１００ｈ
-1（ガス状炭化水素の場合は、ＧＨＳＶを１０００〜１
０００００ｈ-1）として、この条件下で改質反応を行
う。また、スチ−ム添加する場合は、Ｓ／Ｃ比０．４〜
４で行うことが好ましい。上記Ｏ2 は、通常空気として
導入する。また、Ｏ2 導入量が多いと、Ｃn Ｈmは完全
にＣＯ2 とＨ2 Ｏとなる完全酸化反応が生ずるため好ま
しくない。なお、上記反応にはＨ2 Ｏが共存しても良
い。この部分酸化による改質方法も燃料電池用の水素製
造法として好適である。The reforming catalyst of the present invention can efficiently produce hydrogen even when used in producing hydrogen by partial oxidation. The reaction formula of the partial oxidation reaction is represented as follows. C n H m + nO 2 → nCO 2 + (m / 2) H ( In the formula, C n H m in. Shows the average structure of the hydrocarbon) 2 catalyst under reforming of the present invention, the reaction pressure atmospheric pressure -5 MPa, reaction temperature 400-1100 ° C., oxygen (O 2 ) / carbon ratio 0.2-0.8, LHSV 0.1-100 h
-1 (for gaseous hydrocarbons, GHSV is 1000-1
00000 h −1 ), and the reforming reaction is performed under these conditions. When steam is added, the S / C ratio should be 0.4 to less.
It is preferable to carry out in step 4. The O 2 is usually introduced as air. On the other hand, if the amount of O 2 introduced is large, C n H m is not preferable because a complete oxidation reaction of completely converting CO 2 and H 2 O occurs. Note that H 2 O may coexist in the above reaction. This reforming method by partial oxidation is also suitable as a method for producing hydrogen for a fuel cell.
【００２４】また、本発明の改質用触媒は、オートサー
マルリフォーミングにより水素を製造する場合に使用し
ても効率的に水素を製造できる。オートサーマルリフォ
ーミングとは、炭化水素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改質することに
より、反応熱のバランスをとりながら水素を製造する方
法である。リフォーミングガスとしては、例えば、酸
素、スチーム、炭酸ガス等が使用され、炭化水素とリフ
ォーミングガスの割合は反応システムの熱バランス、目
標とする反応率等を勘案し適宜選択することができる。
実際は、原料を完全に改質するために化学量論比より過
剰のリフォーミングガスを導入することが好ましく、通
常、スチーム／カーボン比（水分子の数／原料中の炭素
原子の数の比）で0.１〜１０、更に0.４〜４であること
が好ましい。同様に酸素／カーボン比（酸素分子の数／
原料中の炭素原子の数の比）は0.１〜１、更に0.２〜0.
８であることが好ましい。更に、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／原料中の炭素原子の数の比）は0.１〜
５、更に0.１〜３であることが好ましい。Further, the reforming catalyst of the present invention can efficiently produce hydrogen even when used for producing hydrogen by autothermal reforming. Autothermal reforming is a method for producing hydrogen while balancing the heat of reaction by partially oxidizing a hydrocarbon raw material with oxygen and reforming the raw material with a reforming gas such as steam. As the reforming gas, for example, oxygen, steam, carbon dioxide gas, or the like is used, and the ratio between the hydrocarbon and the reforming gas can be appropriately selected in consideration of the heat balance of the reaction system, the target reaction rate, and the like.
In practice, it is preferable to introduce a reforming gas in excess of the stoichiometric ratio in order to completely reform the raw material, and usually the steam / carbon ratio (the ratio of the number of water molecules / the number of carbon atoms in the raw material) Is preferably from 0.1 to 10, more preferably from 0.4 to 4. Similarly, the oxygen / carbon ratio (number of oxygen molecules /
Ratio of the number of carbon atoms in the raw material) is 0.1 to 1, more preferably 0.2 to 0.2.
8 is preferable. Further, when carbon dioxide 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 0.1.
5, more preferably 0.1 to 3.
【００２５】反応形式は特に制限はなく、固定床式、移
動床式、流動床式などの方式がいずれも使用できるが、
通常、固定床式反応器が用いられる。反応温度として
は、酸素とスチームのみで反応させる場合は２００〜１
２００℃、更に４００〜１１００℃であり、特に５００
〜９００℃の範囲が好ましい。炭酸ガスを加えて反応さ
せる場合は、２００〜１３００℃、更に４００〜１２０
０℃であり、特に６００〜１１００℃の範囲が好まし
い。 反応圧力は特に限定されないが、燃料電池用水素
の製造を目的とする場合は０〜５ＭＰａ・Ｇ、更に０〜
１ＭＰａ・Ｇの範囲が好ましい。また、原料油の質量空
間速度（ＷＨＳＶ）は0.０５〜１００ｈ-1、好ましくは
0.１〜１０ｈ-1である。The reaction system is not particularly limited, and any system such as a fixed bed system, a moving bed system and a fluidized bed system can be used.
Usually, a fixed bed reactor is used. The reaction temperature is 200 to 1 when reacting only with oxygen and steam.
200 ° C., further 400 to 1100 ° C., especially 500
The range of -900 ° C is preferred. When reacting by adding carbon dioxide gas, 200 to 1300 ° C., and further 400 to 120
0 ° C., and particularly preferably in the range of 600 to 1100 ° C. The reaction pressure is not particularly limited. However, when the purpose is to produce hydrogen for a fuel cell, the reaction pressure is 0 to 5 MPa · G, and 0 to 5 MPa · G.
A range of 1 MPa · G is preferred. The mass hourly space velocity (WHSV) of the feedstock is 0.05 to 100 h -1 , preferably
0.1 to 10 h -1 .
【００２６】[0026]
【実施例】次に、本発明を実施例により、さらに具体的
に説明するが、本発明は、これらの例によってなんら限
定されるものではない。なお、各例で得られた改質触媒
の改質反応の活性（Ｃ１転化率）及びＳの値は、下記の
方法により測定・評価した。 ＜Ｃ１転化率の測定＞各触媒1.５ｃｃを内径２０ｍｍの
石英反応管に充填した。反応管内で触媒を水素気流中
で、６００℃で１時間水素による還元処理を行なった
後、硫黄濃度0.１重量ｐｐｍ以下まで脱硫した市販のＪ
ＩＳ１号灯油を原料油として用い、ＬＨＳＶ：6.５
ｈ-1、スチーム／カーボン比（Ｓ／Ｃ）＝２．０の条件
でＪＩＳ１号灯油及び水蒸気を導入し、６５０℃で水蒸
気改質反応を実施した。得られたガスをサンプリングし
てガスクロマトグラフィーにてその濃度を測定した。こ
の結果をもとに、プロパンの転化率を下式により求め
た。結果を第１表に示す。EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. The activity (C1 conversion) of the reforming reaction and the value of S of the reforming catalyst obtained in each example were measured and evaluated by the following methods. <Measurement of C1 Conversion> 1.5 cc of each catalyst was filled in a quartz reaction tube having an inner diameter of 20 mm. After reducing the catalyst with hydrogen at 600 ° C. for 1 hour in a hydrogen stream in a reaction tube, commercially available J was desulfurized to a sulfur concentration of 0.1 wt ppm or less.
LHSV: 6.5 using IS1 kerosene as feedstock
JIS No. 1 kerosene and steam were introduced under the conditions of h −1 and steam / carbon ratio (S / C) = 2.0, and a steam reforming reaction was performed at 650 ° C. The obtained gas was sampled and its concentration was measured by gas chromatography. Based on this result, the conversion of propane was determined by the following equation. The results are shown in Table 1.
【００２７】Ｃ１転化率（％）＝（Ａ／Ｂ）×１００ 〔上記式において、Ａ＝ＣＯモル流量＋ＣＯ2 モル流量
＋ＣＨ4 モル流量（いずれも反応器出口における流
量）、Ｂ＝反応器入口側の灯油の炭素モル流量であ
る。〕 ＜Ｓの測定＞触媒の円柱底面と平行に切断した断面にお
いて、触媒表面からその半径の３分の１の距離までの外
周部分に含まれるＲｕ金属の量をエレクトロンプローブ
・マイクロアナライザー（ＥＰＭＡ）を用いて線分析し
て得た値Ｎとし、触媒全体に含まれるＲｕ金属の線分析
値をＮｏとした時のＳの値を、Ｓ＝（Ｎ／Ｎｏ）×１０
０の式から求めた。C1 conversion rate (%) = (A / B) × 100 [A = CO mole flow rate + CO 2 mole flow rate + CH 4 mole flow rate (both at the reactor outlet), B = reactor inlet Is the carbon molar flow rate of the side kerosene. <Measurement of S> In a cross section cut parallel to the bottom of the cylinder of the catalyst, the amount of Ru metal contained in the outer peripheral portion from the catalyst surface to a distance of one-third of its radius is measured by an electron probe microanalyzer (EPMA). And the value of S when the linear analysis value of Ru metal contained in the entire catalyst is No. S = (N / No) × 10
0 was obtained from the equation.
【００２８】実施例１ ３〜５μｍの粒子径を持つα−アルミナ粉体と水（粉体
の２０重量％）をニーダーを用いて混合した後、成形機
を用いて１4.７ＭＰａで圧縮成形し、直径３ｍｍ、高さ
３ｍｍの円柱成形体を得た。この成形体を焼成用のガス
炉の予熱を利用して乾燥し、１２８０℃のガス炉で２６
時間焼成して得られた成形体を触媒担体に供した。なお
この担体の細孔容積は、０．２６ｃｃ／ｇ、平均細孔径
は１．６μｍであった。一方、ジルコニウムのオキシ塩
化物（ＺｒＯ（ＯＨ）Ｃｌ）の水溶液（ＺｒＯ 2 として
３５％、第一稀元素工業社製：ＺＣ−２）３．５５ｇ
に、三塩化ルテニウム（ＲｕＣｌ3 ・ｎＨ2 Ｏ：Ｒｕ３
８％含有）０．３３ｇ、硝酸マグネシウム（Ｍｇ（ＮＯ
3 ）2 ・６Ｈ2 Ｏ）３．１８ｇ、及び硝酸コバルト（Ｃ
ｏ（ＮＯ3）3 ・６Ｈ2 Ｏ）2 ．１．２４ｇを溶解し、
溶液の総量を５ｃｃとした。この溶液を１時間以上スタ
ーラにて攪拌したものを含浸液とした。この時のｐＨは
０．５以下であった。この含浸液を、前記α−アルミナ
多孔体５０ｇに常圧含浸担持した。担持直後、１２０℃
の乾燥器内で１２時間乾燥を行ない改質触媒を得た。Example 1 α-alumina powder having a particle size of 3 to 5 μm and water (powder
Was mixed using a kneader.
Compression molded at 14.7MPa, 3mm in diameter, height
A 3 mm cylindrical molded body was obtained. A gas for firing this compact
It is dried using the preheating of the furnace.
The molded body obtained by firing for a time was provided as a catalyst carrier. Note that
The pore volume of this carrier is 0.26 cc / g, the average pore diameter
Was 1.6 μm. On the other hand, zirconium oxysalt
(ZrO (OH) Cl) aqueous solution (ZrO (OH) Cl) TwoAs
35%, 3.55 g, manufactured by Daiichi Rare Element Industry Co., Ltd .: ZC-2)
Ruthenium trichloride (RuClThree・ NHTwoO: Ru3
0.33 g of magnesium nitrate (containing 8%)
Three) 2.6HTwoO) 3.18 g, and cobalt nitrate (C
o (NOThree)Three・ 6HTwoO)Two. Dissolve 1.24 g,
The total amount of the solution was 5 cc. Stir this solution for at least one hour.
What was stirred with a stirrer was used as an impregnating liquid. The pH at this time is
0.5 or less. The impregnating liquid was treated with the α-alumina
Atmospheric pressure impregnation was carried on 50 g of the porous body. Immediately after loading, 120 ° C
Drying was performed in a dryer for 12 hours to obtain a reforming catalyst.
【００２９】実施例２ 実施例１において、含浸液をα−アルミナ多孔体５０ｇ
に含浸担持した後、１２０℃で乾燥を行う前に、３時間
室温放置した以外は実施例１と同様にして触媒を調製し
た。 実施例３ 実施例１において得られた触媒を更に５００℃で２時間
焼成した以外は実施例１と同様にして触媒を調製した。
結果を第１表に示す。 比較例１ 実施例１において、含浸液に７ｃｃのイオン交換水を加
え溶液の総量を１３ｃｃとし、α−アルミナ多孔体５０
ｇに常圧含浸担持する代わりに、α−アルミナ多孔体５
０ｇに真空含浸担持を行い、更に該真空含浸担持後、１
２０℃で乾燥を行う前に、３時間室温放置した以外は実
施例１と同様にして触媒を調製した。 比較例２ 比較例１において得られた触媒を更に５００℃で２時間
焼成した以外は比較例１と同様にして触媒を調製した。
結果を第１表に示す。Example 2 In Example 1, 50 g of the α-alumina porous material was used instead of the impregnating liquid.
After being impregnated and supported, a catalyst was prepared in the same manner as in Example 1 except that the catalyst was left at room temperature for 3 hours before drying at 120 ° C. Example 3 A catalyst was prepared in the same manner as in Example 1 except that the catalyst obtained in Example 1 was further calcined at 500 ° C. for 2 hours.
The results are shown in Table 1. Comparative Example 1 In Example 1, 7 cc of ion-exchanged water was added to the impregnating solution to make the total amount of the solution 13 cc, and the α-alumina porous material 50 was used.
g-alumina porous material 5
0 g was subjected to vacuum impregnation, and after the vacuum impregnation,
A catalyst was prepared in the same manner as in Example 1, except that the catalyst was left at room temperature for 3 hours before drying at 20 ° C. Comparative Example 2 A catalyst was prepared in the same manner as in Comparative Example 1, except that the catalyst obtained in Comparative Example 1 was further calcined at 500 ° C. for 2 hours.
The results are shown in Table 1.
【００３０】[0030]
【表１】 [Table 1]
【００３１】[0031]
【発明の効果】本発明により、担持ルテニウム当たりの
触媒活性が著しく優れ、かつ焼成や反応時の高温下にお
いてもその高活性を維持することができる炭化水素の改
質触媒、及び該改質触媒を用い燃料電池用水素を効率よ
く得ることのできる炭化水素の水蒸気改質方法、部分酸
化改質方法及びオートサーマルリフォーミング法を提供
することができる。Industrial Applicability According to the present invention, a hydrocarbon reforming catalyst which has remarkably excellent catalytic activity per supported ruthenium and can maintain its high activity even at a high temperature during calcination or reaction, and the reforming catalyst , A steam reforming method for hydrocarbons, a partial oxidation reforming method, and an autothermal reforming method capable of efficiently obtaining hydrogen for fuel cells.
【図１】本発明の改質用触媒の一例の断面図、及び幅方
向距離とＸ線強度の関係を示す図である。FIG. 1 is a cross-sectional view of an example of a reforming catalyst of the present invention and a diagram showing a relationship between a width direction distance and an X-ray intensity.
フロントページの続き Ｆターム(参考） 4G040 EA03 EA06 EA07 EC01 EC02 EC03 EC05 4G069 AA01 AA03 AA08 BA01A BA01B BC10A BC10B BC51A BC51B BC67A BC67B BC70A BC70B CC17 DA06 EA02X EC22X FA02 FB30 FC08 5H027 AA02 BA01 Continued on the front page F-term (reference) 4G040 EA03 EA06 EA07 EC01 EC02 EC03 EC05 4G069 AA01 AA03 AA08 BA01A BA01B BC10A BC10B BC51A BC51B BC67A BC67B BC70A BC70B CC17 DA06 EA02X EC22X FA02 FB30 FC02 5H01A
Claims (11)
してなる炭化水素の改質用触媒において、該触媒の断面
を、エレクトロンプローブ・マイクロアナリシス（ＥＰ
ＭＡ）装置を用いて、一方向にルテニウム原子について
線分析測定をして得られる断面幅方向距離ｒ（中心から
触媒表面までの距離）とＸ線強度Ｉとの関係を示す図に
おいて、上記ｒが一方の触媒表面−ｒ0 から他方の触媒
表面ｒ 0 の間におけるＩ（ｒ）の積分値Ｎ0 から、−２
／３ｒ0 から２／３ｒ0 の間におけるＩ（ｒ）の積分値
Ｎ1 を減じた値をＮとし、上記Ｎ0 に対するＮの割合Ｓ
＝（Ｎ／Ｎ0 ）×１００の値が５０以上であることを特
徴とする炭化水素の改質用触媒。1. A carrier that carries at least a ruthenium component
The cross section of the catalyst for reforming hydrocarbons
To Electron Probe Microanalysis (EP
MA) Using a device to determine the direction of ruthenium atoms in one direction
Cross-section width direction distance r obtained from line analysis measurement (from center
In the figure showing the relationship between the distance to the catalyst surface) and the X-ray intensity I
Where r is one of the catalyst surfaces -r0From the other catalyst
Surface r 0The integral value N of I (r) between0From -2
/ 3r0From 2 / 3r0Integral value of I (r) during
N1Is defined as N, and the above N0Of N to S
= (N / N0) × 100 is 50 or more.
A catalyst for hydrocarbon reforming.
項１記載の触媒。2. The catalyst according to claim 1, which has a spherical or cylindrical shape.
項１又は２に記載の触媒。3. The catalyst according to claim 1, wherein the support comprises porous α-alumina.
てなる請求項１〜３のいずれかに記載の触媒。4. The catalyst according to claim 1, wherein the support further supports a zirconium component.
請求項４記載の触媒。5. The catalyst according to claim 4, further comprising a magnesium component.
比で0.０１〜３０となるように担持してなる請求項１〜
５のいずれかに記載の触媒。6. The method according to claim 1, further comprising supporting a cobalt component in a Co / Ru atomic ratio of 0.01 to 30.
5. The catalyst according to any one of 5.
してなる炭化水素の改質用触媒の製造方法において、上
記担体の吸水量以下の量の含浸液を、該担体に含浸させ
ることを特徴とする改質用触媒の製造方法。7. A method for producing a hydrocarbon reforming catalyst comprising at least a ruthenium component supported on a carrier, characterized in that the carrier is impregnated with an impregnating liquid having an amount equal to or less than the water absorption of the carrier. A method for producing a reforming catalyst.
である請求項７記載の記載の製造方法。8. The method according to claim 7, wherein the carrier comprises porous α-alumina.
用いた炭化水素の水蒸気改質方法。9. A method for steam reforming a hydrocarbon using the catalyst according to claim 1. Description:
を用いた炭化水素の部分酸化改質方法。10. A method for partially oxidizing and reforming hydrocarbons using the catalyst according to claim 1. Description:
を用いた炭化水素のオートサーマルリフォーミング法。11. A method for autothermal reforming of hydrocarbons using the catalyst according to claim 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005224722A (en) * | 2004-02-13 | 2005-08-25 | Toda Kogyo Corp | Autothermal reforming catalyst, method for manufacturing the same and method for producing hydrogen by using the same |
| JP2005296938A (en) * | 2004-03-12 | 2005-10-27 | Cosmo Oil Co Ltd | Catalyst for producing hydrogen from hydrocarbon, producing method for the catalyst and hydrogen producing method using the catalyst |
| JP2006045049A (en) * | 2004-06-28 | 2006-02-16 | Osaka Gas Co Ltd | Method for producing synthesis gas |
| JP2007098385A (en) * | 2005-09-08 | 2007-04-19 | Cosmo Oil Co Ltd | Catalyst for producing hydrogen from hydrocarbon, production method for the catalyst and production method for hydrogen using the catalyst |
| JP2007098386A (en) * | 2005-09-08 | 2007-04-19 | Cosmo Oil Co Ltd | Catalyst for producing hydrogen from hydrocarbon, production method for the catalyst and production method for hydrogen using the catalyst |
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2000
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US7553794B2 (en) | 2002-12-20 | 2009-06-30 | Showa Denko K.K. | Heteropolyacid and or its salt supported catalyst, production process of the catalyst and production process of compound using the catalyst |
| JP2005224722A (en) * | 2004-02-13 | 2005-08-25 | Toda Kogyo Corp | Autothermal reforming catalyst, method for manufacturing the same and method for producing hydrogen by using the same |
| JP2005296938A (en) * | 2004-03-12 | 2005-10-27 | Cosmo Oil Co Ltd | Catalyst for producing hydrogen from hydrocarbon, producing method for the catalyst and hydrogen producing method using the catalyst |
| JP4494254B2 (en) * | 2004-03-12 | 2010-06-30 | コスモ石油株式会社 | Catalyst for producing hydrogen from hydrocarbon, method for producing the catalyst, and method for producing hydrogen using the catalyst |
| JP2006045049A (en) * | 2004-06-28 | 2006-02-16 | Osaka Gas Co Ltd | Method for producing synthesis gas |
| JP2007098385A (en) * | 2005-09-08 | 2007-04-19 | Cosmo Oil Co Ltd | Catalyst for producing hydrogen from hydrocarbon, production method for the catalyst and production method for hydrogen using the catalyst |
| JP2007098386A (en) * | 2005-09-08 | 2007-04-19 | Cosmo Oil Co Ltd | Catalyst for producing hydrogen from hydrocarbon, production method for the catalyst and production method for hydrogen using the catalyst |
| JP4647564B2 (en) * | 2005-09-08 | 2011-03-09 | コスモ石油株式会社 | Catalyst for producing hydrogen from hydrocarbon, method for producing the catalyst, and method for producing hydrogen using the catalyst |
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