JP2010240646A - Catalyst for producing hydrogen, and method of producing hydrogen using the same - Google Patents
Catalyst for producing hydrogen, and method of producing hydrogen using the same Download PDFInfo
- Publication number
- JP2010240646A JP2010240646A JP2010059900A JP2010059900A JP2010240646A JP 2010240646 A JP2010240646 A JP 2010240646A JP 2010059900 A JP2010059900 A JP 2010059900A JP 2010059900 A JP2010059900 A JP 2010059900A JP 2010240646 A JP2010240646 A JP 2010240646A
- Authority
- JP
- Japan
- Prior art keywords
- component
- catalyst
- ammonia
- oxide
- manganese
- 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 277
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000001257 hydrogen Substances 0.000 title claims abstract description 82
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title abstract description 37
- 150000002431 hydrogen Chemical class 0.000 title description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 356
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 178
- 238000002485 combustion reaction Methods 0.000 claims description 101
- 238000000354 decomposition reaction Methods 0.000 claims description 65
- 238000004519 manufacturing process Methods 0.000 claims description 53
- 229910052751 metal Inorganic materials 0.000 claims description 32
- 239000007789 gas Substances 0.000 claims description 31
- 239000002184 metal Substances 0.000 claims description 29
- 239000013078 crystal Substances 0.000 claims description 27
- 239000011572 manganese Substances 0.000 claims description 27
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 25
- WYCDUUBJSAUXFS-UHFFFAOYSA-N [Mn].[Ce] Chemical group [Mn].[Ce] WYCDUUBJSAUXFS-UHFFFAOYSA-N 0.000 claims description 25
- 229910052748 manganese Inorganic materials 0.000 claims description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 22
- 239000001301 oxygen Substances 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 22
- 238000002441 X-ray diffraction Methods 0.000 claims description 19
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 18
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 15
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 14
- 230000000737 periodic effect Effects 0.000 claims description 13
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims description 11
- 150000004706 metal oxides Chemical class 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 150000001340 alkali metals Chemical class 0.000 claims description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 9
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 9
- LQWKWJWJCDXKLK-UHFFFAOYSA-N cerium(3+) manganese(2+) oxygen(2-) Chemical compound [O--].[Mn++].[Ce+3] LQWKWJWJCDXKLK-UHFFFAOYSA-N 0.000 claims description 9
- UOROWBGGYAMZCK-UHFFFAOYSA-N lanthanum(3+) manganese(2+) oxygen(2-) Chemical compound [O-2].[La+3].[Mn+2] UOROWBGGYAMZCK-UHFFFAOYSA-N 0.000 claims description 9
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 8
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 8
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- -1 lanthanoid rare earth metal Chemical class 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 42
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 239000007864 aqueous solution Substances 0.000 description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 39
- 239000007788 liquid Substances 0.000 description 25
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 20
- 239000000843 powder Substances 0.000 description 18
- 238000004438 BET method Methods 0.000 description 17
- 238000010521 absorption reaction Methods 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 16
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 229910052792 caesium Inorganic materials 0.000 description 14
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 14
- 239000012495 reaction gas Substances 0.000 description 14
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
- 238000005259 measurement Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 238000005470 impregnation Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- RPHMKFLEZSBWPT-UHFFFAOYSA-N [Ce].[Mn].[Ag].[Co] Chemical class [Ce].[Mn].[Ag].[Co] RPHMKFLEZSBWPT-UHFFFAOYSA-N 0.000 description 7
- 229910017052 cobalt Inorganic materials 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 229910052684 Cerium Inorganic materials 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- VJFCXDHFYISGTE-UHFFFAOYSA-N O=[Co](=O)=O Chemical compound O=[Co](=O)=O VJFCXDHFYISGTE-UHFFFAOYSA-N 0.000 description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 150000002697 manganese compounds Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 229910001961 silver nitrate Inorganic materials 0.000 description 6
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 5
- PJZQAECXDHMIJZ-UHFFFAOYSA-N [O-2].[Ce+3].[Mn+2].[Ag+].[Co+2].[O-2].[O-2].[O-2] Chemical compound [O-2].[Ce+3].[Mn+2].[Ag+].[Co+2].[O-2].[O-2].[O-2] PJZQAECXDHMIJZ-UHFFFAOYSA-N 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 5
- 238000000975 co-precipitation Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910052809 inorganic oxide Inorganic materials 0.000 description 4
- YMKHJSXMVZVZNU-UHFFFAOYSA-N manganese(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YMKHJSXMVZVZNU-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- AUICSCOFCCUPDH-UHFFFAOYSA-N [La].[Co].[Ag].[Mn] Chemical compound [La].[Co].[Ag].[Mn] AUICSCOFCCUPDH-UHFFFAOYSA-N 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 235000012255 calcium oxide Nutrition 0.000 description 3
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- FZKDURCLMTYEER-UHFFFAOYSA-N cobalt lanthanum Chemical compound [Co].[Co].[Co].[La] FZKDURCLMTYEER-UHFFFAOYSA-N 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 3
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- WUKNAVUORMYQFG-UHFFFAOYSA-N [La].[Ag].[Mn] Chemical compound [La].[Ag].[Mn] WUKNAVUORMYQFG-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 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
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000009841 combustion method Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002604 lanthanum compounds Chemical class 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000013021 overheating Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- PAFSGNQMSUQFPD-UHFFFAOYSA-N [Ce].[Mn].[Ag] Chemical compound [Ce].[Mn].[Ag] PAFSGNQMSUQFPD-UHFFFAOYSA-N 0.000 description 1
- QIMZHEUFJYROIY-UHFFFAOYSA-N [Co].[La] Chemical class [Co].[La] QIMZHEUFJYROIY-UHFFFAOYSA-N 0.000 description 1
- PSMIPFSQQFNOBR-UHFFFAOYSA-N [O-2].[Ce+3].[Mn+2].[Cu+2].[Co+2] Chemical compound [O-2].[Ce+3].[Mn+2].[Cu+2].[Co+2] PSMIPFSQQFNOBR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- DOARWPHSJVUWFT-UHFFFAOYSA-N lanthanum nickel Chemical compound [Ni].[La] DOARWPHSJVUWFT-UHFFFAOYSA-N 0.000 description 1
- GDHNMQIBSKTFPO-UHFFFAOYSA-N lanthanum silver Chemical compound [Ag].[La] GDHNMQIBSKTFPO-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- YSMUYULFBOSFBU-UHFFFAOYSA-N silver cerium(3+) manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Ce+3].[Mn+2].[Ag+].[Ni+2].[O-2].[O-2].[O-2] YSMUYULFBOSFBU-UHFFFAOYSA-N 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Catalysts (AREA)
Abstract
Description
本発明は、アンモニアを原料とし水素を製造するために用いる触媒およびその水素製造方法に関するものである。 The present invention relates to a catalyst used for producing hydrogen from ammonia as a raw material and a method for producing the same.
水素製造技術については、他の工業プロセス、例えば、鉄鋼製造プロセスからの副生水素や、石炭・石油の改質により製造される水素等がある。かかるプロセスから生じる水素は設備依存性が強く、適宜、簡便に水素を利用するという面では利便性が少ないものである。 As for the hydrogen production technology, there are other industrial processes such as by-product hydrogen from the steel production process and hydrogen produced by reforming coal and petroleum. Hydrogen generated from such a process is highly equipment-dependent, and is less convenient in terms of using hydrogen as appropriate.
一方、簡便に水素を得る手段として、アンモニアの分解反応を利用する方法がある。反応式はＮＨ3 → ０．５Ｎ2 ＋ １．５Ｈ2である。この反応は１０．９ｋｃａｌ／ｍｏｌの大きな吸熱反応であることから、系外からの反応熱供給が必要となる。この反応熱の供給方法として、原料であるアンモニアやアンモニア分解反応で生成した水素の一部を燃焼し、その燃焼熱をアンモニア分解の反応熱として用いるオートサーマルリフォーマー（ＡＴＲ）がある（特許文献１，非特許文献１）。燃焼反応はＮＨ3 ＋ ０．７５Ｏ2 → ０．５Ｎ2 ＋ １．５Ｈ2Ｏ；Ｈ2 ＋ ０．５Ｏ2 → Ｈ2Ｏである。ＡＴＲに用いる触媒としては、Ｒｕをアルミナに担持した触媒（特許文献１）、Ｐｔ、Ｒｈをアルミナに担持した触媒（非特許文献１）がある。 On the other hand, as a means for easily obtaining hydrogen, there is a method utilizing a decomposition reaction of ammonia. The reaction formula is NH 3 → 0.5N 2 + 1.5H 2 . Since this reaction is a large endothermic reaction of 10.9 kcal / mol, it is necessary to supply reaction heat from outside the system. As a method for supplying the reaction heat, there is an autothermal reformer (ATR) in which a part of ammonia as a raw material or a part of hydrogen generated by the ammonia decomposition reaction is combusted and the combustion heat is used as a reaction heat for ammonia decomposition (Patent Document 1). Non-patent document 1). The combustion reaction is NH 3 + 0.75O 2 → 0.5N 2 + 1.5H 2 O; H 2 + 0.5O 2 → H 2 O. As a catalyst used for ATR, there are a catalyst in which Ru is supported on alumina (Patent Document 1) and a catalyst in which Pt and Rh are supported on alumina (Non-Patent Document 1).
しかし、これらの触媒を用いる場合、触媒組成によっては反応制御が難しく、定常的に一定濃度の水素を得ることは容易ではないことがある。また、触媒層温度が変化することでアンモニア改質器が損傷したり、触媒の劣化を招くことがある。 However, when these catalysts are used, depending on the catalyst composition, it is difficult to control the reaction, and it may not be easy to constantly obtain a constant concentration of hydrogen. Moreover, the ammonia reformer may be damaged or the catalyst may be deteriorated by changing the catalyst layer temperature.
これらの要因からアンモニア分解反応が不安定となり、分解率が充分でないと、反応後のガスに多量のアンモニアが残存することとなり、水素燃料として質の良くない燃料を提供することになる。また、先に提案されている触媒は、いずれも希少金属で資源的制約のあるＲｕ、Ｒｈ、Ｐｔ等の貴金属元素を触媒活性成分としたものであるため、触媒が高価なものとなりコスト面で実用上、問題が大きい。 Due to these factors, the ammonia decomposition reaction becomes unstable, and if the decomposition rate is not sufficient, a large amount of ammonia remains in the gas after the reaction, thereby providing a poor quality fuel as hydrogen fuel. In addition, the previously proposed catalysts are all rare metals and noble metal elements such as Ru, Rh, and Pt, which are resource-constrained, are used as catalytic active components. There is a big problem in practical use.
本発明は、アンモニアの一部を燃焼し、当該燃焼熱をアンモニア分解反応に利用し、効率的にアンモニアから水素を製造することができる安価で実用的な触媒を見出すことを課題としている。また、当該触媒を用いて効率的にアンモニアから水素を製造する技術を提供することも課題としている。 An object of the present invention is to find an inexpensive and practical catalyst capable of burning a part of ammonia and efficiently producing hydrogen from ammonia by using the heat of combustion for an ammonia decomposition reaction. Another object of the present invention is to provide a technique for efficiently producing hydrogen from ammonia using the catalyst.
本発明者らは、鋭意検討の結果、下記触媒および当該触媒を用いてアンモニアから水素を製造する方法を見出し、本発明を完成した。 As a result of intensive studies, the present inventors have found the following catalyst and a method for producing hydrogen from ammonia using the catalyst, and completed the present invention.
本発明にかかる水素製造触媒は、アンモニアと酸素を含むガスから水素を得るための触媒であって、アンモニア燃焼触媒成分とアンモニア分解触媒成分とを含むことを特徴とする。 The hydrogen production catalyst according to the present invention is a catalyst for obtaining hydrogen from a gas containing ammonia and oxygen, and includes an ammonia combustion catalyst component and an ammonia decomposition catalyst component.
前記アンモニア燃焼触媒成分は、Ａ成分としてマンガン酸化物を含有するものが好ましく、Ａ成分としてマンガン−セリウム酸化物およびＢ成分として周期表８〜１１族に属する金属元素の中から選ばれる少なくとも一種以上の金属元素を含有しており、マンガン−セリウム酸化物がマンガンを二酸化マンガン換算で１〜６０質量％含有していることがより好ましく、Ａ成分として含有されるマンガン−セリウム酸化物がＸ線回折測定にて二酸化セリウムの蛍石型構造を有していると同定されるマンガン−セリウム均密混合酸化物であることがさらに好ましい。 The ammonia combustion catalyst component preferably contains a manganese oxide as the A component, and at least one selected from manganese-cerium oxide as the A component and a metal element belonging to Groups 8 to 11 of the periodic table as the B component. More preferably, the manganese-cerium oxide contains 1 to 60% by mass of manganese in terms of manganese dioxide, and the manganese-cerium oxide contained as component A is X-ray diffraction. More preferred is a manganese-cerium homogeneous mixed oxide identified by measurement to have a cerium dioxide fluorite structure.
また、前記アンモニア燃焼触媒成分は、Ａ成分としてマンガン−ランタン酸化物を含有していてもよい。この場合、Ａ成分として含有されるマンガン−ランタン酸化物がＸ線回折測定にてペロブスカイト型構造を有していると同定されるものが好ましい。Ａ成分として含有されるペロブスカイト型マンガン−ランタン酸化物が更にＣ成分としてアルカリ金属、アルカリ土類金属、ランタノイド系希土類金属、および、周期表８〜１１族に属する金属元素の中から選ばれる少なくとも一種以上の金属元素を結晶構造中に含有するものがより好ましい。 The ammonia combustion catalyst component may contain manganese-lanthanum oxide as the A component. In this case, it is preferable that the manganese-lanthanum oxide contained as the component A is identified as having a perovskite structure by X-ray diffraction measurement. The perovskite-type manganese-lanthanum oxide contained as the A component is further at least one selected from alkali metals, alkaline earth metals, lanthanoid rare earth metals, and metal elements belonging to Groups 8 to 11 of the periodic table as the C component. What contains the above metal element in crystal structure is more preferable.
さらに、前記アンモニア燃焼触媒成分は、更にＤ成分としてアルカリ金属およびアルカリ土類金属から選ばれる少なくとも一種以上の金属元素を含有することも好適である。 Further, the ammonia combustion catalyst component preferably further contains at least one metal element selected from alkali metals and alkaline earth metals as a D component.
一方、前記アンモニア分解触媒成分は、周期表の６〜１０族から選ばれる少なくとも一種の元素を含有するものが好ましい。更にＥ成分として酸化アルミニウム、酸化チタン、酸化ジルコニウム、酸化セリウム、酸化ランタン、ゼオライト、酸化マグネシウム、酸化カルシウム、酸化バリウム、酸化イットリウム、酸化タングステン、二酸化ケイ素、シリカ−アルミナおよびチタン系複合酸化物からなる群から選ばれる少なくとも一種の金属酸化物を含有するものがより好ましい。更にＦ成分としてアルカリ金属およびアルカリ土類金属から選ばれる少なくとも一種以上の金属元素を含有するものがさらに好ましい。 On the other hand, the ammonia decomposition catalyst component preferably contains at least one element selected from Groups 6 to 10 of the periodic table. Furthermore, as an E component, it consists of aluminum oxide, titanium oxide, zirconium oxide, cerium oxide, lanthanum oxide, zeolite, magnesium oxide, calcium oxide, barium oxide, yttrium oxide, tungsten oxide, silicon dioxide, silica-alumina, and titanium-based composite oxide. Those containing at least one metal oxide selected from the group are more preferred. More preferably, the component F contains at least one metal element selected from alkali metals and alkaline earth metals.
本発明にかかる水素製造方法は、前記水素製造触媒を用いてアンモニアと酸素を含むガスから水素を製造することを特徴とするものである。この製造方法において、アンモニア１モルに対して酸素を０．０５モル以上０．７５モル未満添加することが好ましい。また、アンモニアと酸素を含むガスの流れに対して、前段にアンモニア燃焼触媒成分、後段にアンモニア分解触媒成分を配置し、アンモニアを分解して水素を得ることが好ましい。 The hydrogen production method according to the present invention is characterized in that hydrogen is produced from a gas containing ammonia and oxygen using the hydrogen production catalyst. In this production method, it is preferable to add 0.05 mol or more and less than 0.75 mol of oxygen to 1 mol of ammonia. Moreover, it is preferable to arrange | position an ammonia combustion catalyst component in the front | former stage and arrange | position an ammonia decomposition | disassembly catalyst component in the back | latter stage with respect to the flow of the gas containing ammonia and oxygen, and decompose hydrogen and obtain hydrogen.
本発明は、アンモニアを分解して水素を得る方法として、反応器外部からの過大な加熱をすることなく、アンモニアの一部を燃焼させて得た燃焼熱をアンモニア分解に利用することで自立的な反応を進行させ、効率的にアンモニアから水素を製造することができる安価で実用的な触媒を提供することができた。また、当該触媒を用いて効率的にアンモニアから水素を製造する技術を提供することができた。 As a method of decomposing ammonia to obtain hydrogen by decomposing ammonia, the combustion heat obtained by burning a part of ammonia is utilized for ammonia decomposition without excessive heating from the outside of the reactor. Thus, an inexpensive and practical catalyst capable of efficiently producing hydrogen from ammonia can be provided. Moreover, the technique which manufactures hydrogen efficiently from ammonia using the said catalyst was able to be provided.
＜水素製造方法＞
本発明にかかる水素製造方法は、アンモニアを分解して水素を得るに際して、ＡＴＲを用いるものであり、アンモニア分解に必要な熱量をアンモニア燃焼反応で発生させた燃焼熱により供給して水素を製造するものである。詳しくは、アンモニアに所定量の酸素を加えて反応ガスとし、当該反応ガスをアンモニア燃焼触媒成分と接触させ、酸素を燃焼反応により実質的に完全に消費させて燃焼熱を得て、当該燃焼熱を利用し、アンモニア分解触媒成分を用いて残存アンモニアを分解して水素を製造するものである。
<Hydrogen production method>
The hydrogen production method according to the present invention uses ATR when decomposing ammonia to obtain hydrogen, and produces hydrogen by supplying the amount of heat necessary for ammonia decomposition by the combustion heat generated in the ammonia combustion reaction. Is. Specifically, a predetermined amount of oxygen is added to ammonia to form a reaction gas, the reaction gas is brought into contact with an ammonia combustion catalyst component, oxygen is consumed substantially completely by a combustion reaction to obtain combustion heat, and the combustion heat is obtained. And hydrogen is produced by decomposing residual ammonia using an ammonia decomposition catalyst component.
本発明の水素製造反応では、アンモニア分解に必要な熱量をアンモニア燃焼反応で発生させた燃焼熱により供給して水素を製造することができれば、アンモニア燃焼触媒成分とアンモニア分解触媒成分の配置はどのようなものであっても良く、反応ガス流れに対して入口側にアンモニア燃焼触媒成分を配置し、出口側にアンモニア分解触媒成分を配置する、アンモニア燃焼触媒成分とアンモニア分解触媒成分の双方の成分を含んだ混合触媒層に反応ガスを供給する、等を例示することができる（例えば、図１〜図４の１、２）。好ましい形態としては、反応ガス流れに対して入口側にアンモニア燃焼触媒成分を配置し、出口側にアンモニア分解触媒成分を配置する形態である（図１、２の１、２）。なお、以下においては、触媒入口側を前段、触媒出口側を後段と記載することがある。 In the hydrogen production reaction of the present invention, if hydrogen can be produced by supplying the amount of heat necessary for ammonia decomposition by the combustion heat generated in the ammonia combustion reaction, what is the arrangement of the ammonia combustion catalyst component and the ammonia decomposition catalyst component? The ammonia combustion catalyst component is disposed on the inlet side with respect to the reaction gas flow, and the ammonia decomposition catalyst component is disposed on the outlet side. For example, the reaction gas is supplied to the mixed catalyst layer that is included (for example, 1 and 2 in FIGS. 1 to 4). As a preferred form, an ammonia combustion catalyst component is arranged on the inlet side with respect to the reaction gas flow, and an ammonia decomposition catalyst component is arranged on the outlet side (1, 2 in FIGS. 1 and 2). In the following, the catalyst inlet side may be referred to as the front stage and the catalyst outlet side as the rear stage.
アンモニア分解反応は吸熱反応であり、当該反応を効率良く進行させるには、外部から熱を供給することが必要である。しかし、単純に反応器外部から加熱すると部分的に、特に反応器外周部において過剰加熱が生じやすく、その結果、アンモニア分解反応が不均一なものとなり、定常的に一定濃度の水素を得ることが困難となる場合がある。また、部分的に過剰加熱された触媒の熱劣化が進行してアンモニア分解率が低下する等の問題もある。上記のような問題に対し、本発明の製造方法では、アンモニア分解反応に先立ち、当該アンモニアに所定量の酸素を加えて反応ガスとし、当該反応ガスをアンモニア燃焼触媒成分と接触させ、燃焼反応により実質的に酸素を完全に消費させて燃焼熱を得る。また、当該燃焼熱により温度上昇した無酸素状態の反応ガスを、アンモニア分解触媒成分に接触させ、当該ガス中のアンモニアを分解して水素を製造する。このようにアンモニアの一部を酸化し、反応器内で効率的に分解反応に必要な熱を供給することで、反応器外部からの熱供給時に発生しやすい部分過剰加熱に起因する問題を抑制し、アンモニアを水素と窒素に分解することを有効に行うことができる。 The ammonia decomposition reaction is an endothermic reaction, and it is necessary to supply heat from the outside in order to make the reaction proceed efficiently. However, if heating is simply performed from the outside of the reactor, overheating is likely to occur in part, particularly at the outer periphery of the reactor, resulting in non-uniform ammonia decomposition reaction and obtaining a constant concentration of hydrogen. It can be difficult. In addition, there is a problem that the thermal decomposition of the partially heated catalyst proceeds and the ammonia decomposition rate decreases. To solve the above problems, in the production method of the present invention, prior to the ammonia decomposition reaction, a predetermined amount of oxygen is added to the ammonia to form a reaction gas, which is brought into contact with the ammonia combustion catalyst component, Combustion heat is obtained by substantially completely consuming oxygen. In addition, an oxygen-free reaction gas whose temperature has been increased by the combustion heat is brought into contact with an ammonia decomposition catalyst component, and ammonia in the gas is decomposed to produce hydrogen. In this way, a part of ammonia is oxidized, and heat necessary for the decomposition reaction is efficiently supplied in the reactor, thereby suppressing problems caused by partial overheating that is likely to occur when heat is supplied from the outside of the reactor. Then, it is possible to effectively decompose ammonia into hydrogen and nitrogen.
前記製造方法において、アンモニア分解触媒成分１００容量部に対して、アンモニア燃焼触媒成分が５〜１００容量部であることが好ましく、更に好ましくは１０〜５０容量部である。 In the said manufacturing method, it is preferable that an ammonia combustion catalyst component is 5-100 volume parts with respect to 100 volume parts of ammonia decomposition catalyst components, More preferably, it is 10-50 volume parts.
本発明に用いるガスはアンモニアと酸素を含むものであれば良く、アンモニアに対する酸素のモル比率は、０．０５以上０．７５未満が好ましく、０．１以上０．５以下がより好ましく、もっとも好ましくは０．１２以上０．３以下である。アンモニアに対して酸素を加える際、酸素添加量の増加にともない燃焼熱が増加するため、分解反応の速度は向上するが、過剰な酸素添加により触媒層が分解反応に必要な温度より過度に高い温度になると、触媒の熱劣化が引き起こされるため、触媒の性能や寿命を損なうことになり好ましくない。加えて、過剰な酸素添加は、アンモニアからの水素収率を低下させることとなるため、効率的な水素製造の観点からも好ましくない。 The gas used in the present invention only needs to contain ammonia and oxygen, and the molar ratio of oxygen to ammonia is preferably 0.05 or more and less than 0.75, more preferably 0.1 or more and 0.5 or less. Is 0.12 or more and 0.3 or less. When adding oxygen to ammonia, the heat of combustion increases as the amount of oxygen added increases, so the speed of the decomposition reaction increases, but the catalyst layer is excessively higher than the temperature required for the decomposition reaction due to excess oxygen addition. If the temperature is reached, thermal deterioration of the catalyst is caused, which is not preferable because the performance and life of the catalyst are impaired. In addition, excessive oxygen addition reduces the hydrogen yield from ammonia, which is not preferable from the viewpoint of efficient hydrogen production.
反応ガスの空間速度（ＳＶ）は、１００〜７００，０００ｈ-1が好ましく、より好ましくは１，０００〜１００，０００ｈ-1である。１００ｈ-1未満である場合は、反応器が大きすぎ非効率的となるおそれがある。７００，０００ｈ-1を超える場合は、反応率が低下して水素収率が低下するおそれがある。 The space velocity of the reaction gas (SV) is preferably from 100～700,000H -1, more preferably 1,000~100,000h -1. If it is less than 100 h −1 , the reactor may be too large and inefficient. If it exceeds 700,000 h −1 , the reaction rate may decrease and the hydrogen yield may decrease.
触媒層入口側に供給する反応ガスの温度は、１００〜７００℃が好ましく、より好ましくは１２０〜５００℃である。反応ガスの圧力は特に限定されないが、アンモニア分解反応が分子数増加反応であるため平衡的には減圧から微加圧で実施することが好ましい。 The temperature of the reaction gas supplied to the catalyst layer inlet side is preferably 100 to 700 ° C, more preferably 120 to 500 ° C. The pressure of the reaction gas is not particularly limited. However, since the ammonia decomposition reaction is an increase in the number of molecules, it is preferably carried out from a reduced pressure to a slightly increased pressure in equilibrium.
反応ガスの流れに対して入口側にアンモニア燃焼触媒成分を、出口側にアンモニア分解触媒成分を配置してアンモニア分解による水素製造を実施する場合の、触媒出口側（後段）への供給反応ガス温度は３００〜９００℃が好ましく、より好ましくは４００〜７００℃である。反応ガスの圧力は特に限定されないが、後段でのアンモニア分解反応が分子数増加反応であるため平衡的には減圧から微加圧で実施することが好ましい。 Reaction gas temperature supplied to the catalyst outlet side (rear stage) when ammonia combustion catalyst component is placed on the inlet side and ammonia decomposition catalyst component is placed on the outlet side for the reaction gas flow to produce hydrogen by ammonia decomposition Is preferably 300 to 900 ° C, more preferably 400 to 700 ° C. The pressure of the reaction gas is not particularly limited. However, since the ammonia decomposition reaction in the latter stage is a reaction for increasing the number of molecules, it is preferable to carry out from a reduced pressure to a slightly increased pressure in equilibrium.
＜アンモニア燃焼触媒成分＞
本発明のアンモニア燃焼触媒成分とは、５０〜３００℃の温度条件下でアンモニア燃焼反応を進行させ、供給酸素の実質的全量を消費できる触媒性能を有するものである。本発明のアンモニア燃焼触媒成分は、Ａ成分としてマンガン酸化物を含有するものが好ましい。
<Ammonia combustion catalyst component>
The ammonia combustion catalyst component of the present invention has catalytic performance that allows the ammonia combustion reaction to proceed under a temperature condition of 50 to 300 ° C. and consumes substantially the entire amount of supplied oxygen. The ammonia combustion catalyst component of the present invention preferably contains manganese oxide as the A component.
Ａ成分はマンガン−セリウム酸化物（以下、このアンモニア燃焼触媒成分を「Ｍｎ−Ｃｅ系燃焼成分」と省略する）とすることができる。このＭｎ−Ｃｅ系燃焼成分において、マンガンを二酸化マンガン換算で１〜６０質量％含有することが好ましい。 The component A can be manganese-cerium oxide (hereinafter, this ammonia combustion catalyst component is abbreviated as “Mn—Ce-based combustion component”). In this Mn—Ce-based combustion component, it is preferable to contain 1 to 60% by mass of manganese in terms of manganese dioxide.
前記Ｍｎ−Ｃｅ系燃焼成分は、粉末Ｘ線回折測定にて二酸化セリウムの蛍石型構造を有していると同定されるマンガン−セリウム均密混合酸化物であることが好ましい。本発明のＡ成分の好ましい形態であるマンガン−セリウム均密混合酸化物とは、粉末Ｘ線回折にて測定した際に、酸化マンガンに由来する回折ピークは見られず、蛍石型の二酸化セリウムの結晶ピークを主ピークとして有するものである。粉末試料の結晶構造は格子面間隔（ｄ値）を測定することにより確認することが可能である。Ｘ線回折の測定条件は、ＣｕＫα線源、電圧４５ＫＶ、電流４０ｍＡ、走査範囲１０〜９０°、走査速度０．１９８°／ｍｉｎで実施することができる。本発明により得られたマンガン−セリウム均密混合酸化物のＸ線回折の測定結果では、主ピークのｄ値は３．０７〜３．１５の範囲にあり、ＪＣＰＤＳ（Ｊｏｉｎｔ Ｃｏｍｍｉｔｔｅｅ ｆｏｒ Ｐｏｗｄｅｒ Ｄｉｆｆｒａｃｔｉｏｎ Ｓｔａｎｄａｒｄｓ）カードに記載された二酸化セリウムの蛍石型構造のｄ値である３．１２とほぼ一致する。また、カードに記載されている二酸化セリウムのｄ値は相対強度が高い順に、３．１２、１．９１、１．６３、２．７１等であり、主ピーク以外もほぼ一致した位置（ｄ値±０．０５）に結晶ピークが検出され、マンガン−セリウム均密混合酸化物の結晶構造は二酸化セリウム蛍石型構造にほぼ一致していると考えられる。 The Mn—Ce-based combustion component is preferably a manganese-cerium homogeneous mixed oxide identified as having a fluorite structure of cerium dioxide by powder X-ray diffraction measurement. The manganese-cerium dense mixed oxide, which is a preferred form of the component A of the present invention, shows no diffraction peak derived from manganese oxide when measured by powder X-ray diffraction, and fluorite-type cerium dioxide The crystal peak is the main peak. The crystal structure of the powder sample can be confirmed by measuring the lattice spacing (d value). The measurement conditions of X-ray diffraction can be implemented by a CuKα radiation source, a voltage of 45 KV, a current of 40 mA, a scanning range of 10 to 90 °, and a scanning speed of 0.198 ° / min. In the measurement result of the X-ray diffraction of the manganese-cerium homogeneous mixed oxide obtained by the present invention, the d value of the main peak is in the range of 3.07 to 3.15, and JCPDS (Joint Committee for Powder Diffraction Standards). This is almost the same as 3.12 which is the d value of the cerium dioxide fluorite structure described on the card. In addition, the d value of cerium dioxide written on the card is 3.12, 1.91, 1.63, 2.71, etc., in descending order of relative intensity, and the positions (d value) that are almost identical except for the main peak. A crystal peak is detected at ± 0.05), and the crystal structure of the manganese-cerium dense mixed oxide is considered to be almost identical to the cerium dioxide fluorite structure.
前記Ｍｎ−Ｃｅ系燃焼成分はマンガンを二酸化マンガン換算で１〜６０質量％含有することが好ましい。より好ましくは２〜５０質量％、さらに好ましくは５〜４０質量％である。このように高い含有率でマンガンを含有するにも関わらず、マンガン−セリウム均密混合酸化物では、酸化マンガンに由来する回折ピークが見られないことから、酸化マンガンはアモルファスな状態で酸化セリウム上に高分散されていると推定される。 The Mn—Ce-based combustion component preferably contains 1 to 60% by mass of manganese in terms of manganese dioxide. More preferably, it is 2-50 mass%, More preferably, it is 5-40 mass%. In spite of containing manganese at such a high content, the manganese-cerium dense mixed oxide does not show a diffraction peak derived from manganese oxide, so that manganese oxide is in an amorphous state on cerium oxide. Is highly dispersed.
Ｍｎ−Ｃｅ系燃焼成分におけるマンガンの二酸化マンガン換算の含有率が１質量％未満である場合は、アンモニア燃焼活性が不十分となり効率的なアンモニア燃焼反応が行えなくなる。６０質量％を超える場合は、酸化マンガンが粗大化しやすくなり耐熱性やアンモニア燃焼活性の低下を招くので好ましくない。 When the content of manganese in terms of manganese dioxide in the Mn—Ce-based combustion component is less than 1% by mass, the ammonia combustion activity becomes insufficient and an efficient ammonia combustion reaction cannot be performed. When the amount exceeds 60% by mass, manganese oxide is likely to be coarsened, resulting in a decrease in heat resistance and ammonia combustion activity.
一般に酸化マンガンの結晶構造としてはＭｎＯ、ＭｎＯ2、Ｍｎ2Ｏ3、Ｍｎ3Ｏ4などの形態があり、特にＭｎＯ2は活性二酸化マンガンと呼ばれ強い酸化力を有していることが知られている。しかしながら、ＭｎＯ2は熱により相変化しやすいため、高温条件下で使用されるアンモニア燃焼触媒として使用することは困難であった。後述する製造方法により得られるＭｎ−Ｃｅ系燃焼成分、特にマンガン−セリウム均密混合酸化物は９００℃の高温で熱曝露しても、Ｘ線回折測定において、ほぼ二酸化セリウムの蛍石型の結晶ピークのみが検出されており、熱的安定性に関しても大幅な改善効果が得られることが判った。 In general, the crystal structure of manganese oxide includes MnO, MnO 2 , Mn 2 O 3 , Mn 3 O 4 and the like, and especially MnO 2 is known as active manganese dioxide and has a strong oxidizing power. ing. However, since MnO 2 easily changes in phase due to heat, it has been difficult to use it as an ammonia combustion catalyst used under high temperature conditions. Even if Mn—Ce-based combustion components obtained by the production method described below, especially manganese-cerium dense mixed oxide, are exposed to heat at a high temperature of 900 ° C., X-ray diffraction measurement shows almost cerium dioxide fluorite crystals. Only the peak was detected, and it was found that a significant improvement effect was obtained with respect to thermal stability.
次にＭｎ−Ｃｅ系燃焼成分の製造方法について説明する。Ｍｎ−Ｃｅ系燃焼成分は、固相混合法、固液混合法、液相共沈法、アルコキシドを用いたゾルゲル法等により製造することができる。Ｍｎ−Ｃｅ系燃焼成分の好ましい形態であるマンガン−セリウム均密混合酸化物の調製法としては、特に安価な原料を用い、簡便な製造装置を用いて高活性な均密混合酸化物を製造することができる固液混合法が好ましい製造方法として挙げられる。固液混合法とは、マンガンまたはセリウムのどちらかを、使用する溶媒に不溶な固体原料として用いて、もう一方の金属塩を水などの溶媒に溶解した溶液とし、両者を混合して調製する方法である。セリウム源を固体原料とし、マンガン源を溶液として使用することが好ましい。 Next, a method for producing a Mn—Ce-based combustion component will be described. The Mn—Ce-based combustion component can be produced by a solid phase mixing method, a solid-liquid mixing method, a liquid phase coprecipitation method, a sol-gel method using an alkoxide, or the like. As a method for preparing a manganese-cerium homogeneous mixed oxide, which is a preferred form of the Mn—Ce-based combustion component, a highly active homogeneous mixed oxide is produced using a simple production apparatus using a particularly inexpensive raw material. A solid-liquid mixing method that can be used is a preferable production method. The solid-liquid mixing method uses either manganese or cerium as a solid raw material insoluble in the solvent to be used, and prepares a solution in which the other metal salt is dissolved in a solvent such as water and mixes both. Is the method. It is preferable to use a cerium source as a solid raw material and a manganese source as a solution.
本発明のＭｎ−Ｃｅ系燃焼成分の具体的な製造方法は、酸化セリウム、または酸化セリウムの前駆体と、マンガン化合物溶液を十分に混合し、乾燥後に空気中で３００〜９００℃で焼成する方法が好ましい。この製造方法により、２０〜１００ｍ2／ｇの比表面積を有するマンガン−セリウム均密混合酸化物を調製することができる。セリウム源としては、結晶性の低い酸化セリウム、炭酸セリウム、水酸化セリウム等の酸化セリウムの前駆体が使用可能であり、特に多孔質で高比表面積なマンガン−セリウム均密混合酸化物を得ることができる炭酸セリウムをセリウム源として用いることが好ましい。マンガン源としては、硝酸マンガン、塩化マンガン、酢酸マンガン等の水などの溶媒に溶解可能なマンガン化合物の溶液を使用することができ、特に硝酸マンガン水溶液を使用することが好ましい。水などの溶媒の添加量は固液の均質な混合が可能な範囲とし、混合装置や乾燥装置の仕様に合わせて適宜変更できる。乾燥は水などの溶媒を除去するものであり、８０〜２００℃の範囲で１〜２４時間実施し、その後空気中で３００〜９００℃、好ましくは５００〜７００℃で焼成することでマンガン−セリウム均密混合酸化物を調製することができる。 The specific method for producing the Mn—Ce-based combustion component of the present invention is a method in which cerium oxide or a precursor of cerium oxide and a manganese compound solution are thoroughly mixed, and dried in air at 300 to 900 ° C. Is preferred. By this production method, a manganese-cerium homogeneous mixed oxide having a specific surface area of 20 to 100 m 2 / g can be prepared. As the cerium source, precursors of cerium oxide such as cerium oxide, cerium carbonate, cerium hydroxide and the like having low crystallinity can be used, and in particular, to obtain a porous manganese-cerium dense mixed oxide having a high specific surface area. It is preferable to use cerium carbonate that can be used as a cerium source. As a manganese source, a solution of a manganese compound that can be dissolved in a solvent such as water, such as manganese nitrate, manganese chloride, and manganese acetate, can be used, and an aqueous manganese nitrate solution is particularly preferable. The addition amount of a solvent such as water is within a range in which solid and liquid can be homogeneously mixed, and can be appropriately changed according to the specifications of the mixing apparatus and the drying apparatus. Drying is to remove a solvent such as water, and is carried out in the range of 80 to 200 ° C. for 1 to 24 hours, and then fired in air at 300 to 900 ° C., preferably 500 to 700 ° C., thereby producing manganese-cerium. A dense mixed oxide can be prepared.
また、前記Ｍｎ−Ｃｅ系燃焼成分の製造工程において、マンガン化合物溶液に酢酸、クエン酸、マレイン酸、リンゴ酸、コハク酸等の有機酸を添加することにより、さらに高活性で微細構造を有したマンガン−セリウム均密混合酸化物を得ることができる。有機酸の添加量としてはマンガン化合物１モルに対して０．１〜２モルが好ましく、より好ましくは０．３〜１．５モル、さらに好ましくは０．５〜１モルである。有機酸の添加量が０．１モルより少ない場合は添加効果が得られず、２モルを超える場合は焼成時に還元雰囲気となりマンガン−セリウム均密混合酸化物の性状に悪影響を与える可能性があるため好ましくない。 In addition, in the manufacturing process of the Mn-Ce-based combustion component, by adding an organic acid such as acetic acid, citric acid, maleic acid, malic acid, succinic acid, etc. to the manganese compound solution, it has a more highly active and fine structure. A manganese-cerium homogeneous mixed oxide can be obtained. The addition amount of the organic acid is preferably 0.1 to 2 mol, more preferably 0.3 to 1.5 mol, and still more preferably 0.5 to 1 mol with respect to 1 mol of the manganese compound. If the addition amount of the organic acid is less than 0.1 mol, the addition effect cannot be obtained. If the addition amount exceeds 2 mol, there is a possibility that a reducing atmosphere is formed during firing and the properties of the manganese-cerium homogeneous mixed oxide are adversely affected. Therefore, it is not preferable.
本発明で用いるＭｎ−Ｃｅ系燃焼成分は、Ｂ成分として周期表８〜１１族に属する元素の中から選ばれる少なくとも一種以上の金属元素を含有することができる。８族の鉄、ルテニウム、オスミウム、９族のコバルト、ロジウム、イリジウム、１０族のニッケル、パラジウム、白金および１１族の銅、銀、金などが使用可能である。コスト面で好ましいＢ成分としては、鉄、コバルト、ニッケル、銅および銀から選ばれる少なくとも一種の元素である。尚、Ｂ成分は各元素の金属または金属酸化物として含有することが好ましい。 The Mn—Ce-based combustion component used in the present invention can contain at least one metal element selected from elements belonging to Groups 8 to 11 of the periodic table as the B component. Group 8 iron, ruthenium, osmium, group 9 cobalt, rhodium, iridium, group 10 nickel, palladium, platinum and group 11 copper, silver, gold, etc. can be used. B component preferable in terms of cost is at least one element selected from iron, cobalt, nickel, copper and silver. In addition, it is preferable to contain B component as a metal or metal oxide of each element.
Ｂ成分として、銀および／または銅を含有させることで、アンモニア燃焼活性を向上させることができ、低温での高いアンモニア燃焼活性を得ることができる。また、鉄、ニッケル、コバルトから選ばれる少なくとも一種の金属元素を含有させることで、アンモニア燃焼触媒成分にアンモニア分解性能を具備させることができる。アンモニア分解活性を有するアンモニア燃焼触媒成分を用いることにより、アンモニア燃焼反応による発熱をアンモニア分解反応による吸熱に利用すると同時に、アンモニア燃焼触媒成分の過度な温度上昇を抑制でき、アンモニア燃焼触媒成分の熱による性能劣化を防止することができる。したがって、Ｂ成分としては、銀および／または銅と、鉄、ニッケル、コバルトから選ばれる少なくとも一種の金属元素の両方を含有させることが好ましい。 By containing silver and / or copper as the component B, ammonia combustion activity can be improved, and high ammonia combustion activity at low temperatures can be obtained. Moreover, the ammonia combustion catalyst component can be provided with ammonia decomposition performance by containing at least one metal element selected from iron, nickel, and cobalt. By using the ammonia combustion catalyst component having ammonia decomposition activity, the heat generated by the ammonia combustion reaction can be used for the endotherm by the ammonia decomposition reaction, and at the same time, the excessive temperature rise of the ammonia combustion catalyst component can be suppressed. Performance deterioration can be prevented. Therefore, it is preferable to contain both silver and / or copper and at least one metal element selected from iron, nickel, and cobalt as the B component.
本発明のＭｎ−Ｃｅ系燃焼成分は、前記Ａ成分としてマンガン−セリウム酸化物を１０〜９９．９５質量％、Ｂ成分として周期表８〜１１族の金属元素を当該金属元素の酸化物換算で０．０５〜８０質量％含有することが好ましい。Ａ成分であるマンガン−セリウム酸化物が１０質量％未満である場合は、アンモニアの酸化速度が遅くなり高いアンモニア燃焼活性が得られ難くなる。好ましくは１５質量％以上、より好ましくは２０質量％以上である。また、Ｂ成分である周期表８〜１１族の金属元素が０．０５質量％より少ない場合は、低温でのアンモニア酸化性能が不十分となり、８０質量％を超えても性能向上効果はほとんど得られず分散性が低下して粒子成長する可能性があるので好ましくない。 In the Mn—Ce-based combustion component of the present invention, 10 to 99.95% by mass of manganese-cerium oxide as the A component, and a metal element of Groups 8 to 11 of the periodic table as the B component in terms of oxide of the metal element. It is preferable to contain 0.05-80 mass%. When the manganese-cerium oxide, which is the component A, is less than 10% by mass, the oxidation rate of ammonia is slow, and it is difficult to obtain high ammonia combustion activity. Preferably it is 15 mass% or more, More preferably, it is 20 mass% or more. In addition, when the amount of the metal element belonging to Group 8 to 11 of the periodic table, which is the B component, is less than 0.05% by mass, the ammonia oxidation performance at low temperature becomes insufficient. This is not preferable because the dispersibility may be lowered and particle growth may occur.
本発明のＭｎ−Ｃｅ系燃焼成分の製造方法においてＢ成分の添加方法は特に限定されるものではなく、例えば（１）〜（３）の方法が例示される。（１）Ｍｎ−Ｃｅ系燃焼成分の粉体に、Ｂ成分の金属元素の硝酸塩、硫酸塩などの水溶液を噴霧や浸漬して乾燥焼成して担持してから、これら触媒組成物を成形して乾燥焼成して製造する方法、（２）Ｍｎ−Ｃｅ系燃焼成分の粉末とＢ成分の金属塩溶液と混練して成形してから乾燥焼成して製造する方法、（３）Ｍｎ−Ｃｅ系燃焼成分を含有する触媒組成物を成形して乾燥焼成後に触媒Ｂ成分の金属塩溶液に含浸し、乾燥焼成する方法。前記触媒成分の焼成温度としては３００〜９００℃、好ましくは４００〜６００℃にて空気中で焼成することである。 In the method for producing a Mn—Ce-based combustion component of the present invention, the method for adding the B component is not particularly limited, and examples thereof include the methods (1) to (3). (1) Mn-Ce-based combustion component powder is sprayed or dipped in an aqueous solution of the B component metal element nitrate, sulfate, etc., dried and fired, and then supported by molding these catalyst compositions. (2) Mn-Ce-based combustion method, (2) Mn-Ce-based combustion component powder and B-component metal salt solution are kneaded and molded, then dried and fired, and (3) Mn-Ce-based combustion method A method in which a catalyst composition containing a component is molded, dried and fired, impregnated in a metal salt solution of the catalyst B component, and dried and fired. The catalyst component is calcined in air at 300 to 900 ° C., preferably 400 to 600 ° C.
本発明のアンモニア燃焼触媒成分は、他の態様としてマンガン−ランタン酸化物をＡ成分として含有することができる（以下、このアンモニア燃焼触媒成分を「Ｍｎ−Ｌａ系燃焼成分」と省略する）。当該Ｍｎ−Ｌａ系燃焼成分は、粉末Ｘ線回折測定にてペロブスカイト型構造を有していると同定されるものが好ましい。 As another embodiment, the ammonia combustion catalyst component of the present invention can contain manganese-lanthanum oxide as the A component (hereinafter, this ammonia combustion catalyst component is abbreviated as “Mn—La-based combustion component”). The Mn—La combustion component is preferably identified as having a perovskite structure by powder X-ray diffraction measurement.
前記ペロブスカイト型Ｍｎ−Ｌａ系燃焼成分は、更にＣ成分としてリチウム等のアルカリ金属、カルシウム、ストロンチウム等のアルカリ土類金属、セリウム、プラセオジム等のランタノイド系希土類金属、および、周期表８〜１１族に属する金属元素の中から選ばれる少なくとも一種以上の金属元素を結晶構造中に含有することが好ましい。当該ペロブスカイト型Ｍｎ−Ｌａ系燃焼成分に含まれるマンガン含有量は、ペロブスカイト型結晶構造に組み込まれるＣ成分量との関係で変化するが、通常、マンガンを二酸化マンガン換算で１０〜５０質量％含有することが好ましい。 The perovskite-type Mn—La combustion component further includes, as a C component, an alkali metal such as lithium, an alkaline earth metal such as calcium and strontium, a lanthanoid rare earth metal such as cerium and praseodymium, and groups 8 to 11 of the periodic table. It is preferable that the crystal structure contains at least one metal element selected from the metal elements to which it belongs. The manganese content contained in the perovskite type Mn—La combustion component varies depending on the amount of the C component incorporated into the perovskite type crystal structure, but usually contains 10 to 50% by mass of manganese in terms of manganese dioxide. It is preferable.
Ｃ成分として、銀および／または銅を含有させることで、アンモニア燃焼活性を向上させることができる。また、鉄、ニッケル、コバルトから選ばれる少なくとも一種の金属元素を含有させることで、当該アンモニア燃焼触媒成分にアンモニア分解性能を具備させることができる。したがって、Ｃ成分としては、銀および／または銅と、鉄、ニッケル、コバルトから選ばれる少なくとも一種の金属元素の両方を含有させることが好ましい。 By containing silver and / or copper as component C, ammonia combustion activity can be improved. Further, by containing at least one metal element selected from iron, nickel, and cobalt, the ammonia combustion catalyst component can be provided with ammonia decomposition performance. Therefore, it is preferable to contain both silver and / or copper and at least one metal element selected from iron, nickel, and cobalt as the C component.
マンガン−ランタン酸化物の好ましい形態であるペロブスカイト型マンガン−ランタン酸化物は、固相混合法、固液混合法、液相共沈法、アルコキシドを用いたゾルゲル法等により製造することができる。特に安価な原料を用い、簡便な製造装置で粒子サイズが小さく、ペロブスカイト構造以外の不純な結晶相の少ない高活性なペロブスカイト型酸化物を製造することができる液相共沈法が好ましい製造方法として挙げられる。液相共沈法とは、例えば、所定量のマンガン化合物とランタン化合物を含む水溶液を、過剰なアンモニアや水酸化テトラメチルアンモニウム（ＴＭＡＨ）等の塩基性物質を含む水溶液中に撹拌下、滴下して沈殿物を生成させ、当該沈殿物をろ過、水洗後、乾燥し、５００〜９００℃で熱処理して結晶化させればよい。 Perovskite-type manganese-lanthanum oxide, which is a preferred form of manganese-lanthanum oxide, can be produced by a solid phase mixing method, a solid-liquid mixing method, a liquid phase coprecipitation method, a sol-gel method using an alkoxide, or the like. A liquid phase coprecipitation method that can produce a highly active perovskite oxide with a small particle size and a small amount of impure crystal phases other than the perovskite structure, using a particularly inexpensive raw material as a preferred production method. Can be mentioned. In the liquid phase coprecipitation method, for example, an aqueous solution containing a predetermined amount of a manganese compound and a lanthanum compound is dropped into an aqueous solution containing a basic substance such as excess ammonia or tetramethylammonium hydroxide (TMAH) with stirring. A precipitate is generated, and the precipitate is filtered, washed with water, dried, and heat-treated at 500 to 900 ° C. for crystallization.
また、Ｃ成分の添加方法については、例えば、液相共沈法で結晶構造中にＣ成分を含むＭｎ−Ｌａ系燃焼成分を調製する場合は、所定量のマンガン化合物とランタン化合物を含む水溶液に所定量のＣ成分の水溶性塩を加えた混合水溶液を調製し、当該水溶液を、過剰なアンモニアやＴＭＡＨ等の塩基性物質を含む水溶液中に撹拌下、滴下して沈殿物を生成させ、当該沈殿物をろ過、水洗後、乾燥し、５００〜９００℃で熱処理して結晶化させることで、Ｃ成分をペロブスカイト構造中に組み込むことができる。 As for the method of adding C component, for example, when preparing a Mn-La combustion component containing C component in the crystal structure by liquid phase coprecipitation method, an aqueous solution containing a predetermined amount of manganese compound and lanthanum compound is used. A mixed aqueous solution to which a predetermined amount of a water-soluble salt of component C is added is prepared, and the aqueous solution is dropped into an aqueous solution containing an excess of basic substances such as ammonia and TMAH to form a precipitate. The C component can be incorporated into the perovskite structure by filtering, washing with water, drying, and crystallizing by heat treatment at 500 to 900 ° C.
本発明のアンモニア燃焼触媒成分（Ｍｎ−Ｃｅ系燃焼成分、Ｍｎ−Ｌａ系燃焼成分の両方を含む、以下同じ）は、前述Ａ成分およびＢ成分（またはＣ成分）に加えて、アルミナ、シリカ、シリカ−アルミナ、チタニア、ジルコニア、ゼオライト、マグネシア、カルシア、酸化ランタンおよびチタン系複合酸化物からなる群から選ばれる少なくとも一種の耐火性無機酸化物を含有することもできる。耐火性無機酸化物を含有させる場合は、０〜５０質量％含有させることができる。耐火性無機酸化物を添加することによりＡ成分およびＢ成分（またはＣ成分）の分散性向上による活性向上や触媒の機械的強度の向上が得られる。耐火性無機酸化物が５０質量％を超える場合は、Ａ成分およびＢ成分（またはＣ成分）の含有量が少なくなり、十分な触媒活性が得られなくなるので好ましくない。 In addition to the A component and the B component (or C component), the ammonia combustion catalyst component of the present invention (including both the Mn—Ce combustion component and the Mn—La combustion component) is alumina, silica, It can also contain at least one refractory inorganic oxide selected from the group consisting of silica-alumina, titania, zirconia, zeolite, magnesia, calcia, lanthanum oxide and titanium-based composite oxide. When it contains a refractory inorganic oxide, it can be contained in an amount of 0 to 50% by mass. By adding a refractory inorganic oxide, it is possible to improve the activity and improve the mechanical strength of the catalyst by improving the dispersibility of the A component and the B component (or C component). When the refractory inorganic oxide exceeds 50% by mass, the contents of the A component and the B component (or C component) are decreased, and a sufficient catalytic activity cannot be obtained.
前記アンモニア燃焼触媒成分に、Ｄ成分として更にアルカリ金属および／またはアルカリ土類金属を含有させることができる。Ｄ成分の添加により、アンモニア燃焼触媒成分に具備させたアンモニア分解能をさらに向上させることができる。Ｄ成分の含有量は、アンモニア燃焼触媒成分に対して０．１〜１０質量％、より好ましくは、０．３〜７質量％である。Ｄ成分の含有量が０．１質量％未満であると、アンモニア分解能向上効果が得られない。１０質量％を超えてＤ成分を添加すると、アンモニア燃焼活性が低下するため好ましくない。 The ammonia combustion catalyst component may further contain an alkali metal and / or an alkaline earth metal as the D component. By adding the D component, the ammonia decomposing ability of the ammonia combustion catalyst component can be further improved. Content of D component is 0.1-10 mass% with respect to an ammonia combustion catalyst component, More preferably, it is 0.3-7 mass%. When the content of the D component is less than 0.1% by mass, the effect of improving ammonia resolution cannot be obtained. If the D component is added in excess of 10% by mass, the ammonia combustion activity decreases, which is not preferable.
Ｄ成分は、アンモニア燃焼触媒成分の調製工程で所定量を添加してもよく、調製後のアンモニア燃焼触媒成分に対して添加してもよい。 The D component may be added in a predetermined amount in the preparation process of the ammonia combustion catalyst component, or may be added to the ammonia combustion catalyst component after preparation.
＜アンモニア分解触媒成分＞
アンモニア分解触媒成分としては、３００〜９００℃の温度条件下でアンモニア分解反応を進行させ、アンモニアから水素と窒素を製造できる触媒性能を有するものである。本発明のアンモニア分解触媒成分は、周期表の６〜１０族に属する遷移金属元素から選ばれる少なくとも一種の元素を含有するものが好ましい。中でも、モリブデン、鉄、コバルト、ニッケルを含むものがより好ましい。これらの元素は金属であっても酸化物であってもよく、通常安定に存在するものであればよい。
<Ammonia decomposition catalyst component>
The ammonia decomposing catalyst component has a catalytic performance that allows ammonia decomposing reaction to proceed under a temperature condition of 300 to 900 ° C. to produce hydrogen and nitrogen from ammonia. The ammonia decomposition catalyst component of the present invention preferably contains at least one element selected from transition metal elements belonging to Groups 6 to 10 of the periodic table. Among these, those containing molybdenum, iron, cobalt, and nickel are more preferable. These elements may be metals or oxides, and may be any elements that normally exist stably.
当該周期表の６〜１０族に属する遷移金属元素から選ばれる少なくとも一種の元素は、アンモニア分解触媒成分の必須成分であり、その含有量は、アンモニア分解触媒成分１００質量％に対して、好ましくは５〜９０質量％、より好ましくは１０〜８０質量％である。 At least one element selected from transition metal elements belonging to Group 6 to Group 10 of the periodic table is an essential component of the ammonia decomposition catalyst component, and the content thereof is preferably 100% by mass of the ammonia decomposition catalyst component. It is 5-90 mass%, More preferably, it is 10-80 mass%.
当該元素は、それ単独で使用することもできるが、担体に担持して用いることもでき、担体としては酸化アルミニウム、酸化チタン、酸化ジルコニウム、酸化セリウム、酸化ランタン、ゼオライト、酸化マグネシウム、酸化カルシウム、酸化バリウム、酸化イットリウム、酸化タングステン、二酸化ケイ素、シリカ−アルミナおよびチタン系複合酸化物を用いることができる（Ｅ成分）。 The element can be used alone, but can also be used by being supported on a carrier, such as aluminum oxide, titanium oxide, zirconium oxide, cerium oxide, lanthanum oxide, zeolite, magnesium oxide, calcium oxide, Barium oxide, yttrium oxide, tungsten oxide, silicon dioxide, silica-alumina, and titanium-based composite oxide can be used (E component).
当該Ｅ成分の含有量は、アンモニア分解触媒成分１００質量％に対して、好ましくは１０〜９５質量％、より好ましくは２０〜９０質量％である。 The content of the E component is preferably 10 to 95% by mass, more preferably 20 to 90% by mass with respect to 100% by mass of the ammonia decomposition catalyst component.
また、当該アンモニア分解触媒成分には、ナトリウム、カリウム、ルビジウム、セシウム等のアルカリ金属、マグネシウム、カルシウム、バリウム等のアルカリ土類金属、ランタン、セリウム、プラセオジム、ネオジム等の希土類金属を含有することもできる（Ｆ成分）。Ｆ成分はＥ成分である金属酸化物と複合化させた状態として添加する方法、触媒をＥ成分である金属酸化物に担持した後にＦ成分を添加する方法など、種々の添加方法を採用することができる。当該複合化とは、単に各成分同士の混合ばかりではなく、固溶体、複合酸化物を形成することなども包含する。 The ammonia decomposition catalyst component may also contain alkali metals such as sodium, potassium, rubidium and cesium, alkaline earth metals such as magnesium, calcium and barium, and rare earth metals such as lanthanum, cerium, praseodymium and neodymium. Yes (F component). Various addition methods such as a method in which the F component is added in a state of being complexed with the metal oxide that is the E component, a method in which the F component is added after the catalyst is supported on the metal oxide that is the E component, etc. Can do. The complexing includes not only mixing of the components but also forming a solid solution or a complex oxide.
当該Ｆ成分の含有量は、アンモニア分解触媒成分１００質量％に対して、０〜２５質量％、好ましくは０．２〜１５質量％、より好ましくは０．４〜１０質量％未満である。 Content of the said F component is 0-25 mass% with respect to 100 mass% of ammonia decomposition catalyst components, Preferably it is 0.2-15 mass%, More preferably, it is less than 0.4-10 mass%.
アンモニア分解触媒成分の調製方法としては、金属酸化物系や金属系の触媒を調製する通常の方法を用いることができ、例えば、（１）各成分の金属酸化物を所定の形状に成型して当該成分とし、必要であれば還元ガスで還元する方法、（２）担体となる金属酸化物（Ｅ成分）を、周期表の６〜１０族に属する遷移金属元素から選ばれる少なくとも一種の元素を含有する溶液に浸して担持後、乾燥・焼成し、必要であれば還元ガスで還元する方法、（３）複数の触媒成分を混合するときに、各々の触媒成分を別個の担体となる金属酸化物（Ｅ成分）に含浸し、乾燥・焼成して粉体とし、粉体同士を混合し、必要であれば還元ガスで還元する方法、（４）各金属酸化物同士を混合し、所定の形状に成型後、必要であれば還元ガスで還元して当該成分とする方法、（５）金属や金属酸化物を他の成分である添加成分の水溶液に浸し、乾燥・焼成し、所定の形状に成型後、必要であれば還元ガスで還元する方法、（６）複合酸化物、固溶体酸化物などの金属酸化物を構成する元素の水溶性金属塩を所定量含む金属塩含有水溶液を調製し、当該水溶液をアンモニア、炭酸アンモニウム、水酸化カリウム、ＴＭＡＨなどの塩基性物質を溶解した強塩基性水溶液中に加え、金属水酸化物を析出させ、当該金属水酸化物をろ過、水洗、回収して乾燥後、熱処理して目的とする複合酸化物、固溶体酸化物を調製する方法等を採用することができる。 As a method for preparing the ammonia decomposition catalyst component, a normal method for preparing a metal oxide or metal catalyst can be used. For example, (1) the metal oxide of each component is molded into a predetermined shape. A method of reducing with a reducing gas if necessary, and (2) a metal oxide (component E) serving as a carrier, at least one element selected from transition metal elements belonging to Groups 6 to 10 in the periodic table. A method in which the catalyst component is immersed in a solution, dried, calcined, and reduced with a reducing gas if necessary. (3) When a plurality of catalyst components are mixed, each catalyst component is used as a separate carrier. Impregnating the product (E component), drying and firing to obtain powder, mixing the powders, if necessary, reducing with a reducing gas, (4) mixing each metal oxide, After molding into a shape, if necessary, reduce with reducing gas (5) A method in which a metal or metal oxide is immersed in an aqueous solution of an additive component as another component, dried and fired, molded into a predetermined shape, and reduced with a reducing gas if necessary. 6) A metal salt-containing aqueous solution containing a predetermined amount of a water-soluble metal salt of an element constituting a metal oxide such as a complex oxide or a solid solution oxide is prepared, and the aqueous solution is made of ammonia, ammonium carbonate, potassium hydroxide, TMAH or the like. In addition to a strongly basic aqueous solution in which a basic substance is dissolved, a metal hydroxide is precipitated, the metal hydroxide is filtered, washed, recovered, dried, and then heat treated to obtain the desired composite oxide or solid solution oxidation. A method of preparing a product can be employed.
アンモニア燃焼触媒成分、アンモニア分解触媒成分は、一定の形に成型して使用することができる。成型体の形状は、リング状、馬蹄形、ハニカム状等を例示することができる。またアンモニア燃焼触媒成分、アンモニア分解触媒成分を、ハニカムやコルゲート等のモノリス、球状、サドル状の不活性の構造体に被覆して用いることもできる。 The ammonia combustion catalyst component and the ammonia decomposition catalyst component can be used after being molded into a certain shape. Examples of the shape of the molded body include a ring shape, a horseshoe shape, and a honeycomb shape. Further, the ammonia combustion catalyst component and the ammonia decomposition catalyst component can be used by being coated on a monolith such as a honeycomb or a corrugate, a spherical or saddle-like inactive structure.
以下、実施例により本発明を具体的に説明するが、本発明はこれら実施例のみに限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited only to these Examples.
（アンモニア燃焼触媒成分の製造例）
（実験例１）
固液混合法によりＡ成分であるマンガン−セリウム均密混合酸化物を以下の方法で調製した。粉末状の炭酸セリウムおよび硝酸マンガンの水溶液を計量して、マンガン−セリウム均密混合酸化物中の酸化マンガンの含有率がＭｎＯ2換算で５０質量％となるように十分に混合して、混合物を１５０℃で一晩乾燥して５００℃で５時間焼成して、ハンマ−ミルで粉砕してマンガン−セリウム均密混合酸化物粉体を得た。得られたマンガン−セリウム均密混合酸化物をＣｕＫα線源、電圧４５ＫＶ、電流４０ｍＡ、走査範囲１０〜９０°、走査速度０．１９８°／ｍｉｎでＸ線回折測定を実施した結果、二酸化セリウムの蛍石型結晶構造を示す位置に主ピークが検出されマンガン由来の結晶ピークは観察されなかった。またＢＥＴ法で測定した比表面積は５５ｍ2／ｇであった。
(Ammonia combustion catalyst component production example)
(Experimental example 1)
A manganese-cerium homogeneous mixed oxide as component A was prepared by the following method by a solid-liquid mixing method. The powdered cerium carbonate and manganese nitrate aqueous solution is weighed and mixed well so that the manganese oxide content in the manganese-cerium homogeneous mixed oxide is 50% by mass in terms of MnO 2. It was dried at 150 ° C. overnight, calcined at 500 ° C. for 5 hours, and pulverized with a hammer mill to obtain a manganese-cerium homogeneous mixed oxide powder. The obtained manganese-cerium homogeneous mixed oxide was subjected to X-ray diffraction measurement with a CuKα ray source, a voltage of 45 KV, a current of 40 mA, a scanning range of 10 to 90 °, and a scanning speed of 0.198 ° / min. A main peak was detected at a position showing a fluorite-type crystal structure, and no manganese-derived crystal peak was observed. The specific surface area measured by the BET method was 55 m 2 / g.
上記で得られた粉体に硝酸銀の水溶液を加えて、得られる銀−マンガン−セリウム均密混合酸化物中の酸化銀の含有率がＡｇ2Ｏ換算で１０質量％となるように十分に混合し、この混合物を１５０℃で一晩乾燥した後、５００℃で５時間焼成して、Ｍｎ−Ｃｅ系のアンモニア燃焼触媒成分である触媒１を得た。 An aqueous solution of silver nitrate is added to the powder obtained above, and sufficiently mixed so that the silver oxide content in the obtained silver-manganese-cerium homogeneous mixed oxide is 10% by mass in terms of Ag 2 O. The mixture was dried at 150 ° C. overnight and then calcined at 500 ° C. for 5 hours to obtain a catalyst 1 as an Mn—Ce-based ammonia combustion catalyst component.
（実験例２）
硝酸マンガン六水和物２８．７ｇ、硝酸銀４．２５ｇおよび硝酸ランタン六水和物５４．１ｇを純水１０００ｍＬに投入し、マンガン−銀−ランタン混合水溶液を調製した。次いで、２５質量％ＴＭＡＨ水溶液１０５０ｇに純水を追加して液量約３Ｌとした希釈ＴＭＡＨ水溶液を激しく撹拌した中に、前記マンガン−銀−ランタン混合水溶液をゆっくりと滴下した。滴下終了後、３０分程度撹拌を継続することで熟成を行った。熟成後、ろ過し、純水で水洗後、１１０℃で乾燥し、乾燥物を粉砕後、空気雰囲気中、４００℃で１時間、更に昇温して６５０℃で２時間焼成して、マンガン−銀−ランタン複合酸化物を得た（触媒２）。当該触媒２を、実験例１と同条件でＸ線回折測定を行ったところ、触媒２がペロブスカイト型構造を有する複合酸化物であることが確認された。またＢＥＴ法で測定した触媒２の比表面積は３１ｍ2／ｇであった。
(Experimental example 2)
Manganese nitrate hexahydrate 28.7 g, silver nitrate 4.25 g, and lanthanum nitrate hexahydrate 54.1 g were added to 1000 mL of pure water to prepare a manganese-silver-lanthanum mixed aqueous solution. Then, the manganese-silver-lanthanum mixed aqueous solution was dropped slowly while vigorously stirring the diluted TMAH aqueous solution in which pure water was added to 1050 g of 25 mass% TMAH aqueous solution to make the liquid volume about 3 L. After completion of dropping, aging was carried out by continuing stirring for about 30 minutes. After aging, filtered, washed with pure water, dried at 110 ° C., the dried product was pulverized, fired in an air atmosphere at 400 ° C. for 1 hour, further heated at 650 ° C. for 2 hours, manganese- A silver-lanthanum composite oxide was obtained (Catalyst 2). When X-ray diffraction measurement was performed on the catalyst 2 under the same conditions as in Experimental Example 1, it was confirmed that the catalyst 2 was a complex oxide having a perovskite structure. Moreover, the specific surface area of the catalyst 2 measured by BET method was 31 m < 2 > / g.
（実験例３）
硝酸マンガン六水和物６．６ｇ、硝酸コバルト六水和物２５．４ｇおよび硝酸銀１．４７ｇを蒸留水に溶解させ、当該水溶液中に炭酸セリウム粉末１９．６ｇを添加した。次いで、ホットスターラーで撹拌しながら昇温して水分を蒸発させて乾固物を得た。当該乾固物を１５０℃で一晩乾燥させた後、粉砕し、空気雰囲気下、５００℃で２時間焼成して、コバルト−銀−マンガン−セリウム酸化物からなる粉体を調製した（触媒３）。当該触媒３について、実験例１と同条件でＸ線回折測定を行ったところ、二酸化セリウムの蛍石型結晶構造を示すピーク、および四三酸化コバルトの構造を示すピークのみが検出され、銀およびマンガン由来の結晶ピークは観察されず、マンガンはマンガン−セリウム均密混合酸化物として存在していることが確認された。またＢＥＴ法で測定した触媒３の比表面積は５１ｍ2／ｇであった。
(Experimental example 3)
6.6 g of manganese nitrate hexahydrate, 25.4 g of cobalt nitrate hexahydrate and 1.47 g of silver nitrate were dissolved in distilled water, and 19.6 g of cerium carbonate powder was added to the aqueous solution. Next, the temperature was raised while stirring with a hot stirrer to evaporate the water and obtain a dried product. The dried product was dried at 150 ° C. overnight, pulverized, and calcined at 500 ° C. for 2 hours in an air atmosphere to prepare a powder composed of cobalt-silver-manganese-cerium oxide (Catalyst 3). ). When X-ray diffraction measurement was performed on the catalyst 3 under the same conditions as in Experimental Example 1, only the peak indicating the fluorite-type crystal structure of cerium dioxide and the peak indicating the structure of cobalt trioxide were detected. The crystal peak derived from manganese was not observed, and it was confirmed that manganese exists as a manganese-cerium homogeneous mixed oxide. Further, the specific surface area of the catalyst 3 measured by the BET method was 51 m 2 / g.
（実験例４）
実験例３における硝酸コバルト六水和物の使用量を１４．５ｇに、炭酸セリウム粉末の使用量を２５．４ｇに変更した以外は実験例３と同様にしてコバルト−銀−マンガン−セリウム酸化物からなる粉体を調製した（触媒４）。当該触媒４について、実験例１と同条件でＸ線回折測定を行ったところ、二酸化セリウムの蛍石型結晶構造を示すピーク、および四三酸化コバルトの構造を示すピークのみが検出され、銀およびマンガン由来の結晶ピークは観察されず、マンガンはマンガン−セリウム均密混合酸化物として存在していることが確認された。またＢＥＴ法で測定した触媒４の比表面積は４９ｍ2／ｇであった。
(Experimental example 4)
Cobalt-silver-manganese-cerium oxide in the same manner as in Experimental Example 3, except that the amount of cobalt nitrate hexahydrate used in Experimental Example 3 was changed to 14.5 g and the amount of cerium carbonate powder used was changed to 25.4 g. (Catalyst 4) was prepared. When X-ray diffraction measurement was performed on the catalyst 4 under the same conditions as in Experimental Example 1, only the peak indicating the fluorite-type crystal structure of cerium dioxide and the peak indicating the structure of cobalt trioxide were detected. The crystal peak derived from manganese was not observed, and it was confirmed that manganese exists as a manganese-cerium homogeneous mixed oxide. Further, the specific surface area of the catalyst 4 measured by the BET method was 49 m 2 / g.
（実験例５）
実験例３における硝酸コバルト六水和物の使用量を３６．２６ｇに、炭酸セリウム粉末の使用量を１３．７ｇに変更した以外は実験例３と同様にしてコバルト−銀−マンガン−セリウム酸化物からなる粉体を調製した（触媒５）。当該触媒５について、実験例１と同条件でＸ線回折測定を行ったところ、二酸化セリウムの蛍石型結晶構造を示すピーク、および四三酸化コバルトの構造を示すピークのみが検出され、銀およびマンガン由来の結晶ピークは観察されず、マンガンはマンガン−セリウム均密混合酸化物として存在していることが確認された。またＢＥＴ法で測定した触媒５の比表面積は３４ｍ2／ｇであった。
(Experimental example 5)
Cobalt-silver-manganese-cerium oxide in the same manner as in Experimental Example 3, except that the amount of cobalt nitrate hexahydrate used in Experimental Example 3 was changed to 36.26 g and the amount of cerium carbonate powder used was changed to 13.7 g. (Catalyst 5) was prepared. When X-ray diffraction measurement was performed on the catalyst 5 under the same conditions as in Experimental Example 1, only the peak indicating the fluorite-type crystal structure of cerium dioxide and the peak indicating the structure of cobalt trioxide were detected. The crystal peak derived from manganese was not observed, and it was confirmed that manganese exists as a manganese-cerium homogeneous mixed oxide. Moreover, the specific surface area of the catalyst 5 measured by BET method was 34 m < 2 > / g.
（実験例６）
実験例３における硝酸コバルト六水和物の使用量を４７．１４ｇに、炭酸セリウム粉末の使用量を７．８２ｇに変更した以外は実験例３と同様にしてコバルト−銀−マンガン−セリウム酸化物からなる粉体を調製した（触媒６）。当該触媒６について、実験例１と同条件でＸ線回折測定を行ったところ、二酸化セリウムの蛍石型結晶構造を示すピーク、および四三酸化コバルトの構造を示すピークのみが検出され、銀およびマンガン由来の結晶ピークは観察されず、マンガンはマンガン−セリウム均密混合酸化物として存在していることが確認された。またＢＥＴ法で測定した触媒６の比表面積は２８ｍ2／ｇであった。
(Experimental example 6)
Cobalt-silver-manganese-cerium oxide in the same manner as in Experimental Example 3 except that the amount of cobalt nitrate hexahydrate used in Experimental Example 3 was changed to 47.14 g and the amount of cerium carbonate powder used was changed to 7.82 g. A powder consisting of (Catalyst 6) was prepared. When X-ray diffraction measurement was performed on the catalyst 6 under the same conditions as in Experimental Example 1, only the peak indicating the fluorite-type crystal structure of cerium dioxide and the peak indicating the structure of cobalt trioxide were detected. The crystal peak derived from manganese was not observed, and it was confirmed that manganese exists as a manganese-cerium homogeneous mixed oxide. The specific surface area of the catalyst 6 measured by the BET method was 28 m 2 / g.
（実験例７）
硝酸マンガン六水和物５．３ｇ、硝酸コバルト六水和物５４．４ｇおよび硝酸銀１．１７ｇを蒸留水に溶解させ、当該水溶液中に炭酸セリウム粉末５．１ｇを添加した。次いで、ホットスターラーで撹拌しながら昇温して水分を蒸発させて乾固物を得た。当該乾固物を１５０℃で一晩乾燥させた後、粉砕し、空気雰囲気下、５００℃で２時間焼成してコバルト−銀−マンガン−セリウム酸化物からなる粉体を調製した（触媒７）。当該触媒７について、実験例１と同条件でＸ線回折測定を行ったところ、二酸化セリウムの蛍石型結晶構造を示すピーク、および四三酸化コバルトの構造を示すピークのみが検出され、銀およびマンガン由来の結晶ピークは観察されず、マンガンはマンガン−セリウム均密混合酸化物として存在していることが確認された。またＢＥＴ法で測定した触媒７の比表面積は２７ｍ2／ｇであった。
(Experimental example 7)
Manganese nitrate hexahydrate 5.3 g, cobalt nitrate hexahydrate 54.4 g and silver nitrate 1.17 g were dissolved in distilled water, and 5.1 g of cerium carbonate powder was added to the aqueous solution. Next, the temperature was raised while stirring with a hot stirrer to evaporate the water and obtain a dried product. The dried product was dried at 150 ° C. overnight, pulverized, and calcined at 500 ° C. for 2 hours in an air atmosphere to prepare a powder composed of cobalt-silver-manganese-cerium oxide (catalyst 7). . When X-ray diffraction measurement was performed on the catalyst 7 under the same conditions as in Experimental Example 1, only the peak indicating the fluorite-type crystal structure of cerium dioxide and the peak indicating the structure of cobalt trioxide were detected. The crystal peak derived from manganese was not observed, and it was confirmed that manganese exists as a manganese-cerium homogeneous mixed oxide. Further, the specific surface area of the catalyst 7 measured by the BET method was 27 m 2 / g.
（実験例８）
実験例３における硝酸銀を硝酸銅三水和物３．０４ｇに変更した以外は実験例３と同様にしてコバルト−銅−マンガン−セリウム酸化物からなる粉体を調製した（触媒８）。当該触媒８について、実験例１と同条件でＸ線回折測定を行ったところ、二酸化セリウムの蛍石型結晶構造を示すピーク、および四三酸化コバルトの構造を示すピークのみが検出され、銅およびマンガン由来の結晶ピークは観察されず、マンガンはマンガン−セリウム均密混合酸化物として存在していることが確認された。またＢＥＴ法で測定した触媒８の比表面積は７３ｍ2／ｇであった。
(Experimental example 8)
A powder composed of cobalt-copper-manganese-cerium oxide was prepared in the same manner as in Experimental Example 3 except that the silver nitrate in Experimental Example 3 was changed to 3.04 g of copper nitrate trihydrate (Catalyst 8). When X-ray diffraction measurement was performed on the catalyst 8 under the same conditions as in Experimental Example 1, only the peak indicating the fluorite-type crystal structure of cerium dioxide and the peak indicating the structure of cobalt trioxide were detected. The crystal peak derived from manganese was not observed, and it was confirmed that manganese exists as a manganese-cerium homogeneous mixed oxide. Further, the specific surface area of the catalyst 8 measured by the BET method was 73 m 2 / g.
（実験例９）
実験例３における硝酸コバルト六水和物を硝酸ニッケル六水和物２７．３ｇに変更した以外は実験例３と同様にしてニッケル−銀−マンガン−セリウム酸化物からなる粉体を調製した（触媒９）。当該触媒９について、実験例１と同条件でＸ線回折測定を行ったところ、二酸化セリウムの蛍石型結晶構造を示すピーク、および酸化ニッケルの構造を示すピークのみが検出され、銀およびマンガン由来の結晶ピークは観察されず、マンガンはマンガン−セリウム均密混合酸化物として存在していることが確認された。またＢＥＴ法で測定した触媒９の比表面積は４７ｍ2／ｇであった。
(Experimental example 9)
A powder comprising nickel-silver-manganese-cerium oxide was prepared in the same manner as in Experimental Example 3 except that the cobalt nitrate hexahydrate in Experimental Example 3 was changed to 27.3 g of nickel nitrate hexahydrate (catalyst) 9). The catalyst 9 was subjected to X-ray diffraction measurement under the same conditions as in Experimental Example 1. As a result, only the peak indicating the fluorite-type crystal structure of cerium dioxide and the peak indicating the structure of nickel oxide were detected. Thus, it was confirmed that manganese was present as a manganese-cerium homogeneous mixed oxide. Further, the specific surface area of the catalyst 9 measured by the BET method was 47 m 2 / g.
（実験例１０）
実験例３で調製した触媒３に対して、水酸化セシウムを用いて、乾燥した触媒の吸水量と同じ体積の含浸液がセシウム換算で１質量％になるように水溶液を調製し、触媒３に対して均一になるように含浸した。含浸後、１５０℃で一晩乾燥させ、１質量％セシウム修飾コバルト−銀−マンガン−セリウム均密混合酸化物を得た（触媒１０）。
(Experimental example 10)
For the catalyst 3 prepared in Experimental Example 3, an aqueous solution was prepared using cesium hydroxide so that the impregnating liquid having the same volume as the water absorption of the dried catalyst was 1% by mass in terms of cesium. It was impregnated so as to be uniform. After impregnation, it was dried at 150 ° C. overnight to obtain a 1% by mass cesium-modified cobalt-silver-manganese-cerium homogeneous mixed oxide (catalyst 10).
（実験例１１）
実験例３で調製した触媒３に対して、水酸化セシウムを用いて、乾燥した触媒の吸水量と同じ体積の含浸液がセシウム換算で０．５質量％になるように水溶液を調製し、触媒３に対して均一になるように含浸した。含浸後、１５０℃で一晩乾燥させ、０．５質量％セシウム修飾コバルト−銀−マンガン−セリウム均密混合酸化物を得た（触媒１１）。
(Experimental example 11)
For the catalyst 3 prepared in Experimental Example 3, an aqueous solution was prepared using cesium hydroxide so that the impregnating liquid having the same volume as the water absorption of the dried catalyst was 0.5% by mass in terms of cesium. 3 was impregnated uniformly. After impregnation, it was dried at 150 ° C. overnight to obtain a 0.5 mass% cesium-modified cobalt-silver-manganese-cerium homogeneous mixed oxide (catalyst 11).
（実験例１２）
実験例３で調製した触媒３に対して、水酸化セシウムを用いて、乾燥した触媒の吸水量と同じ体積の含浸液がセシウム換算で２質量％になるように水溶液を調製し、触媒３に対して均一になるように含浸した。含浸後、１５０℃で一晩乾燥させ、２質量％セシウム修飾コバルト−銀−マンガン−セリウム均密混合酸化物を得た（触媒１２）。
(Experimental example 12)
For the catalyst 3 prepared in Experimental Example 3, an aqueous solution was prepared using cesium hydroxide so that the impregnating liquid having the same volume as the water absorption of the dried catalyst was 2% by mass in terms of cesium. It was impregnated so as to be uniform. After impregnation, the mixture was dried at 150 ° C. overnight to obtain a 2% by mass cesium-modified cobalt-silver-manganese-cerium homogeneous mixed oxide (catalyst 12).
（実験例１３）
実験例３で調製した触媒３に対して、水酸化セシウムを用いて、乾燥した触媒の吸水量と同じ体積の含浸液がセシウム換算で５質量％になるように水溶液を調製し、触媒３に対して均一になるように含浸した。含浸後、１５０℃で一晩乾燥させ、５質量％セシウム修飾コバルト−銀−マンガン−セリウム均密混合酸化物を得た（触媒１３）。
（実験例１４）
実験例３で調製した触媒３に対して、水酸化セシウムを用いて、乾燥した触媒の吸水量と同じ体積の含浸液がセシウム換算で１０質量％になるように水溶液を調製し、触媒３に対して均一になるように含浸した。含浸後、１５０℃で一晩乾燥させ、１０質量％セシウム修飾コバルト−銀−マンガン−セリウム均密混合酸化物を得た（触媒１４）。
(Experimental example 13)
For the catalyst 3 prepared in Experimental Example 3, an aqueous solution was prepared using cesium hydroxide so that the impregnating liquid having the same volume as the water absorption of the dried catalyst was 5% by mass in terms of cesium. It was impregnated so as to be uniform. After impregnation, it was dried at 150 ° C. overnight to obtain a 5 mass% cesium-modified cobalt-silver-manganese-cerium homogeneous mixed oxide (catalyst 13).
(Experimental example 14)
For the catalyst 3 prepared in Experimental Example 3, an aqueous solution was prepared using cesium hydroxide so that the impregnating liquid having the same volume as the water absorption of the dried catalyst was 10% by mass in terms of cesium. It was impregnated so as to be uniform. After impregnation, it was dried at 150 ° C. overnight to obtain a 10 mass% cesium-modified cobalt-silver-manganese-cerium homogeneous mixed oxide (catalyst 14).
（実験例１５）
実験例３で調製した触媒３に対して、水酸化カリウムを用いて、乾燥した触媒の吸水量と同じ体積の含浸液がカリウム換算で１質量％になるように水溶液を調製し、触媒３に対して均一になるように含浸した。含浸後、１５０℃で一晩乾燥させ、１質量％カリウム修飾コバルト−銀−マンガン−セリウム均密混合酸化物を得た（触媒１５）。
(Experimental example 15)
With respect to the catalyst 3 prepared in Experimental Example 3, an aqueous solution was prepared using potassium hydroxide so that the impregnating liquid having the same volume as the water absorption amount of the dried catalyst was 1% by mass in terms of potassium. It was impregnated so as to be uniform. After impregnation, the mixture was dried at 150 ° C. overnight to obtain a 1% by mass potassium-modified cobalt-silver-manganese-cerium homogeneous mixed oxide (catalyst 15).
（実験例１６）
実験例３で調製した触媒３に対して、酢酸バリウムを用いて、乾燥した触媒の吸水量と同じ体積の含浸液がバリウム換算で１質量％になるように水溶液を調製し、触媒３に対して均一になるように含浸した。含浸後、１５０℃で一晩乾燥させ、１質量％バリウム修飾コバルト−銀−マンガン−セリウム均密混合酸化物を得た（触媒１６）。
(Experimental example 16)
For the catalyst 3 prepared in Experimental Example 3, an aqueous solution was prepared using barium acetate so that the impregnating liquid having the same volume as the water absorption of the dried catalyst was 1% by mass in terms of barium. Impregnated uniformly. After impregnation, it was dried at 150 ° C. overnight to obtain a 1% by mass barium-modified cobalt-silver-manganese-cerium homogeneous mixed oxide (catalyst 16).
（実験例１７）
硝酸マンガン六水和物６．６ｇ、硝酸銀０．９８ｇ、硝酸コバルト六水和物８．４ｇおよび硝酸ランタン六水和物２４．９ｇを純水１０００ｍＬに投入し、マンガン−銀−コバルト−ランタン混合水溶液を調製した。次いで、２５質量％ＴＭＡＨ水溶液５００ｇに純水を追加して液量約３Ｌとした希釈ＴＭＡＨ水溶液を激しく撹拌した中に、前記マンガン−銀−コバルト−ランタン混合水溶液をゆっくりと滴下した。滴下終了後、３０分程度撹拌を継続することで熟成を行った。ブフナー漏斗を用いてろ過し、純水で水洗後、１１０℃で乾燥し、乾燥物を粉砕後、空気雰囲気中、４００℃で１時間、更に昇温して６５０℃で２時間焼成して、マンガン−銀−コバルト−ランタン複合酸化物を得た（触媒１７）。当該触媒１７を、実験例１と同条件でＸ線回折測定を行ったところ、触媒１７がペロブスカイト型構造を有する複合酸化物であることが確認された。またＢＥＴ法で測定した触媒１７の比表面積は１８ｍ2／ｇであった。
(Experimental example 17)
6.6 g of manganese nitrate hexahydrate, 0.98 g of silver nitrate, 8.4 g of cobalt nitrate hexahydrate and 24.9 g of lanthanum nitrate hexahydrate are put into 1000 mL of pure water, and mixed with manganese-silver-cobalt-lanthanum. An aqueous solution was prepared. Subsequently, the manganese-silver-cobalt-lanthanum mixed aqueous solution was slowly added dropwise while dilute TMAH aqueous solution in which pure water was added to 500 g of 25 mass% TMAH aqueous solution to a liquid volume of about 3 L was vigorously stirred. After completion of dropping, aging was carried out by continuing stirring for about 30 minutes. Filtration using a Buchner funnel, washing with pure water, drying at 110 ° C., crushing the dried product, firing in an air atmosphere at 400 ° C. for 1 hour, further heating to 650 ° C. for 2 hours, Manganese-silver-cobalt-lanthanum composite oxide was obtained (catalyst 17). When X-ray diffraction measurement was performed on the catalyst 17 under the same conditions as in Experimental Example 1, it was confirmed that the catalyst 17 was a complex oxide having a perovskite structure. Further, the specific surface area of the catalyst 17 measured by the BET method was 18 m 2 / g.
（アンモニア分解触媒成分の製造例）
（実験例１８）
硝酸コバルト六水和物３４．９２ｇ、硝酸セリウム六水和物５．２１ｇおよびジルコゾール（登録商標）ＺＮ（第一稀元素化学工業株式会社製のオキシ硝酸ジルコニウム水溶液：酸化ジルコニウムとして２５質量％含有）５．９１ｇを蒸留水５００ｍＬに添加、混合し、均一水溶液を調製した。当該溶液を攪拌しながら、５００ｍＬの蒸留水に水酸化カリウム４４．３ｇを溶解させた溶液に滴下して、沈殿物を生成させた。得られた沈殿物をろ過、水洗後、１２０℃で一晩乾燥させた。その後、乾燥固体を粉砕し、管状炉に充填して１０容量％水素ガス（窒素希釈）を用いて４５０℃で１時間還元し、コバルト担持セリア−ジルコニアを得た（触媒１８）。ＢＥＴ法で測定した触媒１８の比表面積は５２ｍ2／ｇであった。
(Example of production of ammonia decomposition catalyst component)
(Experiment 18)
Cobalt nitrate hexahydrate 34.92 g, cerium nitrate hexahydrate 5.21 g, and Zircosol (registered trademark) ZN (Zirconium oxynitrate aqueous solution manufactured by Daiichi Rare Chemicals Co., Ltd .: containing 25% by mass as zirconium oxide) 5.91 g was added to and mixed with 500 mL of distilled water to prepare a uniform aqueous solution. While stirring the solution, the solution was added dropwise to a solution in which 44.3 g of potassium hydroxide was dissolved in 500 mL of distilled water to generate a precipitate. The resulting precipitate was filtered, washed with water, and dried overnight at 120 ° C. Thereafter, the dried solid was pulverized, filled into a tubular furnace, and reduced at 450 ° C. for 1 hour using 10 vol% hydrogen gas (diluted with nitrogen) to obtain cobalt-ceria-ceria-zirconia (catalyst 18). The specific surface area of the catalyst 18 measured by the BET method was 52 m 2 / g.
（実験例１９）
実験例１８における硝酸セリウム六水和物の使用量を１７．４ｇに、ジルコゾール（登録商標）ＺＮ（第一稀元素化学工業株式会社製のオキシ硝酸ジルコニウム水溶液：酸化ジルコニウムとして２５質量％含有）の使用量を１９．７ｇとし、水酸化カリウムの使用量を６９．１ｇに変更した以外は実験例１８と同様にしてコバルト担持セリア−ジルコニアを得た（触媒１９）。ＢＥＴ法で測定した触媒１９の比表面積は８３ｍ2／ｇであった。
(Experimental example 19)
The amount of cerium nitrate hexahydrate used in Experimental Example 18 was changed to 17.4 g, and Zircosol (registered trademark) ZN (zirconium oxynitrate aqueous solution manufactured by Daiichi Rare Element Chemical Co., Ltd .: containing 25% by mass as zirconium oxide) Cobalt-supported ceria-zirconia was obtained in the same manner as in Experimental Example 18 except that the amount used was 19.7 g and the amount of potassium hydroxide used was changed to 69.1 g (Catalyst 19). The specific surface area of the catalyst 19 measured by the BET method was 83 m 2 / g.
（実験例２０）
実験例１８における硝酸セリウム六水和物の使用量を２．６ｇに、ジルコゾール（登録商標）ＺＮ（第一稀元素化学工業株式会社製のオキシ硝酸ジルコニウム水溶液：酸化ジルコニウムとして２５質量％含有）の使用量を２．９６ｇとし、水酸化カリウムの使用量を３９．０ｇに変更した以外は実験例１８と同様にしてコバルト担持セリア−ジルコニアを得た（触媒２０）。ＢＥＴ法で測定した触媒２０の比表面積は４６ｍ2／ｇであった。
(Experiment 20)
The amount of cerium nitrate hexahydrate used in Experimental Example 18 was 2.6 g, and Zircosol (registered trademark) ZN (zirconium oxynitrate aqueous solution manufactured by Daiichi Rare Element Chemical Co., Ltd .: containing 25% by mass as zirconium oxide) Cobalt-supported ceria-zirconia was obtained in the same manner as in Experimental Example 18 except that the amount used was 2.96 g and the amount of potassium hydroxide was changed to 39.0 g (Catalyst 20). The specific surface area of the catalyst 20 measured by the BET method was 46 m 2 / g.
（実験例２１）
実験例１８における硝酸コバルト六水和物３４．９２ｇを硝酸ニッケル六水和物３４．８９ｇに変更した以外は実験例１８と同様にしてニッケル担持セリア−ジルコニアを得た（触媒２１）。ＢＥＴ法で測定した触媒２１の比表面積は６０ｍ2／ｇであった。
(Experimental example 21)
Nickel-supported ceria-zirconia was obtained in the same manner as in Experimental Example 18 except that 34.92 g of cobalt nitrate hexahydrate in Experimental Example 18 was changed to 34.89 g of nickel nitrate hexahydrate (Catalyst 21). The specific surface area of the catalyst 21 measured by the BET method was 60 m 2 / g.
（実験例２２）
実験例１８における硝酸コバルト六水和物３４．９２ｇを硝酸鉄九水和物４８．４８ｇに変更した以外は実験例１８と同様にして鉄担持セリア−ジルコニアを得た（触媒２２）。ＢＥＴ法で測定した触媒２２の比表面積は３０ｍ2／ｇであった。
(Experimental example 22)
Iron-supported ceria-zirconia was obtained in the same manner as in Experimental Example 18 except that 34.92 g of cobalt nitrate hexahydrate in Experimental Example 18 was changed to 48.48 g of iron nitrate nonahydrate (Catalyst 22). The specific surface area of the catalyst 22 measured by the BET method was 30 m 2 / g.
（実験例２３）
硝酸コバルト六水和物１４．６ｇ、硝酸ランタン六水和物２１．７ｇを純水４００ｍＬに投入し、コバルト−ランタン混合水溶液を調製した。２５質量％ＴＭＡＨ水溶液１１０ｇに純水を追加して液量約２Ｌとした希釈ＴＭＡＨ水溶液を激しく撹拌した中に、コバルト−ランタン混合水溶液をゆっくりと滴下した。滴下終了後、３０分程度撹拌を継続することで熟成を行った。熟成後、ろ過し、純水で水洗後、１１０℃で乾燥し、乾燥物を粉砕後、空気雰囲気中、４００℃で１時間、更に昇温して６５０℃で２時間焼成して、コバルト−ランタン複合酸化物を得た（触媒２３）。当該触媒２３を、実験例１と同条件でＸ線回折測定を行ったところ、触媒２３がペロブスカイト型構造を有する複合酸化物であることが確認された。またＢＥＴ法で測定した触媒２３の比表面積は２５ｍ2／ｇであった。
(Experimental example 23)
Cobalt nitrate hexahydrate 14.6 g and lanthanum nitrate hexahydrate 21.7 g were added to 400 mL of pure water to prepare a cobalt-lanthanum mixed aqueous solution. While dilute TMAH aqueous solution in which pure water was added to 110 g of 25% by mass TMAH aqueous solution to a volume of about 2 L was vigorously stirred, the cobalt-lanthanum mixed aqueous solution was slowly added dropwise. After completion of dropping, aging was carried out by continuing stirring for about 30 minutes. After aging, filtered, washed with pure water, dried at 110 ° C., the dried product was pulverized, calcined in an air atmosphere at 400 ° C. for 1 hour, further heated at 650 ° C. for 2 hours, cobalt- Lanthanum composite oxide was obtained (catalyst 23). When X-ray diffraction measurement was performed on the catalyst 23 under the same conditions as in Experimental Example 1, it was confirmed that the catalyst 23 was a complex oxide having a perovskite structure. The specific surface area of the catalyst 23 measured by the BET method was 25 m 2 / g.
（実験例２４）
実験例２３における硝酸コバルト六水和物を硝酸ニッケル六水和物１４．６ｇに変更した以外は実験例２３と同様にしてニッケル−ランタン複合酸化物を得た（触媒２４）。当該触媒２４を、実験例１と同条件でＸ線回折測定を行ったところ、触媒２４がペロブスカイト型構造を有する複合酸化物であることが確認された。またＢＥＴ法で測定した触媒２４の比表面積は２３ｍ2／ｇであった。
(Experimental example 24)
A nickel-lanthanum composite oxide was obtained in the same manner as in Experimental Example 23 except that the cobalt nitrate hexahydrate in Experimental Example 23 was changed to 14.6 g of nickel nitrate hexahydrate (Catalyst 24). When X-ray diffraction measurement was performed on the catalyst 24 under the same conditions as in Experimental Example 1, it was confirmed that the catalyst 24 was a complex oxide having a perovskite structure. The specific surface area of the catalyst 24 measured by the BET method was 23 m 2 / g.
（実験例２５）
実施例１８で調製した触媒１８に対して、硝酸セシウムを用いて、乾燥した触媒の吸水量と同じ体積の含浸液がセシウム換算で１質量％になるように水溶液を調製し、触媒１８に対して均一になるように含浸した。含浸後、１５０℃で一晩乾燥させた。この乾燥物を粉砕し、管状炉に充填し、１０容量％水素ガス（窒素希釈）を用いて、６００℃で１時間還元処理し、１質量％セシウム修飾コバルト担持セリア−ジルコニアを得た（触媒２５）。
(Experimental example 25)
For the catalyst 18 prepared in Example 18, an aqueous solution was prepared using cesium nitrate so that the impregnating liquid having the same volume as the water absorption of the dried catalyst was 1% by mass in terms of cesium. Impregnated uniformly. After impregnation, it was dried at 150 ° C. overnight. The dried product was pulverized, filled into a tubular furnace, and reduced at 600 ° C. for 1 hour using 10 vol% hydrogen gas (diluted with nitrogen) to obtain 1 mass% cesium-modified cobalt-supported ceria-zirconia (catalyst 25).
（実験例２６）
実施例１８で調製した触媒１８に対して、硝酸セシウムを用いて、乾燥した触媒の吸水量と同じ体積の含浸液がセシウム換算で０．５質量％になるように水溶液を調製した以外は、実験例２５と同様にして０．５質量％セシウム修飾コバルト担持セリア−ジルコニアを得た（触媒２６）。
(Experimental example 26)
Except for the catalyst 18 prepared in Example 18, using cesium nitrate, an aqueous solution was prepared so that the impregnating liquid having the same volume as the water absorption of the dried catalyst was 0.5% by mass in terms of cesium. In the same manner as in Experimental Example 25, 0.5 mass% cesium-modified cobalt-supported ceria-zirconia was obtained (catalyst 26).
（実験例２７）
実施例１８で調製した触媒１８に対して、硝酸セシウムを用いて、乾燥した触媒の吸水量と同じ体積の含浸液がセシウム換算で２質量％になるように水溶液を調製した以外は、実験例２５と同様にして２質量％セシウム修飾コバルト担持セリア−ジルコニアを得た（触媒２７）。
(Experiment 27)
Experimental example, except that an aqueous solution was prepared with respect to the catalyst 18 prepared in Example 18 using cesium nitrate so that the impregnating liquid having the same volume as the water absorption of the dried catalyst was 2% by mass in terms of cesium. In the same manner as in No. 25, 2% by mass of cesium-modified cobalt-supported ceria-zirconia was obtained (catalyst 27).
（実験例２８）
実施例１８で調製した触媒１８に対して、硝酸セシウムを用いて、乾燥した触媒の吸水量と同じ体積の含浸液がセシウム換算で４質量％になるように水溶液を調製した以外は、実験例２５と同様にして４質量％セシウム修飾コバルト担持セリア−ジルコニアを得た（触媒２８）。
(Experimental example 28)
Experimental example, except that an aqueous solution was prepared with respect to the catalyst 18 prepared in Example 18 using cesium nitrate such that the impregnating liquid having the same volume as the water absorption of the dried catalyst was 4% by mass in terms of cesium. In the same manner as in No. 25, 4 mass% cesium-modified cobalt-supported ceria-zirconia was obtained (catalyst 28).
（実験例２９）
実施例１８で調製した触媒１８に対して、硝酸セシウムを用いて、乾燥した触媒の吸水量と同じ体積の含浸液がセシウム換算で６質量％になるように水溶液を調製した以外は、実験例２５と同様にして６質量％セシウム修飾コバルト担持セリア−ジルコニアを得た（触媒２９）。
(Experimental example 29)
Experimental example, except that an aqueous solution was prepared with respect to the catalyst 18 prepared in Example 18 using cesium nitrate such that the impregnating liquid having the same volume as the water absorption of the dried catalyst was 6% by mass in terms of cesium. In the same manner as in No. 25, 6 mass% cesium-modified cobalt-supported ceria-zirconia was obtained (catalyst 29).
（実験例３０）
実施例１８で調製した触媒１８に対して、硝酸セシウムを用いて、乾燥した触媒の吸水量と同じ体積の含浸液がセシウム換算で１０質量％になるように水溶液を調製した以外は、実験例２５と同様にして１０質量％セシウム修飾コバルト担持セリア−ジルコニアを得た（触媒３０）。
(Experiment 30)
Experimental example, except that an aqueous solution was prepared with respect to the catalyst 18 prepared in Example 18 using cesium nitrate so that the impregnating liquid having the same volume as the water absorption of the dried catalyst was 10% by mass in terms of cesium. In the same manner as in No. 25, 10 mass% cesium-modified cobalt-supported ceria-zirconia was obtained (catalyst 30).
（実験例３１）
実施例１８で調製した触媒１８に対して、硝酸カリウムを用いて、乾燥した触媒の吸水量と同じ体積の含浸液がカリウム換算で１質量％になるように水溶液を調製した以外は、実験例２５と同様にして１質量％カリウム修飾コバルト担持セリア−ジルコニアを得た（触媒３１）。
(Experimental example 31)
Experimental Example 25 except that an aqueous solution was prepared using potassium nitrate so that the impregnating liquid having the same volume as the water absorption of the dried catalyst was 1% by mass in terms of potassium with respect to the catalyst 18 prepared in Example 18. In the same manner as above, 1 mass% potassium-modified cobalt-supported ceria-zirconia was obtained (catalyst 31).
（実験例３２）
実施例１８で調製した触媒１８に対して、硝酸バリウムを用いて、乾燥した触媒の吸水量と同じ体積の含浸液がバリウム換算で１質量％になるように水溶液を調製した以外は、実験例２５と同様にして１質量％バリウム修飾コバルト担持セリア−ジルコニアを得た（触媒３２）。
(Experimental example 32)
Experimental example, except that an aqueous solution was prepared from the catalyst 18 prepared in Example 18 using barium nitrate so that the impregnating liquid having the same volume as the water absorption amount of the dried catalyst was 1% by mass in terms of barium. In the same manner as in No. 25, 1 mass% barium-modified cobalt-carrying ceria-zirconia was obtained (catalyst 32).
（実験例３３）
実施例２１で調製した触媒２１に対して、硝酸セシウムを用いて、乾燥した触媒の吸水量と同じ体積の含浸液がセシウム換算で１質量％になるように水溶液を調製し、触媒２１に対して均一になるように含浸した。含浸後、１５０℃で一晩乾燥させた。この乾燥物を粉砕し、管状炉に充填し、１０容量％水素ガス（窒素希釈）を用いて、６００℃で１時間還元処理し、１質量％セシウム修飾ニッケル担持セリア−ジルコニアを得た（触媒３３）。
(Experimental example 33)
For the catalyst 21 prepared in Example 21, an aqueous solution was prepared using cesium nitrate so that the impregnating liquid having the same volume as the water absorption of the dried catalyst was 1% by mass in terms of cesium. Impregnated uniformly. After impregnation, it was dried at 150 ° C. overnight. This dried product was pulverized, filled into a tubular furnace, and reduced at 600 ° C. for 1 hour using 10% by volume hydrogen gas (diluted with nitrogen) to obtain 1% by mass cesium-modified nickel-supported ceria-zirconia (catalyst 33).
（実験例３４）
実施例２３で調製した触媒２３に対して、硝酸セシウムを用いて、乾燥した触媒の吸水量と同じ体積の含浸液がセシウム換算で５質量％になるように水溶液を調製し、触媒２３に対して均一になるように含浸した。含浸後、１５０℃で一晩乾燥させた。この乾燥物を粉砕し、管状炉に充填し、１０容量％水素ガス（窒素希釈）を用いて、６００℃で１時間還元処理し、５質量％セシウム修飾コバルト−ランタン複合酸化物を得た（触媒３４）。
(Experimental example 34)
For the catalyst 23 prepared in Example 23, an aqueous solution was prepared using cesium nitrate so that the impregnating liquid having the same volume as the water absorption of the dried catalyst was 5% by mass in terms of cesium. Impregnated uniformly. After impregnation, it was dried at 150 ° C. overnight. The dried product was pulverized, filled into a tubular furnace, and reduced at 600 ° C. for 1 hour using 10 vol% hydrogen gas (diluted with nitrogen) to obtain a 5 mass% cesium-modified cobalt-lanthanum composite oxide ( Catalyst 34).
（水素製造反応）
１０ｍｍφの石英反応管を用い実験例１〜１７で調製したアンモニア燃焼触媒成分および実験例１８〜３４で調製したアンモニア分解触媒成分を使用し、９９．９％容量以上の純度のアンモニアと空気を用いて、酸素／アンモニアのモル比０．１５６でアンモニア分解による水素製造反応を行った。
(Hydrogen production reaction)
Using an ammonia combustion catalyst component prepared in Experimental Examples 1 to 17 and an ammonia decomposition catalyst component prepared in Experimental Examples 18 to 34 using a 10 mmφ quartz reaction tube, ammonia and air having a purity of 99.9% capacity or more were used. Then, a hydrogen production reaction by ammonia decomposition was performed at an oxygen / ammonia molar ratio of 0.156.
常圧下、ＳＶ＝３６，０００ｈ-１で、２００℃に加温した反応ガスを触媒層に供給してアンモニア分解による水素製造反応を実施し、触媒層出口ガスを分析して水素収率を測定した。水素収率の測定結果を表１に示した。表１には、各試験時の触媒層最高温度についても併記した。 Under normal pressure, at SV = 36,000 h −1 , a reaction gas heated to 200 ° C. is supplied to the catalyst layer to perform hydrogen production reaction by ammonia decomposition, and the hydrogen gas yield is measured by analyzing the catalyst layer outlet gas did. The measurement results of hydrogen yield are shown in Table 1. Table 1 also shows the maximum catalyst layer temperature during each test.
（反応例１〜１４）
ガス流れ方向に対して上記反応管の出口側に触媒２５を充填し、ガス流れ方向に対して上記反応管の入口側に充填する触媒を触媒１〜１４に変更してアンモニア分解による水素製造反応を実施した。触媒充填量は、ガス流れ方向に対して入口側のアンモニア燃焼触媒成分を１ｍＬ、出口側のアンモニア分解触媒成分を４ｍＬとした。反応条件は、前記の通りとした。水素収率および触媒層最高温度の測定結果を表１に示す。
(Reaction Examples 1 to 14)
The catalyst 25 is filled on the outlet side of the reaction tube with respect to the gas flow direction, and the catalyst charged on the inlet side of the reaction tube with respect to the gas flow direction is changed to the catalysts 1 to 14, and hydrogen production reaction by ammonia decomposition is performed. Carried out. The catalyst filling amount was 1 mL of the ammonia combustion catalyst component on the inlet side and 4 mL of the ammonia decomposition catalyst component on the outlet side with respect to the gas flow direction. The reaction conditions were as described above. The measurement results of the hydrogen yield and the maximum catalyst layer temperature are shown in Table 1.
（反応例１５〜１９）
ガス流れ方向に対して上記反応管の入口側に触媒１０を充填し、ガス流れ方向に対して上記反応管の出口側に充填する触媒を触媒２６〜３０に変更してアンモニア分解による水素製造反応を実施した。触媒充填量は、ガス流れ方向に対して入口側のアンモニア燃焼触媒成分を１ｍＬ、出口側のアンモニア分解触媒成分を４ｍＬとした。反応条件は、前記の通りとした。水素収率および触媒層最高温度の測定結果を表１に示す。
(Reaction Examples 15 to 19)
Hydrogen production reaction by ammonia decomposition by filling catalyst 10 on the inlet side of the reaction tube with respect to the gas flow direction and changing the catalyst charged on the outlet side of the reaction tube with respect to the gas flow direction to catalysts 26-30 Carried out. The catalyst filling amount was 1 mL of the ammonia combustion catalyst component on the inlet side and 4 mL of the ammonia decomposition catalyst component on the outlet side with respect to the gas flow direction. The reaction conditions were as described above. The measurement results of the hydrogen yield and the maximum catalyst layer temperature are shown in Table 1.
（反応例２０〜２２）
ガス流れ方向に対して上記反応管の出口側に触媒２５を充填し、ガス流れ方向に対して上記反応管の入口側に充填する触媒を触媒１５〜１７に変更してアンモニア分解による水素製造反応を実施した。触媒充填量は、ガス流れ方向に対して入口側のアンモニア燃焼触媒成分を１ｍＬ、出口側のアンモニア分解触媒成分を４ｍＬとした。反応条件は、前記の通りとした。水素収率および触媒層最高温度の測定結果を表２に示す。
(Reaction examples 20 to 22)
Hydrogen production reaction by ammonia decomposition by filling the catalyst 25 on the outlet side of the reaction tube with respect to the gas flow direction and changing the catalyst charged on the inlet side of the reaction tube with respect to the gas flow direction to the catalysts 15 to 17 Carried out. The catalyst filling amount was 1 mL of the ammonia combustion catalyst component on the inlet side and 4 mL of the ammonia decomposition catalyst component on the outlet side with respect to the gas flow direction. The reaction conditions were as described above. The measurement results of the hydrogen yield and the maximum catalyst layer temperature are shown in Table 2.
（反応例２３〜３３）
ガス流れ方向に対して上記反応管の入口側に触媒１０を充填し、ガス流れ方向に対して上記反応管の出口側に充填する触媒を触媒１８〜２４、３１〜３４に変更してアンモニア分解による水素製造反応を実施した。触媒充填量は、ガス流れ方向に対して入口側のアンモニア燃焼触媒成分を１ｍＬ、出口側のアンモニア分解触媒成分を４ｍＬとした。反応条件は、前記の通りとした。水素収率および触媒層最高温度の測定結果を表２に示す。
(Reaction Examples 23 to 33)
The catalyst 10 is filled on the inlet side of the reaction tube with respect to the gas flow direction, and the catalyst charged on the outlet side of the reaction tube with respect to the gas flow direction is changed to catalysts 18 to 24 and 31 to 34 to decompose ammonia. A hydrogen production reaction was carried out. The catalyst filling amount was 1 mL of the ammonia combustion catalyst component on the inlet side and 4 mL of the ammonia decomposition catalyst component on the outlet side with respect to the gas flow direction. The reaction conditions were as described above. The measurement results of the hydrogen yield and the maximum catalyst layer temperature are shown in Table 2.
（反応例３４）
１ｍＬの触媒３と４ｍＬの触媒２５を均一になるように物理的に混合し、アンモニア分解による水素製造反応を実施した。反応条件は、前記の通りとした。水素収率および触媒層最高温度の測定結果を表２に示す。
(Reaction Example 34)
1 mL of catalyst 3 and 4 mL of catalyst 25 were physically mixed so as to be uniform, and a hydrogen production reaction by ammonia decomposition was carried out. The reaction conditions were as described above. The measurement results of the hydrogen yield and the maximum catalyst layer temperature are shown in Table 2.
なお、水素収率（％）は以下の式で求めた。 The hydrogen yield (%) was determined by the following formula.
本発明は水素製造方法に適用できるものである。更に水素は燃料電池用の燃料、水素エンジンの燃料等に用いることができる。 The present invention is applicable to a hydrogen production method. Furthermore, hydrogen can be used as fuel for fuel cells, fuel for hydrogen engines, and the like.
１：アンモニア燃焼触媒成分、２：アンモニア分解触媒成分、３：アンモニアと酸素を含むガス、４：アンモニア燃焼により温度上昇するとともに、実質的に酸素が完全消費された状態の反応ガス、５：水素と窒素とを含むガス 1: Ammonia combustion catalyst component, 2: Ammonia decomposition catalyst component, 3: Gas containing ammonia and oxygen, 4: Reactant gas in which the temperature rises due to ammonia combustion and oxygen is completely consumed, 5: Hydrogen Containing nitrogen and nitrogen
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