JPH0929098A - Steam reforming catalyst of hydrocarbon - Google Patents
Steam reforming catalyst of hydrocarbonInfo
- Publication number
- JPH0929098A JPH0929098A JP7185183A JP18518395A JPH0929098A JP H0929098 A JPH0929098 A JP H0929098A JP 7185183 A JP7185183 A JP 7185183A JP 18518395 A JP18518395 A JP 18518395A JP H0929098 A JPH0929098 A JP H0929098A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- ruthenium
- compound
- zirconium
- component
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 23
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 23
- 238000000629 steam reforming Methods 0.000 title claims abstract description 23
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 14
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 36
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 34
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 22
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims description 45
- 230000000694 effects Effects 0.000 abstract description 26
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 239000000306 component Substances 0.000 description 57
- 239000000243 solution Substances 0.000 description 36
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 26
- 238000000034 method Methods 0.000 description 24
- 229910052761 rare earth metal Inorganic materials 0.000 description 18
- 150000003304 ruthenium compounds Chemical class 0.000 description 15
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 14
- 238000005470 impregnation Methods 0.000 description 13
- 239000001294 propane Substances 0.000 description 13
- 150000003755 zirconium compounds Chemical class 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 150000001342 alkaline earth metals Chemical class 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- -1 alkaline earth metal aluminate Chemical class 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 150000001869 cobalt compounds Chemical class 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 150000002816 nickel compounds Chemical class 0.000 description 4
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229910052712 strontium Inorganic materials 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process 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
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 3
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 2
- 229910052693 Europium Inorganic materials 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
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- 229910052775 Thulium Inorganic materials 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 150000003303 ruthenium Chemical class 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 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
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-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
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 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
- 229910052692 Dysprosium Inorganic materials 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
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000274 adsorptive 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
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- GBDZMMXUOBAJMN-UHFFFAOYSA-K azane;ruthenium(3+);trichloride Chemical compound N.N.N.N.N.N.[Cl-].[Cl-].[Cl-].[Ru+3] GBDZMMXUOBAJMN-UHFFFAOYSA-K 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- 230000008859 change Effects 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
- 229940045032 cobaltous nitrate Drugs 0.000 description 1
- 239000013078 crystal Substances 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
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 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
- KSYURTCLCUKLSF-UHFFFAOYSA-H disodium;hexafluorozirconium(2-) Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[Na+].[Na+].[Zr+4] KSYURTCLCUKLSF-UHFFFAOYSA-H 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 150000002663 lutetium compounds Chemical class 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 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
- 125000002950 monocyclic group Chemical group 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910017604 nitric acid Inorganic materials 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
- 229910000510 noble metal Inorganic materials 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
- 235000006408 oxalic acid Nutrition 0.000 description 1
- BBMRFTLCEAZQEQ-UHFFFAOYSA-N oxalic acid;oxozirconium Chemical compound [Zr]=O.OC(=O)C(O)=O BBMRFTLCEAZQEQ-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-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
- 239000008188 pellet Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 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
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 150000003600 thulium compounds Chemical class 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 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、炭化水素の水蒸気
改質用触媒に関し、詳しくは、ルテニウムを活性成分と
し、高活性で耐熱性に優れ、各種水素製造プロセス、特
に燃料電池に組込まれた水素製造プロセスに好適に適用
される炭化水素の水蒸気改質用触媒に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrocarbon steam reforming catalyst, and more particularly to a catalyst having ruthenium as an active ingredient, which has high activity and excellent heat resistance, and has been incorporated into various hydrogen production processes, particularly fuel cells. The present invention relates to a hydrocarbon steam reforming catalyst suitably applied to a hydrogen production process.
【０００２】[0002]
【従来の技術】ルテニウム成分を含有する炭化水素の水
蒸気改質用触媒は、高活性でかつ低スチーム／カーボン
比の運転条件下でも耐炭素析出性に優れるという優れた
触媒性能を示すことから、最近は、低スチーム／カーボ
ン比の運転条件下で長寿命の水蒸気改質用触媒を必要と
する燃料電池に広く用いられている。そのためには、高
活性で、耐熱性に優れた触媒の開発が要望されている。2. Description of the Prior Art A catalyst for steam reforming of hydrocarbons containing a ruthenium component exhibits excellent catalytic performance that is highly active and excellent in carbon deposition resistance even under operating conditions of low steam / carbon ratio. Recently, it has been widely used in fuel cells that require a long-life steam reforming catalyst under low steam / carbon ratio operating conditions. For that purpose, development of a catalyst having high activity and excellent heat resistance has been demanded.
【０００３】一方、ルテニウムは貴金属であるので、こ
れを含有する触媒は一般的に高価なものとなる。従っ
て、ルテニウム成分を含有する触媒の工業的な使用を普
及させるためには、触媒価格を低減させる必要がある。On the other hand, since ruthenium is a noble metal, the catalyst containing it is generally expensive. Therefore, in order to popularize the industrial use of the catalyst containing the ruthenium component, it is necessary to reduce the catalyst price.
【０００４】ルテニウム成分を含有する触媒に関して、
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用触媒が開示されてい
る。Regarding the catalyst containing the ruthenium component,
Japanese Unexamined Patent Publication (Kokai) No. 5-220397 discloses a hydrocarbon steam reforming catalyst in which aluminum oxide containing an alkaline earth metal aluminate is loaded with zirconium oxide having a zirconia sol as a precursor and a ruthenium component. .
【０００５】この触媒においては、ジルコニアゾル自体
１００オングストローム以上の粒子であることから、こ
れから生成した酸化ジルコニウムの粒子は大きく成長し
ていると考えられる。また、アルカリ土類金属アルミネ
ートは結晶相であり酸化ジルコニウムと同様粒子は大き
く成長していると考えられる。したがってこの触媒で
は、特に低表面積の担体では十分な活性を有する触媒は
得られない。In this catalyst, since the zirconia sol itself has a particle size of 100 angstroms or more, it is considered that the zirconium oxide particles produced from this catalyst are growing large. In addition, it is considered that the alkaline earth metal aluminate is in a crystal phase and the particles grow large similarly to zirconium oxide. Therefore, with this catalyst, a catalyst having sufficient activity cannot be obtained, especially with a low surface area support.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、担持
ルテニウム当りの活性が著しく優れ高活性で、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耐
熱性に優れた炭化水素の水蒸気改質用触媒を提供するこ
とにある。It is an object of the present invention that the activity per supported ruthenium is remarkably excellent and the activity is high, and the carbonization is excellent in heat resistance to maintain the high activity even at high temperature during firing and reaction. It is to provide a catalyst for steam reforming of hydrogen.
【０００７】[0007]
【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した結果、α−アルミナ担体
にルテニウム成分及びジルコニウム成分を含有させた触
媒中のα−アルミナのＸ線回折の最強ピーク強度ＩAに
対するα−アルミナ以外の化合物のＸ線回折の最強ピー
ク強度ＩSの比ＩS／ＩAが０．０１以下である触媒が、
高活性で耐熱性にも優れていることを見出し、この知見
に基づいて本発明を完成するに至った。Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, X-rays of α-alumina in a catalyst containing a ruthenium component and a zirconium component in an α-alumina carrier. A catalyst in which the ratio I S / I A of the strongest peak intensity I S of X-ray diffraction of compounds other than α-alumina to the strongest peak intensity I A of diffraction is 0.01 or less,
They have found that they have high activity and excellent heat resistance, and have completed the present invention based on this finding.
【０００８】すなわち、本発明は、α−アルミナ担体に
ルテニウム成分及びジルコニウム成分を含有させた触媒
であって、α−アルミナのＸ線回折の最強ピーク強度Ｉ
Aに対するα−アルミナ以外の化合物のＸ線回折の最強
ピーク強度ＩSの比ＩS／ＩAが０．０１以下であること
を特徴とする炭化水素の水蒸気改質用触媒を提供するも
のである。That is, the present invention is a catalyst in which a ruthenium component and a zirconium component are contained in an α-alumina carrier, and the strongest peak intensity I of X-ray diffraction of α-alumina is I.
A catalyst for steam reforming of hydrocarbons, characterized in that the ratio I S / I A of the strongest peak intensity I S of X-ray diffraction of compounds other than α-alumina to A is 0.01 or less. is there.
【０００９】[0009]
【発明の実施の形態】本発明の触媒においては、ジルコ
ニウム成分が微粒子で存在するために触媒の表面積が著
しく大きくなり高活性な触媒となるとともに、また耐熱
性にも優れた触媒が得られる。BEST MODE FOR CARRYING OUT THE INVENTION In the catalyst of the present invention, since the zirconium component is present in the form of fine particles, the surface area of the catalyst is remarkably increased, the catalyst becomes highly active, and the catalyst having excellent heat resistance can be obtained.
【００１０】前記ＩS／ＩAの値が０．０１を超える触媒
においては、触媒活性が低下し、本発明の目的を達成す
ることができない。The catalyst having an I S / I A value of more than 0.01 has low catalytic activity and cannot attain the object of the present invention.
【００１１】各担持成分の最終的な担持量は、担体の種
類や表面積等の性状、或いは、触媒の用途すなわち対象
とする反応の種類や性質等の諸条件を考慮して適宜選定
すればよい。多くの場合には、担体重量を基準とする担
持量として、ルテニウム成分をルテニウム金属に換算し
て、通常、０．０５〜５重量％、好ましくは０．０５〜
２重量％、更に好ましくは０．１〜１重量％、ジルコニ
ウム成分をジルコニウム金属に換算して、通常、０．１
〜２０重量％、好ましくは０．１〜１５重量％、更に好
ましくは１．０〜１５重量％の範囲に選定するのが好適
である。The final supported amount of each supported component may be appropriately selected in consideration of properties such as the type and surface area of the carrier, or various conditions such as the use of the catalyst, that is, the type and properties of the reaction to be targeted. . In many cases, the amount of the ruthenium component converted to the ruthenium metal is usually 0.05 to 5% by weight, preferably 0.05 to 5% by weight, based on the weight of the carrier.
2% by weight, and more preferably 0.1 to 1% by weight, and the zirconium component is converted to zirconium metal, and is usually 0.1.
It is suitable to select in the range of -20% by weight, preferably 0.1-15% by weight, more preferably 1.0-15% by weight.
【００１２】また、アルカリ土類金属成分及び希土類元
素成分から選ばれる１種又は２種以上の成分が含有され
ていてもよい。これらの成分含有割合はジルコニウム成
分中のジルコニウム原子のモル数との比（モル比）で通
常０．０１〜５、好ましくは０．１〜５、更に好ましく
は０．１〜１の範囲に選定するのが好適である。ここで
アルカリ土類金属又は希土類金属としては、Ｂｅ、Ｍ
ｇ、Ｃａ、Ｓｒ、Ｂａ、Ｒａ、Ｓｒ、Ｙ、Ｌａ、Ｃｅ、
Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈ
ｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ等自由に選択できる。Further, one or more components selected from alkaline earth metal components and rare earth element components may be contained. The content ratio of these components is usually 0.01 to 5, preferably 0.1 to 5, and more preferably 0.1 to 1 in terms of the ratio (molar ratio) to the number of moles of zirconium atoms in the zirconium component. Is preferred. Here, as the alkaline earth metal or the rare earth metal, Be, M
g, Ca, Sr, Ba, Ra, Sr, Y, La, Ce,
Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, H
It is possible to freely select o, Er, Tm, Yb, Lu and the like.
【００１３】本発明のＩS／ＩAの値が０．０１以下であ
る触媒は、例えば、α−アルミナに、少なくとも、１種
又は２種以上のルテニウム化合物と、１種又は２種以上
のジルコニウム化合物と、必要に応じアルカリ土類金属
化合物及び希土類元素化合物から選ばれる１種又は２種
以上の化合物とを溶解含有する溶液を接触含浸させるこ
とによって製造することができる。このような方法によ
って、その触媒担体の表面や細孔内にルテニウム成分と
ジルコニウム成分とを分散性よくむらなく担持すること
ができ、また、その後、通常行われるような高温での焼
成や還元等の前処理を行っても、そのルテニウム成分と
ジルコニウム成分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。The catalyst having an I S / I A value of 0.01 or less according to the present invention is, for example, α-alumina and at least one or more ruthenium compounds and one or more of ruthenium compounds. It can be produced by contact impregnation with a solution containing a zirconium compound and, if necessary, one or more compounds selected from alkaline earth metal compounds and rare earth element compounds. By such a method, the ruthenium component and the zirconium component can be evenly supported on the surface and the pores of the catalyst carrier with good dispersibility, and thereafter, firing or reduction at a high temperature which is usually performed, etc. Even if the pretreatment is carried out, the highly dispersed state of the ruthenium component and the zirconium component can be maintained sufficiently stable, and the high-performance supported ruthenium catalyst can be easily obtained.
【００１４】触媒製造に用いる溶液はルテニウム化合
物、ジルコニウム化合物、必要に応じアルカリ土類金属
化合物及び希土類元素化合物を含有しているが、酸性に
調整することが望ましい。その際、好ましくはｐＨが３
以下、更に好ましくはｐＨ１．５以下に調整する。ｐＨ
が高くな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
なるためである。更に、以下に示すように、ルテニウム
化合物とジルコニウム化合物が互いに反応し、錯体様の
化合物を形成することによってＩS／ＩAの値が０．０１
以下となるものと考えられる。The solution used for producing the catalyst contains a ruthenium compound, a zirconium compound, and if necessary, an alkaline earth metal compound and a rare earth element compound, but it is desirable to adjust it to be acidic. At that time, the pH is preferably 3
Hereafter, the pH is adjusted to preferably 1.5 or less. pH
This is because when the value becomes higher, each compound tends to precipitate or aggregate in a gel state, and it becomes difficult to carry out highly dispersed support. Further, as shown below, the ruthenium compound and the zirconium compound react with each other to form a complex-like compound, whereby the value of I S / I A is 0.01.
It is considered to be as follows.
【００１５】更に、ルテニウム化合物及びジルコニウム
化合物に加えて、アルカリ土類金属化合物及び希土類元
素化合物から選ばれる成分を溶液に添加して製造された
アルカリ土類金属成分及び希土類元素成分を含有する触
媒は、ルテニウム成分及びジルコニウム成分の表面積
が、焼成や反応時の高温でも維持され、更に優れた耐熱
性が得られる。Further, a catalyst containing an alkaline earth metal component and a rare earth element component produced by adding a component selected from an alkaline earth metal compound and a rare earth element compound to a solution in addition to a ruthenium compound and a zirconium compound is The surface areas of the ruthenium component and the zirconium component are maintained even at high temperatures during firing and reaction, and more excellent heat resistance can be obtained.
【００１６】本発明の触媒の製造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、ジルコニウム化合物、並びに、
必要に応じて用いられるアルカリ土類金属の化合物及び
希土類元素の化合物から選ばれる化合物が溶解されるよ
うなものであれば自由に選択できる。なかでも、溶解性
の高い水又は水を主成分とする水系溶媒が好適に用いら
れる。また、その調製原料として用いる各化合物として
は、溶媒に溶解し得るものであれば、一般にどのような
種類あるいは形態のものを用いてもよい。The solvent of the solution used for producing the catalyst of the present invention is, for example, water or an aqueous solvent containing water as a main component or an organic solvent such as alcohol or ether, and at least a ruthenium compound, a zirconium compound, and ,
Any compound can be freely selected as long as it dissolves a compound selected from compounds of alkaline earth metals and compounds of rare earth elements which are used as necessary. Among them, highly soluble water or an aqueous solvent containing water as a main component is preferably used. In addition, as each compound used as a raw material for its preparation, generally any kind or form may be used as long as it can be dissolved in a solvent.
【００１７】すなわち、調製原料として用いるルテニウ
ム化合物としては、通常は、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、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が好適に使用される
が、これらに限定されるものではなく、通常、ある種の
溶媒に溶解性を示すものに限らず、酸や酸性化合物等の
添加あるい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、
或いはオキシハロゲン化物などのｐＨが７付近の水には
不溶性であったり溶解しにくいものでも、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。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。That is, the ruthenium compound used as the starting material is usually, for example, various ruthenium halides such as ruthenium trichloride and various halogenated ruthenium salts such as potassium hexachlororuthenate.
Various ruthenium salts such as potassium tetraoxorthenate, ruthenium tetroxide, various ammine complex salts such as hexaammineruthenium trichloride, cyano complex salts such as potassium hexacyanoruthenate are preferably used, but are not limited to these. However, it is not limited to those that are soluble in a certain solvent, and various types can be used as long as they can be sufficiently dissolved by the addition or coexistence of an acid or an acidic compound. Therefore, for example, ruthenium oxide such as diruthenium trioxide and ruthenium hydroxide,
Alternatively, even an oxyhalide or the like that is insoluble or difficult to dissolve in water having a pH of about 7 can be used by appropriately adding an acid such as hydrochloric acid and dissolving it. Incidentally, these ruthenium compounds may be used alone,
Two or more kinds may be used in combination.
【００１８】これら各種の原料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適に使用される。Among these various starting ruthenium compounds, ruthenium trichloride is particularly preferably used because it is widely used industrially and is easily available.
【００１９】前記ジルコニウム化合物についても同様
に、ある種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などして酸性溶媒として溶媒中
に溶解し、溶液となすことができる各種のものを調製原
料として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若しくはこれ
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或いは有機系の配位化合物など、
更には、ジルコニウムのアルコキシド、水酸化物、各種
の錯塩などを例示することができる。Similarly, with respect to the zirconium compound, a compound which is soluble in a certain solvent, or an acid such as hydrochloric acid or an acidic compound is dissolved in the solvent as an acidic solvent to form a solution. Various materials capable of producing can be used as a raw material for preparation. Specifically, for example, various halides such as zirconium tetrachloride or partial hydrolysis products thereof, various oxyhalides such as zirconyl chloride (zirconium oxychloride), various kinds of zirconyl sulfate, zirconium nitrate, zirconyl nitrate, etc. Oxygenates, potassium tetraoxozirconate, various zirconates such as sodium hexafluorozirconate, zirconium acetate, zirconyl acetate, zirconyl oxalate, various organic acid salts such as potassium tetraoxalatozirconate Coordination compounds, etc.
Furthermore, alkoxide of zirconium, hydroxide, various complex salts, etc. can be illustrated.
【００２０】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・ｎＨ2ＯやＺｒＯ（ＯＨ）Ｃｌ・ｎ
Ｈ2Ｏ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、好適に用いられる。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。Of these various zirconium compounds, zirconium oxychloride is particularly preferable. For example, ZrOCl 2 .nH 2 O and ZrO (OH) Cl.n.
A hydrate represented by H 2 O, a commercially available product in the form of a solution, and the like are preferably used because they easily form a complex-like compound with ruthenium. These zirconium compounds may be used alone or in combination of two or more.
【００２１】前記アルカリ土類金属化合物及び希土類元
素化合物についても、同様に、ある種の溶媒に溶解性を
示すものや、塩酸等の酸や酸性化合物等を添加するなど
して溶解し水溶液となすことができる各種のものを調製
原料として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。なお、
これらのアルカリ土類金属化合物及び希土類元素化合物
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。前記アルカリ土類金属の化合物としては、ベリリ
ウム、マグネシウム、カルシウム、ストロンチウム、バ
リウム及びラジウムの化合物が挙げられるが、なかでも
マグネシウム、カルシウム、ストロンチウム及びバリウ
ムの化合物が好ましく、特に、ジルコニウム、アルミナ
との反応性の高いマグネシウム、カルシウムの化合物が
好適に用いられる。具体的には、例えば、硝酸マグネシ
ウム、硝酸カルシウム、硝酸ストロンチウム、硝酸バリ
ウム、塩化マグネシウム、塩化カルシウム、塩化ストロ
ンチウム、塩化バリウムなどを例示することができる。
また、前記希土類元素の化合物としては、スカンジウ
ム、イットリウム、ランタン、セリウム、プラセオジ
ム、ネオジム、プロメチウム、サマリウム、ユーロピウ
ム、カドリニウム、テルビウム、ジスプロシウム、ホル
ミウム、エルビウム、ツリウム、イッテルビウム及びル
テチウムの化合物が挙げられるが、なかでもイットリウ
ム、ランタン及びセリウムの化合物が好ましく、特に、
ジルコニウム、アルミナとの反応性の高いイットリウム
及びランタンの化合物が好適に用いられる。具体的に
は、例えば、硝酸イットリウム、硝酸ランタン、塩化イ
ットリウム、塩化ランタンなどを例示することができ
る。The alkaline earth metal compound and the rare earth element compound are similarly dissolved by adding an acid such as hydrochloric acid or an acid compound such as hydrochloric acid to form an aqueous solution. Various substances that can be used can be used as a preparation raw material. Usually, highly soluble compounds such as nitrates and chlorides are preferably used. In addition,
These alkaline earth metal compounds and rare earth element compounds may be used alone or in combination of two or more. Examples of the alkaline earth metal compound include compounds of beryllium, magnesium, calcium, strontium, barium and radium. Among them, compounds of magnesium, calcium, strontium and barium are preferable, and particularly, reaction with zirconium and alumina. Compounds of magnesium and calcium, which have high properties, are preferably used. Specific examples include magnesium nitrate, calcium nitrate, strontium nitrate, barium nitrate, magnesium chloride, calcium chloride, strontium chloride and barium chloride.
Examples of the compound of the rare earth element include scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, cadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium compounds. Among them, yttrium, lanthanum and cerium compounds are preferable, and particularly,
Compounds of yttrium and lanthanum, which have high reactivity with zirconium and alumina, are preferably used. Specific examples include yttrium nitrate, lanthanum nitrate, yttrium chloride, and lanthanum chloride.
【００２２】これら各種のアルカリ土類金属化合物及び
希土類元素化合物のなかでも、硝酸マグネシウム、硝酸
イットリウム、硝酸ランタン及びこれらの各種含水塩が
特に好適に用いられる。Among these various alkaline earth metal compounds and rare earth element compounds, magnesium nitrate, yttrium nitrate, lanthanum nitrate and various hydrous salts thereof are particularly preferably used.
【００２３】本発明に用いられる上記溶液を調製するに
際して、溶媒、ルテニウム化合物、ジルコニウム化合
物、アルカリ土類金属化合物、希土類元素化合物、酸等
の各成分の添加、混合、溶解の順序及び方式については
特に制限はない。例えば、溶媒又は予め酸を添加した酸
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し、或いは、各
成分の溶液を別途に調製し、これらの溶液を混合しても
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。When preparing the above-mentioned solution used in the present invention, the order and method of addition, mixing and dissolution of each component such as solvent, ruthenium compound, zirconium compound, alkaline earth metal compound, rare earth element compound and acid are described. There is no particular limitation. For example, a predetermined component may be simultaneously added and dissolved in a solvent or an acidic solution to which an acid has been added, or may be added stepwise and dissolved, or a solution of each component may be prepared separately. However, these solutions may be mixed, or 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 preferably about room temperature, but may be heated up to about 80 ° C. to promote dissolution.
【００２４】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。このとき、ｐＨは
比較的強酸性に調整し、好ましくは３以下、さらに好ま
しくは１．５以下となるようにする。ｐＨを３又は１．
５より高くすると、上記各種の化合物が沈殿することが
ある。As the acid to be added as necessary for improving the solubility and adjusting the pH, 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 used. It may be appropriately selected and used. At this time, the pH is adjusted to a relatively strong acidity, preferably 3 or less, more preferably 1.5 or less. Adjust the pH to 3 or 1.
When it is higher than 5, various compounds described above may be precipitated.
【００２５】本発明に用いられる溶液において、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（Ｚｒ）とルテニウム原子（Ｒ
ｕ）のモル比（Ｚｒ／Ｒｕ）で表すと、該モル比（Ｚｒ
／Ｒｕ）が、１００以下、好ましくは１〜２０、更に好
ましくは２〜１０の範囲になるように選定するのが好適
である。ここで、もし、該モル比（Ｚｒ／Ｒｕ）が１又
は２より小さい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／Ｒ
ｕ）を１００、２０或は１０より大きくしても、それに
見合った分散性等の更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、或いは、担体本来の特性が大きく変化し損われ
るなどの支障を生じるおそれがある。In the solution used in the present invention, the ratio of the ruthenium compound and the zirconium compound to be dissolved and contained is such that the zirconium atom (Zr) and the ruthenium atom (R
u) is expressed as a molar ratio (Zr / Ru), the molar ratio (Zr / Ru)
/ Ru) is preferably 100 or less, preferably 1 to 20, and more preferably 2 to 10. Here, if the molar ratio (Zr / Ru) is less than 1 or 2, the proportion of zirconium becomes too small and a part of ruthenium cannot be a complex-like compound, so that the ruthenium easily aggregates, and the dispersibility is increased accordingly. And the ruthenium component may not be supported in the vicinity of the zirconium component. On the other hand, this molar ratio (Zr / R
Even if u) is made larger than 100, 20 or 10, it is difficult to obtain a further improvement effect such as dispersibility corresponding to it, and the amount of ruthenium component exposed on the surface is decreased in some cases, or the carrier is There is a risk that the original characteristics may change significantly and may be impaired.
【００２６】上記溶液に必要に応じて溶解含有させるア
ルカリ土類金属化合物及び希土類元素化合物から選ばれ
る化合物の量は、アルカリ土類金属の原子及び希土類元
素の原子の合計（Ａとする）とジルコニウム化合物のジ
ルコニウム原子（Ｚｒ）とのモル比（Ａ／Ｚｒ）で表す
と、該モル比（Ａ／Ｚｒ）が、通常、０．０１〜５、好
ましくは０．１〜５、更に好ましくは０．１〜１の範囲
になるように選定するのが好適である。ここで、もし、
該モル比（Ａ／Ｚｒ）が０．０１又は０．１より小さい
とアルカリ土類金属及び希土類元素の割合が少ないた
め、担持成分の表面積低下の更なる抑制効果や、耐熱性
の更なる向上効果が不十分となることがある。一方、こ
のモル比（Ａ／Ｚｒ）を５又は１より大きくしても、そ
れに見合った耐熱性の更なる向上効果が得られにくい。
また、得られる触媒体の塩基性が強くなる傾向にあるた
め、例えば担体と溶液との接触を数回にわけて行う場合
には、２回目以降の接触において、担体と溶液を接触さ
せたときに溶液中の各成分、主としてジルコニウム成分
が担体上へ移動する前にゲル化してしまい、担体表面に
高分散の状態に担持することができなくなるおそれがあ
る。The amount of the compound selected from the alkaline earth metal compounds and the rare earth element compounds to be dissolved and contained in the above-mentioned solution as necessary is such that the total amount of the alkaline earth metal atoms and the rare earth element atoms (A) and zirconium The molar ratio (A / Zr) of the compound to the zirconium atom (Zr) is usually 0.01 to 5, preferably 0.1 to 5, and more preferably 0. It is preferable to select it so that it falls within the range of 1 to 1. Here, if
When the molar ratio (A / Zr) is less than 0.01 or 0.1, the proportion of the alkaline earth metal and the rare earth element is small, so that the effect of further suppressing the surface area reduction of the supported component and the further improvement of heat resistance are obtained. The effect may be insufficient. On the other hand, even if this molar ratio (A / Zr) is set to be greater than 5 or 1, it is difficult to obtain the corresponding further improvement effect of heat resistance.
Moreover, since the basicity of the obtained catalyst body tends to be strong, for example, when the contact between the carrier and the solution is divided into several times, when the carrier and the solution are contacted with each other after the second contact. In addition, each component in the solution, mainly the zirconium component, gels before moving onto the carrier, which may make it impossible to support the carrier surface in a highly dispersed state.
【００２７】上記溶液中に溶解せしめる各化合物の量
（濃度）としては、特に制限はないが、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、
０．００１ｍｏｌ／ｌ以上、好ましくは０．０１〜１０
ｍｏｌ／ｌ、更に好ましくは０．０２〜２ｍｏｌ／ｌと
なるように選定するのが好ましい。The amount (concentration) of each compound to be dissolved in the above solution is not particularly limited, but the concentration of the ruthenium compound is usually the molar concentration of ruthenium atoms.
0.001 mol / l or more, preferably 0.01 to 10
It is preferable to select it so that it is mol / l, more preferably 0.02 to 2 mol / l.
【００２８】なお、本発明で用いる上記溶液には、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
ニウム化合物及びジルコニウム化合物、また必要に応じ
て添加されるアルカリ土類金属化合物、希土類元素化合
物並びに溶解性調整用の酸以外の他の成分を適宜添加し
てもよい。The above-mentioned solution used in the present invention contains ruthenium compounds and zirconium compounds as essential compounds, and alkaline earth metal compounds and rare earth elements which are added as necessary, as long as the object of the present invention is not impaired. Other components than the compound and the acid for adjusting the solubility may be appropriately added.
【００２９】例えば、上記溶液中に、上記ルテニウム化
合物、ジルコニウム化合物並びにアルカリ土類金属化合
物及び希土類元素化合物から選ばれる化合物に加えて、
更に、ニッケル化合物及びコバルト化合物から選ばれる
少なくとも１種の化合物を溶解させた溶液を用いること
により、より水蒸気改質活性に優れた触媒を得ることが
できる。For example, in the above solution, in addition to the compound selected from the ruthenium compound, the zirconium compound, the alkaline earth metal compound and the rare earth element compound,
Furthermore, by using a solution in which at least one compound selected from nickel compounds and cobalt compounds is dissolved, a catalyst having more excellent steam reforming activity can be obtained.
【００３０】これらのニッケル化合物及びコバルト化合
物としても、同様に、ある種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などして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調
製原料として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、例えば、硝酸ニッケル（ＩＩ）、塩基性硝酸ニ
ッケル、硝酸第一コバルト、塩基性硝酸コバルト、二塩
化ニッケル、二塩化コバルト、これらの各種含水塩など
を例示することができる。なかでも、硝酸ニッケル（Ｉ
Ｉ）、硝酸第一コバルト等が特に好適に用いられる。な
お、これらのニッケル化合物及びコバルト化合物は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 these nickel compounds and cobalt compounds, those exhibiting solubility in a certain kind of solvent, acids such as hydrochloric acid, acidic compounds, etc. may be added to adjust the pH.
Various substances that can be dissolved by adjusting the above can be used as a preparation raw material. Usually, highly soluble compounds such as nitrates and chlorides are preferably used. Specifically, for example, nickel nitrate (II), basic nickel nitrate, primary cobalt nitrate, basic cobalt nitrate, nickel dichloride, cobalt dichloride, various hydrous salts of these and the like can be illustrated. Among them, nickel nitrate (I
I), cobaltous nitrate and the like are particularly preferably used. In addition, these nickel compounds and cobalt compounds may be used individually by 1 type, and may use 2 or more types together.
【００３１】上記溶液に必要に応じて溶解含有させるニ
ッケル化合物及びコバルト化合物から選ばれる化合物の
量は、ニッケル原子及びコバルト原子の合計（Ｂとす
る）とルテニウム化合物のルテニウム原子（Ｒｕ）との
モル比（Ｂ／Ｒｕ）で表すと、該モル比（Ｂ／Ｒｕ）
が、通常、０．０１〜３０、好ましくは０．１〜３０、
更に好ましくは０．１〜１０の範囲になるように選定す
るのが好適である。ここで、もし、該モル比（Ｂ／Ｒ
ｕ）が０．０１又は０．１より小さいとニッケル又はコ
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（Ｂ／Ｒｕ）を３０又は１０より大きくして
も、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、及
び低スチーム／カーボン比の運転条件下でも炭素析出を
抑制するという効果が損われるおそれがある。The amount of the compound selected from the nickel compound and the cobalt compound to be dissolved and contained in the above-mentioned solution as required is the molar amount of the total of nickel and cobalt atoms (denoted by B) and the ruthenium atom (Ru) of the ruthenium compound. When expressed as a ratio (B / Ru), the molar ratio (B / Ru)
Is usually 0.01 to 30, preferably 0.1 to 30,
It is more preferable to select it so as to fall within the range of 0.1 to 10. Here, if the molar ratio (B / R
When u) is less than 0.01 or 0.1, the proportion of nickel or cobalt decreases, and the effect of improving the activity due to these components may not be obtained as expected. On the other hand, even if this molar ratio (B / Ru) is increased to more than 30 or 10, the amount of ruthenium becomes relatively small, and the hydrocarbon containing ruthenium has high activity as a steam reforming catalyst and low steam / carbon. The effect of suppressing carbon precipitation may be impaired even under the operating conditions of the ratio.
【００３２】各化合物を均一に溶解させる方法として
は、通常、溶液のＰＨを低くすることが挙げられる。具
体的には、ｐＨが３以下、好ましくは１．５以下となる
ように調整することが望ましい。ここで、溶液のｐＨが
３又は１．５より大きいと、ジルコニウム化合物が加水
分解されやすくなり、水酸化物様のゾルやゲルを形成し
やすくなる。このような溶液中に生成する水酸化物様の
ゾルやゲルは、ルテニウム成分と前記のような錯体様化
合物を形成しにくいため、期待される程には分散性等の
改善効果が達成できなくなるおそれがある。As a method for uniformly dissolving each compound, the pH of the solution may be lowered. Specifically, it is desirable to adjust the pH to 3 or less, preferably 1.5 or less. Here, if the pH of the solution is higher than 3 or 1.5, the zirconium compound is easily hydrolyzed, and a hydroxide-like sol or gel is easily formed. Hydroxide-like sols and gels generated in such a solution are unlikely to form the above-mentioned complex-like compound with the ruthenium component, so that the effect of improving dispersibility and the like cannot be achieved as expected. There is a risk.
【００３３】担体としては、α−アルミナが用いられ
る。α−アルミナを担体として用いると、溶液と担体と
の接触時にルテニウム成分及びジルコニウム成分が担体
中に固定化されやすい。As the carrier, α-alumina is used. When α-alumina is used as the carrier, the ruthenium component and the zirconium component are easily fixed in the carrier when the solution and the carrier come into contact with each other.
【００３４】なお、本発明の触媒の調製にあたり、α−
アルミナはこうした担体は、従来の場合と同様に、添加
物の添加や予備処理の実施あるいは調製法の選定等によ
って、組成や物性が調整あるいは制御されたものとして
使用することができる。例えば、酸処理、塩基処理、イ
オン交換処理等の化学的処理を行って酸性度等の調整を
行ったり、加熱や焼成等による水分やＯＨ含量の調整を
行ったり、更には、各種の手段により細孔径や細孔径分
布の制御、表面積の制御を行ったりして、組成や触媒担
体としての特性の調整や改善がなされているものでもよ
い。また、場合によっては、予め適当な金属成分等を含
有若しくは担持してあるものを用いてもよい。また、こ
のα−アルミナ担体は、予め乾燥や焼成が施されている
ものでもよいし、未焼成のものや未乾燥のものでもよい
し、加水分解等によって調製したゾル状のものなどスラ
リー状のものでもよい。In preparing the catalyst of the present invention, α-
Alumina can be used as such a carrier, the composition and physical properties of which are adjusted or controlled by addition of additives, execution of preliminary treatment, selection of preparation method, and the like, as in the conventional case. For example, chemical treatment such as acid treatment, base treatment, ion exchange treatment, etc. is performed to adjust the acidity, etc., water or OH content is adjusted by heating or baking, and further, by various means. The composition and properties of the catalyst carrier may be adjusted or improved by controlling the pore size and the pore size distribution and the surface area. Further, in some cases, a material containing or supporting an appropriate metal component in advance may be used. The α-alumina carrier may be dried or calcined in advance, may be uncalcined or undried, or may be in the form of a slurry such as a sol prepared by hydrolysis or the like. It may be one.
【００３５】α−アルミナ担体の形状やサイズとして
も、特に制限はなく、例えば、粉末状、ビーズ状、ペレ
ット状、顆粒状、モノリス等の構造体にコーティングし
たもの、微粒子状、超微粒子状のものを適宜使用するこ
とができる。即ち、造粒や成形を施したものでもよい
し、或いは、特にそのような処理を施していないもので
もよい。The shape and size of the α-alumina carrier is not particularly limited, and examples thereof include powder, beads, pellets, granules, monoliths and other structures coated with the particles, fine particles, and ultrafine particles. The thing can be used suitably. That is, it may be granulated or molded, or may not be particularly treated.
【００３６】上記溶液とα−アルミナ担体の接触による
含浸担持操作は、常法に従って行うことができ、例え
ば、常用される各種の含浸法（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、あるいはこれらの任意の組み合わせ法等）、
浸漬法、軽度浸潤法、湿式吸着法、湿式混練法、スプレ
ー法、塗布法など、或いはこれらの組み合わせ法など、
溶液とα−アルミナ担体とを接触させて担持させる方式
であればどのような方式によってもよい。また、この含
浸担持、乾燥、焼成の一連の操作は、少なくとも１回は
行われるが、必要に応じて、これらの操作を２回以上に
わけて複数回繰り返してもよい。The impregnation-supporting operation by contacting the above-mentioned solution with the α-alumina carrier can be carried out by a conventional method. For example, various commonly used impregnation methods (heat impregnation method, room temperature impregnation method, vacuum impregnation method, atmospheric pressure method). Impregnation method, impregnation dryness method, pore filling method, etc., or any combination thereof, etc.),
Immersion method, light infiltration method, wet adsorption method, wet kneading method, spray method, coating method, etc., or a combination thereof,
Any method may be used as long as the solution and the α-alumina carrier are brought into contact with each other and supported. The series of operations of impregnating, supporting, drying and firing is performed at least once, but if necessary, these operations may be repeated twice or more and repeated multiple times.
【００３７】ここで、用いるα−アルミナ担体と溶液の
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、含浸担持方式の種類、用いる
α−アルミナ担体の細孔容積や比表面積などによって異
なるので一律に定めることができないが、少なくとも、
担持しようとするα−アルミナ担体を十分に濡らす量の
溶液を使用し、一方、α−アルミナ担体に対する溶液の
使用量の上限については、特に制限はないが、通常は、
使用するα−アルミナ担体の乾燥重量１００ｇ当り、溶
液の使用量を１００ｍｌ以下の範囲に選定し、好ましく
は、溶液をα−アルミナ担体に固有の吸水量に近くなる
まで減じ、更に好ましくは吸水量と一致する体積の溶液
を用いる。Here, the amount ratio of the α-alumina carrier to be used is a target active metal component loading rate, the concentration of the metal compound in the aqueous solution to be used, the type of the impregnation-supporting system, and the type of the α-alumina carrier to be used. Since it depends on the pore volume and specific surface area, etc., it cannot be set uniformly, but at least
An amount of a solution that sufficiently wets the α-alumina carrier to be supported is used, while the upper limit of the amount of the solution used for the α-alumina carrier is not particularly limited, but usually,
The amount of the solution used is selected within a range of 100 ml or less per 100 g of the dry weight of the α-alumina carrier to be used, preferably, the solution is reduced to a water absorption amount close to the inherent water absorption amount of the α-alumina carrier, and more preferably the water absorption amount. Use a volume of solution consistent with.
【００３８】この接触操作（含浸担持操作）は、従来の
場合と同様に、大気圧下或いは減圧下（減圧排気下）で
好適に行うことができ、その際の操作温度としても特に
制限はなく、室温或いは室温付近でも行うことができる
し、必要に応じて加熱或いは加温し、例えば室温〜８０
℃程度の温度でも好適に行うことができる。This contacting operation (impregnation supporting operation) can be suitably carried out under atmospheric pressure or under reduced pressure (under reduced pressure exhaust) as in the conventional case, and the operating temperature at that time is not particularly limited. It can be carried out at room temperature or near room temperature, and is heated or heated as necessary, for example, room temperature to 80.
It can be suitably performed even at a temperature of about ° C.
【００３９】上記溶液とα−アルミナ担体との接触後の
乾燥は、特に限定されないが、通常、５０〜１５０℃、
好ましくは１００〜１２０℃の範囲で１〜６時間行う。
室温での風乾では、１昼夜（２４時間）程度行う。但
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 drying after contacting the above solution with the α-alumina carrier is not particularly limited, but usually 50 to 150 ° C.
It is preferably carried out at 100 to 120 ° C. for 1 to 6 hours.
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 dried state can be obtained. Therefore, in such a case, a separate drying operation is not necessarily required.
【００４０】前記焼成も、常法に従って行うことがで
き、通常は空気中若しくは空気気流中で、４００〜８０
０℃、好ましくは４５０〜８００℃、更に好ましくは４
５０〜６００℃の温度範囲で好適に実施される。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。The above-mentioned calcination can also be carried out according to a conventional method, usually 400 to 80 in air or in an air stream.
0 ° C, preferably 450 to 800 ° C, more preferably 4
It is preferably carried out in the temperature range of 50 to 600 ° C. In addition,
In addition to air, an oxygen-containing gas such as pure oxygen or oxygen-enriched air may be substituted or used together. The firing time is usually 1 to
About 24 hours is sufficient.
【００４１】なお、必要に応じて、焼成前のいずれかの
適当な時点で担持組成物を所定の形状及びサイズに成形
してもよい。成形を行う場合は、この成形は、常法に従
って行うことができ、必要に応じて、適当なバインダー
成分を添加してもよい。If desired, the supporting composition may be molded into a predetermined shape and size at any suitable time before firing. When molding is carried out, this molding can be carried out by a conventional method, and if necessary, a suitable binder component may be added.
【００４２】この焼成によって得られる触媒中のルテニ
ウム成分、ジルコニウム成分、アルカリ土類金属成分及
び希土類元素成分、ニッケル及びコバルト成分は、通
常、酸化物若しく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ている。The ruthenium component, zirconium component, alkaline earth metal component and rare earth element component, nickel and cobalt component in the catalyst obtained by this calcination are usually in the form of oxides or complex oxides in the vicinity of the respective components. It is carried in a highly dispersed state.
【００４３】こうして得た触媒は、そのまま、所定の触
媒反応の触媒或は触媒成分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。The catalyst thus obtained can be used as it is as a catalyst or a catalyst component for a predetermined catalytic reaction, but if necessary, various suitable pretreatments are carried out for activation before the catalytic reaction. You may use. This pretreatment can be performed according to a conventional method. For example, it may be appropriately reduced with a reducing agent such as hydrogen to convert the ruthenium component into highly dispersed metallic ruthenium and used for the reaction.
【００４４】なお、この水素還元による分散金属化処理
は、例えば、５００〜８５０℃でＨ 2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。Incidentally, this dispersive metallization treatment by hydrogen reduction is carried out.
Is, for example, H at 500 to 850 ° C. TwoConsumption of
It is preferable to reduce until it disappears.
【００４５】本発明の炭化水素の水蒸気改質用触媒を用
いる炭化水素の水蒸気改質方法の原料炭化水素として
は、特に制限はなく、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
若しく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等、各種の
炭化水素が用いられる。また、上記各種炭化水素の２種
以上の混合物も用いられる。また、その他に好ましく用
いられるものとしては、沸点範囲が３００℃以下の都市
ガス、ＬＰＧ、ナフサ、灯油等の各種の炭化水素が挙げ
られる。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
１ｐｐｍ程度以下になるまで脱硫を行うことが望まし
い。原料炭化水素中の硫黄分が１ｐｐｍ程度より多くな
ると、触媒が失活する原因となることがあるからであ
る。脱硫方法は特に限定されないが、水添脱硫、吸着脱
硫などが行われる。There are no particular restrictions on the starting hydrocarbon used in the method for steam reforming of hydrocarbons using the catalyst for steam reforming of hydrocarbons of the present invention, and examples thereof include methane, ethane, propane, butane, pentane, hexane, and heptane. , Octane, nonane, decane, etc., straight or branched saturated aliphatic hydrocarbons having about 1 to 16 carbon atoms, alicyclic saturated hydrocarbons such as cyclohexane, methylcyclohexane, cyclooctane, monocyclic and polycyclic Various hydrocarbons such as aromatic hydrocarbons are used. Also, a mixture of two or more of the above various hydrocarbons is used. Other preferable examples include various hydrocarbons having a boiling point range of 300 ° C. or lower, such as city gas, LPG, naphtha, and kerosene. Further, in general, when a sulfur content is present in these raw material hydrocarbons, it is usually desirable to perform desulfurization through the desulfurization step until the sulfur content becomes about 1 ppm or less. This is because if the sulfur content in the raw material hydrocarbon exceeds about 1 ppm, the catalyst may be deactivated. The desulfurization method is not particularly limited, but hydrodesulfurization, adsorptive desulfurization and the like are performed.
【００４６】炭化水素と反応させる水蒸気としては特に
制限はない。There are no particular restrictions on the steam that is reacted with the hydrocarbon.
【００４７】炭化水素と水蒸気を反応させる場合、通
常、スチーム／カーボン比が１．５〜１０、好ましくは
１．５〜５、更に好ましくは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。なお、本
発明の水蒸気改質方法においては、このスチーム／カー
ボン比を３以下にしても炭素析出が抑えられるので、排
熱の有効利用を図ることができる。When the hydrocarbon is reacted with steam, the amount of hydrocarbon and the amount of steam are usually such that the steam / carbon ratio is 1.5 to 10, preferably 1.5 to 5, and more preferably 2 to 4. Is preferably determined. With such a steam / carbon ratio, a product gas having a high hydrogen content can be efficiently obtained. In the steam reforming method of the present invention, carbon precipitation can be suppressed even when the steam / carbon ratio is 3 or less, so that exhaust heat can be effectively used.
【００４８】反応温度は、通常、４００〜９００℃、好
ましくは６００〜９００℃、更に好ましくは６５０〜８
００℃である。The reaction temperature is generally 400 to 900 ° C, preferably 600 to 900 ° C, more preferably 650 to 8 ° C.
00 ° C.
【００４９】反応圧力は、通常、０〜３０ｋｇ／ｃｍ2
Ｇ、好ましくは０〜１０ｋｇ／ｃｍ2Ｇである。The reaction pressure is usually 0 to 30 kg / cm 2.
G, preferably 0 to 10 kg / cm 2 G.
【００５０】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、連続流通式が好適で
ある。The reaction system may be either a continuous flow system or a batch system, but a continuous flow system is preferred.
【００５１】反応方式として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ガス空間速度（Ｇ
ＨＳＶ）は、通常、１００〜４０，０００ｈ-1、好まし
くは１００〜２０，０００ｈ-1、更に好ましくは５００
〜２０，０００ｈ-1である。When the continuous flow system is adopted as the reaction system, the gas space velocity (G
HSV) is usually 100 to 40,000 h -1 , preferably 100 to 20,000 h -1 , more preferably 500.
˜20,000 h −1 .
【００５２】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。The reaction system is not particularly limited and may be a fixed bed system, a moving bed system, a fluidized bed system or the like.
The form of the reactor is not particularly limited, and for example, a tubular reactor can be used.
【００５３】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、
メタン、一酸化炭素等の混合物が得られ、燃料電池の水
素製造プロセスに好適に採用され、水素を５０容量％以
上含む混合物を得ることができる。By reacting a hydrocarbon with steam using the catalyst of the present invention under the above conditions, hydrogen,
A mixture of methane, carbon monoxide and the like is obtained, which is suitably adopted for the hydrogen production process of a fuel cell, and a mixture containing 50% by volume or more of hydrogen can be obtained.
【００５４】[0054]
【実施例】以下に、本発明の実施例とその比較例によっ
て、本発明を更に詳細に説明するが、本発明はこれらの
実施例に限定されるものではない。The present invention will be described in more detail below with reference to examples of the present invention and comparative examples thereof, but the present invention is not limited to these examples.
【００５５】実施例１ オキシ塩化ジルコニウム（ＺｒＯＣｌ2・８Ｈ2Ｏ）１
３．０８ｇ、塩化ルテニウム（ＲｕＣｌ3・ｎＨ2Ｏ：Ｒ
ｕ３８％含有）１．３２ｇ及び硝酸マグネシウム（Ｍｇ
（ＮＯ3）2・６Ｈ2Ｏ）１２．７２ｇを水に溶解して４
０ｃｃの水溶液とした。この溶液を１時間以上スタラー
にて撹拌したものを含浸液とした。この時の含浸液の色
は、赤橙色を呈し、ｐＨは０．５以下であった。この含
浸液のうち２０ｃｃを用いて、α−アルミナ成型体１０
０ｇにポアフィリング法にて含浸担持した。担持後、１
２０℃で５時間乾燥を行い、更に５００℃で２時間空気
中で焼成を行った。次に、残りの含浸液２０ｃｃを用い
て上記の焼成した担体に対し、再度、上記と同様の手順
で含浸担持、乾燥、焼成を行い、最終的な触媒とした。
得られた触媒の組成分析による各元素の含有量は、Ｚ
ｒ：３．７重量％、Ｍｇ：１．２重量％、Ｒｕ：０．５
重量％であった。この触媒の粉末Ｘ線回折測定を以下の
条件で実施した。Ｘ線回折図形を図１に示す。 装置：株式会社リガク製ＲＡＤ−Ｃシステム 条件：２θ＝２５〜６０ｄｅｇ 管電流、電圧：４０ｋＶ、４０ｍＡ（CuKα線） ステップスキャン方式 ステップ幅：０．０１ｄｅｇ サンプリング時間：１秒 バックグラウンドの除去：なし α−アルミナの最強回折線は、２θ＝４３．３ｄｅｇに
存在する。このカウント数をＩAとする。一方、α−ア
ルミナ以外の化合物の回折線の中で最強のピークをＩS
とする。このα−アルミナの最強回折線に対するα−ア
ルミナ以外の化合物の回折線の中で最強の回折線の強度
（カウント数）比ＩS／ＩAの値を表１に示す。Example 1 Zirconium oxychloride (ZrOCl 2 .8H 2 O) 1
3.08 g, ruthenium chloride (RuCl 3 · nH 2 O: R
u38% content) 1.32 g and magnesium nitrate (Mg
The (NO 3) 2 · 6H 2 O) 12.72g is dissolved in water 54
It was an aqueous solution of 0 cc. This solution was stirred for 1 hour or more with a stirrer to obtain an impregnating solution. At this time, the color of the impregnation liquid was red-orange, and the pH was 0.5 or less. Using 20 cc of this impregnating liquid, the α-alumina molded body 10
0 g was impregnated and supported by the pore filling method. After loading, 1
It was dried at 20 ° C. for 5 hours, and further baked at 500 ° C. for 2 hours in the air. Next, the above-mentioned calcined carrier was impregnated and supported, dried and calcined again using the remaining impregnation liquid 20 cc in the same procedure as described above to obtain a final catalyst.
The content of each element by the composition analysis of the obtained catalyst is Z
r: 3.7% by weight, Mg: 1.2% by weight, Ru: 0.5
% By weight. The powder X-ray diffraction measurement of this catalyst was carried out under the following conditions. The X-ray diffraction pattern is shown in FIG. Equipment: RAD-C system manufactured by Rigaku Co., Ltd. Condition: 2θ = 25 to 60 deg Tube current, voltage: 40 kV, 40 mA (CuKα line) Step scan method Step width: 0.01 deg Sampling time: 1 second Background removal: None α The strongest diffraction line of alumina is at 2θ = 43.3 deg. This count number is I A. On the other hand, the strongest peak in the diffraction lines of compounds other than α-alumina is I S
And Table 1 shows the value of the intensity (count number) ratio I S / I A of the strongest diffraction line among the diffraction lines of the compounds other than α-alumina to the strongest diffraction line of α-alumina.
【００５６】この触媒のＢＥＴ表面積測定を以下の装
置、条件にて実施した。 装置：オムニクロン テクノロジー社製 ＯＭＮＩＳＯ
ＲＰ ３６０ 条件：触媒を粉砕し３２メッシュ以上、１６メッシュ以
下に整粒したものを、５ｇとり試料容器に入れる。この
容器を装置に装着した後、前処理として０．１ｔｏｒｒ
以下に排気し３００℃、３ｈｒの処理を実施する。前処
理後、Ｎ2吸着を１５０ｔｏｒｒまで実施して、触媒上
へのＮ2吸着量よりＢＥＴ表面積を求めた。測定結果を
表１に示す。The BET surface area of this catalyst was measured under the following apparatus and conditions. Device: OMNISO made by Omnicron Technology Co., Ltd.
RP 360 conditions: 5 g of a catalyst pulverized and sized to 32 mesh or more and 16 mesh or less is placed in a sample container. After installing this container in the apparatus, 0.1 torr as pretreatment
Exhaust is performed below and a treatment at 300 ° C. for 3 hours is performed. After pretreatment, N 2 adsorption was performed up to 150 torr, and the BET surface area was determined from the amount of N 2 adsorption on the catalyst. Table 1 shows the measurement results.
【００５７】この触媒のプロパンの水蒸気改質反応の活
性を以下の方法で測定した。The activity of the propane steam reforming reaction of this catalyst was measured by the following method.
【００５８】触媒１ｃｃ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（Ｈ2ガスのＧ
ＨＳＶ：１０００ｈ-1）、５００℃で２時間水素による
還元処理を行った後、反応条件、６００℃プロパンのＧ
ＨＳＶ：２０００ｈ-1、スチーム／カーボン比（Ｓ／
Ｃ）＝３．０という条件でプロパン及び水蒸気を導入
し、プロパンの水蒸気改質反応を実施した。この時の生
成ガスをサンプリングしてガスクロにて生成ガス濃度を
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。1 cc of the catalyst was filled in a quartz reaction tube having an inner diameter of 20 mm. In the reaction tube, the catalyst was passed through a hydrogen stream (H 2 gas G
HSV: 1000 h −1 ), after reduction treatment with hydrogen at 500 ° C. for 2 hours, reaction conditions, 600 ° C. G of propane
HSV: 2000h -1 , steam / carbon ratio (S /
Propane and steam were introduced under the condition of C) = 3.0 to carry out a steam reforming reaction of propane. The produced gas at this time was sampled and the produced gas concentration was measured by gas chromatography. Based on this result, the conversion of propane was determined by the following equation.
【００５９】[0059]
【数１】 更に反応温度を５５０℃から８００℃まで上昇させた
後、再び５５０℃にした時のプロパンの転化率を同様に
求めた。[Equation 1] Further, after raising the reaction temperature from 550 ° C. to 800 ° C., the conversion rate of propane when the temperature was raised to 550 ° C. again was similarly obtained.
【００６０】８００℃の高温での反応前後の５５０℃に
おける活性の比を下式より求めた。The activity ratio at 550 ° C. before and after the reaction at a high temperature of 800 ° C. was determined by the following formula.
【００６１】[0061]
【数２】 これらの結果を表１に示す。[Equation 2] Table 1 shows the results.
【００６２】実施例２ 含浸液に加える硝酸マグネシウム量を９．５４ｇとした
以外は、実施例１と同様に触媒を調製した。得られた触
媒の組成分析による各元素の含有量は、Ｚｒ：３．７、
Ｍｇ：０．９、Ｒｕ：０．５重量％であった。Ｘ線回折
図形の測定、ＢＥＴ表面積測定は実施例１と同様に行っ
た。Ｘ線回析図形を図１に、ＢＥＴ表面積を表１に示
す。プロパンの水蒸気改質反応評価も実施例１と同様に
行い、結果を表１に示す。Example 2 A catalyst was prepared in the same manner as in Example 1 except that the amount of magnesium nitrate added to the impregnation liquid was changed to 9.54 g. The content of each element by the composition analysis of the obtained catalyst was Zr: 3.7,
It was Mg: 0.9 and Ru: 0.5% by weight. The X-ray diffraction pattern and BET surface area were measured in the same manner as in Example 1. The X-ray diffraction pattern is shown in FIG. 1, and the BET surface area is shown in Table 1. Evaluation of the steam reforming reaction of propane was performed in the same manner as in Example 1, and the results are shown in Table 1.
【００６３】実施例３ 含浸液に加える硝酸マグネシウム量を６．３６ｇとした
以外は、実施例１と同様に触媒を調製した。得られた触
媒の組成分析による各元素の含有量は、Ｚｒ：３．７、
Ｍｇ：０．６、Ｒｕ：０．５重量％であった。Ｘ線回折
図形の測定、ＢＥＴ表面積測定は実施例１と同様に行っ
た。Ｘ線回析図形を図１に、ＢＥＴ表面積を表１に示
す。プロパンの水蒸気改質反応評価も実施例１と同様に
行い、結果を表１に示す。Example 3 A catalyst was prepared in the same manner as in Example 1 except that the amount of magnesium nitrate added to the impregnation liquid was changed to 6.36 g. The content of each element by the composition analysis of the obtained catalyst was Zr: 3.7,
It was Mg: 0.6 and Ru: 0.5% by weight. The X-ray diffraction pattern and BET surface area were measured in the same manner as in Example 1. The X-ray diffraction pattern is shown in FIG. 1, and the BET surface area is shown in Table 1. Evaluation of the steam reforming reaction of propane was performed in the same manner as in Example 1, and the results are shown in Table 1.
【００６４】比較例１ 含浸液に加える硝酸マグネシウム量を３．１８ｇとした
以外は、実施例１と同様に触媒を調製した。得られた触
媒の組成分析による各元素の含有量は、Ｚｒ：３．７、
Ｍｇ：０．３、Ｒｕ：０．５重量％、であった。Ｘ線回
折図形の測定、ＢＥＴ表面積測定は実施例１と同様に行
った。Ｘ線回折図形を図１に、ＢＥＴ表面積を表１に示
す。プロパンの水蒸気改質反応評価も実施例１と同様に
行い、結果を表１に示す。Comparative Example 1 A catalyst was prepared in the same manner as in Example 1 except that the amount of magnesium nitrate added to the impregnation liquid was changed to 3.18 g. The content of each element by the composition analysis of the obtained catalyst was Zr: 3.7,
It was Mg: 0.3, Ru: 0.5 weight%. The X-ray diffraction pattern and BET surface area were measured in the same manner as in Example 1. The X-ray diffraction pattern is shown in FIG. 1, and the BET surface area is shown in Table 1. Evaluation of the steam reforming reaction of propane was performed in the same manner as in Example 1, and the results are shown in Table 1.
【００６５】比較例２ 含浸液に硝酸マグネシウムを添加しない以外は各元素の
含有量は、実施例１と同様に触媒を調製した。得られた
触媒の組成分析による各元素の含有量は、Ｚｒ：３．
７、Ｒｕ：０．５重量％であった。Ｘ線回折図形の測
定、ＢＥＴ表面積測定は実施例１と同様に行った。Ｘ線
回析図形を図１に、ＢＥＴ表面積を表１に示す。プロパ
ンの水蒸気改質反応評価も実施例１と同様に行い、結果
を表１に示す。Comparative Example 2 A catalyst was prepared in the same manner as in Example 1 except that magnesium nitrate was not added to the impregnating solution. The content of each element in the composition analysis of the obtained catalyst was Zr: 3.
7, Ru: 0.5% by weight. The X-ray diffraction pattern and BET surface area were measured in the same manner as in Example 1. The X-ray diffraction pattern is shown in FIG. 1, and the BET surface area is shown in Table 1. Evaluation of the steam reforming reaction of propane was performed in the same manner as in Example 1, and the results are shown in Table 1.
【００６６】[0066]
【表１】 実施例１〜３はＩS／ＩAが０．００５以下と小さく、表
面積が８ｍ2／ｇ以上と大きい。これらはプロパン転化
率が高く、耐熱性指標となるＣ1／Ｃ0も９０以上と大き
く、本反応に対する活性、耐熱性ともに優れている。実
施例のＩS／ＩAが小さいのは、表面積が大きくなること
からわかるように、担持した酸化ジルコニウム等の各成
分が微粒子で存在しているためと考えられる。[Table 1] In Examples 1 to 3, I S / I A is as small as 0.005 or less and the surface area is as large as 8 m 2 / g or more. These have a high propane conversion rate and a large C 1 / C 0 index of heat resistance of 90 or more, and are excellent in both activity for this reaction and heat resistance. The small I S / I A in the examples is considered to be because the supported components such as zirconium oxide are present in the form of fine particles, as can be seen from the increase in the surface area.
【００６７】一方、比較例１〜２はＩS／ＩAが０．０１
より大きく、表面積が３ｍ2／ｇ以下と小さい。これら
はプロパン転化率及び耐熱性指標となるＣ1／Ｃ0が小さ
く、本反応に対する活性、耐熱性が大きく劣っている。On the other hand, in Comparative Examples 1 and 2, I S / I A was 0.01.
It is larger and the surface area is as small as 3 m 2 / g or less. These have a small propane conversion and C 1 / C 0 as an index of heat resistance, and are largely inferior in activity and heat resistance to this reaction.
【００６８】[0068]
【発明の効果】本発明の炭化水素の水蒸気改質用触媒
は、含有ルテニウム成分当りの活性が高く、かつ耐熱性
に優れ、その高活性を高温下でも十分に維持するコスト
的にも触媒活性的にも極めて有利な触媒であるThe hydrocarbon steam reforming catalyst of the present invention has a high activity per contained ruthenium component and an excellent heat resistance, and it is cost-effective to maintain its high activity even at high temperatures. Is a very advantageous catalyst
【図１】実施例及び比較例の触媒のＸ線回折図形。FIG. 1 is an X-ray diffraction pattern of catalysts of Examples and Comparative Examples.
Claims (2)
ジルコニウム成分を含有させた触媒であって、α−アル
ミナのＸ線回折の最強ピーク強度ＩAに対するα−アル
ミナ以外の化合物のＸ線回折の最強ピーク強度ＩSの比
ＩS／ＩAが０．０１以下であることを特徴とする炭化水
素の水蒸気改質用触媒。1. A catalyst in which a ruthenium component and a zirconium component are contained in an α-alumina carrier, wherein the strongest peak intensity I A of X-ray diffraction of α-alumina is the strongest X-ray diffraction of a compound other than α-alumina. A catalyst for steam reforming of hydrocarbons, wherein the ratio I S / I A of the peak intensity I S is 0.01 or less.
ルテニウム金属に換算して０．０５〜５重量％及びジル
コニウム成分をジルコニウム金属に換算して０．１〜２
０重量％含有する請求項１記載の炭化水素の水蒸気改質
用触媒。2. The ruthenium component is converted to ruthenium metal in an amount of 0.05 to 5% by weight, and the zirconium component is converted to zirconium metal in an amount of 0.1 to 2 based on the weight of the carrier.
The catalyst for steam reforming of hydrocarbon according to claim 1, which contains 0% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18518395A JP3784859B2 (en) | 1995-07-21 | 1995-07-21 | Hydrocarbon steam reforming catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18518395A JP3784859B2 (en) | 1995-07-21 | 1995-07-21 | Hydrocarbon steam reforming catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0929098A true JPH0929098A (en) | 1997-02-04 |
| JP3784859B2 JP3784859B2 (en) | 2006-06-14 |
Family
ID=16166305
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18518395A Expired - Fee Related JP3784859B2 (en) | 1995-07-21 | 1995-07-21 | Hydrocarbon steam reforming catalyst |
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| Country | Link |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001072416A1 (en) * | 2000-03-29 | 2001-10-04 | Idemitsu Kosan Co., Ltd. | Catalyst for reforming hydrocarbon and method for producing the same |
| JP2001279269A (en) * | 2000-03-31 | 2001-10-10 | Idemitsu Kosan Co Ltd | Method for producing fuel oil for fuel cell and hydrogen for fuel cell |
| JP2001279274A (en) * | 2000-03-31 | 2001-10-10 | Idemitsu Kosan Co Ltd | Fuel oil for fuel cell, desulfurization method and method for producing hydrogen |
| JP2003523450A (en) * | 2000-02-17 | 2003-08-05 | インペリアル・ケミカル・インダストリーズ・ピーエルシー | Desulfurization |
| EP1894622A1 (en) | 2001-03-29 | 2008-03-05 | Idemitsu Kosan Co., Ltd. | Catalytic processes for reforming a hydrocarbon |
-
1995
- 1995-07-21 JP JP18518395A patent/JP3784859B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003523450A (en) * | 2000-02-17 | 2003-08-05 | インペリアル・ケミカル・インダストリーズ・ピーエルシー | Desulfurization |
| WO2001072416A1 (en) * | 2000-03-29 | 2001-10-04 | Idemitsu Kosan Co., Ltd. | Catalyst for reforming hydrocarbon and method for producing the same |
| JP2001279269A (en) * | 2000-03-31 | 2001-10-10 | Idemitsu Kosan Co Ltd | Method for producing fuel oil for fuel cell and hydrogen for fuel cell |
| JP2001279274A (en) * | 2000-03-31 | 2001-10-10 | Idemitsu Kosan Co Ltd | Fuel oil for fuel cell, desulfurization method and method for producing hydrogen |
| EP1894622A1 (en) | 2001-03-29 | 2008-03-05 | Idemitsu Kosan Co., Ltd. | Catalytic processes for reforming a hydrocarbon |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3784859B2 (en) | 2006-06-14 |
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