JP2006239542A - Catalyst for water gas shift reaction and method for manufacturing the same - Google Patents
Catalyst for water gas shift reaction and method for manufacturing the same Download PDFInfo
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- JP2006239542A JP2006239542A JP2005057421A JP2005057421A JP2006239542A JP 2006239542 A JP2006239542 A JP 2006239542A JP 2005057421 A JP2005057421 A JP 2005057421A JP 2005057421 A JP2005057421 A JP 2005057421A JP 2006239542 A JP2006239542 A JP 2006239542A
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- JP
- Japan
- Prior art keywords
- catalyst
- iron
- gas shift
- shift reaction
- water gas
- Prior art date
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- Granted
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- 239000003054 catalyst Substances 0.000 title claims abstract description 211
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims description 42
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 181
- 229910052742 iron Inorganic materials 0.000 claims abstract description 94
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 63
- 229910052751 metal Inorganic materials 0.000 claims abstract description 61
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 43
- 239000010936 titanium Substances 0.000 claims abstract description 43
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000243 solution Substances 0.000 claims abstract description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000006104 solid solution Substances 0.000 claims abstract description 21
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 16
- 239000011701 zinc Substances 0.000 claims abstract description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 13
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 229910052737 gold Inorganic materials 0.000 claims abstract description 10
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 10
- 229910052709 silver Inorganic materials 0.000 claims abstract description 10
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 9
- 239000012670 alkaline solution Substances 0.000 claims abstract description 7
- 230000032683 aging Effects 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000010304 firing Methods 0.000 claims abstract 2
- 239000002184 metal Substances 0.000 claims description 44
- 239000000463 material Substances 0.000 claims description 21
- 239000002002 slurry Substances 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 239000000919 ceramic Substances 0.000 claims description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- 229910052779 Neodymium Inorganic materials 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052788 barium Inorganic materials 0.000 claims description 7
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 229910052712 strontium Inorganic materials 0.000 claims description 7
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 115
- 230000000694 effects Effects 0.000 abstract description 18
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 abstract description 7
- 239000010941 cobalt Substances 0.000 abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 7
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 40
- 239000000203 mixture Substances 0.000 description 40
- 239000007864 aqueous solution Substances 0.000 description 29
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 20
- 229910052739 hydrogen Inorganic materials 0.000 description 20
- 239000001257 hydrogen Substances 0.000 description 19
- 238000005470 impregnation Methods 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 17
- IXSUHTFXKKBBJP-UHFFFAOYSA-L azanide;platinum(2+);dinitrite Chemical compound [NH2-].[NH2-].[Pt+2].[O-]N=O.[O-]N=O IXSUHTFXKKBBJP-UHFFFAOYSA-L 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 17
- 235000003891 ferrous sulphate Nutrition 0.000 description 17
- 239000011790 ferrous sulphate Substances 0.000 description 17
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 17
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 17
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 17
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 17
- 230000009467 reduction Effects 0.000 description 16
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 15
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 15
- 239000011565 manganese chloride Substances 0.000 description 15
- 235000002867 manganese chloride Nutrition 0.000 description 15
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 229910017604 nitric acid Inorganic materials 0.000 description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- 239000010948 rhodium Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000010931 gold Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000010944 silver (metal) Substances 0.000 description 8
- 239000000446 fuel Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000005245 sintering Methods 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 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
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 150000003752 zinc compounds Chemical class 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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Fuel Cell (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Catalysts (AREA)
Abstract
Description
本発明は、水性ガスシフト反応に好適に用いることができる触媒及びその製造方法に関するものである。 The present invention relates to a catalyst that can be suitably used for a water gas shift reaction and a method for producing the same.
水性ガスシフト反応（ＣＯ＋Ｈ２Ｏ→ＣＯ２＋Ｈ２）は、コークスや天然ガスなどの炭化水素及び水蒸気から得られる水性ガスに含まれるＣＯとＨ２Ｏの比率を変える、あるいはＨ２の製造等のため、化学工業プロセスにおいて利用されている大変重要な反応である。 The water gas shift reaction (CO + H 2 O → CO 2 + H 2 ) changes the ratio of CO and H 2 O contained in water gas obtained from hydrocarbons and steam such as coke and natural gas, or production of H 2 , etc. Therefore, it is a very important reaction used in the chemical industry process.
また、近年注目を浴びている燃料電池の燃料となる水素を、都市ガス等を改質して得る場合、副生したＣＯが燃料電池電極を被毒して発電効率が低下するため、この副生したＣＯを低減させる反応としてより高活性な水性ガスシフト反応に注目が集まっている。こうした水性ガスシフト反応の触媒は、一般に、１５０〜２３０℃程度の低温においては銅−亜鉛系や白金／アルミナ系が、３５０〜４５０℃程度の高温においては鉄−クロム系が使用される。 In addition, when hydrogen, which is the fuel of fuel cells that has been attracting attention in recent years, is obtained by reforming city gas or the like, the by-produced CO poisons the fuel cell electrode, reducing power generation efficiency. Attention has been focused on a highly active water gas shift reaction as a reaction for reducing the generated CO. As a catalyst for such a water gas shift reaction, a copper-zinc system or a platinum / alumina system is generally used at a low temperature of about 150 to 230 ° C., and an iron-chromium system is used at a high temperature of about 350 to 450 ° C.
しかし、銅−亜鉛系触媒は、酸化やシンタリングによって短時間で失活してしまう問題点がある。またビーズ形状の場合には爆裂することもあり、使用に際して細心を払わなくてはならない。白金／アルミナ系触媒の耐熱性は高いが、高い活性を発現させるためには白金の担持量を多くする必要があるため触媒自体が非常に高価になってしまう問題点がある。さらには稀少な元素を大量に使用することによって枯渇問題やさらなる値段の高騰などの問題が懸念される。 However, the copper-zinc catalyst has a problem that it deactivates in a short time due to oxidation or sintering. In the case of a bead shape, it may explode and must be used with great care. Although the heat resistance of the platinum / alumina catalyst is high, there is a problem that the catalyst itself becomes very expensive because it is necessary to increase the amount of platinum supported in order to exhibit high activity. Furthermore, there are concerns about problems such as depletion and higher prices due to the use of rare elements in large quantities.
また、鉄−クロム系触媒の耐熱性は高いが反応温度が高温であるため、平衡ガス組成のＣＯ濃度がある一定基準より下がらないという問題点がある。また、これらの触媒を成形した触媒体は、高温で焼結させられないために、圧縮成型されることが多いが、この方法では摩擦や衝撃によって表面から徐々に粉体が脱落する粉化現象が起こりやすく、その粉による触媒反応管の閉塞や反応場圧の上昇が起こりやすくなってしまう。 Further, although the heat resistance of the iron-chromium catalyst is high, the reaction temperature is high, so that there is a problem that the CO concentration of the equilibrium gas composition does not fall below a certain standard. In addition, the catalyst bodies that are molded from these catalysts are often compression molded because they cannot be sintered at high temperatures, but in this method, the powdering phenomenon in which the powder gradually falls off the surface due to friction and impact. The catalyst reaction tube is blocked by the powder and the reaction field pressure is likely to increase.
上記問題点を克服した、大量の貴金属を使用しない高活性な触媒が得られれば、一定条件下の化学工業プロセスのみならず、特に変動条件下における種々の利用が期待され、燃料電池に使用される燃料の改質、即ち、電極触媒の触媒毒となるＣＯを燃料電池に有用な燃料の水素に転化させる利用が期待される。 If a highly active catalyst that does not use a large amount of precious metals and that overcomes the above problems is obtained, it can be used not only in chemical industry processes under certain conditions but also in various variable conditions, and is used in fuel cells. Therefore, it is expected that CO, which is a catalyst poison of an electrode catalyst, is converted to hydrogen, a fuel useful for fuel cells.
また、通常触媒を使用するときは成型体として使用するので何らかの方法で成型体を作成する必要があり、触媒粉体を型に詰め、圧力をかける方法が広く用いられている。 In addition, since a catalyst is usually used as a molded body, it is necessary to prepare the molded body by some method, and a method in which catalyst powder is packed in a mold and pressure is applied is widely used.
鉄系触媒について記された特許文献を以下に示す。
少量の貴金属でも高い活性を有する触媒は、現在最も要求されているところであるが、この要求を満たすような水性ガスシフト反応用の触媒は未だ提供されていない。 A catalyst having high activity even with a small amount of noble metal is currently most demanded, but a catalyst for a water gas shift reaction that satisfies this requirement has not yet been provided.
即ち、前記特許文献１〜３記載の技術は、活性金属成分を担持していない為、低温では活性が高いとは言い難いものである。また、前記特許文献１〜２記載の技術は、鉄と他の金属が固溶体を成していないので、より低活性である。よって水性ガスシフト反応に用いる触媒として優れた特性を有するとは言い難いものである。 That is, since the techniques described in Patent Documents 1 to 3 do not carry an active metal component, it is difficult to say that the activity is high at low temperatures. Moreover, since the technique of the said patent documents 1-2 is not forming the solid solution with iron and another metal, it is lower activity. Therefore, it cannot be said that it has excellent characteristics as a catalyst used in the water gas shift reaction.
本発明は、上記した特許文献１〜３に記載された従来技術の現状に鑑みてなされたものであり、水性ガスシフト反応において、より活性の高い触媒及びその成型体を提供することを技術的課題とする。 The present invention has been made in view of the current state of the prior art described in Patent Documents 1 to 3 above, and it is a technical problem to provide a more active catalyst and a molded body thereof in a water gas shift reaction. And
本発明者らは、この点について鋭意検討を重ねたところ、特定の酸化物を使用し、成型体を作成することにより前記課題を解消できるとの知見を得て発明を完成するに至った。 The inventors of the present invention have made extensive studies on this point. As a result, the inventors have obtained knowledge that the above problems can be solved by using a specific oxide and forming a molded body, and have completed the invention.
前記技術的課題は、次の通りの本発明によって達成できる。 The technical problem can be achieved by the present invention as follows.
即ち、本発明は、少なくとも鉄、ｍ及び活性金属元素ｎからなる触媒で、鉄及びｍが酸化物固溶体をなしており、ｍはＭｎ，Ｃｏ，Ｔｉ，Ｎｉ，Ｚｎの中から選ばれる１種または２種以上の元素であり、活性金属元素ｎはＡｕ，Ａｇ，Ｃｕ，Ｐｔ，Ｆｅ，Ｐｄ，Ｎｉ，Ｉｒ，Ｒｈ，Ｃｏ，Ｏｓ，Ｒｕの中から選ばれる１種または２種以上の活性金属元素である水性ガスシフト反応用の触媒である（本発明１）。 That is, the present invention is a catalyst comprising at least iron, m, and an active metal element n, wherein iron and m form an oxide solid solution, and m is one selected from Mn, Co, Ti, Ni, and Zn. Or two or more elements, and the active metal element n is one or more selected from Au, Ag, Cu, Pt, Fe, Pd, Ni, Ir, Rh, Co, Os, and Ru. It is a catalyst for water gas shift reaction which is a metal element (Invention 1).
また、本発明は、本発明１の触媒中のｍ元素の含有量が、触媒中の元素の比で０．０１〜２０ｍｏｌ％であることを特徴とする水性ガスシフト反応用の触媒である（本発明２）。 Further, the present invention is a catalyst for water gas shift reaction, wherein the content of element m in the catalyst of the present invention 1 is 0.01 to 20 mol% in terms of the ratio of elements in the catalyst (this book) Invention 2).
また、本発明は、本発明１又は２の触媒を構成する活性金属元素の存在量が０．００１〜２ｍｏｌ％であることを特徴とする水性ガスシフト反応用の触媒である（本発明３）。 Further, the present invention is a catalyst for water gas shift reaction, wherein the abundance of active metal elements constituting the catalyst of the present invention 1 or 2 is 0.001 to 2 mol% (Invention 3).
また、本発明は、本発明１乃至３のいずれかに記載の触媒において、アルミニウム、ジルコニウム、珪素、マグネシウム、カルシウム、ストロンチウム、バリウム、チタン、亜鉛、ランタン及びネオジウムの中から選ばれる１種または２種以上の異種金属元素の酸化物を、触媒に対して１〜９００重量％含有させたことを特徴とする水性ガスシフト反応用の触媒である（本発明４）。 Further, the present invention provides the catalyst according to any one of the first to third aspects of the present invention, wherein one or two selected from aluminum, zirconium, silicon, magnesium, calcium, strontium, barium, titanium, zinc, lanthanum, and neodymium. It is a catalyst for water gas shift reaction characterized by containing 1 to 900% by weight of oxides of different kinds of different metal elements with respect to the catalyst (Invention 4).
また、本発明は、本発明１乃至３のいずれかに記載の触媒において、アルミニウム、ジルコニウム、珪素、マグネシウム、カルシウム、ストロンチウム、バリウム、チタン、亜鉛、ランタン及びネオジウムの中から選ばれる１種又は２種以上の異種金属元素の酸化物を、触媒に対して１〜９００重量％含有し、さらに、活性金属元素を０．０００１〜２ｍｏｌ％担持させたことを特徴とする水性ガスシフト反応用の触媒である（本発明５）。 Further, the present invention provides the catalyst according to any one of the first to third aspects, wherein one or two selected from aluminum, zirconium, silicon, magnesium, calcium, strontium, barium, titanium, zinc, lanthanum and neodymium. A catalyst for a water gas shift reaction, characterized in that it contains 1 to 900% by weight of an oxide of different kinds of different metal elements with respect to the catalyst, and further supports 0.0001 to 2 mol% of an active metal element. There is (Invention 5).
また、本発明は、サポート材に、本発明１乃至５のいずれかに記載の触媒を存在させたことを特徴とする水性ガスシフト反応用の触媒体である（本発明６）。 Further, the present invention is a catalyst body for water gas shift reaction, characterized in that the catalyst according to any one of the present invention 1 to 5 is present in a support material (Invention 6).
また、本発明は、サポート材に、本発明１乃至５のいずれかに記載の触媒を存在させ、更に、活性金属元素を０．０００１〜２ｍｏｌ％担持させたことを特徴とする水性ガスシフト反応用の触媒体である（本発明７）。 Further, the present invention provides a water gas shift reaction characterized in that the catalyst according to any one of the present invention 1 to 5 is present in a support material and 0.0001 to 2 mol% of an active metal element is further supported. (Invention 7).
また、本発明は、アルカリ性溶液と、鉄、ｍ及びｎを含む溶液とを混合、熟成して得られる粒子を濾別、水洗した後、焼成することを特徴とする本発明１記載の水性ガスシフト反応用の触媒の製造方法である（本発明８）。 Further, the present invention provides the water gas shift according to the present invention 1, wherein particles obtained by mixing and aging an alkaline solution and a solution containing iron, m and n are filtered, washed with water, and then fired. It is a manufacturing method of the catalyst for reaction (this invention 8).
また、本発明は、アルカリ性溶液と、鉄、ｍ及びｎを含む溶液とを混合、熟成して得られる粒子を濾別、水洗した後、活性金属元素ｎを担持させ、焼成することを特徴とする前記請求項１記載の水性ガスシフト反応用の触媒の製造方法である（本発明９）。 Further, the present invention is characterized in that particles obtained by mixing and aging an alkaline solution and a solution containing iron, m, and n are separated by filtration, washed with water, supported with an active metal element n, and fired. The method for producing a catalyst for a water gas shift reaction according to claim 1 (Invention 9).
また、本発明は、サポート材の表面にセラミックスを含むスラリーを塗布して焼成した後、請求項１乃至５のいずれかに記載の触媒を担持し、更に、活性金属元素を担持させることを特徴とする本発明６又は７記載の水性ガスシフト反応用の触媒体の製造方法である（本発明１０）。 Further, the present invention is characterized in that after the slurry containing ceramics is applied to the surface of the support material and fired, the catalyst according to any one of claims 1 to 5 is supported, and an active metal element is further supported. This is a method for producing a catalyst body for water gas shift reaction according to the present invention 6 or 7 (present invention 10).
本発明に係る触媒は、少なくとも鉄及びｍを含む酸化物固溶体を形成し、且つ、活性金属元素ｎを担持することで、水性ガスシフト反応をより効率よく行えるという優れた効果を奏する。 The catalyst according to the present invention has an excellent effect that a water gas shift reaction can be performed more efficiently by forming an oxide solid solution containing at least iron and m and supporting an active metal element n.
また、本発明４又は５に係るアルミニウム酸化物などを含有させた触媒は、水性ガスシフト反応時の粒子成長を抑制することができるので、より効率よく水性ガスシフト反応を行うことができる。 Moreover, since the catalyst containing the aluminum oxide according to the present invention 4 or 5 can suppress the particle growth during the water gas shift reaction, the water gas shift reaction can be performed more efficiently.
また、本発明６又は７に係るサポート材に触媒を存在させた場合には、触媒のほぼ全量が水性ガスシフト反応に寄与することができるので、触媒の機能を十分に発揮することができる。 In addition, when the catalyst is present in the support material according to the sixth or seventh aspect of the invention, almost the entire amount of the catalyst can contribute to the water gas shift reaction, so that the function of the catalyst can be sufficiently exhibited.
本発明の構成をより詳しく説明すれば次の通りである。 The configuration of the present invention will be described in more detail as follows.
本発明に係る触媒は、鉄と、Ｍｎ，Ｃｏ，Ｔｉ，Ｎｉ，Ｚｎの中から選ばれる１種または２種以上の元素（以下、「ｍ」という。）とを必須成分とした固溶体酸化物に、Ａｕ，Ａｇ，Ｃｕ，Ｐｔ，Ｆｅ，Ｐｄ，Ｎｉ，Ｉｒ，Ｒｈ，Ｃｏ，Ｏｓ，Ｒｕの中から選ばれる１種または２種以上の活性金属元素ｎが存在する触媒からなる。 The catalyst according to the present invention is a solid solution oxide containing iron and one or more elements selected from Mn, Co, Ti, Ni and Zn (hereinafter referred to as “m”) as essential components. And a catalyst containing one or more active metal elements n selected from Au, Ag, Cu, Pt, Fe, Pd, Ni, Ir, Rh, Co, Os, and Ru.
本発明に係る触媒は、鉄及びｍを含む固溶体酸化物からなる担体に、活性金属元素ｎを担持させた触媒からなる水性ガスシフト反応用の触媒である。担体が固溶体を形成しなければ水性ガスシフト反応用の触媒として機能が十分ではない。 The catalyst according to the present invention is a water gas shift reaction catalyst comprising a catalyst in which an active metal element n is supported on a carrier comprising a solid solution oxide containing iron and m. If the support does not form a solid solution, the function as a catalyst for the water gas shift reaction is not sufficient.
一般に、鉄とクロムの固溶体は高温水性ガスシフト用触媒として古くから用いられており、鉄とクロムが固溶体を成すことで酸素の貯蔵放出能が向上し、効率よく触媒反応が達成されるものであるが、水性ガスシフト反応において、その作用機構については充分解明されていない。本発明では、触媒として鉄及びｍからなる酸化物固溶体とすることで、酸素の貯蔵放出能が向上し効率よく水性ガスシフト反応が行えると推察される。また、鉄及びｍからなる酸化物固溶体とすることで、鉄酸化物単独の場合よりも高い比表面積をもつ担体を得ることができる。 In general, solid solutions of iron and chromium have long been used as catalysts for high-temperature water gas shift, and the ability to store and release oxygen is improved when iron and chromium form a solid solution, so that a catalytic reaction can be achieved efficiently. However, the mechanism of action in the water gas shift reaction has not been fully elucidated. In the present invention, it is presumed that by using an oxide solid solution composed of iron and m as a catalyst, the ability to store and release oxygen is improved and water gas shift reaction can be performed efficiently. Moreover, the support | carrier which has a higher specific surface area than the case of an iron oxide alone can be obtained by setting it as the oxide solid solution which consists of iron and m.
本発明に係る触媒の結晶構造はスピネル型であることが好ましく、Ｆｅ３Ｏ４に基づくマグネタイト、γ−Ｆｅ２Ｏ３に基づくマグヘマイト、又は両者の混合体からなることが好ましい。 The crystal structure of the catalyst according to the present invention is preferably a spinel type, and is preferably composed of magnetite based on Fe 3 O 4 , maghemite based on γ-Fe 2 O 3 , or a mixture of both.
本発明に係る触媒の鉄元素のうち、価数が２価であるものの割合は、０〜４０ｍｏｌ％の範囲内であることが好ましい。 Of the iron elements of the catalyst according to the present invention, the ratio of those having a valence of 2 is preferably in the range of 0 to 40 mol%.
なお、比表面積が増大すると担持した金属が高分散し、活性点が増加しやすくなり、活性が向上しやすくなることは知られており、酸素の貯蔵放出能の向上は、酸素原子の移動によって達成されるとされる水性ガスシフト反応活性の向上の要因となり得ると推察される。 In addition, it is known that when the specific surface area is increased, the supported metal is highly dispersed, the active sites are likely to increase, and the activity is likely to be improved. It is surmised that it can be a factor for improving the water gas shift reaction activity that is supposed to be achieved.
本発明１〜３の触媒を構成するｍの含有量は、触媒中の元素の比で０．０１〜２０ｍｏｌ％の範囲内であることが好ましい。ｍが前記範囲外の場合には、本発明の目的とする効果が得られない。より好ましくは０．５〜１０ｍｏｌ％の範囲内である。 The content of m constituting the catalysts of the present invention 1 to 3 is preferably in the range of 0.01 to 20 mol% in terms of the ratio of elements in the catalyst. When m is outside the above range, the intended effect of the present invention cannot be obtained. More preferably, it exists in the range of 0.5-10 mol%.
本発明に係る触媒の活性金属元素は、前記触媒の表面に担持させる形態又は、触媒中に含有させる形態のいずれの形態でもよく、好ましくは、触媒の表面に担持させる形態である。活性金属元素の存在量は、触媒中の元素の比で０．００１〜５．０ｍｏｌ％が好ましく、より好ましくは０．０１〜１．５ｍｏｌ％である。活性金属元素の存在量が前記範囲外の場合には、十分な活性を得ることができない。 The active metal element of the catalyst according to the present invention may be in the form of being supported on the surface of the catalyst or in the form of being contained in the catalyst, preferably in the form of being supported on the surface of the catalyst. The abundance of the active metal element is preferably 0.001 to 5.0 mol%, more preferably 0.01 to 1.5 mol% in terms of the ratio of elements in the catalyst. If the amount of the active metal element is outside the above range, sufficient activity cannot be obtained.
本発明１〜３に係る触媒のＢＥＴ比表面積は３０ｍ２／ｇ以上が好ましく、より好ましくは５０ｍ２／ｇ以上である。上限は３００ｍ２／ｇ程度である。 The BET specific surface area of the catalysts according to the present invention 1 to 3 is preferably 30 m 2 / g or more, more preferably 50 m 2 / g or more. The upper limit is about 300 m 2 / g.
本発明１〜３に係る触媒のＣＯ転化率は、後述する評価法において、３０％以上が好ましく、より好ましくは５０％以上である。 The CO conversion rate of the catalysts according to the present invention 1 to 3 is preferably 30% or more, more preferably 50% or more, in the evaluation method described later.
本発明４に係る触媒は、前記本発明１乃至３の触媒に、アルミニウム、ジルコニウム、珪素、マグネシウム、カルシウム、ストロンチウム、バリウム、チタン、亜鉛、ランタン及びネオジウムの中から選ばれる１種または２種以上の異種金属元素から成る酸化物（以下、「異種金属元素の酸化物」という。）を含有するものである。異種金属元素の酸化物が存在することによって、これらが障壁となり、水性ガスシフト反応時に本発明１乃至３の触媒を構成する粒子の成長を抑制し、触媒活性を高く保持することができる。 The catalyst according to the present invention 4 is the catalyst according to the present invention 1 to 3, wherein one or more selected from aluminum, zirconium, silicon, magnesium, calcium, strontium, barium, titanium, zinc, lanthanum and neodymium. And an oxide composed of a different metal element (hereinafter referred to as “oxide of a different metal element”). By the presence of oxides of different metal elements, these serve as barriers, and during the water gas shift reaction, the growth of particles constituting the catalysts of the present inventions 1 to 3 can be suppressed and the catalytic activity can be kept high.
本発明４に係る触媒において、異種金属元素の酸化物の含有量は、本発明１〜３の触媒に対して、１〜９００重量％含有することが好ましい。異種金属元素の酸化物の含有量が１重量％未満の場合には、障壁としての効果が得られず、９００重量％を越える場合には、本発明１乃至３の触媒成分が少なくなるので、活性が低下してしまうため好ましくない。より好ましくは２０〜８００重量％である。 In the catalyst according to the present invention 4, the content of the oxide of the different metal element is preferably 1 to 900% by weight with respect to the catalyst of the present invention 1 to 3. When the content of the oxide of the dissimilar metal element is less than 1% by weight, the effect as a barrier cannot be obtained, and when it exceeds 900% by weight, the catalyst components of the present invention 1 to 3 are reduced. Since activity falls, it is not preferable. More preferably, it is 20 to 800% by weight.
本発明４に係る触媒のＢＥＴ比表面積は、前記本発明１〜３に係る触媒と同程度である。 The BET specific surface area of the catalyst according to the present invention 4 is approximately the same as that of the catalyst according to the present inventions 1 to 3.
本発明４に係る触媒のＣＯ転化率は、後述する評価法において、４０％以上が好ましく、より好ましくは６０％以上である。 The CO conversion rate of the catalyst according to the present invention 4 is preferably 40% or more, more preferably 60% or more, in the evaluation method described later.
本発明５に係る触媒は、前記本発明４に係る触媒に対して、更に、Ａｕ，Ａｇ，Ｃｕ，Ｐｔ，Ｆｅ，Ｐｄ，Ｎｉ，Ｉｒ，Ｒｈ，Ｃｏ，Ｏｓ，Ｒｕの中から選ばれる１種または２種以上の活性金属元素を触媒に対し０．０００１〜２ｍｏｌ％担持させた触媒であり、担持量はより好ましくは、０．０１〜１ｍｏｌ％である。なお、触媒中の活性金属元素の全含有量は０．１〜１．５ｍｏｌ％が好ましい。 The catalyst according to the present invention 5 is further selected from Au, Ag, Cu, Pt, Fe, Pd, Ni, Ir, Rh, Co, Os, and Ru with respect to the catalyst according to the present invention 1 The catalyst is a catalyst in which 0.0001 to 2 mol% of a seed or two or more active metal elements are supported on the catalyst, and the supported amount is more preferably 0.01 to 1 mol%. In addition, the total content of active metal elements in the catalyst is preferably 0.1 to 1.5 mol%.
本発明５に係る触媒のＣＯ転化率は、後述する評価法において、４０％以上が好ましく、より好ましくは６０％以上である。 The CO conversion rate of the catalyst according to the present invention 5 is preferably 40% or more, more preferably 60% or more, in the evaluation method described later.
本発明１乃至５に係る触媒は、使用する各用途に合わせて成形しても良い。形状やサイズは特に限定しないが、例えば、球状、円柱状、管状や、ハニカム体への塗布などでもよい。通常、球状や円柱状、管状の形状を持つ触媒体の場合のサイズは０．１〜３０ｍｍ程度が好適である。条件によっては有機物や無機物などの各種バインダーを添加することで成形体の強度や細孔分布密度を調整しても良い。 You may shape | mold the catalyst which concerns on this invention 1 thru | or 5 according to each use to be used. The shape and size are not particularly limited, but may be, for example, spherical, cylindrical, tubular, or applied to a honeycomb body. In general, the size of a catalyst body having a spherical, cylindrical, or tubular shape is preferably about 0.1 to 30 mm. Depending on conditions, the strength and pore distribution density of the molded body may be adjusted by adding various binders such as organic substances and inorganic substances.
本発明６に係る触媒体は、サポート材に本発明１乃至５に係るいずれかの触媒を付着・被覆したものである。 The catalyst body according to the present invention 6 is obtained by adhering / coating any of the catalysts according to the present invention 1 to 5 to a support material.
本発明におけるサポート材としては、鉄板、ＳＵＳ管、ムライト、アルミナ、シリカ、コージェライト等から成る成型体であり、好ましくはシリカ、アルミナ、コージェライト等である。 The support material in the present invention is a molded body made of iron plate, SUS tube, mullite, alumina, silica, cordierite or the like, preferably silica, alumina, cordierite or the like.
なお、本発明においては、前記サポート材の表面をケイ素、アルミニウム、ジルコニウム等の酸化物又は水酸化物などであらかじめ被覆してもよい。 In the present invention, the surface of the support material may be coated in advance with an oxide or hydroxide of silicon, aluminum, zirconium or the like.
サポート材と本発明に係る触媒の線膨張係数の相違は少ないほど理想であり、好ましくは±１％以下、より好ましくは±０．５％以下が良い。 The smaller the difference in linear expansion coefficient between the support material and the catalyst according to the present invention, the more ideal it is, and preferably ± 1% or less, more preferably ± 0.5% or less.
また、前記サポート材に本発明１乃至５の触媒を存在させることによって、触媒の使用量を減らすことができ、より安価な触媒を作成できる。 In addition, by using the catalyst of the present invention 1 to 5 in the support material, the amount of the catalyst used can be reduced, and a cheaper catalyst can be produced.
本発明７に係る触媒体は、サポート材に本発明１乃至５に係るいずれかの触媒を被覆し、且つ、Ａｕ，Ａｇ，Ｃｕ，Ｐｔ，Ｆｅ，Ｐｄ，Ｎｉ，Ｉｒ，Ｒｈ，Ｃｏ，Ｏｓ，Ｒｕの中から選ばれる１種または２種以上の活性金属元素を触媒に対し０．０００１〜５．０重量％担持したものである。より好ましくは、０．０１〜３重量％担持させた触媒である。なお、触媒体中の活性金属元素の全含有量は０．１〜４．０重量％が好ましい。 The catalyst body according to the present invention 7 covers the support material with any one of the catalysts according to the present invention 1 to 5, and Au, Ag, Cu, Pt, Fe, Pd, Ni, Ir, Rh, Co, Os. , One or more active metal elements selected from Ru are supported on the catalyst in an amount of 0.0001 to 5.0% by weight. More preferably, the catalyst is supported by 0.01 to 3% by weight. The total content of active metal elements in the catalyst body is preferably 0.1 to 4.0% by weight.
次に、本発明に係る触媒の製造法について述べる。 Next, a method for producing the catalyst according to the present invention will be described.
まず、本発明１乃至３に係る触媒は、アルカリ性溶液と、鉄及びｍを含む溶液とを混合、熟成した後、濾別、水洗、乾燥し、次いで、２００〜１３００℃の温度範囲で加熱して触媒とする製造方法において、Ａｕ，Ａｇ，Ｃｕ，Ｐｔ，Ｆｅ，Ｐｄ，Ｎｉ，Ｉｒ，Ｒｈ，Ｃｏ，Ｏｓ，Ｒｕから選ばれる１種又は２種以上からなる活性金属元素の溶液を鉄などと同様に添加・混合する方法、又は、加熱後の酸化物固溶体に前記活性金属元素を担持する方法のいずれかによっても得ることができる。 First, the catalysts according to the first to third aspects of the present invention are mixed and aged with an alkaline solution and a solution containing iron and m, then filtered, washed with water, dried, and then heated in a temperature range of 200 to 1300 ° C. In the production method using a catalyst, a solution of one or more active metal elements selected from Au, Ag, Cu, Pt, Fe, Pd, Ni, Ir, Rh, Co, Os, and Ru is used as iron or the like. It can be obtained by either the method of adding and mixing in the same manner as described above, or the method of supporting the active metal element on the heated oxide solid solution.
鉄を含む溶液としては、第一硫酸鉄水溶液、第二硫酸鉄水溶液、第一塩化鉄水溶液、第二塩化鉄水溶液、硝酸鉄水溶液等であり、２価又は３価の鉄塩水溶液を用いればよい。また、２価又は３価の鉄塩水溶液を併用してもよく、併用する場合には２価鉄と３価鉄との割合が１０：９０〜９０：１０が好ましい。 Examples of the iron-containing solution include a ferrous sulfate aqueous solution, a ferric sulfate aqueous solution, a ferrous chloride aqueous solution, a ferric chloride aqueous solution, an iron nitrate aqueous solution, and the like. If a divalent or trivalent iron salt aqueous solution is used, Good. Moreover, you may use together divalent or trivalent iron salt aqueous solution, and when using together, the ratio of divalent iron and trivalent iron is 10: 90-90: 10.
熟成時のｐＨは３〜１４が好ましく特に５〜１３が好ましい。 The pH during aging is preferably from 3 to 14, particularly preferably from 5 to 13.
加熱温度は、３００〜８００℃がより好ましい。また、加熱雰囲気は、大気中が好ましい。 As for heating temperature, 300-800 degreeC is more preferable. The heating atmosphere is preferably in the air.
鉄及びｍからなる酸化物固溶体は、鉄及びｍを含む水溶液を同時に混合し熟成するので、ここで生成した沈澱粒子は、元素の組成が均一な粒子になり、各元素が高分散し、固溶体を形成しやすくなる。 The oxide solid solution composed of iron and m is mixed and aged with an aqueous solution containing iron and m at the same time, so the precipitated particles produced here become particles with a uniform element composition, each element is highly dispersed, and the solid solution It becomes easy to form.
本発明においては、活性金属元素の水溶液を、鉄及びｍを含む水溶液と同時、又は鉄などの複合化合物がスラリー状態のときに添加するので、活性金属元素が高分散しやすくなり、活性金属元素が高分散することによって活性金属元素の表面積が増加し、触媒活性が向上する。 In the present invention, the aqueous solution of the active metal element is added simultaneously with the aqueous solution containing iron and m, or when a composite compound such as iron is in a slurry state. Highly dispersed increases the surface area of the active metal element and improves the catalytic activity.
活性金属元素の種類によってはアルカリ性溶液と活性金属元素の溶液を混合しても活性金属元素が沈殿しにくい元素も存在するため、そのような元素は含浸法によって担持させることが好ましい。 Depending on the type of the active metal element, there is an element in which the active metal element is difficult to precipitate even when the alkaline solution and the active metal element solution are mixed. Therefore, it is preferable to support such an element by an impregnation method.
活性金属元素を含浸法によって担持させた場合でも、本発明においては、鉄及びｍが固溶した酸化物であるので、高い触媒活性を有するものである。 Even when the active metal element is supported by the impregnation method, the present invention has high catalytic activity because it is an oxide in which iron and m are dissolved.
本発明４に係る触媒は、前記製造方法で得られた触媒とアルミナなどの異種金属元素の酸化物とを混合して得ることができる。 The catalyst according to the present invention 4 can be obtained by mixing the catalyst obtained by the above production method and an oxide of a different metal element such as alumina.
前記混合は、乾式混合、湿式混合のいずれでもよい。 The mixing may be either dry mixing or wet mixing.
本発明５に係る触媒は、前記製造方法で得られた触媒とアルミナなどの異種金属元素の酸化物とを混合した後、含浸法などにより活性金属元素を担持させることができる。 The catalyst according to the fifth aspect of the present invention can support the active metal element by an impregnation method or the like after mixing the catalyst obtained by the above production method and an oxide of a different metal element such as alumina.
触媒は通常、触媒を成形した触媒体として使用されることが多く、その製造方法も多岐にわたる。一般的な触媒体の製法としては触媒粉体を型に詰めて加圧成型する方法、ケーキ状の触媒を押し出し機によって押し出しその後焼成する方法、若しくは触媒粉体をパンに入れ転動させて造粒する方法等が挙げられる。 Usually, the catalyst is often used as a catalyst body obtained by molding the catalyst, and its production methods are diverse. As a general method for producing a catalyst body, a method in which a catalyst powder is packed in a mold and press-molded, a method in which a cake-like catalyst is extruded by an extruder and then calcined, or a catalyst powder is placed in a pan and rolled. The method of granulating etc. is mentioned.
しかし、実際に触媒を使用する場合、触媒反応に用いられるガスは主に触媒体の表面付近で反応し、触媒体内部にまでは侵入しにくい。よって触媒体内部の触媒成分は触媒反応に十分に寄与することができなくなる。特に、触媒が高価な材料からなる場合、触媒体内部の触媒は無駄になることとなる。
そこで、本発明１０では、セラミックス又はメタル等のサポート材の表面に、前記本発明１〜５のいずれかの触媒を含むスラリーを、必要により、セラミックスを含むスラリーとともに塗布、焼成してコーティングさせることで、サポート材表面に触媒成分の相を形成させ、触媒成分を有効に活用することができる。
However, when a catalyst is actually used, the gas used for the catalytic reaction reacts mainly near the surface of the catalyst body and hardly penetrates into the catalyst body. Therefore, the catalyst component inside the catalyst body cannot sufficiently contribute to the catalytic reaction. In particular, when the catalyst is made of an expensive material, the catalyst inside the catalyst body is wasted.
Therefore, in the present invention 10, a slurry containing the catalyst according to any one of the present inventions 1 to 5 is coated on a surface of a support material such as ceramics or metal, if necessary, together with a slurry containing ceramics, and coated. Thus, a catalyst component phase is formed on the surface of the support material, and the catalyst component can be effectively utilized.
本発明においては、サポート材上にアルミナ等のセラミックスをコーティングさせた後に、前記本発明１〜５のいずれかの触媒をコーティングさせる、若しくは、前記本発明１〜５のいずれかの触媒をコーティングさせた後にセラミックスをごく薄くコーティングさせてもよく、さらに多層にコーティングさせてもよい。サポート材上にセラミックスをコーティングさせた後に前記本発明１〜５のいずれかの触媒をコーティングさせることで、サポート材上に触媒をより強固にコーティングさせることができる。 In the present invention, the support material is coated with a ceramic such as alumina, and then the catalyst according to any one of the present inventions 1 to 5 is coated, or the catalyst according to any one of the present inventions 1 to 5 is coated. After that, the ceramics may be coated very thinly, or may be further coated in multiple layers. The catalyst can be coated more firmly on the support material by coating the catalyst on any one of the first to fifth aspects of the present invention after coating the ceramic on the support material.
サポート材上に前記本発明１〜５の触媒をコーティングさせた後にごく薄くセラミックスをコーティングする場合は、触媒体同士又は容器などと接触したときの磨耗によって前記触媒が剥離するのを防ぐことができる。この場合、コーティングするセラミックスが多孔質でなければ触媒成分まで反応ガスが届かない。 When coating the ceramics of the present invention 1-5 on the support material very thinly, it is possible to prevent the catalyst from peeling off due to wear when contacting the catalyst bodies or containers. . In this case, the reaction gas does not reach the catalyst component unless the ceramic to be coated is porous.
従来の方法でも本発明１〜５の触媒をコーティングできるが、金属水溶液に浸しているので触媒層を厚くすることが難しく、触媒層の紛化も起こり易い。担体元素と触媒原料との化学反応により別相の生成も起こり予想以上の活性劣化も起こる。また、触媒層にある程度の厚みがないと十分な触媒活性が得られない。しかし、本発明においては触媒を含有するスラリーを塗布することができるため、触媒層を容易に厚くでき、粉化も抑制できる。 Although the catalysts of the present invention 1 to 5 can also be coated by conventional methods, it is difficult to increase the thickness of the catalyst layer because it is immersed in a metal aqueous solution, and the catalyst layer is easily pulverized. Due to the chemical reaction between the support element and the catalyst raw material, another phase is generated and the activity is deteriorated more than expected. Further, sufficient catalytic activity cannot be obtained unless the catalyst layer has a certain thickness. However, in the present invention, since the slurry containing the catalyst can be applied, the catalyst layer can be easily thickened and pulverization can be suppressed.
次に、本発明に係る触媒を用いた水性ガスシフト反応について述べる。 Next, the water gas shift reaction using the catalyst according to the present invention will be described.
本発明に係る触媒の存在下で、水及び一酸化炭素を５０℃〜８００℃の温度範囲で反応させることで、水素と二酸化炭素が得られる。触媒の存在割合は水と一酸化炭素を合わせたガス空間速度で１００／ｈ以上が好ましい。 Hydrogen and carbon dioxide are obtained by reacting water and carbon monoxide in the temperature range of 50 ° C. to 800 ° C. in the presence of the catalyst according to the present invention. The presence ratio of the catalyst is preferably 100 / h or more in terms of gas space velocity in which water and carbon monoxide are combined.
＜作用＞
本発明において、鉄及びｍを含む酸化物固溶体からなる担体に、Ａｕ，Ａｇ，Ｃｕ，Ｐｔ，Ｆｅ，Ｐｄ，Ｎｉ，Ｉｒ，Ｒｈ，Ｃｏ，Ｏｓ，Ｒｕの中から選ばれる１種または２種以上の活性金属元素を存在させた触媒は、より高い活性を示す。
また、本発明においては、鉄にｍを固溶させることによって、ｍが固溶しておらず単独の化合物で存在する触媒に対し、比表面積の増加又は触媒の酸素の貯蔵放出能が向上することによって、高い触媒活性が達成される。
<Action>
In the present invention, one or two kinds selected from Au, Ag, Cu, Pt, Fe, Pd, Ni, Ir, Rh, Co, Os, and Ru are used as a support made of an oxide solid solution containing iron and m. The catalyst in which the above active metal element is present exhibits higher activity.
Further, in the present invention, by dissolving m in iron, the specific surface area is increased or the oxygen storage and release ability of the catalyst is improved with respect to a catalyst in which m is not dissolved but exists as a single compound. In this way, high catalytic activity is achieved.
本発明においては、鉄とｍが固溶体を形成し結晶構造がスピネル型であることによって、酸素の貯蔵放出能が向上し、効率よく水性ガスシフト反応が行えると推察される。 In the present invention, it is speculated that iron and m form a solid solution and the crystal structure is a spinel type, so that the ability to store and release oxygen is improved and water gas shift reaction can be efficiently performed.
なお、比表面積が増大すると担持した活性金属元素が高分散し、活性点が増加しやすくなり、活性が向上しやすくなることは一般的によく知られており、酸素の貯蔵放出能の向上は、酸素原子の移動によって達成されるとされる水性ガスシフト反応において、触媒活性の向上の要因になり得ると推察される。 In addition, it is generally well known that when the specific surface area is increased, the supported active metal element is highly dispersed, the active sites are easily increased, and the activity is easily improved. In the water gas shift reaction that is achieved by the movement of oxygen atoms, it is speculated that it can be a factor for improving the catalytic activity.
鉄などの固溶体に活性金属元素を担持させる方法として、活性金属元素の塩を含有する水溶液に乾燥させた鉄などの複合体を浸し、蒸発乾固させる含浸法が一般的であり、本発明においても同様に活性金属元素を含浸法によって担持してもよい。 As a method for supporting an active metal element in a solid solution such as iron, an impregnation method in which a dried complex such as iron is immersed in an aqueous solution containing a salt of the active metal element and evaporated to dryness is generally used. Similarly, an active metal element may be supported by an impregnation method.
さらに、上記触媒にアルミナなどを添加することによって、アルミナなどが前記本発明１〜３の触媒の障壁となり、製造時やシフト反応時に本発明１〜３の触媒粒子の成長又は焼結を抑制することができる。 Furthermore, by adding alumina or the like to the catalyst, alumina or the like becomes a barrier to the catalyst of the first to third aspects of the invention, and suppresses the growth or sintering of the catalyst particles of the first to third aspects of the invention during the production or shift reaction. be able to.
触媒粉体を圧縮成型して触媒体とする方法が一般的であるが、この方法では粉化がおこりやすい。これに対し、安価なサポート材（シリカなどの成型体）の表面に前記本発明１〜５の触媒をコーティングすることによって、触媒の使用量を減らすことができ、より安価な触媒を作成できる。さらに、触媒層を容易に厚くでき、粉化も起こりにくい触媒成型体を得ることができる。 A method of compressing and molding catalyst powder to form a catalyst body is common, but this method tends to cause pulverization. On the other hand, by coating the catalyst of the present invention 1-5 on the surface of an inexpensive support material (molded body such as silica), the amount of the catalyst used can be reduced, and a cheaper catalyst can be created. Furthermore, a catalyst molded body can be obtained in which the catalyst layer can be easily thickened and hardly pulverized.
以下、実施例に基づき本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail based on examples.
触媒を構成する金属元素、ジルコニウム、マンガン、マグネシウム、カルシウム、ストロンチウム、バリウム、チタン、亜鉛、ランタン、ネオジウム、アルミニウム、鉄、Ａｕ，Ａｇ，Ｃｕ，Ｐｔ，Ｐｄ，Ｎｉ，Ｉｒ，Ｒｈ，Ｃｏ，Ｏｓ，Ｒｕの含有量は、該触媒を酸で溶解し、「プラズマ発光分光分析装置 ＳＰＳ４０００（セイコー電子工業（株））」で測定して求めた。 Metal elements constituting the catalyst, zirconium, manganese, magnesium, calcium, strontium, barium, titanium, zinc, lanthanum, neodymium, aluminum, iron, Au, Ag, Cu, Pt, Pd, Ni, Ir, Rh, Co, Os , Ru content was obtained by dissolving the catalyst with an acid and measuring it with a “plasma emission spectrometer SPS4000 (Seiko Electronics Co., Ltd.)”.
ＢＥＴ比表面積値は、窒素によるＢＥＴ法により測定した。 The BET specific surface area value was measured by the BET method using nitrogen.
相の同定は、Ｘ線回折測定で行った。Ｘ線回折装置は「Ｘ線回折装置ＲＩＮＴ−２５００（理学電機（株）製）」（管球：Ｃｕ、管電圧：４０ｋＶ、管電流：３００ｍＡ、ゴニオメーター：広角ゴニオメーター、サンプリング幅：０．０２０°、走査速度：２°／ｍｉｎ、発散スリット：１°、散乱スリット：１°、受光スリット：０．５０ｍｍ）を使用した。 The phase was identified by X-ray diffraction measurement. The X-ray diffractometer is “X-ray diffractometer RINT-2500 (manufactured by Rigaku Corporation)” (tube: Cu, tube voltage: 40 kV, tube current: 300 mA, goniometer: wide-angle goniometer, sampling width: 0. 020 °, scanning speed: 2 ° / min, divergence slit: 1 °, scattering slit: 1 °, light receiving slit: 0.50 mm).
実施例１
第一硫酸鉄、第二硫酸鉄及び二塩化マンガンに純水を加えて５００ｍｌとしてよく撹拌したものを溶液１−１とし、苛性ソーダを水に溶解し５００ｍｌとしたものを溶液１−２とする。なお、第一硫酸鉄と第二硫酸鉄との鉄のモル比は１：２とした。溶液１−２を６０℃に加熱して攪拌しておき、そこに溶液１−１を投入し、８０℃で３時間熟成した。得られた沈殿物を濾過、洗浄し、４００℃で１時間焼成した。これにジニトロジアンミン白金硝酸水溶液を用いて含浸法により白金を担持し、４００℃で１時間焼成した後、２００℃で水素還元を行った。
白金、鉄、マンガンの組成比（モル比）は０．４：９６．６：３であった。
ＸＲＤ測定では、得られた触媒はＦｅ３Ｏ４に帰属され、格子定数のうちａ軸長は８．３５４３Åであって後出する比較例１より増加しており、マンガン化合物に起因するピークもみられないことから、マンガンが固溶していることが確認された。
Example 1
Pure water is added to ferrous sulfate, ferric sulfate, and manganese dichloride, and the mixture is well stirred to 500 ml. Solution 1-1 is obtained, and caustic soda is dissolved in water to 500 ml. The molar ratio of iron between ferrous sulfate and ferric sulfate was 1: 2. The solution 1-2 was heated to 60 ° C. and stirred, and the solution 1-1 was added thereto and aged at 80 ° C. for 3 hours. The resulting precipitate was filtered, washed and baked at 400 ° C. for 1 hour. This was loaded with platinum by an impregnation method using a dinitrodiammine platinum nitric acid aqueous solution, calcined at 400 ° C. for 1 hour, and then subjected to hydrogen reduction at 200 ° C.
The composition ratio (molar ratio) of platinum, iron, and manganese was 0.4: 96.6: 3.
In the XRD measurement, the obtained catalyst was attributed to Fe 3 O 4, and the a-axis length of the lattice constant was 8.3543 mm, which was increased from Comparative Example 1 described later, and peaks due to the manganese compound were also observed. It was confirmed that manganese was in solid solution.
実施例２
二塩化マンガンの変わりに二塩化コバルトを使用して実施例１と同様に合成した。白金、鉄、コバルトの組成比（モル比）は０．４：９６．６：３であった。
ＸＲＤ測定によって求めた触媒の格子定数のうちａ軸長は、８．３４８６Åであって後出する比較例１より減少しており、コバルト化合物に起因するピークもみられないことから、コバルトが固溶していることが確認された。
Example 2
Synthesis was performed in the same manner as in Example 1 except that cobalt dichloride was used instead of manganese dichloride. The composition ratio (molar ratio) of platinum, iron, and cobalt was 0.4: 96.6: 3.
Of the lattice constants of the catalyst determined by XRD measurement, the a-axis length is 8.3486 mm, which is smaller than that of Comparative Example 1 to be described later, and no peak due to the cobalt compound is observed. It was confirmed that
実施例３
二塩化マンガンの変わりに四塩化チタンを使用して実施例１と同様に合成した。白金、鉄、チタンの組成比（モル比）は０．４：９６．６：３であった。
ＸＲＤ測定によって求めた触媒の格子定数のうちａ軸長は、８．３４２２Åであって後出する比較例１より減少しており、チタン化合物に起因するピークもみられないことから、チタンが固溶していることが確認された。
Example 3
Synthesis was performed in the same manner as in Example 1 using titanium tetrachloride instead of manganese dichloride. The composition ratio (molar ratio) of platinum, iron, and titanium was 0.4: 96.6: 3.
Of the lattice constants of the catalyst determined by XRD measurement, the a-axis length is 8.3422 mm, which is smaller than that of Comparative Example 1 to be described later, and no peak due to the titanium compound is observed. It was confirmed that
実施例４
二塩化マンガンの変わりに二塩化ニッケルを使用して実施例１と同様に合成した。白金、鉄、ニッケルの組成比（モル比）は０．４：９６．６：３であった。
ＸＲＤ測定によって求めた触媒の格子定数のうちａ軸長は、８．３４３４Åであって後出する比較例１より減少しており、ニッケル化合物に起因するピークもみられないことから、ニッケルが固溶していることが確認された。
Example 4
Synthesis was performed in the same manner as in Example 1 except that nickel dichloride was used instead of manganese dichloride. The composition ratio (molar ratio) of platinum, iron, and nickel was 0.4: 96.6: 3.
Of the lattice constants of the catalyst determined by XRD measurement, the a-axis length is 8.3434 mm, which is smaller than that of Comparative Example 1 to be described later, and no peak due to the nickel compound is observed. It was confirmed that
実施例５
二塩化マンガンの変わりに二塩化亜鉛を使用して実施例１と同様に合成した。白金、鉄、亜鉛の組成比（モル比）は０．４：９６．６：３であった。
ＸＲＤ測定によって求めた触媒の格子定数のうちａ軸長は、８．３４９１Åであって後出する比較例１より減少しており、亜鉛化合物に起因するピークもみられないことから、亜鉛が固溶していることが確認された。
Example 5
Synthesis was performed in the same manner as in Example 1 except that zinc dichloride was used instead of manganese dichloride. The composition ratio (molar ratio) of platinum, iron, and zinc was 0.4: 96.6: 3.
Of the lattice constants of the catalyst determined by XRD measurement, the a-axis length is 8.3491 mm, which is smaller than that of Comparative Example 1 to be described later, and no peak due to the zinc compound is observed. It was confirmed that
実施例６
二塩化マンガンの変わりに四塩化チタンを、ジニトロジアンミン白金の変わりに硝酸ロジウムを使用して実施例１と同様に合成した。ロジウム、鉄、チタンのｍｏｌ％は０．４：９６．６：３であった。
Example 6
Titanium tetrachloride was synthesized in the same manner as in Example 1, using titanium tetrachloride instead of manganese dichloride and rhodium nitrate instead of dinitrodiammine platinum. The mol% of rhodium, iron, and titanium was 0.4: 96.6: 3.
実施例７
二塩化マンガンの変わりに四塩化チタンを、ジニトロジアンミン白金の変わりに硝酸パラジウムを使用して実施例１と同様に合成した。パラジウム、鉄、チタンの組成比（モル比）は０．４：９６．６：３であった。
Example 7
Titanium tetrachloride was synthesized in the same manner as in Example 1 using titanium nitrate instead of manganese dichloride and palladium nitrate instead of dinitrodiammine platinum. The composition ratio (molar ratio) of palladium, iron, and titanium was 0.4: 96.6: 3.
実施例８
二塩化マンガンの変わりに四塩化チタンを、ジニトロジアンミン白金の変わりに硝酸ルテニウムを使用して実施例１と同様に合成した。ルテニウム、鉄、チタンの組成比（モル比）は０．４：９６．６：３であった。
Example 8
Titanium tetrachloride was synthesized in the same manner as in Example 1 using ruthenium nitrate instead of dinitrodiammine platinum instead of manganese dichloride. The composition ratio (molar ratio) of ruthenium, iron, and titanium was 0.4: 96.6: 3.
実施例９
二塩化マンガンの変わりに四塩化チタンを使用して実施例１と同様に合成した。白金、鉄、チタンの組成比（モル比）は０．２：９６．８：３であった。
Example 9
Synthesis was performed in the same manner as in Example 1 using titanium tetrachloride instead of manganese dichloride. The composition ratio (molar ratio) of platinum, iron, and titanium was 0.2: 96.8: 3.
実施例１０
二塩化マンガンの変わりに四塩化チタンを使用して実施例１と同様に合成した。白金、鉄、チタンの組成比（モル比）は０．６：９６．４：３であった。
Example 10
Synthesis was performed in the same manner as in Example 1 using titanium tetrachloride instead of manganese dichloride. The composition ratio (molar ratio) of platinum, iron, and titanium was 0.6: 96.4: 3.
実施例１１
第一硫酸鉄、第二硫酸鉄及び二塩化マンガンに加えて四塩化チタンを使用して実施例１と同様に合成した。白金、鉄、マンガン、チタンの組成比（モル比）は０．４：９６．６：１：２であった。
Example 11
Synthesis was performed in the same manner as in Example 1 using titanium tetrachloride in addition to ferrous sulfate, ferric sulfate and manganese dichloride. The composition ratio (molar ratio) of platinum, iron, manganese, and titanium was 0.4: 96.6: 1: 2.
実施例１２
第一硫酸鉄、第二硫酸鉄、二塩化コバルト及び四塩化チタンを使用して実施例１と同様に合成した。白金、鉄、コバルト、チタンの組成比（モル比）は０．４：９６．６：１：２であった。
Example 12
Synthesis was performed in the same manner as in Example 1 using ferrous sulfate, ferric sulfate, cobalt dichloride and titanium tetrachloride. The composition ratio (molar ratio) of platinum, iron, cobalt, and titanium was 0.4: 96.6: 1: 2.
実施例１３
第一硫酸鉄、第二硫酸鉄、二塩化ニッケル及び四塩化チタンを使用して実施例１と同様に合成した。白金、鉄、ニッケル、チタンの組成比（モル比）は０．４：９６．６：１：２であった。
Example 13
Synthesis was performed in the same manner as in Example 1 using ferrous sulfate, ferric sulfate, nickel dichloride and titanium tetrachloride. The composition ratio (molar ratio) of platinum, iron, nickel, and titanium was 0.4: 96.6: 1: 2.
実施例１４
第一硫酸鉄、第二硫酸鉄、二塩化亜鉛及び四塩化チタンを使用して実施例１と同様に合成した。白金、鉄、亜鉛、チタンの組成比（モル比）は０．４：９６．６：１：２であった。
Example 14
Synthesis was performed in the same manner as in Example 1 using ferrous sulfate, ferric sulfate, zinc dichloride and titanium tetrachloride. The composition ratio (molar ratio) of platinum, iron, zinc, and titanium was 0.4: 96.6: 1: 2.
実施例１５
組成比を変化させた以外は、実施例１と同様に合成した。白金、鉄、マンガンの組成比（モル比）は０．４：９４．６：５であった。
Example 15
The synthesis was performed in the same manner as in Example 1 except that the composition ratio was changed. The composition ratio (molar ratio) of platinum, iron, and manganese was 0.4: 94.6: 5.
実施例１６
二塩化マンガンの変わりに二塩化コバルトを使用して実施例１と同様に合成した。白金、鉄、コバルトの組成比（モル比）は０．４：９４．６：５であった。
Example 16
Synthesis was performed in the same manner as in Example 1 except that cobalt dichloride was used instead of manganese dichloride. The composition ratio (molar ratio) of platinum, iron, and cobalt was 0.4: 94.6: 5.
実施例１７
二塩化マンガンの変わりに四塩化チタンを使用して実施例１と同様に合成した。白金、鉄、チタンの組成比（モル比）は０．４：９４．６：５であった。
Example 17
Synthesis was performed in the same manner as in Example 1 using titanium tetrachloride instead of manganese dichloride. The composition ratio (molar ratio) of platinum, iron, and titanium was 0.4: 94.6: 5.
実施例１８
二塩化マンガンの変わりに二塩化ニッケルを使用して実施例１と同様に合成した。白金、鉄、ニッケルの組成比（モル比）は０．４：９４．６：５であった。
Example 18
Synthesis was performed in the same manner as in Example 1 except that nickel dichloride was used instead of manganese dichloride. The composition ratio (molar ratio) of platinum, iron, and nickel was 0.4: 94.6: 5.
実施例１９
二塩化マンガンの変わりに二塩化亜鉛を使用して実施例１と同様に合成した。白金、鉄、亜鉛の組成比（モル比）は０．４：９４．６：５であった。
Example 19
Synthesis was performed in the same manner as in Example 1 except that zinc dichloride was used instead of manganese dichloride. The composition ratio (molar ratio) of platinum, iron, and zinc was 0.4: 94.6: 5.
実施例２０
硝酸ロジウム、第一硫酸鉄、第二硫酸鉄及び四塩化チタンに純水を加えて５００ｍｌとしてよく撹拌したものを溶液２−１とし、苛性ソーダを水に溶解し５００ｍｌとしたものを溶液２−２とする。溶液１−２を６０℃に加熱して攪拌しておき、そこに溶液２−１を投入し、８０℃で３時間熟成した。得られた沈殿物を濾過、洗浄し、４００℃で１時間焼成した後、２００℃で水素還元を行った。
ロジウム、鉄、チタンの組成比（モル比）は０．４：９６．６：３であった。
Example 20
A solution prepared by adding pure water to rhodium nitrate, ferrous sulfate, ferric sulfate and titanium tetrachloride to make 500 ml is made solution 2-1, and caustic soda is dissolved in water to make 500 ml. And The solution 1-2 was heated to 60 ° C. and stirred, and the solution 2-1 was added thereto and aged at 80 ° C. for 3 hours. The obtained precipitate was filtered, washed, calcined at 400 ° C. for 1 hour, and then subjected to hydrogen reduction at 200 ° C.
The composition ratio (molar ratio) of rhodium, iron, and titanium was 0.4: 96.6: 3.
実施例２１
硝酸ルテニウム、第一硫酸鉄、第二硫酸鉄及び四塩化チタンに純水を加えて５００ｍｌとしてよく撹拌したものを溶液３−１とし、苛性ソーダを水に溶解し５００ｍｌとしたものを溶液４−２とする。溶液１−２を６０℃に加熱して攪拌しておき、そこに溶液５−１を投入し、８０℃で３時間熟成した。得られた沈殿物を濾過、洗浄し、４００℃で１時間焼成した後、２００℃で水素還元を行った。
ルテニウム、鉄、チタンの組成比（モル比）は０．４：９６．６：３であった。
Example 21
Pure water is added to ruthenium nitrate, ferrous sulfate, ferric sulfate and titanium tetrachloride to make 500 ml, and the mixture is stirred well to make solution 3-1, and caustic soda is dissolved in water to make 500 ml. And Solution 1-2 was heated to 60 ° C. and stirred, and then solution 5-1 was added thereto and aged at 80 ° C. for 3 hours. The obtained precipitate was filtered, washed, calcined at 400 ° C. for 1 hour, and then subjected to hydrogen reduction at 200 ° C.
The composition ratio (molar ratio) of ruthenium, iron, and titanium was 0.4: 96.6: 3.
実施例２２
第一硫酸鉄と第二硫酸鉄との鉄のモル比を１：１とした以外は実施例３と同様に合成した。白金、鉄、チタンの組成比（モル比）は０．４：９６．６：３であった。
Example 22
The synthesis was performed in the same manner as in Example 3 except that the molar ratio of iron of ferrous sulfate and ferric sulfate was 1: 1. The composition ratio (molar ratio) of platinum, iron, and titanium was 0.4: 96.6: 3.
実施例２２
第一硫酸鉄と第二硫酸鉄との鉄のモル比を２：１とした以外は実施例３と同様に合成した。白金、鉄、チタンの組成比（モル比）は０．４：９６．６：３であった。
Example 22
The synthesis was performed in the same manner as in Example 3 except that the molar ratio of iron of ferrous sulfate and ferric sulfate was 2: 1. The composition ratio (molar ratio) of platinum, iron, and titanium was 0.4: 96.6: 3.
比較例１
第一硫酸鉄及び第二硫酸鉄に純水を加えて５００ｍｌとしてよく撹拌したものを溶液４−１とし、苛性ソーダを水に溶解し５００ｍｌとしたものを溶液４−２とする。なお、第一硫酸鉄と第二硫酸鉄との鉄のモル比は１：２とした。溶液４−２を６０℃に加熱して攪拌しておき、そこに溶液４−１を投入し、８０℃で３時間熟成した。得られた沈殿物を濾過、洗浄し、４００℃で１時間焼成した。これにジニトロジアンミン白金硝酸水溶液を用いて、含浸法により白金を担持し、４００℃で１時間焼成した後、２００℃で水素還元を行った。
白金、鉄の組成比（モル比）は０．４：９９．６であった。
ＸＲＤ測定によって求めた触媒の格子定数のうちａ軸長は、８．３５１５Åであった。
Comparative Example 1
A solution prepared by adding pure water to ferrous sulfate and ferric sulfate to 500 ml and stirring well is designated as Solution 4-1, and a solution obtained by dissolving caustic soda in water to obtain 500 ml is designated as Solution 4-2. The molar ratio of iron between ferrous sulfate and ferric sulfate was 1: 2. The solution 4-2 was heated to 60 ° C. and stirred, and the solution 4-1 was added thereto and aged at 80 ° C. for 3 hours. The resulting precipitate was filtered, washed and baked at 400 ° C. for 1 hour. A dinitrodiammine platinum nitric acid aqueous solution was used for this, and platinum was supported by an impregnation method. After baking at 400 ° C. for 1 hour, hydrogen reduction was performed at 200 ° C.
The composition ratio (molar ratio) of platinum and iron was 0.4: 99.6.
Of the lattice constants of the catalyst determined by XRD measurement, the a-axis length was 8.3515 mm.
比較例２
第一硫酸鉄及び第二硫酸鉄に純水を加えて５００ｍｌとしてよく撹拌したものを溶液５−１とし、苛性ソーダを水に溶解し５００ｍｌとしたものを溶液５−２とする。なお、第一硫酸鉄と第二硫酸鉄との鉄のモル比は１：２とした。溶液５−２を６０℃に加熱して攪拌しておき、そこに溶液５−１を投入し、８０℃で３時間熟成した。得られた沈殿物を濾過、洗浄し、４００℃で１時間焼成し、その後チタニアを混合した。これにジニトロジアンミン白金硝酸水溶液を用いて、含浸法により白金を担持し、４００℃で１時間焼成した後、２００℃で水素還元を行った。
白金、鉄、チタンの組成比（モル比）は０．４：９６．６：３であった。
ＸＲＤ測定によって求めた触媒の格子定数のうちａ軸長は、８．３５１４Åであり比較例１と同等であった。
Comparative Example 2
A solution obtained by adding pure water to ferrous sulfate and ferric sulfate to 500 ml and stirring well is designated as Solution 5-1, and a solution obtained by dissolving caustic soda in water to obtain 500 ml is designated as Solution 5-2. The molar ratio of iron between ferrous sulfate and ferric sulfate was 1: 2. The solution 5-2 was heated to 60 ° C. and stirred, and the solution 5-1 was added thereto and aged at 80 ° C. for 3 hours. The obtained precipitate was filtered, washed, and calcined at 400 ° C. for 1 hour, and then titania was mixed. A dinitrodiammine platinum nitric acid aqueous solution was used for this, and platinum was supported by an impregnation method. After baking at 400 ° C. for 1 hour, hydrogen reduction was performed at 200 ° C.
The composition ratio (molar ratio) of platinum, iron, and titanium was 0.4: 96.6: 3.
Of the lattice constants of the catalyst determined by XRD measurement, the a-axis length was 8.3514 mm, which was equivalent to Comparative Example 1.
比較例３
第一硫酸鉄及び第二硫酸鉄に純水を加えて５００ｍｌとしてよく撹拌したものを溶液５−１とし、苛性ソーダを水に溶解し５００ｍｌとしたものを溶液５−２とする。なお、第一硫酸鉄と第二硫酸鉄との鉄のモル比は１：２とした。溶液５−２を６０℃に加熱して攪拌しておき、そこに溶液５−１を投入し、８０℃で３時間熟成した。得られた沈殿物を濾過、洗浄し、４００℃で１時間焼成し、その後酸化コバルトを混合した。これにジニトロジアンミン白金硝酸水溶液を用いて、含浸法により白金を担持し、４００℃で１時間焼成した後、２００℃で水素還元を行った。
白金、鉄、コバルトの組成比（モル比）は０．４：９６．６：３であった。
ＸＲＤ測定によって求めた触媒の格子定数のうちａ軸長は、８．３５１３Åであり比較例１と同等であった。
Comparative Example 3
A solution obtained by adding pure water to ferrous sulfate and ferric sulfate to 500 ml and stirring well is designated as Solution 5-1, and a solution obtained by dissolving caustic soda in water to obtain 500 ml is designated as Solution 5-2. The molar ratio of iron between ferrous sulfate and ferric sulfate was 1: 2. The solution 5-2 was heated to 60 ° C. and stirred, and the solution 5-1 was added thereto and aged at 80 ° C. for 3 hours. The obtained precipitate was filtered, washed, and calcined at 400 ° C. for 1 hour, and then cobalt oxide was mixed. A dinitrodiammine platinum nitric acid aqueous solution was used for this, and platinum was supported by an impregnation method. After baking at 400 ° C. for 1 hour, hydrogen reduction was performed at 200 ° C.
The composition ratio (molar ratio) of platinum, iron, and cobalt was 0.4: 96.6: 3.
Of the lattice constants of the catalyst determined by XRD measurement, the a-axis length was 8.3513 mm, which was equivalent to Comparative Example 1.
比較例４
γ−アルミナにジニトロジアンミン白金硝酸水溶液を用いて、含浸法により白金を担持し、４００℃で１時間焼成した後、２００℃で水素還元を行った。
白金、アルミの組成比（モル比）は０．４：９９．６であった。
Comparative Example 4
Using an aqueous solution of dinitrodiammine platinum nitrate on γ-alumina, platinum was supported by an impregnation method, calcined at 400 ° C. for 1 hour, and then subjected to hydrogen reduction at 200 ° C.
The composition ratio (molar ratio) of platinum and aluminum was 0.4: 99.6.
実施例２４
白金、鉄、チタンのｍｏｌ比を０．３５：９６．６：３とした以外は、実施例３と同様な方法で製造した触媒とシリカとを重量比が５０：５０となるようによく混合した。これにジニトロジアンミン白金硝酸水溶液を用いて、含浸法により白金を担持し、４００℃で１時間焼成した後、２００℃で水素還元を行った。
白金、鉄、チタンの組成比（モル比）は０．４：９６．６：３であった。
Example 24
Except for the molar ratio of platinum, iron and titanium of 0.35: 96.6: 3, the catalyst prepared in the same manner as in Example 3 and silica were mixed well so that the weight ratio was 50:50. did. A dinitrodiammine platinum nitric acid aqueous solution was used for this, and platinum was supported by an impregnation method. After baking at 400 ° C. for 1 hour, hydrogen reduction was performed at 200 ° C.
The composition ratio (molar ratio) of platinum, iron, and titanium was 0.4: 96.6: 3.
実施例２５
白金、鉄、チタンのｍｏｌ比を０．３５：９６．６：３とした以外は、実施例３と同様な方法で製造した触媒とチタニアとを重量比が５０：５０となるようによく混合した。これにジニトロジアンミン白金硝酸水溶液を用いて、含浸法により白金を担持し、４００℃で１時間焼成した後、２００℃で水素還元を行った。
白金、鉄、チタンの組成比（モル比）は０．４：９６．６：３であった。
Example 25
Except for the molar ratio of platinum, iron and titanium of 0.35: 96.6: 3, the catalyst produced by the same method as in Example 3 and titania were mixed well so that the weight ratio was 50:50. did. A dinitrodiammine platinum nitric acid aqueous solution was used for this, and platinum was supported by an impregnation method. After baking at 400 ° C. for 1 hour, hydrogen reduction was performed at 200 ° C.
The composition ratio (molar ratio) of platinum, iron, and titanium was 0.4: 96.6: 3.
実施例２６
白金、鉄、チタンのｍｏｌ比を０．３５：９６．６：３とした以外は、実施例３と同様な方法で製造した触媒とアルミナとを重量比が５０：５０となるようによく混合した。これにジニトロジアンミン白金硝酸水溶液を用いて、含浸法により白金を担持し、４００℃で１時間焼成した後、２００℃で水素還元を行った。最終的な白金、鉄、チタンの組成比（モル比）は０．４：９６．６：３であった。
Example 26
Except for the molar ratio of platinum, iron and titanium of 0.35: 96.6: 3, the catalyst prepared in the same manner as in Example 3 and alumina were mixed well so that the weight ratio was 50:50. did. A dinitrodiammine platinum nitric acid aqueous solution was used for this, and platinum was supported by an impregnation method. After baking at 400 ° C. for 1 hour, hydrogen reduction was performed at 200 ° C. The final composition ratio (molar ratio) of platinum, iron, and titanium was 0.4: 96.6: 3.
実施例２７
白金、鉄、チタンのｍｏｌ比を０．３５：９６．６：３とした以外は、実施例３と同様な方法で製造した触媒とアルミナとを重量比が７５：２５となるようによく混合した。これにジニトロジアンミン白金硝酸水溶液を用いて、含浸法により白金を担持し、４００℃で１時間焼成した後、２００℃で水素還元を行った。
白金、鉄、チタンの組成比（モル比）は０．４：９６．６：３であった。
Example 27
Except for the molar ratio of platinum, iron and titanium of 0.35: 96.6: 3, the catalyst prepared in the same manner as in Example 3 and alumina were mixed well so that the weight ratio was 75:25. did. A dinitrodiammine platinum nitric acid aqueous solution was used for this, and platinum was supported by an impregnation method. After baking at 400 ° C. for 1 hour, hydrogen reduction was performed at 200 ° C.
The composition ratio (molar ratio) of platinum, iron, and titanium was 0.4: 96.6: 3.
実施例２８
白金、鉄、チタンのｍｏｌ比を０．３５：９６．６：３とした以外は、実施例３と同様な方法で製造した触媒とアルミナとを重量比が２５：７５となるようによく混合した。これにジニトロジアンミン白金硝酸水溶液を用いて、含浸法により白金を担持し、４００℃で１時間焼成した後、２００℃で水素還元を行った。
白金、鉄、チタンの組成比（モル比）は０．４：９６．６：３であった。
Example 28
Except for the molar ratio of platinum, iron and titanium of 0.35: 96.6: 3, the catalyst produced by the same method as in Example 3 and alumina were mixed well so that the weight ratio was 25:75. did. A dinitrodiammine platinum nitric acid aqueous solution was used for this, and platinum was supported by an impregnation method. After baking at 400 ° C. for 1 hour, hydrogen reduction was performed at 200 ° C.
The composition ratio (molar ratio) of platinum, iron, and titanium was 0.4: 96.6: 3.
実施例２９
実施例３と同様な方法で製造した触媒とシリカとを重量比が５０：５０となるようによく混合した。これにジニトロジアンミン白金硝酸水溶液を用いて、含浸法により白金を担持し、４００℃で１時間焼成した後、２００℃で水素還元を行った。
白金、鉄、チタンの組成比（モル比）は０．４：９６．６：３であった。
Example 29
The catalyst produced by the same method as in Example 3 and silica were mixed well so that the weight ratio was 50:50. A dinitrodiammine platinum nitric acid aqueous solution was used for this, and platinum was supported by an impregnation method. After baking at 400 ° C. for 1 hour, hydrogen reduction was performed at 200 ° C.
The composition ratio (molar ratio) of platinum, iron, and titanium was 0.4: 96.6: 3.
比較例５
白金、鉄、チタンのｍｏｌ比を０．３５：９６．６：３とした以外は、実施例３と同様な方法で製造した触媒とアルミナとを重量比が５：９５となるようによく混合した。これにジニトロジアンミン白金硝酸水溶液を用いて、含浸法により白金を担持し、４００℃で１時間焼成した後、２００℃で水素還元を行った。
白金、鉄、チタンの組成比（モル比）は０．４：９６．６：３であった。
Comparative Example 5
Except for the molar ratio of platinum, iron, and titanium of 0.35: 96.6: 3, the catalyst produced in the same manner as in Example 3 and alumina were mixed well so that the weight ratio was 5:95. did. A dinitrodiammine platinum nitric acid aqueous solution was used for this, and platinum was supported by an impregnation method. After baking at 400 ° C. for 1 hour, hydrogen reduction was performed at 200 ° C.
The composition ratio (molar ratio) of platinum, iron, and titanium was 0.4: 96.6: 3.
これらの触媒を、１から２ｍｍに整粒した。この触媒の触媒層を電気炉で加熱し、所定の温度でＣＯが３３体積％、水蒸気が６７体積％のガスを空間速度（ＧＨＳＶ）２００００ｈ−１で流通させた。このときの出口ガス組成をガスクロマトグラフで測定した。 These catalysts were sized to 1 to 2 mm. The catalyst layer of this catalyst was heated in an electric furnace, and a gas having a volume of CO of 33% by volume and water vapor of 67% by volume was passed at a predetermined temperature at a space velocity (GHSV) of 20000 h −1 . The outlet gas composition at this time was measured with a gas chromatograph.
各触媒について、白金、ロジウム、パラジウム、ルテニウム、鉄、マンガン、コバルト、チタン、ニッケル、亜鉛のｍｏｌ％、比表面積、２００℃においてのＣＯ転化率を表１に示した。 Table 1 shows platinum, rhodium, palladium, ruthenium, iron, manganese, cobalt, titanium, nickel, zinc mol%, specific surface area, and CO conversion at 200 ° C. for each catalyst.
また、本発明３の、本発明１又は２の触媒にアルミニウム、ジルコニウム、珪素、マグネシウム、カルシウム、ストロンチウム、バリウム、チタン、亜鉛、ランタン及びネオジウムの中から選ばれる１種または２種以上の元素からなる酸化物を前記触媒に対して、０．００１〜９００重量％添加し、Ａｕ，Ａｇ，Ｃｕ，Ｐｔ，Ｆｅ，Ｐｄ，Ｎｉ，Ｉｒ，Ｒｈ，Ｃｏ，Ｏｓ，Ｒｕの中から選ばれる１種または２種以上の金属元素を０．０００１〜５．０重量％担持させた触媒のＣＯ転化率を表２に示した。 In addition, the catalyst of the present invention 3 of the present invention 1 or 2 is made of one or more elements selected from aluminum, zirconium, silicon, magnesium, calcium, strontium, barium, titanium, zinc, lanthanum and neodymium. One type selected from Au, Ag, Cu, Pt, Fe, Pd, Ni, Ir, Rh, Co, Os, and Ru. Alternatively, Table 2 shows the CO conversion of the catalyst in which 0.0001 to 5.0% by weight of two or more metal elements are supported.
なお、ＣＯ転化率が１００％にならないのは、反応平衡に依存するからである。 The reason why the CO conversion rate does not reach 100% is that it depends on the reaction equilibrium.
表１に示すとおり、本発明に係る触媒はいずれも反応温度が２００℃であっても、高いＣＯ転化率を有するものであることが確認された。従って、低い反応温度でも高いＣＯ転化率を有するものである。 As shown in Table 1, it was confirmed that all the catalysts according to the present invention have a high CO conversion rate even when the reaction temperature is 200 ° C. Therefore, it has a high CO conversion even at a low reaction temperature.
本発明の触媒と構成元素の重量比が同じであっても、固溶体となっていなければ高い活性を示さない。 Even if the weight ratio of the catalyst of the present invention and the constituent elements is the same, high activity is not exhibited unless the catalyst is a solid solution.
表２より、本発明の触媒とアルミナ等を混合した触媒は、高い活性を示す。 From Table 2, a catalyst obtained by mixing the catalyst of the present invention with alumina or the like exhibits high activity.
実施例３０
実施例２２の触媒を、水ガラス及びＰＶＡと共にカイコウして２０％スラリーとした。アルミナの成型体をこのスラリーに浸し、触媒成分を担持後、成型体をスラリーから引き上げ、余分なスラリーを吹き飛ばし、乾燥させ、４００℃にて焼成を行った。これにジニトロジアンミン白金硝酸水溶液を用いて、含浸法により白金を担持し、４００℃で１時間焼成した後、２００℃で水素還元を行った。
Example 30
The catalyst of Example 22 was silkwormed with water glass and PVA to give a 20% slurry. The alumina molded body was immersed in this slurry, and after supporting the catalyst component, the molded body was pulled up from the slurry, excess slurry was blown off, dried, and fired at 400 ° C. A dinitrodiammine platinum nitric acid aqueous solution was used for this, and platinum was supported by an impregnation method. After baking at 400 ° C. for 1 hour, hydrogen reduction was performed at 200 ° C.
比較例６
アルミナの成型体を塩化鉄、塩化チタン水溶液に浸し、鉄及びチタンを担持後、成型体をこの水溶液から引き上げ、乾燥させ、４００℃にて焼成を行った。これにジニトロジアンミン白金硝酸水溶液を用いて、含浸法により白金を担持し、４００℃で１時間焼成した後、２００℃で水素還元を行った。
Comparative Example 6
The alumina molded body was immersed in an aqueous solution of iron chloride and titanium chloride, and after supporting iron and titanium, the molded body was pulled up from the aqueous solution, dried, and fired at 400 ° C. A dinitrodiammine platinum nitric acid aqueous solution was used for this, and platinum was supported by an impregnation method. After baking at 400 ° C. for 1 hour, hydrogen reduction was performed at 200 ° C.
比較例６では、水溶液を浸透させるので、アルミナ成型体上の触媒層を厚くすることが難しく、粉化がおこりやすい。これに対し、実施例２８ではアルミナ成型体の表面に触媒スラリーを塗布することで、触媒層を容易に厚くでき、粉化も起こりにくい触媒成型体を得ることができる。 In Comparative Example 6, since the aqueous solution is infiltrated, it is difficult to thicken the catalyst layer on the alumina molded body, and powdering is likely to occur. On the other hand, in Example 28, by applying the catalyst slurry to the surface of the alumina molded body, the catalyst layer can be easily thickened and a catalyst molded body that hardly causes pulverization can be obtained.
一般的な触媒の成型方法である粉体に圧力をかけて成型する方法に比べ、実施例２８では前者ほどの高価な装置や金型を必要とせず、比較的安価な装置で済み、焼結させることで、粉化が起こりにくい触媒を得ることができる。 Compared with the method of forming powder by applying pressure to the powder, which is a general catalyst forming method, Example 28 does not require an expensive device and mold as the former, and a relatively inexpensive device can be used. By making it, the catalyst which does not occur powdering easily can be obtained.
本発明に係る触媒は、鉄及びｍを含む酸化物の固溶体に活性金属元素を存在させ、必要より、更に、アルミナなどを混合した触媒は、従来の触媒と比べ水性ガスシフト反応をより効率よく行え優れた効果を奏する。また、本発明の触媒成型体の作成方法を用いることでより、実用的な触媒成型体を得ることができる。
In the catalyst according to the present invention, an active metal element is present in a solid solution of an oxide containing iron and m, and a catalyst in which alumina or the like is further mixed can perform a water gas shift reaction more efficiently than a conventional catalyst. Excellent effect. Moreover, a practical catalyst molded body can be obtained by using the method for producing a molded catalyst body of the present invention.
Claims (10)
6. The catalyst according to any one of claims 1 to 5, further comprising an active metal element supported thereon after applying a slurry containing ceramics on the surface of the support material and firing the slurry. Or 7. A process for producing a catalyst body for water gas shift reaction according to 7.
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