JP6883289B2 - Hydrogen production method and catalyst for hydrogen production - Google Patents
Hydrogen production method and catalyst for hydrogen production Download PDFInfo
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- JP6883289B2 JP6883289B2 JP2017127385A JP2017127385A JP6883289B2 JP 6883289 B2 JP6883289 B2 JP 6883289B2 JP 2017127385 A JP2017127385 A JP 2017127385A JP 2017127385 A JP2017127385 A JP 2017127385A JP 6883289 B2 JP6883289 B2 JP 6883289B2
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- Prior art keywords
- catalyst
- mass
- magnesium
- elements
- ammonia decomposition
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims description 252
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 70
- 239000001257 hydrogen Substances 0.000 title claims description 70
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 63
- 238000004519 manufacturing process Methods 0.000 title claims description 42
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 274
- 229910021529 ammonia Inorganic materials 0.000 claims description 136
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 78
- 229910052749 magnesium Inorganic materials 0.000 claims description 78
- 239000011777 magnesium Substances 0.000 claims description 78
- 239000000395 magnesium oxide Substances 0.000 claims description 66
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 66
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 53
- 239000002994 raw material Substances 0.000 claims description 48
- 239000007789 gas Substances 0.000 claims description 37
- 229910052788 barium Inorganic materials 0.000 claims description 28
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 28
- 229910052772 Samarium Inorganic materials 0.000 claims description 27
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 27
- 229910052759 nickel Inorganic materials 0.000 claims description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- 229910017052 cobalt Inorganic materials 0.000 claims description 19
- 239000010941 cobalt Substances 0.000 claims description 19
- 229910052712 strontium Inorganic materials 0.000 claims description 19
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 19
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 18
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 15
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 13
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 229910052727 yttrium Inorganic materials 0.000 claims description 12
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 12
- 229910052693 Europium Inorganic materials 0.000 claims description 11
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 11
- 229910052691 Erbium Inorganic materials 0.000 claims description 10
- 229910052779 Neodymium Inorganic materials 0.000 claims description 10
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 10
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- 238000000354 decomposition reaction Methods 0.000 description 107
- 238000002360 preparation method Methods 0.000 description 89
- 238000000034 method Methods 0.000 description 61
- 230000000694 effects Effects 0.000 description 45
- 239000000126 substance Substances 0.000 description 43
- 239000007787 solid Substances 0.000 description 27
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 25
- 239000000243 solution Substances 0.000 description 24
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 18
- 239000002131 composite material Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 230000009467 reduction Effects 0.000 description 13
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 12
- 238000010304 firing Methods 0.000 description 11
- 238000001556 precipitation Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 9
- HDCOFJGRHQAIPE-UHFFFAOYSA-N samarium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HDCOFJGRHQAIPE-UHFFFAOYSA-N 0.000 description 8
- 238000004364 calculation method Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- -1 oxides Substances 0.000 description 6
- 239000010970 precious metal Substances 0.000 description 6
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 5
- 150000004767 nitrides Chemical class 0.000 description 5
- 239000012495 reaction gas Substances 0.000 description 5
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000004679 hydroxides Chemical class 0.000 description 4
- 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 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 4
- 229910001954 samarium oxide Inorganic materials 0.000 description 4
- 229940075630 samarium oxide Drugs 0.000 description 4
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 3
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 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
- 229910001940 europium oxide Inorganic materials 0.000 description 3
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 3
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- GOKIPOOTKLLKDI-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O.CC(O)=O GOKIPOOTKLLKDI-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 description 2
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 description 2
- 229910001938 gadolinium oxide Inorganic materials 0.000 description 2
- 229940075613 gadolinium oxide Drugs 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 229910000358 iron sulfate Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 1
- BYDYILQCRDXHLB-UHFFFAOYSA-N 3,5-dimethylpyridine-2-carbaldehyde Chemical compound CC1=CN=C(C=O)C(C)=C1 BYDYILQCRDXHLB-UHFFFAOYSA-N 0.000 description 1
- RCYIWFITYHZCIW-UHFFFAOYSA-N 4-methoxybut-1-yne Chemical compound COCCC#C RCYIWFITYHZCIW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 229910017569 La2(CO3)3 Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- BMPYETKQLHJVDE-UHFFFAOYSA-N O.O.O.O.O.O.[Gd] Chemical compound O.O.O.O.O.O.[Gd] BMPYETKQLHJVDE-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- SQGCCNPBCCXUSW-UHFFFAOYSA-N [Co+2].[O-2].[La+3].[O-2].[Sr+2] Chemical compound [Co+2].[O-2].[La+3].[O-2].[Sr+2] SQGCCNPBCCXUSW-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- ZXGIFJXRQHZCGJ-UHFFFAOYSA-N erbium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Er+3].[Er+3] ZXGIFJXRQHZCGJ-UHFFFAOYSA-N 0.000 description 1
- DBUHPIKTDUMWTR-UHFFFAOYSA-K erbium(3+);triacetate Chemical compound [Er+3].CC([O-])=O.CC([O-])=O.CC([O-])=O DBUHPIKTDUMWTR-UHFFFAOYSA-K 0.000 description 1
- SYDXSHCNMKOQFW-UHFFFAOYSA-H erbium(3+);trisulfate Chemical compound [Er+3].[Er+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O SYDXSHCNMKOQFW-UHFFFAOYSA-H 0.000 description 1
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical compound Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 description 1
- AKFFNTKRAYWFRN-UHFFFAOYSA-N ethyl 5-(trifluoromethyl)-1h-pyrazole-3-carboxylate Chemical compound CCOC(=O)C=1C=C(C(F)(F)F)NN=1 AKFFNTKRAYWFRN-UHFFFAOYSA-N 0.000 description 1
- SULCVUWEGVSCPF-UHFFFAOYSA-L europium(2+);carbonate Chemical compound [Eu+2].[O-]C([O-])=O SULCVUWEGVSCPF-UHFFFAOYSA-L 0.000 description 1
- LNYNHRRKSYMFHF-UHFFFAOYSA-K europium(3+);triacetate Chemical compound [Eu+3].CC([O-])=O.CC([O-])=O.CC([O-])=O LNYNHRRKSYMFHF-UHFFFAOYSA-K 0.000 description 1
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 description 1
- WLYAEQLCCOGBPV-UHFFFAOYSA-N europium;sulfuric acid Chemical compound [Eu].OS(O)(=O)=O WLYAEQLCCOGBPV-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- MEANOSLIBWSCIT-UHFFFAOYSA-K gadolinium trichloride Chemical compound Cl[Gd](Cl)Cl MEANOSLIBWSCIT-UHFFFAOYSA-K 0.000 description 1
- LYQGMALGKYWNIU-UHFFFAOYSA-K gadolinium(3+);triacetate Chemical compound [Gd+3].CC([O-])=O.CC([O-])=O.CC([O-])=O LYQGMALGKYWNIU-UHFFFAOYSA-K 0.000 description 1
- RQXZRSYWGRRGCD-UHFFFAOYSA-H gadolinium(3+);tricarbonate Chemical compound [Gd+3].[Gd+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O RQXZRSYWGRRGCD-UHFFFAOYSA-H 0.000 description 1
- QLAFITOLRQQGTE-UHFFFAOYSA-H gadolinium(3+);trisulfate Chemical compound [Gd+3].[Gd+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O QLAFITOLRQQGTE-UHFFFAOYSA-H 0.000 description 1
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 description 1
- 229910021480 group 4 element Inorganic materials 0.000 description 1
- 229910021472 group 8 element Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 1
- 229960001633 lanthanum carbonate Drugs 0.000 description 1
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 1
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- NFSAPTWLWWYADB-UHFFFAOYSA-N n,n-dimethyl-1-phenylethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=CC=C1 NFSAPTWLWWYADB-UHFFFAOYSA-N 0.000 description 1
- UTWHRPIUNFLOBE-UHFFFAOYSA-H neodymium(3+);tricarbonate Chemical compound [Nd+3].[Nd+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O UTWHRPIUNFLOBE-UHFFFAOYSA-H 0.000 description 1
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 1
- VQVDTKCSDUNYBO-UHFFFAOYSA-N neodymium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VQVDTKCSDUNYBO-UHFFFAOYSA-N 0.000 description 1
- RHVPCSSKNPYQDU-UHFFFAOYSA-H neodymium(3+);trisulfate;hydrate Chemical compound O.[Nd+3].[Nd+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RHVPCSSKNPYQDU-UHFFFAOYSA-H 0.000 description 1
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- AIBQNUOBCRIENU-UHFFFAOYSA-N nickel;dihydrate Chemical compound O.O.[Ni] AIBQNUOBCRIENU-UHFFFAOYSA-N 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- UFQXGXDIJMBKTC-UHFFFAOYSA-N oxostrontium Chemical compound [Sr]=O UFQXGXDIJMBKTC-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- JPDBEEUPLFWHAJ-UHFFFAOYSA-K samarium(3+);triacetate Chemical compound [Sm+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JPDBEEUPLFWHAJ-UHFFFAOYSA-K 0.000 description 1
- QCZFMLDHLOYOQJ-UHFFFAOYSA-H samarium(3+);tricarbonate Chemical compound [Sm+3].[Sm+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QCZFMLDHLOYOQJ-UHFFFAOYSA-H 0.000 description 1
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 description 1
- LVSITDBROURTQX-UHFFFAOYSA-H samarium(3+);trisulfate Chemical compound [Sm+3].[Sm+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LVSITDBROURTQX-UHFFFAOYSA-H 0.000 description 1
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000007736 thin film deposition technique Methods 0.000 description 1
- 229910000347 yttrium sulfate Inorganic materials 0.000 description 1
- QVOIJBIQBYRBCF-UHFFFAOYSA-H yttrium(3+);tricarbonate Chemical compound [Y+3].[Y+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QVOIJBIQBYRBCF-UHFFFAOYSA-H 0.000 description 1
- RTAYJOCWVUTQHB-UHFFFAOYSA-H yttrium(3+);trisulfate Chemical compound [Y+3].[Y+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RTAYJOCWVUTQHB-UHFFFAOYSA-H 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)
Description
本発明は、触媒を用いてアンモニアを窒素と水素に分解して水素を製造する水素の製造方法及び水素製造用触媒に関する。 The present invention relates to a hydrogen production method for producing hydrogen by decomposing ammonia into nitrogen and hydrogen using a catalyst, and a catalyst for hydrogen production.
水素は、世界的なエネルギー需要の増加や地球規模の気候変動といった問題を解決するための新たなエネルギー源として期待されており、関連する様々な技術が開発されている。しかしながら、水素の貯蔵・輸送に高いコストがかかることが、水素エネルギー社会の実現に向けた大きな障害の一つとなっている。水素と比べて低コストでの輸送・貯蔵が可能なアンモニアは、分解反応により比較的容易に水素を生成することが知られており、この反応を効率的に進行させることができれば、アンモニアは水素キャリアとして有望な物質となり得る。そのため、アンモニア分解を触媒により効率的に進行させる技術は、海外で製造された安価なアンモニアを輸送してより安価な水素を製造・使用することを可能とし、産業上非常に有益な技術である。 Hydrogen is expected as a new energy source to solve problems such as increasing global energy demand and global climate change, and various related technologies are being developed. However, the high cost of storing and transporting hydrogen is one of the major obstacles to the realization of a hydrogen energy society. Ammonia, which can be transported and stored at a lower cost than hydrogen, is known to generate hydrogen relatively easily by a decomposition reaction, and if this reaction can proceed efficiently, ammonia will be hydrogen. It can be a promising substance as a carrier. Therefore, the technology for efficiently advancing the decomposition of ammonia with a catalyst makes it possible to transport cheap ammonia produced overseas to produce and use cheaper hydrogen, which is a very useful technology in industry. ..
アンモニア分解の触媒としては、貴金属系触媒としてルテニウムを含む触媒と、非貴金属系触媒としてニッケル、コバルト、鉄を含有する触媒と、の２通りに大別される。一般に、貴金属系触媒の方が高活性であることが知られているが、より安価な非貴金属系触媒がコスト面で有利であり、非貴金属系触媒の高活性化が望まれている。 The catalyst for decomposition of ammonia is roughly classified into two types: a catalyst containing ruthenium as a noble metal catalyst and a catalyst containing nickel, cobalt, and iron as a non-precious metal catalyst. Generally, it is known that a noble metal-based catalyst has higher activity, but a cheaper non-precious metal-based catalyst is advantageous in terms of cost, and high activation of the non-precious metal-based catalyst is desired.
このような背景から、非貴金属系のアンモニア分解触媒の例として、以下のようなものが提案されている。
例えば、特許文献１には、酸化ストロンチウム−酸化ランタン−コバルト金属微粒子触媒が開示されている。
Against this background, the following have been proposed as examples of non-precious metal-based ammonia decomposition catalysts.
For example, Patent Document 1 discloses a strontium oxide-lanthanum oxide-cobalt metal fine particle catalyst.
また、例えば、特許文献２には、セリアとジルコニアとの固溶体（ＣｅＺｒＯｘ）に対し、コバルト又はニッケルを担持させ、更にアルカリ金属又はアルカリ土類金属を添加した触媒が開示されている。 Further, for example, Patent Document 2 discloses a catalyst in which cobalt or nickel is supported on a solid solution (CeZrO x) of ceria and zirconia, and an alkali metal or alkaline earth metal is further added.
更に、非特許文献１、特許文献３及び特許文献４には、希土類酸化物に対し、ニッケルとアルカリ土類金属とを担持した触媒が開示されている。 Further, Non-Patent Document 1, Patent Document 3 and Patent Document 4 disclose a catalyst in which nickel and an alkaline earth metal are supported on a rare earth oxide.
特許文献１に記載のアンモニア分解触媒は、ストロンチウム含有量が高く、かつ、ペロブスカイト構造を有する前駆体を経由するという特殊な場合においてのみ、高いアンモニア分解活性を示す触媒であって、汎用性の高い技術とは言えない。
また、特許文献２では、コバルト及びセリアとジルコニアとの固溶体に、ストロンチウムを添加した触媒が示されているが、このストロンチウムの添加によるアンモニア分解の活性向上の効果は示されていない。
更に、非特許文献１、特許文献３及び特許文献４では、希土類酸化物及びニッケルに対し、ストロンチウム及びバリウムを添加したことによる、アンモニア分解の活性向上効果は示されているが、ストロンチウム及びバリウムを添加しないで、その代りにマグネシウムを添加すると活性が低下することが示されている（具体的には、非特許文献１の図３、特許文献３の比較例３、特許文献４の比較例４）。つまり、非特許文献１、特許文献３及び特許文献４には、マグネシウムの添加が、アンモニア分解の活性を向上させることは何ら示唆されてはいない。
The ammonia decomposition catalyst described in Patent Document 1 is a catalyst that exhibits high ammonia decomposition activity only in a special case where it has a high strontium content and passes through a precursor having a perovskite structure, and is highly versatile. It's not a technology.
Further, Patent Document 2 shows a catalyst in which strontium is added to a solid solution of cobalt, ceria and zirconia, but the effect of improving the activity of ammonia decomposition by the addition of strontium is not shown.
Further, Non-Patent Document 1, Patent Document 3 and Patent Document 4 show the effect of improving the activity of strontium decomposition by adding strontium and barium to rare earth oxides and nickel, but strontium and barium can be used. It has been shown that the activity is reduced when magnesium is added instead of the addition (specifically, FIG. 3 of Non-Patent Document 1, Comparative Example 3 of Patent Document 3, and Comparative Example 4 of Patent Document 4). ). That is, Non-Patent Document 1, Patent Document 3 and Patent Document 4 do not suggest that the addition of magnesium improves the activity of ammonia decomposition.
以上のように、非貴金属触媒について、（１）非貴金属である、ニッケル、コバルト及び鉄、（２）アルカリ金属又はアルカリ土類金属、並びに（３）希土類酸化物の３つの成分については、それぞれがアンモニア分解の活性向上効果を示すことは知られているものの、更に効率的にアンモニアを分解し得る組み合わせ組成、及び汎用性の高い技術は確立されていないのが現状である。
このような状況に鑑み、本発明では、アンモニアを含有する原料ガスから触媒を用いて効率的に水素を製造する水素の製造方法、及び水素製造用触媒を提供することを課題とする。
As described above, regarding non-precious metal catalysts, the three components of (1) non-precious metals such as nickel, cobalt and iron, (2) alkali metals or alkaline earth metals, and (3) rare earth oxides, respectively. Is known to have an effect of improving the activity of ammonia decomposition, but at present, a combination composition capable of more efficiently decomposing ammonia and a highly versatile technique have not been established.
In view of such a situation, it is an object of the present invention to provide a hydrogen production method for efficiently producing hydrogen from a raw material gas containing ammonia by using a catalyst, and a catalyst for hydrogen production.
本発明者らは上記の課題に鑑み鋭意検討した結果、上述の課題に対し、ニッケル、コバルト及び鉄から選ばれる１種以上の元素（Ａ）と、ストロンチウム及びバリウムから選ばれる１種以上の元素（Ｂ）と、希土類元素から選ばれる１種以上の元素（Ｃ）と、マグネシウム（Ｄ）と、を含む触媒（Ｘ）に、アンモニアを含有する原料ガスを接触させて水素製造を行うことにより、同技術を工業的なレベルにまで向上させ、より汎用性の高い技術として本発明を完成させるに至った。 As a result of diligent studies in view of the above problems, the present inventors have made one or more elements (A) selected from nickel, cobalt and iron and one or more elements selected from strontium and barium in response to the above problems. By contacting a raw material gas containing ammonia with a catalyst (X) containing (B), one or more elements (C) selected from rare earth elements, and magnesium (D) to produce hydrogen. , The technology has been improved to an industrial level, and the present invention has been completed as a more versatile technology.
すなわち、本発明には以下の事項が含まれる。
［１］ニッケル、コバルト及び鉄から選ばれる１種以上の元素（Ａ）と、ストロンチウム及びバリウムから選ばれる１種以上の元素（Ｂ）と、希土類元素から選ばれる１種以上の元素（Ｃ）と、マグネシウム（Ｄ）と、を含む触媒（Ｘ）に、アンモニアを含有する原料ガスを接触させる工程を有する水素の製造方法。
That is, the present invention includes the following items.
[1] One or more elements (A) selected from nickel, cobalt and iron, one or more elements (B) selected from strontium and barium, and one or more elements (C) selected from rare earth elements. A method for producing hydrogen, which comprises a step of bringing a raw material gas containing ammonia into contact with a catalyst (X) containing magnesium (D) and magnesium (D).
［２］前記触媒（Ｘ）が、マグネシウム（Ｄ）をマグネシウムの酸化物換算で０．１質量％〜８０質量％の範囲で含む、［１］に記載の水素の製造方法。 [2] The method for producing hydrogen according to [1], wherein the catalyst (X) contains magnesium (D) in the range of 0.1% by mass to 80% by mass in terms of magnesium oxide.
［３］前記元素（Ｃ）が、イットリウム、ランタン、ネオジム、サマリウム、ユウロピウム、ガドリニウム及びエルビウムから選ばれる１種以上の元素である、［１］又は［２］に記載の水素の製造方法。 [3] The method for producing hydrogen according to [1] or [2], wherein the element (C) is one or more elements selected from yttrium, lanthanum, neodymium, samarium, europium, gadolinium and erbium.
［４］前記元素（Ａ）が、ニッケルである、［１］〜［３］のいずれか１つに記載の水素の製造方法。 [4] The method for producing hydrogen according to any one of [1] to [3], wherein the element (A) is nickel.
［５］前記元素（Ｂ）が、バリウムである［１］〜［４］のいずれか１つに記載の水素の製造方法。 [5] The method for producing hydrogen according to any one of [1] to [4], wherein the element (B) is barium.
［６］前記原料ガスが、アンモニアを５０体積％〜１００体積％の範囲で含む、［１］〜［５］のいずれか１つに記載の水素の製造方法。 [6] The method for producing hydrogen according to any one of [1] to [5], wherein the raw material gas contains ammonia in the range of 50% by volume to 100% by volume.
［７］前記原料ガスに接触する際の前記触媒（Ｘ）の温度が、３００℃〜９００℃の範囲である、［１］〜［６］のいずれか１つに記載の水素の製造方法。 [7] The method for producing hydrogen according to any one of [1] to [6], wherein the temperature of the catalyst (X) upon contact with the raw material gas is in the range of 300 ° C. to 900 ° C.
［８］ニッケル、コバルト及び鉄から選ばれる１種以上の元素（Ａ）、ストロンチウム及びバリウムから選ばれる１種以上の元素（Ｂ）、希土類元素から選ばれる１種以上の元素（Ｃ）、並びにマグネシウム（Ｄ）を構成元素として含み、アンモニアを含有する原料ガスを分解して水素を製造することに用いられる水素製造用触媒。 [8] One or more elements selected from nickel, cobalt and iron (A), one or more elements selected from strontium and barium (B), one or more elements selected from rare earth elements (C), and A hydrogen production catalyst containing magnesium (D) as a constituent element and used for decomposing a raw material gas containing ammonia to produce hydrogen.
［９］前記マグネシウム（Ｄ）を、マグネシウムの酸化物換算で０．１質量％〜８０質量％の範囲で含む、［８］に記載の水素製造用触媒。 [9] The catalyst for hydrogen production according to [8], which contains the magnesium (D) in the range of 0.1% by mass to 80% by mass in terms of magnesium oxide.
［１０］ 前記元素（Ｃ）が、イットリウム、ランタン、ネオジム、サマリウム、ユウロピウム、ガドリニウム及びエルビウムから選ばれる１種以上の元素である、［８］又は［９］に記載の水素製造用触媒。 [10] The catalyst for hydrogen production according to [8] or [9], wherein the element (C) is one or more elements selected from yttrium, lanthanum, neodymium, samarium, europium, gadolinium and erbium.
［１１］ 前記元素（Ａ）が、ニッケルである［８］〜［１０］のいずれか１つに記載の水素製造用触媒。 [11] The catalyst for hydrogen production according to any one of [8] to [10], wherein the element (A) is nickel.
［１２］ 前記元素（Ｂ）が、バリウムである［８］〜［１１］のいずれか１つに記載の水素製造用触媒。 [12] The catalyst for hydrogen production according to any one of [8] to [11], wherein the element (B) is barium.
本発明によれば、アンモニアを含有する原料ガスから効率的に水素が製造される水素の製造方法、及び水素製造用触媒が提供される。 According to the present invention, there is provided a method for producing hydrogen in which hydrogen is efficiently produced from a raw material gas containing ammonia, and a catalyst for producing hydrogen.
以下、本発明の水素の製造方法及び水素製造用触媒の一実施形態について説明する。但し、本発明は、以下の実施形態に何ら限定されるものではなく、本発明の目的の範囲内において、適宜変更を加えて実施することができる。
実施形態に係る水素の製造方法は、アンモニアを含有する原料ガスを、後述する触媒（Ｘ）に接触させる工程を有し、この工程にてアンモニア分解反応が起こり、水素が製造される、というものである。
以下、実施形態に係る水素の製造方法の詳細として、原料ガス、触媒（Ｘ）の組成、触媒（Ｘ）の調製方法、反応様式、反応条件、及び生成物について順次詳細に説明する。
Hereinafter, a method for producing hydrogen and an embodiment of a catalyst for producing hydrogen of the present invention will be described. However, the present invention is not limited to the following embodiments, and can be carried out with appropriate modifications within the scope of the object of the present invention.
The method for producing hydrogen according to the embodiment includes a step of bringing a raw material gas containing ammonia into contact with a catalyst (X) described later, and an ammonia decomposition reaction occurs in this step to produce hydrogen. Is.
Hereinafter, as details of the method for producing hydrogen according to the embodiment, the raw material gas, the composition of the catalyst (X), the method for preparing the catalyst (X), the reaction mode, the reaction conditions, and the product will be described in detail in order.
なお、本明細書中、数値範囲を表す「〜」はその上限及び下限の数値を含む範囲を表す。
本明細書中に段階的に記載されている数値範囲において、ある数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。
また、本明細書中に記載されている数値範囲において、ある数値範囲で記載された上限値又は下限値は、実施例に示されている値に置き換えてもよい。
In the present specification, "~" representing a numerical range represents a range including the upper and lower limit numerical values.
In the numerical range described stepwise in the present specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. ..
Further, in the numerical range described in the present specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples.
〔原料ガス〕
本実施形態において、触媒（Ｘ）に接触させる、つまり、アンモニア分解反応に用いる原料ガスについては特に制限は無く、アンモニアを含んでいればアンモニア以外の成分を含んでいてもよい。
原料ガス中のアンモニア濃度には特に制限はないが、アンモニア濃度としては、１体積％〜１００体積％の範囲内であることが好ましく、２０体積％〜１００体積％の範囲内であることがより好ましく、５０体積％〜１００体積％の範囲内であることが更に好ましく、９０体積％〜１００体積％の範囲内であることが特に好ましい。
原料ガス中のアンモニア以外の成分としては特に制限はないが、具体的には、ヘリウム、窒素、アルゴン、水蒸気、二酸化炭素、一酸化炭素、水素、炭化水素類などが挙げられる。中でも、アンモニア以外の成分としては、ヘリウム、窒素、アルゴンが好ましい。
[Raw material gas]
In the present embodiment, the raw material gas to be brought into contact with the catalyst (X), that is, used for the ammonia decomposition reaction is not particularly limited, and may contain a component other than ammonia as long as it contains ammonia.
The concentration of ammonia in the raw material gas is not particularly limited, but the concentration of ammonia is preferably in the range of 1% by volume to 100% by volume, and more preferably in the range of 20% by volume to 100% by volume. It is more preferably in the range of 50% by volume to 100% by volume, and particularly preferably in the range of 90% by volume to 100% by volume.
The components other than ammonia in the raw material gas are not particularly limited, and specific examples thereof include helium, nitrogen, argon, water vapor, carbon dioxide, carbon monoxide, hydrogen, and hydrocarbons. Of these, helium, nitrogen, and argon are preferable as the components other than ammonia.
〔触媒（Ｘ）の組成〕
本実施形態において、アンモニア分解触媒である触媒（Ｘ）は、ニッケル、コバルト及び鉄から選ばれる１種以上の元素（Ａ）と、ストロンチウム及びバリウムから選ばれる１種以上の元素（Ｂ）と、希土類元素から選ばれる１種以上の元素（Ｃ）と、マグネシウム（Ｄ）と、を含み、加えてそれ以外の元素を含んでいてもよいものとする。
[Composition of catalyst (X)]
In the present embodiment, the catalyst (X) which is an ammonia decomposition catalyst includes one or more elements (A) selected from nickel, cobalt and iron, and one or more elements (B) selected from strontium and barium. It is assumed that one or more elements (C) selected from rare earth elements and magnesium (D) are contained, and other elements may be contained in addition.
［元素（Ａ）］
元素（Ａ）は、ニッケル、コバルト及び鉄の３つの元素より選ばれる少なくとも１種の元素であり、好ましくは上記３つの元素より選ばれる１種又は２種の元素であり、より好ましくは上記３つの元素より選ばれる１種の元素である。
元素（Ａ）が上記３つの元素より選ばれる１種の元素である場合については、元素（Ａ）は、ニッケル又はコバルトであることが好ましく、ニッケルであることがより好ましい。
また、元素（Ａ）が上記３つの元素より選ばれる２種の元素である場合については、元素（Ａ）はニッケル及びコバルトであることが好ましい。
[Element (A)]
The element (A) is at least one element selected from the three elements of nickel, cobalt and iron, preferably one or two elements selected from the above three elements, and more preferably the above three elements. It is one kind of element selected from one element.
When the element (A) is one kind of element selected from the above three elements, the element (A) is preferably nickel or cobalt, and more preferably nickel.
When the element (A) is two kinds of elements selected from the above three elements, the element (A) is preferably nickel and cobalt.
触媒（Ｘ）における元素（Ａ）の化学的な形態については特に制限は無く、元素（Ａ）を含んでいれば他の元素を同時に含んだ形態として存在していてもよい。
元素（Ａ）の化学的な形態として具体的には、単体金属、合金、窒化物、酸化物、複合酸化物、炭化物、水酸化物及びこれらの混合物等が挙げられ、中でも、単体金属、合金、窒化物、酸化物、複合酸化物及びこれらの混合物が好ましく、更には、単体金属、合金、窒化物、酸化物、複合酸化物及びこれらの混合物がより好ましい。
元素（Ａ）の化学的な形態としてより具体的には、ニッケル金属、酸化ニッケル（NiO）、窒化ニッケル（Ni3N）、コバルト金属、酸化コバルト（CoO、Co3O4）、又は窒化コバルト（CoxNy）が挙げられ、中でも、ニッケル金属及びコバルト金属が好ましい。
The chemical form of the element (A) in the catalyst (X) is not particularly limited, and may exist as a form containing another element at the same time as long as the element (A) is contained.
Specific examples of the chemical form of the element (A) include single metals, alloys, nitrides, oxides, composite oxides, carbides, hydroxides and mixtures thereof, and among them, single metals and alloys. , Nitridees, oxides, composite oxides and mixtures thereof are preferred, and even more preferred are single metals, alloys, nitrides, oxides, composite oxides and mixtures thereof.
More specifically, the chemical form of the element (A) is nickel metal, nickel oxide (NiO), nickel nitride (Ni 3 N), cobalt metal, cobalt oxide (CoO, Co 3 O 4 ), or cobalt nitride. (Co x N y ), among which nickel metal and cobalt metal are preferable.
触媒（Ｘ）に含まれる元素（Ａ）及びマグネシウム（Ｄ）はそれぞれ異なる化学的な形態を有していてもよいが、元素（Ａ）及びマグネシウム（Ｄ）からなる複合酸化物を形成していてもよい。複合酸化物の構造には特に制限はないが、具体的にはスピネル型酸化物が挙げられる。 The element (A) and magnesium (D) contained in the catalyst (X) may have different chemical forms, but form a composite oxide composed of the element (A) and magnesium (D). You may. The structure of the composite oxide is not particularly limited, and specific examples thereof include spinel-type oxides.
［元素（Ｂ）］
元素（Ｂ）は、ストロンチウム及びバリウムより選ばれる少なくとも１種の元素であり、バリウムを含んでいることが好ましく、バリウムのみを含むことがより好ましい。
[Element (B)]
The element (B) is at least one element selected from strontium and barium, and preferably contains barium, and more preferably contains only barium.
触媒（Ｘ）における元素（Ｂ）の化学的な形態については特に制限は無く、元素（Ｂ）を含んでいれば他の元素を同時に含んだ形態として存在していてもよい。
元素（Ｂ）の好ましい化学的な形態として具体的には、酸化物又は複合酸化物が挙げられ、中でも、酸化ストロンチウム（SrO）、酸化バリウム（BaO）及びその混合物が好ましい。
The chemical form of the element (B) in the catalyst (X) is not particularly limited, and may exist as a form containing another element at the same time as long as the element (B) is contained.
Specific preferred chemical forms of the element (B) include oxides or composite oxides, with strontium oxide (SrO), barium oxide (BaO) and mixtures thereof being preferred.
また、元素（Ｂ）は複数の化学的な形態の混合体として存在していてもよいが、触媒（Ｘ）に含まれる全ての元素（Ｂ）のうち３０質量％〜１００質量％が酸化物又は複合酸化物であることが特に好ましい。
酸化物又は複合酸化物以外の化学的な形態として具体的には、窒化物、水酸化物、炭酸塩などが挙げられる。
Further, the element (B) may exist as a mixture of a plurality of chemical forms, but 30% by mass to 100% by mass of all the elements (B) contained in the catalyst (X) are oxides. Alternatively, it is particularly preferably a composite oxide.
Specific examples of chemical forms other than oxides or composite oxides include nitrides, hydroxides, and carbonates.
［元素（Ｃ）］
元素（Ｃ）は、希土類元素より選ばれる少なくとも１種の元素であり、中でも、スカンジウム、イットリウム、ランタン、セリウム、プラセオジム、ネオジム、サマリウム、ユウロピウム、ガドリニウム、テルビウム、ジスプロシウム、ホルミウム、エルビウム、ツリウム、イッテルビウム及びルテチウムより選ばれる少なくとも１種の元素であることが好ましく、イットリウム、ランタン、ネオジム、サマリウム、ユウロピウム、ガドリニウム及びエルビウムより選ばれる少なくとも１種の元素であることがより好ましく、イットリウム、サマリウム、ユウロピウム及びガドリニウムより選ばれる少なくとも１種の元素であることが更に好ましく、サマリウムであることが特に好ましい。
[Element (C)]
Element (C) is at least one element selected from rare earth elements, among which scandium, ittrium, lantern, cerium, placeodim, neodymium, samarium, europium, gadolinium, samarium, displosium, formium, erbium, turium, itterbium. And at least one element selected from lutetium, more preferably at least one element selected from yttrium, samarium, neodymium, samarium, uropyum, gadrinium and erbium, and more preferably yttrium, samarium, europium and It is more preferably at least one element selected from gadolinium, and particularly preferably samarium.
元素（Ｂ）と元素（Ｃ）との組み合わせとしては以下に示すものが好ましい。
元素（Ｂ）がストロンチウムを含んでいる場合には、元素（Ｃ）はイットリウム、サマリウム、ユウロピウム及びガドリニウムより選ばれる少なくとも１種の元素であることが好ましく、サマリウム及びガドリニウムより選ばれる少なくとも１種の元素であることがより好ましく、サマリウムであることが更に好ましい。
また、元素（Ｂ）がバリウムを含んでいる場合には、元素（Ｃ）はイットリウム、ランタン、ネオジム、サマリウム、ユウロピウム、ガドリニウム及びエルビウムより選ばれる少なくとも１種の元素であることが好ましく、イットリウム、ネオジム、サマリウム、ユウロピウム、ガドリニウム及びエルビウムより選ばれる少なくとも１種の元素であることがより好ましく、イットリウム、サマリウム及びガドリニウムより選ばれる少なくとも１種の元素であることが更に好ましい。
The combination of the element (B) and the element (C) is preferably as shown below.
When the element (B) contains strontium, the element (C) is preferably at least one element selected from yttrium, samarium, europium and gadolinium, and at least one selected from samarium and gadolinium. It is more preferably an element and even more preferably a samarium.
When the element (B) contains barium, the element (C) is preferably at least one element selected from yttrium, lantern, neodymium, samarium, europium, gadolinium and erbium. It is more preferably at least one element selected from neodymium, samarium, europium, gadolinium and erbium, and even more preferably at least one element selected from yttrium, samarium and gadolinium.
触媒（Ｘ）における元素（Ｃ）の化学的な形態については特に制限は無く、元素（Ｃ）を含んでいれば他の元素を同時に含んだ形態として存在していてもよい。好ましい化学的な形態としては酸化物又は複合酸化物が挙げられ、中でも、酸化イットリウム（Y2O3）、酸化ランタン（La2O3）、酸化ネオジム（Nd2O3）、酸化サマリウム（Sm2O3）、酸化ユウロピウム（Eu2O3）、酸化ガドリニウム（Gd2O3）、酸化エルビウム（Er2O3）及びその混合物が好ましい。
また、元素（Ｃ）は複数の形態の混合体として存在していてもよいが、触媒（Ｘ）に含まれる全ての元素（Ｃ）のうち３０質量％〜１００質量％が酸化物又は複合酸化物を形成していることが好ましい。
酸化物又は複合酸化物以外の形態として具体的には、窒化物、水酸化物、炭酸塩などが挙げられる。
The chemical form of the element (C) in the catalyst (X) is not particularly limited, and may exist as a form containing another element at the same time as long as the element (C) is contained. Preferred chemical forms include oxides or composite oxides, among which yttrium oxide (Y 2 O 3 ), lanthanum oxide (La 2 O 3 ), neodymium oxide (Nd 2 O 3 ), samarium oxide (Sm). 2 O 3 ), europium oxide (Eu 2 O 3 ), gadolinium oxide (Gd 2 O 3 ), erbium oxide (Er 2 O 3 ) and mixtures thereof are preferred.
Further, the element (C) may exist as a mixture of a plurality of forms, but 30% by mass to 100% by mass of all the elements (C) contained in the catalyst (X) are oxides or complex oxidations. It is preferable that an object is formed.
Specific examples of forms other than oxides or composite oxides include nitrides, hydroxides, and carbonates.
触媒（Ｘ）に含まれる元素（Ｂ）及び元素（Ｃ）はそれぞれ異なる化学的な形態を有していてもよいが、元素（Ｂ）及び元素（Ｃ）からなる複合酸化物を形成していてもよい。複合酸化物の構造には特に制限はないが、具体的にはペロブスカイト型酸化物、蛍石型酸化物、スピネル型酸化物等が挙げられる。 The element (B) and the element (C) contained in the catalyst (X) may have different chemical forms, but form a composite oxide composed of the element (B) and the element (C). You may. The structure of the composite oxide is not particularly limited, and specific examples thereof include perovskite-type oxides, fluorite-type oxides, and spinel-type oxides.
［マグネシウム（Ｄ）］
触媒（Ｘ）におけるマグネシウム（Ｄ）の化学的な形態については特に制限は無く、マグネシウム（Ｄ）を含んでいれば他の元素を同時に含んだ形態として存在していてもよい。
マグネシウム（Ｄ）の好ましい化学的な形態としては、酸化物又は複合酸化物が挙げられ、中でも、酸化マグネシウム（MgO）が好ましい。
また、マグネシウム（Ｄ）は複数の化学的な形態の混合体として存在していてもよいが、触媒（Ｘ）に含まれる全てのマグネシウム（Ｄ）のうち３０質量％〜１００質量％が酸化物又は複合酸化物であることが特に好ましい。
酸化物又は複合酸化物以外の化学的な形態として具体的には窒化物、水酸化物、炭酸塩などが挙げられる。
[Magnesium (D)]
The chemical form of magnesium (D) in the catalyst (X) is not particularly limited, and may exist as a form containing other elements at the same time as long as magnesium (D) is contained.
Preferred chemical forms of magnesium (D) include oxides or composite oxides, with magnesium oxide (MgO) being preferred.
Further, magnesium (D) may exist as a mixture of a plurality of chemical forms, but 30% by mass to 100% by mass of all magnesium (D) contained in the catalyst (X) is an oxide. Alternatively, it is particularly preferably a composite oxide.
Specific examples of chemical forms other than oxides or composite oxides include nitrides, hydroxides, and carbonates.
［その他の構成元素］
触媒（Ｘ）には、上記以外の構成元素を含んでいてもよい。
触媒（Ｘ）に含まれる上記以外の構成元素としては、具体的には、アルカリ金属元素、マグネシウム、ストロンチウム及びバリウムを除いたアルカリ土類金属元素、４族元素、鉄以外の８族元素、コバルト以外の９族元素、ニッケル以外の１０族元素、アルミニウム、炭素、ケイ素、窒素並びに酸素などが挙げられる。
また、これらの化学的な形態及び触媒（Ｘ）中の含有量のいずれについても、アンモニア分解の活性を低減させない範囲においては特に制限はない。
[Other constituent elements]
The catalyst (X) may contain a constituent element other than the above.
Specific elements other than the above contained in the catalyst (X) include alkali metal elements, alkaline earth metal elements excluding magnesium, strontium and barium, group 4 elements, group 8 elements other than iron, and cobalt. Group 9 elements other than, group 10 elements other than nickel, aluminum, carbon, silicon, nitrogen, oxygen and the like can be mentioned.
Further, neither the chemical form nor the content in the catalyst (X) is particularly limited as long as the activity of ammonia decomposition is not reduced.
触媒（Ｘ）中の各元素（Ａ）〜（Ｄ）の化学的な形態は、以下のようにして確認することができる。
即ち、触媒（Ｘ）を、Ｘ線回折法（XRD）等の公知の方法で測定し、各元素（Ａ）〜（Ｄ）の化学的な形態を確認することができる。
The chemical morphology of each element (A) to (D) in the catalyst (X) can be confirmed as follows.
That is, the catalyst (X) can be measured by a known method such as an X-ray diffraction method (XRD), and the chemical morphology of each element (A) to (D) can be confirmed.
触媒（Ｘ）に含まれる元素（Ａ）、元素（Ｂ）、元素（Ｃ）及びマグネシウム（Ｄ）の量については、元素（Ａ）については単体金属換算で、元素（Ｂ）、元素（Ｃ）及びマグネシウム（Ｄ）については酸化物換算で算出すると、以下に示す範囲が好ましい。更に、それぞれの含有量の算出方法について、以下に詳細を説明する。 Regarding the amount of element (A), element (B), element (C) and magnesium (D) contained in the catalyst (X), the element (A) is converted into a single metal, and the element (B) and element (C). ) And magnesium (D) are calculated in terms of oxides, and the ranges shown below are preferable. Further, the calculation method of each content will be described in detail below.
触媒（Ｘ）に含まれる元素（Ａ）の量は、含まれる全ての元素（Ａ）が単体金属として存在すると仮定して算出する。
元素（Ａ）の合計量は特に制限はないが、触媒（Ｘ）の全質量に対して、元素（Ａ）の単体金属として、０．０１質量％〜８０質量％であることが好ましく、１質量％〜７０質量％であることがより好ましく、１０質量％〜６０質量％であることがより好ましく、２０質量％〜６０質量％であることがより好ましく、３０質量％〜５５質量％が更に好ましく、３０質量％〜５０質量％が特に好ましい。
The amount of the element (A) contained in the catalyst (X) is calculated on the assumption that all the contained elements (A) exist as elemental metals.
The total amount of the element (A) is not particularly limited, but is preferably 0.01% by mass to 80% by mass as the single metal of the element (A) with respect to the total mass of the catalyst (X). It is more preferably from mass% to 70% by mass, more preferably from 10% by mass to 60% by mass, more preferably from 20% by mass to 60% by mass, and further from 30% by mass to 55% by mass. It is preferable, and 30% by mass to 50% by mass is particularly preferable.
触媒（Ｘ）に含まれる元素（Ｂ）の量は、含まれる全ての元素（Ｂ）が酸化物として存在すると仮定して算出する。
元素（Ｂ）の合計量は特に制限はないが、触媒（Ｘ）の全質量に対して、元素（Ｂ）の酸化物として、０．１質量％〜１５質量％の範囲にあることが好ましく、１質量％〜１５質量％の範囲にあることがより好ましく、２質量％〜１５質量％の範囲にあることがより好ましく、２質量％〜１２質量％の範囲にあることがより好ましく、２質量％〜９質量％の範囲にあることがより好ましく、２質量％〜７質量％の範囲にあることが更に好ましく、３質量％〜７質量％の範囲が特に好ましい。
The amount of the element (B) contained in the catalyst (X) is calculated assuming that all the contained elements (B) are present as oxides.
The total amount of the element (B) is not particularly limited, but is preferably in the range of 0.1% by mass to 15% by mass as the oxide of the element (B) with respect to the total mass of the catalyst (X). It is more preferably in the range of 1% by mass to 15% by mass, more preferably in the range of 2% by mass to 15% by mass, and more preferably in the range of 2% by mass to 12% by mass. It is more preferably in the range of mass% to 9% by mass, further preferably in the range of 2% by mass to 7% by mass, and particularly preferably in the range of 3% by mass to 7% by mass.
触媒（Ｘ）に含まれる元素（Ｂ）がバリウムを含む場合には、触媒（Ｘ）の全質量に対するバリウムの量は、バリウムの酸化物として、０．１質量％〜１５質量％であることが好ましく、１質量％〜１５質量％であることがより好ましく、２質量％〜１２質量％であることがより好ましく、２質量％〜９質量％であることがより好ましく、３質量％〜７質量％であることが更に好ましく、４質量％〜６質量％の範囲が特に好ましい。 When the element (B) contained in the catalyst (X) contains barium, the amount of barium with respect to the total mass of the catalyst (X) shall be 0.1% by mass to 15% by mass as an oxide of barium. Is preferable, 1% by mass to 15% by mass is more preferable, 2% by mass to 12% by mass is more preferable, and 2% by mass to 9% by mass is more preferable, and 3% by mass to 7% by mass. It is more preferably by mass%, and particularly preferably in the range of 4% by mass to 6% by mass.
触媒（Ｘ）に含まれる元素（Ｃ）の量は、含まれる全ての元素（Ｃ）が酸化物として存在すると仮定して算出する。
元素（Ｃ）の合計量は特に制限はないが、触媒（Ｘ）の全質量に対して、元素（Ｃ）の酸化物として、０．１質量％〜６０質量％であることが好ましく、１質量％〜４０質量％であることがより好ましく、１質量％〜３５質量％であることが更に好ましく、２質量％〜３０質量％であることが特に好ましい。
触媒（Ｘ）に含まれる元素（Ｃ）がサマリウムを含む場合には、触媒（Ｘ）の全質量に対するサマリウムの量は、サマリウムの酸化物として、０．１質量％〜６０質量％であることが好ましく、１質量％〜４０質量％であることがより好ましく、１質量％〜３５質量％であることがより好ましく、２質量％〜３０質量％であることがより好ましく、２質量％〜２５質量％であることがより好ましく、２質量％〜２０質量％であることがより好ましく、４質量％〜２０質量％であることが更に好ましく、７質量％〜２０質量％であることが特に好ましい。
The amount of the element (C) contained in the catalyst (X) is calculated assuming that all the contained elements (C) are present as oxides.
The total amount of the element (C) is not particularly limited, but is preferably 0.1% by mass to 60% by mass as the oxide of the element (C) with respect to the total mass of the catalyst (X). It is more preferably from mass% to 40% by mass, further preferably from 1% by mass to 35% by mass, and particularly preferably from 2% by mass to 30% by mass.
When the element (C) contained in the catalyst (X) contains samarium, the amount of samarium with respect to the total mass of the catalyst (X) shall be 0.1% by mass to 60% by mass as an oxide of samarium. Is preferable, 1% by mass to 40% by mass is more preferable, 1% by mass to 35% by mass is more preferable, and 2% by mass to 30% by mass is more preferable, and 2% by mass to 25% by mass. It is more preferably by mass%, more preferably 2% by mass to 20% by mass, further preferably 4% by mass to 20% by mass, and particularly preferably 7% by mass to 20% by mass. ..
触媒（Ｘ）に含まれる元素（Ｂ）のモル数と元素（Ａ）のモル数との比率（元素（Ｂ）／元素（Ａ））は、０．０１〜０．２１が好ましく、０．０１〜０．１５がより好ましく、０．０２〜０．１５がより好ましく、０．０２〜０．１２がより好ましく、０．０２〜０．１がより好ましく、０．０２５〜０．１がより好ましく、０．０３〜０．１が更に好ましく、０．０４〜０．１が特に好ましい。
触媒（Ｘ）が元素（Ｂ）としてバリウムを含有する場合には、バリウムのモル数と元素（Ａ）のモル数との比率（バリウム／元素（Ａ））は、０．０１〜０．２１が好ましく、０．０１〜０．１５がより好ましく、０．０２〜０．１５がより好ましく、０．０２〜０．１２がより好ましく、０．０２〜０．１が更に好ましく、０．０２〜０．０８が特に好ましい。
The ratio of the number of moles of the element (B) contained in the catalyst (X) to the number of moles of the element (A) (element (B) / element (A)) is preferably 0.01 to 0.21. 01 to 0.15 is more preferable, 0.02 to 0.15 is more preferable, 0.02 to 0.12 is more preferable, 0.02 to 0.1 is more preferable, and 0.025 to 0.1 is more preferable. More preferably, 0.03 to 0.1 is further preferable, and 0.04 to 0.1 is particularly preferable.
When the catalyst (X) contains barium as the element (B), the ratio of the number of moles of barium to the number of moles of element (A) (barium / element (A)) is 0.01 to 0.21. Is preferable, 0.01 to 0.15 is more preferable, 0.02 to 0.15 is more preferable, 0.02 to 0.12 is more preferable, 0.02 to 0.1 is further preferable, and 0.02 is preferable. ~ 0.08 is particularly preferable.
触媒（Ｘ）に含まれるマグネシウム（Ｄ）の量は、含まれる全てのマグネシウム（Ｄ）が酸化物（即ち、酸化マグネシウム）として存在すると仮定して算出する。
マグネシウム（Ｄ）の量は、触媒（Ｘ）の全質量に対して、酸化物換算（酸化マグネシウムとして）にて、０．１質量％〜８０質量％であることが好ましく、１質量％〜７０質量％であることがより好ましく、１０質量％〜６５質量％であることがより好ましく、１５質量％〜６５質量％であることがより好ましく、２０質量％〜６０質量％であることが更に好ましく、２０質量％〜５５質量％であることが特に好ましい。
The amount of magnesium (D) contained in the catalyst (X) is calculated assuming that all the magnesium (D) contained is present as an oxide (that is, magnesium oxide).
The amount of magnesium (D) is preferably 0.1% by mass to 80% by mass in terms of oxide (as magnesium oxide) with respect to the total mass of the catalyst (X), and is preferably 1% by mass to 70% by mass. It is more preferably 10% by mass to 65% by mass, more preferably 15% by mass to 65% by mass, and further preferably 20% by mass to 60% by mass. , 20% by mass to 55% by mass is particularly preferable.
触媒（Ｘ）に含まれる元素（Ｃ）のモル数とマグネシウム（Ｄ）のモル数との比、即ちモル元素比（元素（Ｃ）／マグネシウム（Ｄ））は、０．００５〜８．００が好ましく、０．０１０〜１．００がより好ましく、０．０１０〜０．６０がより好ましく、０．０１０〜０．５０が更に好ましく、０．０１〜０．４０が特に好ましい。
触媒（Ｘ）が元素（Ｃ）としてサマリウムを含有する場合には、サマリウムのモル数とマグネシウム（Ｄ）のモル数との比率（サマリウム／マグネシウム（Ｄ））は、０．００５〜８．００が好ましく、０．０１０〜１．００がより好ましく、０．０１０〜０．６０がより好ましく、０．０１０〜０．５０がより好ましく、０．０１〜０．４０がより好ましく、０．０１０〜０．２５がより好ましく、０．０１３〜０．２２が更に好ましく、０．０１５〜０．２０が特に好ましい。
The ratio of the number of moles of the element (C) contained in the catalyst (X) to the number of moles of magnesium (D), that is, the molar element ratio (element (C) / magnesium (D)) is 0.005 to 8.00. Is preferable, 0.010 to 1.00 is more preferable, 0.010 to 0.60 is more preferable, 0.010 to 0.50 is further preferable, and 0.01 to 0.40 is particularly preferable.
When the catalyst (X) contains samarium as the element (C), the ratio of the number of moles of samarium to the number of moles of magnesium (D) (samarium / magnesium (D)) is 0.005 to 8.00. Is preferable, 0.010 to 1.00 is more preferable, 0.010 to 0.60 is more preferable, 0.010 to 0.50 is more preferable, 0.01 to 0.40 is more preferable, and 0.010 is preferable. ~ 0.25 is more preferable, 0.013 to 0.22 is further preferable, and 0.015 to 0.20 is particularly preferable.
触媒（Ｘ）に含まれる元素（Ａ）と元素（Ｂ）と元素（Ｃ）とマグネシウム（Ｄ）との量の組み合わせは、すべての元素（Ａ）を単体金属として換算し、元素（Ｂ）、元素（Ｃ）及びマグネシウム（Ｄ）をすべて酸化物として換算し、それらの合計が１００質量％となるように計算すると、以下のようなものが好ましい。
即ち、元素（Ａ）が２０質量％〜６０質量％、元素（Ｂ）が２質量％〜８質量％、元素（Ｃ）が２質量％〜４０質量％及びマグネシウム（Ｄ）が２質量％〜７６質量％である組み合わせが好ましく、元素（Ａ）が３０質量％〜５０質量％、元素（Ｂ）が３質量％〜７質量％、元素（Ｃ）が２質量％〜３５質量％及びマグネシウム（Ｄ）が８質量％〜６５質量％である組み合わせがより好ましく、元素（Ａ）が３０質量％〜５０質量％、元素（Ｂ）が３質量％〜７質量％、元素（Ｃ）が２質量％〜３０質量％及びマグネシウム（Ｄ）が１３質量％〜６５質量％である組み合わせがより好ましく、元素（Ａ）が３５質量％〜５０質量％、元素（Ｂ）が４質量％〜７質量％、元素（Ｃ）が２質量％〜３０質量％及びマグネシウム（Ｄ）が１３質量％〜５９質量％である組み合わせが更に好ましく、元素（Ａ）が３５質量％〜４５質量％、元素（Ｂ）が４質量％〜６質量％、元素（Ｃ）が２質量％〜３０質量％及びマグネシウム（Ｄ）が１９質量％〜５９質量％である組み合わせが特に好ましい。
The combination of the amounts of the element (A), the element (B), the element (C), and the magnesium (D) contained in the catalyst (X) converts all the elements (A) as elemental metals, and the element (B). , Element (C) and magnesium (D) are all converted as oxides, and when calculated so that the total of them is 100% by mass, the following is preferable.
That is, the element (A) is 20% by mass to 60% by mass, the element (B) is 2% by mass to 8% by mass, the element (C) is 2% by mass to 40% by mass, and the magnesium (D) is 2% by mass to 2% by mass. A combination of 76% by mass is preferable, and the element (A) is 30% by mass to 50% by mass, the element (B) is 3% by mass to 7% by mass, the element (C) is 2% by mass to 35% by mass, and magnesium ( A combination in which D) is 8% by mass to 65% by mass is more preferable, element (A) is 30% by mass to 50% by mass, element (B) is 3% by mass to 7% by mass, and element (C) is 2% by mass. A combination of% to 30% by mass and magnesium (D) of 13% by mass to 65% by mass is more preferable, with element (A) of 35% by mass to 50% by mass and element (B) of 4% by mass to 7% by mass. , The combination in which the element (C) is 2% by mass to 30% by mass and the magnesium (D) is 13% by mass to 59% by mass is more preferable, and the element (A) is 35% by mass to 45% by mass, and the element (B). Is 4% by mass to 6% by mass, the element (C) is 2% by mass to 30% by mass, and magnesium (D) is 19% by mass to 59% by mass, which is particularly preferable.
触媒（Ｘ）が元素（Ｃ）としてサマリウムを含む場合には、触媒（Ｘ）に含まれる元素（Ａ）と元素（Ｂ）と元素（Ｃ）とマグネシウム（Ｄ）との量の組み合わせは、すべての元素（Ａ）を単体金属として換算し、元素（Ｂ）、元素（Ｃ）及びマグネシウム（Ｄ）をすべて酸化物として換算し、それらの合計が１００質量％となるように計算すると、以下のようなものが好ましい。
即ち、元素（Ａ）が２０質量％〜６０質量％、元素（Ｂ）が２質量％〜８質量％、元素（Ｃ）が２質量％〜４０質量％及びマグネシウム（Ｄ）が２質量％〜７６質量％である組み合わせが好ましく、元素（Ａ）が３０質量％〜５０質量％、元素（Ｂ）が３質量％〜７質量％、元素（Ｃ）が２質量％〜３５質量％及びマグネシウム（Ｄ）が８質量％〜６５質量％である組み合わせがより好ましく、元素（Ａ）が３０質量％〜５０質量％、元素（Ｂ）が３質量％〜７質量％、元素（Ｃ）が２質量％〜３０質量％及びマグネシウム（Ｄ）が１３質量％〜６５質量％である組み合わせがより好ましく、元素（Ａ）が３０質量％〜５０質量％、元素（Ｂ）が３質量％〜７質量％、元素（Ｃ）が２質量％〜２５質量％及びマグネシウムが１８質量％〜６５質量％である組み合わせがより好ましく、元素（Ａ）が３０質量％〜５０質量％、元素（Ｂ）が３質量％〜７質量％、元素（Ｃ）が３質量％〜２０質量％及びマグネシウム（Ｄ）が２３質量％〜６４質量％である組み合わせがより好ましく、元素（Ａ）が３５質量％〜５０質量％、元素（Ｂ）が４質量％〜７質量％、元素（Ｃ）が５質量％〜２０質量％及びマグネシウム（Ｄ）が２３質量％〜５６質量％である組み合わせが更に好ましく、元素（Ａ）が３５質量％〜４５質量％、元素（Ｂ）が４質量％〜６質量％、元素（Ｃ）が５質量％〜２０質量％及びマグネシウム（Ｄ）が２９質量％〜５６質量％である組み合わせが特に好ましい。
When the catalyst (X) contains samarium as the element (C), the combination of the amounts of the element (A), the element (B), the element (C) and the magnesium (D) contained in the catalyst (X) is Converting all the elements (A) as single metals, converting all the elements (B), element (C) and magnesium (D) as oxides, and calculating so that the total of them is 100% by mass is as follows. Is preferable.
That is, the element (A) is 20% by mass to 60% by mass, the element (B) is 2% by mass to 8% by mass, the element (C) is 2% by mass to 40% by mass, and the magnesium (D) is 2% by mass to 2% by mass. A combination of 76% by mass is preferable, and the element (A) is 30% by mass to 50% by mass, the element (B) is 3% by mass to 7% by mass, the element (C) is 2% by mass to 35% by mass, and magnesium ( A combination in which D) is 8% by mass to 65% by mass is more preferable, element (A) is 30% by mass to 50% by mass, element (B) is 3% by mass to 7% by mass, and element (C) is 2% by mass. A combination of% to 30% by mass and magnesium (D) of 13% by mass to 65% by mass is more preferable, the element (A) is 30% by mass to 50% by mass, and the element (B) is 3% by mass to 7% by mass. , The combination in which the element (C) is 2% by mass to 25% by mass and the magnesium is 18% by mass to 65% by mass is more preferable, the element (A) is 30% by mass to 50% by mass, and the element (B) is 3% by mass. A combination of% to 7% by mass, element (C) of 3% by mass to 20% by mass, and magnesium (D) of 23% by mass to 64% by mass is more preferable, and element (A) is 35% by mass to 50% by mass. , The combination in which the element (B) is 4% by mass to 7% by mass, the element (C) is 5% by mass to 20% by mass, and the magnesium (D) is 23% by mass to 56% by mass is more preferable, and the element (A) Is 35% by mass to 45% by mass, element (B) is 4% by mass to 6% by mass, element (C) is 5% by mass to 20% by mass, and magnesium (D) is 29% by mass to 56% by mass. Is particularly preferable.
触媒（Ｘ）中の各元素（Ａ）〜（Ｄ）の量は、各元素（Ａ）〜（Ｄ）の原料の質量から比で求めることもできるが、以下のようにして測定することができる。
即ち、触媒（Ｘ）中の各元素（Ａ）〜（Ｄ）の量は、原子吸光分析法（AAS）、誘導結合プラズマ原子発光法（ICP-AES）、蛍光Ｘ線分析（XRF）等の公知の方法で測定することもできる。
The amount of each element (A) to (D) in the catalyst (X) can be determined by a ratio from the mass of the raw materials of each element (A) to (D), but can be measured as follows. it can.
That is, the amount of each element (A) to (D) in the catalyst (X) is determined by atomic absorption spectrometry (AAS), inductively coupled plasma atomic emission spectrometry (ICP-AES), fluorescent X-ray analysis (XRF), etc. It can also be measured by a known method.
〔触媒（Ｘ）の調製方法〕
アンモニア分解触媒である触媒（Ｘ）は、前記した元素（Ａ）〜（Ｄ）を含む組成を満たす限り、その調製方法については特に制限はない。
触媒（Ｘ）の調製に用いる手法としては、主に、固体成分を溶液成分に浸漬させて調製する含浸法、気体成分を固体成分と接触させる蒸着法、溶液成分から固体成分を沈殿させる沈殿法、複数種の固体成分を混合する固相混合法、の４種の手法が挙げられる。
[Method for preparing catalyst (X)]
The catalyst (X), which is an ammonia decomposition catalyst, is not particularly limited in its preparation method as long as it satisfies the composition containing the above-mentioned elements (A) to (D).
The methods used for preparing the catalyst (X) are mainly an impregnation method in which a solid component is immersed in a solution component to prepare the catalyst (X), a vapor deposition method in which a gas component is brought into contact with the solid component, and a precipitation method in which the solid component is precipitated from the solution component. , A solid phase mixing method in which a plurality of types of solid components are mixed, and four types of methods can be mentioned.
上記含浸法としては、固体成分を溶液成分に浸漬させて調製する手法であれば公知の手法が特に制限無く用いられる。
含浸法として具体的には、ポアフィリング法、インシピエント・ウェットネス（ｉｎｃｉｐｉｅｎｔ ｗｅｔｎｅｓｓ）法、平衡吸着法、蒸発乾固法、噴霧乾燥法、沈着法、イオン交換法などが挙げられる。
また、含浸法に使用する溶液成分の組成及び濃度について特に制限は無く、複数の成分を含んでいてもよい。
As the impregnation method, a known method can be used without particular limitation as long as it is a method of preparing by immersing a solid component in a solution component.
Specific examples of the impregnation method include a pore filling method, an impingient wetness method, an equilibrium adsorption method, an evaporative drying method, a spray drying method, a deposition method, and an ion exchange method.
Further, the composition and concentration of the solution components used in the impregnation method are not particularly limited, and a plurality of components may be contained.
上記蒸着法としては、気体成分を固体成分と接触させて調製する手法であれば公知の手法が特に制限無く用いられる。
蒸着法として具体的には、化学蒸着法、真空蒸着法、スパッタリング法等が挙げられる。
また、使用する気体成分の組成について特に制限は無く、複数の成分を含んでいてもよく、また、不活性な同伴ガスを含んでいてもよい。
As the above-mentioned vapor deposition method, a known method can be used without particular limitation as long as it is a method of preparing by contacting a gas component with a solid component.
Specific examples of the vapor deposition method include a chemical vapor deposition method, a vacuum vapor deposition method, and a sputtering method.
Further, the composition of the gas component to be used is not particularly limited, and may contain a plurality of components, or may contain an inert accompanying gas.
上記沈殿法としては、溶液成分から固体成分を沈殿させて調製する手法であれば公知の手法が特に制限無く用いられる。
沈殿法として具体的には、１種類のカチオンを含む溶液から沈殿剤添加により同カチオンの難溶性塩を沈殿させる一般的な沈殿法に加え、２種類以上のカチオンを含む溶液から沈殿剤添加により複数の難溶性塩を同時に沈殿させる共沈法、溶液中の溶質を加水分解及び縮重合により沈殿させるゾルゲル法などが挙げられる。
共沈法を用いる場合について、アルカリ土類金属である元素（Ｂ）のカチオンを含む場合については、同カチオンが一般に沈殿し難いため、クエン酸やシュウ酸等の多価カルボン酸を沈殿促進剤として加えてもよい。
As the precipitation method, a known method can be used without particular limitation as long as it is a method of preparing by precipitating a solid component from a solution component.
Specifically, as a precipitation method, in addition to a general precipitation method in which a sparingly soluble salt of the same cation is precipitated by adding a precipitation agent from a solution containing one type of cation, a precipitation agent is added from a solution containing two or more types of cations. Examples thereof include a co-precipitation method in which a plurality of sparingly soluble salts are precipitated at the same time, and a solgel method in which a solute in a solution is precipitated by hydrolysis and condensation polymerization.
When the coprecipitation method is used, when the cation of the element (B) which is an alkaline earth metal is contained, the cation is generally difficult to precipitate, so a polyvalent carboxylic acid such as citric acid or oxalic acid is used as a precipitation accelerator. May be added as.
上記固相混合法としては、複数種の固体成分を混合して調製する手法であれば公知の手法が特に制限無く用いられる。
固相混合法として具体的には、複数種の固体成分を反応を伴わずに物理的に混合するだけの物理混合法、複数種の固体成分を混合し高温処理等により反応させて複合化させる固相合成法などが挙げられる。
As the solid phase mixing method, a known method can be used without particular limitation as long as it is a method of mixing and preparing a plurality of types of solid components.
Specifically, as a solid-phase mixing method, a physical mixing method in which a plurality of types of solid components are simply physically mixed without a reaction, or a physical mixing method in which a plurality of types of solid components are mixed and reacted by high-temperature treatment or the like to be complexed. A solid phase synthesis method and the like can be mentioned.
上記４種の手法（含浸法、蒸着法、沈殿法、固相合成法）を用いて触媒（Ｘ）を調製する場合は、４種の中から複数の手法を組み合わせて用いてもよく、また、同じ手法を複数回用いてもよい。 When the catalyst (X) is prepared by using the above four methods (impregnation method, thin film deposition method, precipitation method, solid phase synthesis method), a plurality of methods may be used in combination from the four methods. , The same method may be used multiple times.
触媒（Ｘ）の具体的な調製方法としては、以下（１）〜（３）の３つの方法が挙げられる。
（１）元素（Ａ）、元素（Ｂ）、元素（Ｃ）を含む溶液成分を用い、マグネシウム（Ｄ）を含む固体成分に対し、元素（Ａ）、元素（Ｂ）、元素（Ｃ）を含浸法により担持させ、触媒（Ｘ）とする。
（２）元素（Ａ）、元素（Ｂ）、元素（Ｃ）及びマグネシウム（Ｄ）を含む溶液成分から、沈殿法により、元素（Ａ）、元素（Ｂ）、元素（Ｃ）及びマグネシウム（Ｄ）を含む固体成分を沈殿させ、触媒（Ｘ）とする。
（３）元素（Ａ）を含む固体成分、元素（Ｂ）を含む固体成分、元素（Ｃ）を含む固体成分、マグネシウム（Ｄ）を含む固体成分を固相混合法により混合し、触媒（Ｘ）とする。
この（１）〜（３）の調製方法の中でも、得られる触媒（Ｘ）が高比表面積となり易いことから、沈殿法が特に好ましい。
Specific methods for preparing the catalyst (X) include the following three methods (1) to (3).
(1) Using a solution component containing element (A), element (B), and element (C), element (A), element (B), and element (C) are added to a solid component containing magnesium (D). It is supported by the impregnation method and used as a catalyst (X).
(2) Element (A), element (B), element (C) and magnesium (D) from a solution component containing element (A), element (B), element (C) and magnesium (D) by a precipitation method. ) Is precipitated to form a catalyst (X).
(3) A solid component containing the element (A), a solid component containing the element (B), a solid component containing the element (C), and a solid component containing magnesium (D) are mixed by a solid phase mixing method, and the catalyst (X) is mixed. ).
Among the preparation methods (1) to (3), the precipitation method is particularly preferable because the obtained catalyst (X) tends to have a high specific surface area.
（１）及び（３）の調製方法で用いる固体成分については特に制限はない。
具体的には、市販品の他、元素（Ａ）、元素（Ｂ）、元素（Ｃ）、又はマグネシウム（Ｄ）を含む溶液から沈殿法により調製した固体成分、などを用いればよい。
（１）及び（３）の調製方法で用いる固体成分の化学的な形態に特に制限はないが、各元素（Ａ）〜（Ｄ）のそれぞれの酸化物が好ましい形態として挙げられる。
There are no particular restrictions on the solid components used in the preparation methods (1) and (3).
Specifically, in addition to commercially available products, a solid component prepared by a precipitation method from a solution containing element (A), element (B), element (C), or magnesium (D) may be used.
The chemical form of the solid component used in the preparation methods (1) and (3) is not particularly limited, but the oxides of the respective elements (A) to (D) are mentioned as preferable forms.
（１）及び（２）の調製方法で用いる溶液成分についても特に制限はないが、各元素（Ａ）〜（Ｄ）のそれぞれを含有する水溶性化合物を水に溶解させ調製した水溶液を用いるのが好ましい。
また、溶液成分として水溶液を用いる場合、（２）の調製方法では、沈殿剤として、アルカリ性化合物を用いるのが好ましい。
アルカリ性化合物として具体的には、アンモニア、水酸化カリウム、水酸化ナトリウム、水酸化テトラメチルアンモニウム、炭酸カリウム、炭酸ナトリウム及びこれらの水溶液などが挙げられる。なお、尿素を溶液中で分解しアンモニアを発生させる方法を用いて、アルカリ性化合物を添加してもよい。
The solution components used in the preparation methods (1) and (2) are not particularly limited, but an aqueous solution prepared by dissolving a water-soluble compound containing each of the elements (A) to (D) in water is used. Is preferable.
When an aqueous solution is used as the solution component, it is preferable to use an alkaline compound as the precipitant in the preparation method (2).
Specific examples of the alkaline compound include ammonia, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, potassium carbonate, sodium carbonate, and an aqueous solution thereof. An alkaline compound may be added by using a method of decomposing urea in a solution to generate ammonia.
触媒（Ｘ）の調製に用いる固体成分及び触媒（Ｘ）の調製過程で得られる固体成分については、必要に応じて、酸化雰囲気での焼成処理及び還元雰囲気での還元処理のうちどちらか一方又は両方を施してもよい。
焼成処理及び還元処理は、触媒（Ｘ）の調製時の、それぞれの調製におけるすべての工程よりも前、工程の途中、及びすべての工程の後のいずれで実施してもよく、また、異なるタイミングで複数回実施してもよい。中でも、特に、すべての工程の後に焼成処理及び還元処理のどちらか一方（好ましくは、両方を順に）を、実施することが好ましい。
The solid component used for the preparation of the catalyst (X) and the solid component obtained in the preparation process of the catalyst (X) may be either a firing treatment in an oxidizing atmosphere or a reducing treatment in a reducing atmosphere, if necessary. Both may be applied.
The firing treatment and the reduction treatment may be carried out at the time of preparing the catalyst (X) before all the steps in each preparation, in the middle of the steps, and after all the steps, and at different timings. It may be carried out multiple times. Above all, it is particularly preferable to carry out either one of the firing treatment and the reduction treatment (preferably both in order) after all the steps.
焼成処理における酸化雰囲気としては、例えば、空気下、酸素と窒素の混合ガス下などが挙げられるが、特にこれらに限定されるものではない。
還元処理における還元雰囲気としては、例えば、水素雰囲気下、一酸化炭素雰囲気下、一酸化窒素雰囲気下などが挙げられるが、特にこれらに限定されるものではない。
Examples of the oxidizing atmosphere in the firing treatment include, but are not limited to, under air and under a mixed gas of oxygen and nitrogen.
Examples of the reducing atmosphere in the reduction treatment include, but are not limited to, a hydrogen atmosphere, a carbon monoxide atmosphere, and a nitric oxide atmosphere.
固体成分に対する焼成処理及び還元処理のそれぞれの処理条件については特に制限はない。
触媒（Ｘ）の調製のすべての工程の後に焼成処理及び還元処理を順に実施する場合には、以下の処理条件が好ましい。
焼成処理温度は、１００℃〜１２００℃の範囲が好ましく、４００℃〜９００℃の範囲がより好ましい。
焼成処理時間は、０．１時間〜４８時間の範囲が好ましく、０．５時間〜２４時間の範囲がより好ましい。
還元処理温度は、１００℃〜１２００℃の範囲が好ましく、４００℃〜９００℃の範囲がより好ましい。
還元処理時間は、０．１時間〜４８時間の範囲が好ましく、０．５時間〜２４時間の範囲がより好ましい。
There are no particular restrictions on the treatment conditions for the firing treatment and the reduction treatment for the solid component.
When the firing treatment and the reduction treatment are sequentially carried out after all the steps of preparing the catalyst (X), the following treatment conditions are preferable.
The firing treatment temperature is preferably in the range of 100 ° C. to 1200 ° C., more preferably in the range of 400 ° C. to 900 ° C.
The firing treatment time is preferably in the range of 0.1 hour to 48 hours, more preferably in the range of 0.5 hour to 24 hours.
The reduction treatment temperature is preferably in the range of 100 ° C. to 1200 ° C., more preferably in the range of 400 ° C. to 900 ° C.
The reduction treatment time is preferably in the range of 0.1 hour to 48 hours, more preferably in the range of 0.5 hour to 24 hours.
固体成分に対する焼成処理及び還元処理のどちらか一方又は両方は、アンモニア分解反応器内において、アンモニア分解反応前に実施してもよい。この場合、処理後の固体成分は、触媒（Ｘ）として、そのままアンモニア分解反応に用いられる。 Either one or both of the firing treatment and the reduction treatment for the solid component may be carried out in the ammonia decomposition reactor before the ammonia decomposition reaction. In this case, the treated solid component is used as it is in the ammonia decomposition reaction as a catalyst (X).
触媒（Ｘ）の形状については特に制限はなく、調製後の粉体のまま用いてもよいが、必要に応じて、所望の形状に成形した成形触媒としてもよい。
なお、触媒（Ｘ）は、粉体又は成形触媒いずれの形状の場合であっても、アンモニア分解反応器内で触媒層を形成させて用いる。
成形触媒としては、粉体の触媒を加圧・圧縮した凝集塊若しくはこの凝集塊を適当な粒径に破砕した圧縮成形体、粉体の触媒を打錠機により一定の形状に圧縮固形化した打錠成形体、粉体の触媒を球状担体にコーティングした球状成形体、粉体の触媒をハニカム担体にコーティングしたハニカム成形体、粉体の触媒にバインダーを加え混練・押出した押出成形体等が挙げられるが、特にこれらに限定されるものではない。
The shape of the catalyst (X) is not particularly limited, and the prepared powder may be used as it is, but if necessary, it may be a molding catalyst molded into a desired shape.
The catalyst (X) is used by forming a catalyst layer in the ammonia decomposition reactor regardless of the shape of the powder or the molding catalyst.
The molding catalyst includes agglomerates obtained by pressurizing and compressing a powder catalyst, a compression molded product obtained by crushing the agglomerates to an appropriate particle size, and a powder catalyst compressed and solidified into a certain shape by a tableting machine. Tableting molded products, spherical molded products in which a powder catalyst is coated on a spherical carrier, honeycomb molded products in which a powder catalyst is coated on a honeycomb carrier, extrusion molded products in which a binder is added to a powder catalyst and kneaded / extruded, etc. However, the present invention is not particularly limited to these.
また、成形触媒は、賦孔剤を加えて成形し、焼成処理を施すことにより細孔を形成させたものであってもよい。
賦孔剤としては、焼成処理により容易に除去される、カルボキシメチルセルロース、ポリスチレン等が挙げられるが、特にこれらに限定されるものではない。
Further, the molding catalyst may be one in which pores are formed by molding by adding a pore-forming agent and performing a firing treatment.
Examples of the pore-forming agent include, but are not limited to, carboxymethyl cellulose, polystyrene, and the like, which are easily removed by a firing treatment.
以上のようにして調製された触媒（Ｘ）、及び触媒（Ｘ）の調製のすべての工程の後に還元処理を行う場合の還元処理前の触媒（Ｘ）の前駆体は、化学的な形態に特に制限はない。
調製された触媒（Ｘ）及び還元処理前の触媒（Ｘ）の前駆体について、元素（Ａ）、元素（Ｂ）、元素（Ｃ）、及びマグネシウム（Ｄ）は、ペロブスカイト構造を形成する場合もあるが、本発明で得られる効果はペロブスカイト構造の有無には特に影響を受けない。
The catalyst (X) prepared as described above, and the precursor of the catalyst (X) before the reduction treatment when the reduction treatment is performed after all the steps of preparation of the catalyst (X) are in chemical form. There are no particular restrictions.
With respect to the prepared catalyst (X) and the precursor of the catalyst (X) before the reduction treatment, the element (A), the element (B), the element (C), and the magnesium (D) may form a perovskite structure. However, the effect obtained in the present invention is not particularly affected by the presence or absence of the perovskite structure.
触媒（Ｘ）の調製に用いられる元素（Ａ）の原料としては、元素（Ａ）を含んでいる化合物であればよく、特に制限はない。
具体的には、ニッケルの原料としては、硝酸ニッケル（II)、酸化ニッケル(II）、塩化ニッケル（II）、水酸化ニッケル（II）、硫酸ニッケル（II）、酢酸ニッケル（II）、炭酸ニッケル（II）、塩基性炭酸ニッケル（II）、金属ニッケルなどが挙げられる。
コバルトの原料としては、硝酸コバルト（II）、酸化コバルト（II）、塩化コバルト（II）、水酸化コバルト（II）、硫酸コバルト（II）、酢酸コバルト（II）、炭酸コバルト（II）、塩基性炭酸コバルト（II）、金属コバルトなどが挙げられる。
鉄の原料としては、硝酸鉄（II）、硝酸鉄（III）、酸化鉄（II）、酸化鉄（III）、塩化鉄（II）、塩化鉄（III）、水酸化鉄（II）、水酸化鉄（III）、硫酸鉄（II）、硫酸鉄（III）、酢酸鉄（II）、塩基性酢酸鉄（III）、炭酸鉄（II）、金属鉄などが挙げられる。
The raw material of the element (A) used for the preparation of the catalyst (X) may be any compound containing the element (A), and is not particularly limited.
Specifically, as raw materials for nickel, nickel nitrate (II), nickel oxide (II), nickel chloride (II), nickel hydroxide (II), nickel sulfate (II), nickel acetate (II), nickel carbonate (II), basic nickel carbonate (II), metallic nickel and the like can be mentioned.
As raw materials for cobalt, cobalt nitrate (II), cobalt oxide (II), cobalt chloride (II), cobalt hydroxide (II), cobalt sulfate (II), cobalt acetate (II), cobalt carbonate (II), and base. Examples include sex cobalt (II) carbonate and metallic cobalt.
As raw materials for iron, iron nitrate (II), iron nitrate (III), iron oxide (II), iron oxide (III), iron chloride (II), iron chloride (III), iron hydroxide (II), water Examples thereof include iron oxide (III), iron sulfate (II), iron sulfate (III), iron acetate (II), basic iron acetate (III), iron carbonate (II), and metallic iron.
触媒（Ｘ）の調製に用いられる元素（Ｂ）の原料としては、元素（Ｂ）を含んでいる化合物であればよく、特に制限はない。
具体的には、ストロンチウムの原料としては、硝酸ストロンチウム、酸化ストロンチウム、塩化ストロンチウム、水酸化ストロンチウム、硫酸ストロンチウム、酢酸ストロンチウム、炭酸ストロンチウムなどが挙げられる。
バリウムの原料としては、硝酸バリウム、酸化バリウム、塩化バリウム、水酸化バリウム、硫酸バリウム、酢酸バリウム、炭酸バリウムなどが挙げられる。
The raw material of the element (B) used for the preparation of the catalyst (X) may be any compound containing the element (B), and is not particularly limited.
Specifically, examples of the raw material of strontium include strontium nitrate, strontium oxide, strontium chloride, strontium hydroxide, strontium sulfate, strontium acetate, and strontium carbonate.
Examples of the raw material of barium include barium nitrate, barium oxide, barium chloride, barium hydroxide, barium sulfate, barium acetate, and barium carbonate.
触媒（Ｘ）の調製に用いられる元素（Ｃ）の原料としては、元素（Ｃ）を含んでいる化合物であればよく、特に制限はない。
具体的には、イットリウムの原料としては、硝酸イットリウム、酸化イットリウム、塩化イットリウム、硫酸イットリウム、酢酸イットリウム、炭酸イットリウムなどが挙げられる。
ランタンの原料としては、硝酸ランタン、酸化ランタン、塩化ランタン、水酸化ランタン、硫酸ランタン、酢酸ランタン、炭酸ランタンなどが挙げられる。
ネオジムの原料としては、硝酸ネオジム、酸化ネオジム、塩化ネオジム、水酸化ネオジム、硫酸ネオジム、酢酸ネオジム、炭酸ネオジムなどが挙げられる。
サマリウムの原料としては、硝酸サマリウム、酸化サマリウム、塩化サマリウム、硫酸サマリウム、酢酸サマリウム、炭酸サマリウムなどが挙げられる。
ユウロピウムの原料としては、硝酸ユウロピウム、酸化ユウロピウム、塩化ユウロピウム、硫酸ユウロピウム、酢酸ユウロピウム、炭酸ユウロピウムなどが挙げられる。
ガドリニウムの原料としては、硝酸ガドリニウム、酸化ガドリニウム、塩化ガドリニウム、硫酸ガドリニウム、酢酸ガドリニウム、炭酸ガドリニウムなどが挙げられる。
エルビウムの原料としては、硝酸エルビウム、酸化エルビウム、塩化エルビウム、硫酸エルビウム、酢酸エルビウム、炭酸エルビウムなどが挙げられる。
The raw material of the element (C) used for the preparation of the catalyst (X) may be any compound containing the element (C), and is not particularly limited.
Specifically, examples of the raw material of yttrium include yttrium nitrate, yttrium oxide, yttrium chloride, yttrium sulfate, yttrium acetate, and yttrium carbonate.
Examples of the raw material of the lanthanum include lanthanum nitrate, lanthanum oxide, lanthanum chloride, lanthanum hydroxide, lanthanum sulfate, lanthanum acetate, and lanthanum carbonate.
Examples of the raw material of neodymium include neodymium nitrate, neodymium oxide, neodymium chloride, neodymium hydroxide, neodymium sulfate, neodymium acetate, and neodymium carbonate.
Examples of the raw material of samarium include samarium nitrate, samarium oxide, samarium chloride, samarium sulfate, samarium acetate, and samarium carbonate.
Examples of the raw material of europium include europium nitrate, europium oxide, europium chloride, europium sulfate, europium acetate, and europium carbonate.
Examples of the raw material for gadolinium include gadolinium nitrate, gadolinium oxide, gadolinium chloride, gadolinium sulfate, gadolinium acetate, and gadolinium carbonate.
Examples of the raw material of erbium include erbium nitrate, erbium oxide, erbium chloride, erbium sulfate, erbium acetate, and erbium carbonate.
触媒（Ｘ）の調製に用いられるマグネシウム（Ｄ）の原料としては、マグネシウムを含んでいる化合物であればよく、特に制限はない。
具体的には、マグネシウムの原料としては、硝酸マグネシウム、酸化マグネシウム、塩化マグネシウム、水酸化マグネシウム、硫酸マグネシウム、酢酸マグネシウム、炭酸マグネシウム、塩基性炭酸マグネシウムなどが挙げられる。
The raw material for magnesium (D) used in the preparation of the catalyst (X) may be any compound containing magnesium, and is not particularly limited.
Specifically, examples of the raw material for magnesium include magnesium nitrate, magnesium oxide, magnesium chloride, magnesium hydroxide, magnesium sulfate, magnesium acetate, magnesium carbonate, and basic magnesium carbonate.
〔反応様式〕
実施形態に係る水素の製造方法を実施するための反応様式としては、固定床式、流動床式、移動床式など特に限定されないが、設備が簡易となり、省スペースとなる、設備費が安価となる等の経済的な点から、固定床式が好適である。
また、固定床式を適用した反応器としては、既知のあらゆる形式の反応器を用いることができ、具体的な形式の反応器としては、触媒充填層型反応器、触媒膜型反応器などが挙げられる。
[Reaction mode]
The reaction mode for implementing the hydrogen production method according to the embodiment is not particularly limited to a fixed bed type, a fluidized bed type, a moving bed type, etc., but the equipment is simplified, space is saved, and the equipment cost is low. The fixed floor type is preferable from the economical point of view.
Further, as the reactor to which the fixed bed type is applied, all known types of reactors can be used, and specific types of reactors include catalyst-filled layer type reactors and catalyst membrane type reactors. Can be mentioned.
反応器の加熱方法にも特に制限は無く、電気ヒーター加熱、バーナー加熱、ケロシンや溶融塩等の熱媒加熱など既知のあらゆる方法を用いることができる。 The heating method of the reactor is not particularly limited, and any known method such as electric heater heating, burner heating, and heat medium heating such as kerosene and molten salt can be used.
反応器に供給される原料ガスについても特に制限は無く、精製ガスを用いてもよいし、ハーバーボッシュ法によるアンモニア合成プラント、排ガスにアンモニアを含む有機性廃棄物処理プラントなど、アンモニアを生成するプロセスからの生成ガスを直接用いてもよい。 The raw material gas supplied to the reactor is not particularly limited, and refined gas may be used, or a process for producing ammonia, such as an ammonia synthesis plant by the Haber Bosch method or an organic waste treatment plant containing ammonia in the exhaust gas. The gas produced from the above may be used directly.
〔反応条件〕
本実施形態に係る水素の製造方法では、触媒（Ｘ）にアンモニアを含有する原料ガスを接触させて、アンモニア分解反応を起こさせるが、その際、以下のような反応条件で行うことが好ましい。
[Reaction conditions]
In the method for producing hydrogen according to the present embodiment, the catalyst (X) is brought into contact with a raw material gas containing ammonia to cause an ammonia decomposition reaction. At that time, it is preferable to carry out the reaction under the following reaction conditions.
（反応温度）
触媒（Ｘ）に原料ガスを接触させる際の触媒の温度としては、２００℃〜１０００℃の範囲内であることが好ましく、３００℃〜９００℃の範囲内であることがより好ましく、４００℃〜８００℃の範囲内であることが特に好ましい。
なお、触媒（Ｘ）はアンモニア分解反応器内で触媒層を形成しているため、この触媒層の温度が上記の範囲を満たすことが好ましい。
(Reaction temperature)
The temperature of the catalyst when the raw material gas is brought into contact with the catalyst (X) is preferably in the range of 200 ° C. to 1000 ° C., more preferably in the range of 300 ° C. to 900 ° C., and 400 ° C. to 400 ° C. It is particularly preferably in the range of 800 ° C.
Since the catalyst (X) forms a catalyst layer in the ammonia decomposition reactor, it is preferable that the temperature of the catalyst layer satisfies the above range.
（反応ガス成分）
アンモニア分解反応に使用する原料ガスは、そのまま触媒（Ｘ）に接触させてもよいが、必要に応じて、その他のガスを同伴させた反応ガスとして触媒（Ｘ）に接触させてもよい。
同伴させるガスとしては、例えば、窒素、アルゴン、ヘリウム、水素、一酸化炭素、水蒸気などが挙げられるが、これらに限定されるものではない。
(Reaction gas component)
The raw material gas used for the ammonia decomposition reaction may be brought into contact with the catalyst (X) as it is, or may be brought into contact with the catalyst (X) as a reaction gas accompanied by another gas, if necessary.
Examples of the accompanying gas include, but are not limited to, nitrogen, argon, helium, hydrogen, carbon monoxide, and water vapor.
（反応圧力）
反応器内の原料ガス又は反応ガスの圧力については、アンモニア分圧として、０．００１ＭＰａ〜３ＭＰａの範囲内であることが好ましく、０．０５ＭＰａ〜１ＭＰａの範囲内であることがより好ましく、０．０５ＭＰａ〜０．２ＭＰａの範囲内であることが更に好ましい。
また、反応器内の原料ガス又は反応ガスの全圧としては、０．００１ＭＰａ〜３ＭＰａの範囲内であることが好ましく、０．０５ＭＰａ〜１ＭＰａの範囲内であることがより好ましく、０．０５ＭＰａ〜０．２ＭＰａの範囲内であることが更に好ましい。
(Reaction pressure)
Regarding the pressure of the raw material gas or the reaction gas in the reactor, the partial pressure of ammonia is preferably in the range of 0.001 MPa to 3 MPa, more preferably in the range of 0.05 MPa to 1 MPa, and 0. It is more preferably in the range of 05 MPa to 0.2 MPa.
The total pressure of the raw material gas or the reaction gas in the reactor is preferably in the range of 0.001 MPa to 3 MPa, more preferably in the range of 0.05 MPa to 1 MPa, and more preferably 0.05 MPa to 1 MPa. It is more preferably in the range of 0.2 MPa.
（接触時間）
原料ガス又は反応ガスと触媒との接触時間について特に制限はないが、下記式（１）で定義される触媒質量当たりの重量空間速度（ＳＶ）として１０００［Ncc/g/h］〜１０００００［Ncc/g/h］の範囲内となるように設定することが好ましく、３０００［Ncc/g/h］〜１０００００［Ncc/g/h］となるように設定することがより好ましい。
なお、原料供給量は、単位時間当たりに供給される、標準状態でのアンモニア気体の体積（Ｎｃｃ）として表記する。
（ＳＶ［Ncc/g/h］）＝（原料供給量［Ncc/h］）／（触媒質量［g］）・・・式（１）
(Contact time)
The contact time between the raw material gas or the reaction gas and the catalyst is not particularly limited, but the weight space velocity (SV) per catalyst mass defined by the following formula (1) is 1000 [Ncc / g / h] to 100,000 [Ncc]. It is preferable to set it within the range of [/ g / h], and it is more preferable to set it to be within the range of 3000 [Ncc / g / h] to 100,000 [Ncc / g / h].
The amount of raw material supplied is expressed as the volume (Ncc) of ammonia gas supplied per unit time in the standard state.
(SV [Ncc / g / h]) = (Raw material supply amount [Ncc / h]) / (Catalyst mass [g]) ... Equation (1)
〔生成物〕
本実施形態に係る水素の製造方法において、アンモニア分解反応の結果得られる生成物について特に制限は無く、水素を含んでいれば水素以外の成分を含んでいてもよい。
生成物中の水素濃度に特に制限はないが、一般的なアンモニア分解ではアンモニア２分子から水素３分子及び窒素１分子が生成するため、原料ガスに窒素及び水素が含まれていない場合には、生成物中に窒素と水素が１：３の体積比で含まれるのが一般的と言える。
また、生成物中にアンモニアを含んでいてもよいが、生成物中のアンモニア含有量は、８０体積％以下であることが好ましく、５０体積％以下であることが更に好ましく、１０体積％以下であることが特に好ましい。
[Product]
In the method for producing hydrogen according to the present embodiment, there is no particular limitation on the product obtained as a result of the ammonia decomposition reaction, and if hydrogen is contained, a component other than hydrogen may be contained.
The hydrogen concentration in the product is not particularly limited, but in general ammonia decomposition, 3 molecules of hydrogen and 1 molecule of nitrogen are produced from 2 molecules of ammonia. Therefore, if the raw material gas does not contain nitrogen and hydrogen, It can be said that the product generally contains nitrogen and hydrogen in a volume ratio of 1: 3.
Ammonia may be contained in the product, but the ammonia content in the product is preferably 80% by volume or less, more preferably 50% by volume or less, and 10% by volume or less. It is particularly preferable to have.
以下、実施例によって本発明を更に詳細に説明するが、本発明はこれらの実施例によって何らかの制限を受けるものではない。
なお、特に断りのない限り、「％」は「質量％」を表す。
また、以下に示す化合物について、その入手先は、同じ化合物であれば同一であるとする。
Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by these examples.
Unless otherwise specified, "%" represents "mass%".
Further, regarding the compounds shown below, it is assumed that the sources are the same as long as they are the same compounds.
［触媒調製例１］５％BaO-Ni-Y2O3
０．２６ｇの硝酸バリウム（和光純薬工業株式会社製）及び５．９４ｇの硝酸ニッケル六水和物（和光純薬工業株式会社製）を蒸留水に溶解して調製した溶液に、１．６５ｇの酸化イットリウム（和光純薬工業株式会社製）を加えて十分に攪拌し、８０℃のウォーターバスを用いて蒸発乾固した。得られた固体成分を、空気下６００℃で５時間焼成を行い５％BaO-Ni-Y2O3を調製した。
[Catalyst Preparation Example 1] 5% BaO-Ni-Y 2 O 3
1.65 g in a solution prepared by dissolving 0.26 g of barium nitrate (manufactured by Wako Pure Chemical Industries, Ltd.) and 5.94 g of nickel nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) in distilled water. Wako Pure Chemical Industries, Ltd. (manufactured by Wako Pure Chemical Industries, Ltd.) was added, the mixture was sufficiently stirred, and the mixture was evaporated to dryness using a water bath at 80 ° C. The obtained solid component was calcined in air at 600 ° C. for 5 hours to prepare 5% BaO-Ni-Y 2 O 3 .
［触媒調製例２］Ni-Y2O3-MgO
７．５４ｇの無水炭酸ナトリウム（和光純薬工業株式会社製）を蒸留水に溶解して別途溶液を調製した。得られた炭酸ナトリウム水溶液を激しく撹拌しながら、５．９４ｇの硝酸ニッケル六水和物、３．０５ｇの硝酸イットリウムｎ水和物（和光純薬工業株式会社製、別途乾燥させて調べるとｎ＝５．１であった）及び５．７３ｇの硝酸マグネシウム六水和物（和光純薬工業株式会社製）を蒸留水に溶解して調製した溶液を加えて懸濁液を得た。懸濁液は室温で３０分撹拌し、熟成させた後、ろ過した。得られた固形成分を蒸留水で洗浄して、空気下６００℃で５時間焼成を行いNi-Y2O3-MgOを調製した。
[Catalyst Preparation Example 2] Ni-Y 2 O 3 -MgO
7.54 g of anhydrous sodium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in distilled water to prepare a separate solution. While vigorously stirring the obtained aqueous sodium carbonate solution, 5.94 g of nickel nitrate hexahydrate and 3.05 g of ittrium nitrate n hydrate (manufactured by Wako Pure Chemical Industries, Ltd., dried separately and examined, n = A solution prepared by dissolving 5.73 g of magnesium nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) in distilled water was added to obtain a suspension. The suspension was stirred at room temperature for 30 minutes, aged and then filtered. The obtained solid component was washed with distilled water and calcined at 600 ° C. in air for 5 hours to prepare Ni-Y 2 O 3- MgO.
［触媒調製例３］５％BaO-Ni-Y2O3-MgO
７．２８ｇの無水炭酸ナトリウムを蒸留水に溶解して別途溶液を調製した。得られた炭酸ナトリウム水溶液を激しく撹拌しながら、０．２６ｇの硝酸バリウム、５．９４ｇの硝酸ニッケル六水和物、２．８０ｇの硝酸イットリウムｎ水和物（別途乾燥させて調べるとｎ＝５．１であった）及び５．２５ｇの硝酸マグネシウム六水和物を蒸留水に溶解して調製した溶液を加えて懸濁液を得た。懸濁液は室温で３０分撹拌し、熟成させた後、ろ過した。得られた固形成分を蒸留水で洗浄して、空気下６００℃で５時間焼成を行い５％BaO-Ni-Y2O3-MgOを調製した。
[Catalyst Preparation Example 3] 5% BaO-Ni-Y 2 O 3- MgO
7.28 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a separate solution. While vigorously stirring the obtained aqueous sodium carbonate solution, 0.26 g of barium nitrate, 5.94 g of nickel nitrate hexahydrate, and 2.80 g of ittium nitrate n-hydrate (n = 5 when separately dried and examined). A solution prepared by dissolving 5.25 g of magnesium nitrate hexahydrate in distilled water was added to obtain a suspension. The suspension was stirred at room temperature for 30 minutes, aged and then filtered. The obtained solid component was washed with distilled water and calcined at 600 ° C. in air for 5 hours to prepare 5% BaO-Ni-Y 2 O 3- MgO.
［触媒調製例４］５％BaO-Ni-Y2O3-MgO
無水炭酸ナトリウムの量を７．８０ｇに変え、硝酸イットリウムｎ水和物の量を１．６８ｇに変え、硝酸マグネシウム六水和物の量を７．３５ｇに変えた以外は触媒調製例３と同様にして、５％BaO-Ni-Y2O3-MgOを調製した。
[Catalyst Preparation Example 4] 5% BaO-Ni-Y 2 O 3- MgO
Same as Catalyst Preparation Example 3 except that the amount of anhydrous sodium carbonate was changed to 7.80 g, the amount of yttrium n hydrate n hydrate was changed to 1.68 g, and the amount of magnesium nitrate hexahydrate was changed to 7.35 g. To prepare 5% BaO-Ni-Y 2 O 3-MgO.
［触媒調製例５］５％BaO-Ni-Sm2O3
４．９１ｇの無水炭酸ナトリウムを蒸留水に溶解して別途溶液を調製した。得られた炭酸ナトリウム水溶液を激しく撹拌しながら、０．２６ｇの硝酸バリウム、５．９４ｇの硝酸ニッケル六水和物、４．２０ｇの硝酸サマリウム六水和物（和光純薬工業株式会社製）を蒸留水に溶解して調製した溶液を加えて懸濁液を得た。懸濁液は室温で３０分撹拌し、熟成させた後、ろ過した。得られた固形成分を蒸留水で洗浄して、空気下６００℃で５時間焼成を行い５％BaO-Ni-Sm2O3を調製した。
[Catalyst Preparation Example 5] 5% BaO-Ni-Sm 2 O 3
4.91 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a separate solution. While vigorously stirring the obtained aqueous sodium carbonate solution, 0.26 g of barium nitrate, 5.94 g of nickel nitrate hexahydrate, and 4.20 g of samarium nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) were added. A solution prepared by dissolving in distilled water was added to obtain a suspension. The suspension was stirred at room temperature for 30 minutes, aged and then filtered. The obtained solid component was washed with distilled water and calcined at 600 ° C. in air for 5 hours to prepare 5% BaO-Ni-Sm 2 O 3 .
［触媒調製例６］Ni-Sm2O3-MgO
無水炭酸ナトリウムの量を４．６５ｇに変え、かつ、硝酸イットリウムｎ水和物３．０５ｇの代わりに１．５３ｇの硝酸サマリウム六水和物を使用した以外は触媒調製例２と同様にして、Ni-Sm2O3-MgOを調製した。
[Catalyst Preparation Example 6] Ni-Sm 2 O 3 -MgO
The same as in Catalyst Preparation Example 2 except that the amount of anhydrous sodium carbonate was changed to 4.65 g and 1.53 g of samarium nitrate hexahydrate was used instead of 3.05 g of yttrium nitrate n hydrate. Ni-Sm 2 O 3 -Mg O was prepared.
［触媒調製例７］５％BaO-Ni-Sm2O3-MgO
無水炭酸ナトリウムの量を６．０２ｇに変え、硝酸イットリウムｎ水和物２．８０ｇの代わりに硝酸サマリウム六水和物２．９４ｇを、また、硝酸マグネシウム六水和物の量を３．１５ｇに変えた以外は触媒調製例３と同様にして、５％BaO-Ni-Sm2O3-MgOを調製した。
[Catalyst Preparation Example 7] 5% BaO-Ni-Sm 2 O 3- MgO
Change the amount of anhydrous sodium carbonate to 6.02 g, change the amount of samarium nitrate hexahydrate to 2.94 g instead of 2.80 g of ittium nitrate n hydrate, and change the amount of magnesium nitrate hexahydrate to 3.15 g. 5% BaO-Ni-Sm 2 O 3- MgO was prepared in the same manner as in Catalyst Preparation Example 3 except that it was changed.
［触媒調製例８］５％BaO-Ni-Sm2O3-MgO
無水炭酸ナトリウムの量を６．７５ｇに変え、硝酸サマリウム六水和物の量を２．１０ｇに変え、また、硝酸マグネシウム六水和物の量を５．２５ｇに変えた以外は触媒調製例７と同様にして、５％BaO-Ni-Sm2O3-MgOを調製した。
[Catalyst Preparation Example 8] 5% BaO-Ni-Sm 2 O 3- MgO
Catalyst Preparation Example 7 except that the amount of anhydrous sodium carbonate was changed to 6.75 g, the amount of samarium hexahydrate nitrate was changed to 2.10 g, and the amount of magnesium nitrate hexahydrate was changed to 5.25 g. In the same manner as above, 5% BaO-Ni-Sm 2 O 3- MgO was prepared.
［触媒調製例９］５％BaO-Ni-Sm2O3-MgO
無水炭酸ナトリウムの量を７．３４ｇに変え、硝酸サマリウム六水和物の量を１．２６ｇに変え、また、硝酸マグネシウム六水和物の量を７．３５ｇに変えた以外は触媒調製例７と同様にして、５％BaO-Ni-Sm2O3-MgOを調製した。
[Catalyst Preparation Example 9] 5% BaO-Ni-Sm 2 O 3- MgO
Catalyst Preparation Example 7 except that the amount of anhydrous sodium carbonate was changed to 7.34 g, the amount of samarium hexahydrate nitrate was changed to 1.26 g, and the amount of magnesium nitrate hexahydrate was changed to 7.35 g. In the same manner as above, 5% BaO-Ni-Sm 2 O 3- MgO was prepared.
［触媒調製例１０］５％BaO-Ni-Sm2O3-MgO
無水炭酸ナトリウムの量を７．８６ｇに変え、硝酸サマリウム六水和物の量を０．８４ｇに変え、また、硝酸マグネシウム六水和物の量を８．４０ｇに変えた以外は触媒調製例７と同様にして、５％BaO-Ni-Sm2O3-MgOを調製した。
[Catalyst Preparation Example 10] 5% BaO-Ni-Sm 2 O 3- MgO
Catalyst Preparation Example 7 except that the amount of anhydrous sodium carbonate was changed to 7.86 g, the amount of samarium hexahydrate nitrate was changed to 0.84 g, and the amount of magnesium nitrate hexahydrate was changed to 8.40 g. In the same manner as above, 5% BaO-Ni-Sm 2 O 3- MgO was prepared.
［触媒調製例１１］５％BaO-Ni-Sm2O3-MgO
無水炭酸ナトリウムの量を８．２３ｇに変え、硝酸サマリウム六水和物の量を０．４２ｇに変え、また、硝酸マグネシウム六水和物の量を９．４５ｇに変えた以外は触媒調製例７と同様にして、５％BaO-Ni-Sm2O3-MgOを調製した。
[Catalyst Preparation Example 11] 5% BaO-Ni-Sm 2 O 3- MgO
Catalyst Preparation Example 7 except that the amount of anhydrous sodium carbonate was changed to 8.23 g, the amount of samarium hexahydrate nitrate was changed to 0.42 g, and the amount of magnesium nitrate hexahydrate was changed to 9.45 g. In the same manner as above, 5% BaO-Ni-Sm 2 O 3- MgO was prepared.
［触媒調製例１２］５％BaO-Ni-Sm2O3-MgO
無水炭酸ナトリウムの量を８．４１ｇに変え、硝酸サマリウム六水和物の量を０．２１ｇに変え、また、硝酸マグネシウム六水和物の量を９．９７ｇに変えた以外は触媒調製例７と同様にして、５％BaO-Ni-Sm2O3-MgOを調製した。
[Catalyst Preparation Example 12] 5% BaO-Ni-Sm 2 O 3- MgO
Catalyst Preparation Example 7 except that the amount of anhydrous sodium carbonate was changed to 8.41 g, the amount of samarium hexahydrate nitrate was changed to 0.21 g, and the amount of magnesium nitrate hexahydrate was changed to 9.97 g. In the same manner as above, 5% BaO-Ni-Sm 2 O 3- MgO was prepared.
［触媒調製例１３］５％SrO-Ni-Sm2O3
硝酸バリウム０．２６ｇの代わりに０．３０ｇの硝酸ストロンチウム（和光純薬工業株式会社製）を、かつ、酸化イットリウム１．６５ｇの代わりに１．６５ｇの酸化サマリウム（和光純薬工業株式会社製）を使用した以外は触媒調製例１と同様にして、５％SrO-Ni-Sm2O3を調製した。
[Catalyst Preparation Example 13] 5% SrO-Ni-Sm 2 O 3
0.30 g of strontium nitrate (manufactured by Wako Pure Chemical Industries, Ltd.) instead of 0.26 g of barium nitrate, and 1.65 g of samarium oxide (manufactured by Wako Pure Chemical Industries, Ltd.) instead of 1.65 g of yttrium oxide 5% SrO-Ni-Sm 2 O 3 was prepared in the same manner as in Catalyst Preparation Example 1 except that
［触媒調製例１４］５％SrO-Ni-Sm2O3-MgO
無水炭酸ナトリウムの量を６．８２ｇに変え、硝酸バリウム０．２６ｇの代わりに硝酸ストロンチウム０．３０ｇ使用した以外は触媒調製例８と同様にして、５％SrO-Ni-Sm2O3-MgOを調製した。
[Catalyst Preparation Example 14] 5% SrO-Ni-Sm 2 O 3- MgO
5% SrO-Ni-Sm 2 O 3 -MgO in the same manner as in Catalyst Preparation Example 8 except that the amount of anhydrous sodium carbonate was changed to 6.82 g and 0.30 g of strontium nitrate was used instead of 0.26 g of barium nitrate. Was prepared.
［触媒調製例１５］５％BaO-Ni-La2O3
酸化イットリウム１．６５ｇの代わりに１．６５ｇの酸化ランタン（和光純薬工業株式会社製）を使用した以外は触媒調製例１と同様にして、５％BaO-Ni-La2O3を調製した。
[Catalyst Preparation Example 15] 5% BaO-Ni-La 2 O 3
5% BaO-Ni-La 2 O 3 was prepared in the same manner as in Catalyst Preparation Example 1 except that 1.65 g of lanthanum oxide (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of 1.65 g of yttrium oxide. ..
［触媒調製例１６］５％BaO-Ni-La2O3-MgO
無水炭酸ナトリウムの量を７．５９ｇに変え、硝酸イットリウムｎ水和物１．６８ｇの代わりに１．３１ｇの硝酸ランタン六水和物（和光純薬工業株式会社製）を使用した以外は触媒調製例４と同様にして、５％BaO-Ni-La2O3-MgOを調製した。
[Catalyst Preparation Example 16] 5% BaO-Ni-La 2 O 3- MgO
Catalyst preparation except that the amount of anhydrous sodium carbonate was changed to 7.59 g and 1.31 g of lanthanum nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of 1.68 g of yttrium nitrate n hydrate. 5% BaO-Ni-La 2 O 3- MgO was prepared in the same manner as in Example 4.
［触媒調製例１７］５％BaO-Ni-Nd2O3
酸化イットリウム１．６５ｇの代わりに１．６５ｇの酸化ネオジム（和光純薬工業株式会社製）を使用した以外は触媒調製例１と同様にして、５％BaO-Ni-Nd2O3を調製した。
[Catalyst Preparation Example 17] 5% BaO-Ni-Nd 2 O 3
5% BaO-Ni-Nd 2 O 3 was prepared in the same manner as in Catalyst Preparation Example 1 except that 1.65 g of neodymium oxide (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of 1.65 g of yttrium oxide. ..
［触媒調製例１８］５％BaO-Ni-Nd2O3-MgO
無水炭酸ナトリウムの量を７．５０ｇに変え、硝酸イットリウムｎ水和物１．６８ｇの代わりに１．２９ｇの硝酸ネオジム六水和物（和光純薬工業株式会社製）を使用した以外は触媒調製例４と同様にして、５％BaO-Ni-Nd2O3-MgOを調製した。
[Catalyst Preparation Example 18] 5% BaO-Ni-Nd 2 O 3- MgO
Catalyst preparation except that the amount of anhydrous sodium carbonate was changed to 7.50 g and 1.29 g of neodymium nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of 1.68 g of ittrium nitrate n hydrate. 5% BaO-Ni-Nd 2 O 3- MgO was prepared in the same manner as in Example 4.
［触媒調製例１９］５％BaO-Ni-Eu2O3
酸化イットリウム１．６５ｇの代わりに１．６５ｇの酸化ユウロピウム（和光純薬工業株式会社製）を使用した以外は触媒調製例１と同様にして、５％BaO-Ni-Eu2O3を調製した。
[Catalyst Preparation Example 19] 5% BaO-Ni-Eu 2 O 3
5% BaO-Ni-Eu 2 O 3 was prepared in the same manner as in Catalyst Preparation Example 1 except that 1.65 g of europium oxide (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of 1.65 g of yttrium oxide. ..
［触媒調製例２０］５％BaO-Ni-Eu2O3-MgO
無水炭酸ナトリウムの量を７．４８ｇに変え、硝酸イットリウムｎ水和物１．６８ｇの代わりに１．２２ｇの硝酸ユウロピウムｎ水和物（和光純薬工業株式会社製、別途乾燥させて調べるとｎ＝５．３であった）を使用した以外は触媒調製例４と同様にして、５％BaO-Ni-Eu2O3-MgOを調製した。
[Catalyst Preparation Example 20] 5% BaO-Ni-Eu 2 O 3- MgO
The amount of anhydrous sodium carbonate was changed to 7.48 g, and instead of 1.68 g of ittrium nitrate n hydrate, 1.22 g of europium nitrate n hydrate (manufactured by Wako Pure Chemical Industries, Ltd., dried separately and examined. = 5.3) was used, but 5% BaO-Ni-Eu 2 O 3- MgO was prepared in the same manner as in Catalyst Preparation Example 4.
［触媒調製例２１］５％BaO-Ni-Gd2O3
酸化イットリウム１．６５ｇの代わりに１．６５ｇの酸化ガドリニウム（和光純薬工業株式会社製）を使用した以外は触媒調製例１と同様にして、５％BaO-Ni-Gd2O3を調製した。
[Catalyst Preparation Example 21] 5% BaO-Ni-Gd 2 O 3
5% BaO-Ni-Gd 2 O 3 was prepared in the same manner as in Catalyst Preparation Example 1 except that 1.65 g of gadolinium oxide (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of 1.65 g of yttrium oxide. ..
［触媒調製例２２］５％BaO-Ni-Gd2O3-MgO
無水炭酸ナトリウムの量を７．４６ｇに変え、硝酸イットリウムｎ水和物１．６８ｇの代わりに１．２３ｇの硝酸ガドリニウム六水和物（和光純薬工業株式会社製）を使用した以外は触媒調製例４と同様にして、５％BaO-Ni-Gd2O3-MgOを調製した。
[Catalyst Preparation Example 22] 5% BaO-Ni-Gd 2 O 3- MgO
Catalyst preparation except that the amount of anhydrous sodium carbonate was changed to 7.46 g and 1.23 g of gadolinium hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of 1.68 g of yttrium nitrate n hydrate. 5% BaO-Ni-Gd 2 O 3- MgO was prepared in the same manner as in Example 4.
［触媒調製例２３］５％BaO-Ni-Er2O3
酸化イットリウム１．６５ｇの代わりに１．６５ｇの酸化エルビウム（和光純薬工業株式会社製）を使用した以外は触媒調製例１と同様にして、５％BaO-Ni-Er2O3を調製した。
[Catalyst Preparation Example 23] 5% BaO-Ni-Er 2 O 3
5% BaO-Ni-Er 2 O 3 was prepared in the same manner as in Catalyst Preparation Example 1 except that 1.65 g of erbium oxide (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of 1.65 g of yttrium oxide. ..
［触媒調製例２４］５％BaO-Ni-Er2O3-MgO
無水炭酸ナトリウムの量を７．５０ｇに変え、硝酸イットリウムｎ水和物１．６８ｇの代わりに１．１４ｇの硝酸エルビウムｎ水和物（和光純薬工業株式会社製、別途乾燥させて調べるとｎ＝４．９であった）を使用した以外は触媒調製例４と同様にして、５％BaO-Ni-Er2O3-MgOを調製した。
[Catalyst Preparation Example 24] 5% BaO-Ni-Er 2 O 3- MgO
Change the amount of anhydrous sodium carbonate to 7.50 g, and instead of 1.68 g of ittrium nitrate n hydrate, 1.14 g of erbium nitrate n hydrate (manufactured by Wako Pure Chemical Industries, Ltd., dried separately and examined. = 4.9) was used, but 5% BaO-Ni-Er 2 O 3- MgO was prepared in the same manner as in Catalyst Preparation Example 4.
［触媒調製例２５］５％BaO-Ni-MgO
酸化イットリウム１．６５ｇの代わりに１．６５ｇの酸化マグネシウム（和光純薬工業株式会社製）を使用した以外は触媒調製例１と同様にして、５％BaO-Ni-MgOを調製した。
[Catalyst Preparation Example 25] 5% BaO-Ni-MgO
5% BaO-Ni-MgO was prepared in the same manner as in Catalyst Preparation Example 1 except that 1.65 g of magnesium oxide (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of 1.65 g of yttrium oxide.
［実施例１］
＜活性評価：アンモニア分解反応＞
触媒調製例３で調製した５％BaO-Ni-Y2O3-MgOついて、固定床流通式反応装置を用いてアンモニア分解反応を行い、アンモニア分解の活性を評価した。
具体的には、５％BaO-Ni-Y2O3-MgO：０．３０ｇを反応管に充填し、アルゴン流通下で６００℃まで昇温させた。
次いで、アルゴン希釈した５０体積％水素を５０Ｎｃｃ／ｍｉｎの流量で反応管に流通させながら、触媒層の温度６００℃、全圧０．１０ＭＰａで２時間流通させ還元処理を行った。還元処理後、ガスを１００体積％アルゴンに切り替え、４５０℃に降温して、触媒層の温度を４５０℃にし、全圧０．１０ＭＰａにおいて流通ガスを１００体積％アンモニアガスに切り替え、３０Ｎｃｃ／ｍｉｎの流量で反応管に２０分間流通させてアンモニア分解反応を行った。その後、５００℃に昇温して、触媒層の温度を５００℃にした以外は同様にして、アンモニア分解反応を行った。
アンモニア分解率は以下の式を用いて算出し、分解率は４５０℃で６９％、５００℃で９７％となった。
アンモニア分解率（％）＝（水素生成量＋窒素生成量）／（２×アンモニア供給量）×１００
[Example 1]
<Activity evaluation: Ammonia decomposition reaction>
The 5% BaO-Ni-Y 2 O 3- MgO prepared in Catalyst Preparation Example 3 was subjected to an ammonia decomposition reaction using a fixed bed flow reactor, and the activity of ammonia decomposition was evaluated.
Specifically, the reaction tube was filled with 5% BaO-Ni-Y 2 O 3- MgO: 0.30 g, and the temperature was raised to 600 ° C. under argon flow.
Next, while flowing argon-diluted 50% by volume hydrogen through the reaction tube at a flow rate of 50 Ncc / min, the catalyst layer was circulated at a temperature of 600 ° C. and a total pressure of 0.10 MPa for 2 hours for reduction treatment. After the reduction treatment, the gas was switched to 100% by volume argon, the temperature was lowered to 450 ° C., the temperature of the catalyst layer was adjusted to 450 ° C., the flowing gas was switched to 100% by volume ammonia gas at a total pressure of 0.10 MPa, and the temperature was 30 Ncc / min. Ammonia decomposition reaction was carried out by passing it through a reaction tube at a flow rate for 20 minutes. Then, the ammonia decomposition reaction was carried out in the same manner except that the temperature was raised to 500 ° C. and the temperature of the catalyst layer was set to 500 ° C.
The ammonia decomposition rate was calculated using the following formula, and the decomposition rate was 69% at 450 ° C and 97% at 500 ° C.
Ammonia decomposition rate (%) = (hydrogen production + nitrogen production) / (2 x ammonia supply) x 100
［実施例２］
触媒として、触媒調製例４で調製した５％BaO-Ni-Y2O3-MgO：０．３０ｇを用いた以外は実施例１と同様にして、アンモニア分解の活性評価を行った。
アンモニア分解率は４５０℃で６８％、５００℃で９６％となった。
[Example 2]
The activity of ammonia decomposition was evaluated in the same manner as in Example 1 except that 5% BaO-Ni-Y 2 O 3- MgO: 0.30 g prepared in Catalyst Preparation Example 4 was used as the catalyst.
The ammonia decomposition rate was 68% at 450 ° C. and 96% at 500 ° C.
［実施例３］
触媒として、触媒調製例７で調製した５％BaO-Ni-Sm2O3-MgO：０．３０ｇを用いた以外は実施例１と同様にして、アンモニア分解の活性評価を行った。
アンモニア分解率は４５０℃で５８％、５００℃で９６％となった。
[Example 3]
The activity of ammonia decomposition was evaluated in the same manner as in Example 1 except that 5% BaO-Ni-Sm 2 O 3- MgO: 0.30 g prepared in Catalyst Preparation Example 7 was used as the catalyst.
The ammonia decomposition rate was 58% at 450 ° C and 96% at 500 ° C.
［実施例４］
触媒として、触媒調製例８で調製した５％BaO-Ni-Sm2O3-MgO：０．３０ｇを用いた以外は実施例１と同様にして、アンモニア分解の活性評価を行った。
アンモニア分解率は４５０℃で６３％、５００℃で９７％となった。
[Example 4]
The activity of ammonia decomposition was evaluated in the same manner as in Example 1 except that 5% BaO-Ni-Sm 2 O 3- MgO: 0.30 g prepared in Catalyst Preparation Example 8 was used as the catalyst.
The ammonia decomposition rate was 63% at 450 ° C. and 97% at 500 ° C.
［実施例５］
触媒として、触媒調製例９で調製した５％BaO-Ni-Sm2O3-MgO：０．３０ｇを用いた以外は実施例１と同様にして、アンモニア分解の活性評価を行った。
アンモニア分解率は４５０℃で７５％、５００℃で９７％となった。
[Example 5]
The activity of ammonia decomposition was evaluated in the same manner as in Example 1 except that 5% BaO-Ni-Sm 2 O 3- MgO: 0.30 g prepared in Catalyst Preparation Example 9 was used as the catalyst.
The ammonia decomposition rate was 75% at 450 ° C. and 97% at 500 ° C.
［実施例６］
触媒として、触媒調製例１０で調製した５％BaO-Ni-Sm2O3-MgO：０．３０ｇを用いた以外は実施例１と同様にして、アンモニア分解の活性評価を行った。
アンモニア分解率は４５０℃で７７％、５００℃で９８％となった。
[Example 6]
The activity of ammonia decomposition was evaluated in the same manner as in Example 1 except that 5% BaO-Ni-Sm 2 O 3- MgO: 0.30 g prepared in Catalyst Preparation Example 10 was used as the catalyst.
The ammonia decomposition rate was 77% at 450 ° C. and 98% at 500 ° C.
［実施例７］
触媒として、触媒調製例１１で調製した５％BaO-Ni-Sm2O3-MgO：０．３０ｇを用いた以外は実施例１と同様にして、アンモニア分解の活性評価を行った。
アンモニア分解率は４５０℃で７２％、５００℃で９７％となった。
[Example 7]
The activity of ammonia decomposition was evaluated in the same manner as in Example 1 except that 5% BaO-Ni-Sm 2 O 3- MgO: 0.30 g prepared in Catalyst Preparation Example 11 was used as the catalyst.
The ammonia decomposition rate was 72% at 450 ° C. and 97% at 500 ° C.
［実施例８］
触媒として、触媒調製例１２で調製した５％BaO-Ni-Sm2O3-MgO：０．３０ｇを用いた以外は実施例１と同様にして、アンモニア分解の活性評価を行った。
アンモニア分解率は４５０℃で６７％、５００℃で９６％となった。
[Example 8]
The activity of ammonia decomposition was evaluated in the same manner as in Example 1 except that 5% BaO-Ni-Sm 2 O 3- MgO: 0.30 g prepared in Catalyst Preparation Example 12 was used as the catalyst.
The ammonia decomposition rate was 67% at 450 ° C. and 96% at 500 ° C.
［実施例９］
触媒として、触媒調製例１４で調製した５％SrO-Ni-Sm2O3-MgO：０．３０ｇを用いた以外は実施例１と同様にして、アンモニア分解の活性評価を行った。
アンモニア分解率は４５０℃で４４％、５００℃で８５％となった。
[Example 9]
The activity of ammonia decomposition was evaluated in the same manner as in Example 1 except that 5% SrO-Ni-Sm 2 O 3- MgO: 0.30 g prepared in Catalyst Preparation Example 14 was used as the catalyst.
The ammonia decomposition rate was 44% at 450 ° C. and 85% at 500 ° C.
［比較例１］
触媒として、触媒調製例１で調製した５％BaO-Ni-Y2O3：０．３０ｇを用いた以外は実施例１と同様にして、アンモニア分解の活性評価を行った。
アンモニア分解率は４５０℃で４３％、５００℃で７６％となった。
[Comparative Example 1]
The activity of ammonia decomposition was evaluated in the same manner as in Example 1 except that 5% BaO-Ni-Y 2 O 3 : 0.30 g prepared in Catalyst Preparation Example 1 was used as the catalyst.
The ammonia decomposition rate was 43% at 450 ° C and 76% at 500 ° C.
［比較例２］
触媒として、触媒調製例５で調製した５％BaO-Ni-Sm2O3：０．３０ｇを用いた以外は実施例１と同様にして、アンモニア分解の活性評価を行った。
アンモニア分解率は４５０℃で４３％、５００℃で８９％となった。
[Comparative Example 2]
The activity of ammonia decomposition was evaluated in the same manner as in Example 1 except that 5% BaO-Ni-Sm 2 O 3 : 0.30 g prepared in Catalyst Preparation Example 5 was used as the catalyst.
The ammonia decomposition rate was 43% at 450 ° C and 89% at 500 ° C.
［比較例３］
触媒として、触媒調製例２５で調製した５％BaO-Ni-MgO：０．３０ｇを用いた以外は実施例１と同様にして、アンモニア分解の活性評価を行った。
アンモニア分解率は４５０℃で４３％、５００℃で８１％となった。
[Comparative Example 3]
The activity of ammonia decomposition was evaluated in the same manner as in Example 1 except that 5% BaO-Ni-MgO: 0.30 g prepared in Catalyst Preparation Example 25 was used as the catalyst.
The ammonia decomposition rate was 43% at 450 ° C. and 81% at 500 ° C.
［比較例４］
触媒として、触媒調製例２で調製したNi-Y2O3-MgO：０．３０ｇを用いた以外は実施例１と同様にして、アンモニア分解の活性評価を行った。
アンモニア分解率は４５０℃で３４％、５００℃で７０％となった。
[Comparative Example 4]
The activity of ammonia decomposition was evaluated in the same manner as in Example 1 except that Ni-Y 2 O 3- MgO: 0.30 g prepared in Catalyst Preparation Example 2 was used as the catalyst.
The ammonia decomposition rate was 34% at 450 ° C. and 70% at 500 ° C.
［比較例５］
触媒として、触媒調製例６で調製したNi-Sm2O3-MgO：０．３０ｇを用いた以外は実施例１と同様にして、アンモニア分解の活性評価を行った。
アンモニア分解率は４５０℃で３３％、５００℃で６９％となった。
[Comparative Example 5]
The activity of ammonia decomposition was evaluated in the same manner as in Example 1 except that Ni-Sm 2 O 3- MgO: 0.30 g prepared in Catalyst Preparation Example 6 was used as the catalyst.
The ammonia decomposition rate was 33% at 450 ° C. and 69% at 500 ° C.
［比較例６］
触媒として、触媒調製例１３で調製した５％SrO-Ni-Sm2O3：０．３０ｇを用いた以外は実施例１と同様にして、アンモニア分解の活性評価を行った。
アンモニア分解率は４５０℃で３９％、５００℃で７７％となった。
[Comparative Example 6]
The activity of ammonia decomposition was evaluated in the same manner as in Example 1 except that 5% SrO-Ni-Sm 2 O 3 : 0.30 g prepared in Catalyst Preparation Example 13 was used as the catalyst.
The ammonia decomposition rate was 39% at 450 ° C. and 77% at 500 ° C.
実施例１〜９及び比較例１〜６で用いた触媒の組成、及びその触媒によるアンモニア分解率を下記表１にまとめた。 The composition of the catalyst used in Examples 1 to 9 and Comparative Examples 1 to 6 and the ammonia decomposition rate by the catalyst are summarized in Table 1 below.
表１から明らかなように、実施例１〜９におけるいずれのアンモニア分解率も、比較例１〜６におけるアンモニア分解率より高く、特に、実施例９におけるアンモニア分解率が比較例６におけるアンモニア分解率よりも高いことから、元素（Ｂ）であるストロンチウム又はバリウムと、元素（Ａ）であるニッケルと、元素（Ｃ）であるイットリウム又はサマリウムと、マグネシウム（Ｄ）と、の組み合せは、アンモニア分解活性の向上に効果があり、アンモニア分解触媒の構成元素として必須であることが示された。
また、実施例４及び９におけるアンモニア分解率と比較例５におけるアンモニア分解率との比較から、ストロンチウム又はバリウムの添加はアンモニア分解活性の向上に効果があることが示され、特に、実施例４から明らかなように、バリウムの添加でアンモニア分解活性が大きく向上することがわかる。
As is clear from Table 1, all the ammonia decomposition rates in Examples 1 to 9 are higher than the ammonia decomposition rates in Comparative Examples 1 to 6, and in particular, the ammonia decomposition rate in Example 9 is the ammonia decomposition rate in Comparative Example 6. Since it is higher than that, the combination of the element (B) strontium or barium, the element (A) nickel, the element (C) ittrium or samarium, and magnesium (D) has an ammonia decomposition activity. It was shown that it is effective in improving the above and is essential as a constituent element of the ammonia decomposition catalyst.
Further, from the comparison between the ammonia decomposition rate in Examples 4 and 9 and the ammonia decomposition rate in Comparative Example 5, it was shown that the addition of strontium or barium was effective in improving the ammonia decomposition activity, and in particular, from Example 4 As is clear, it can be seen that the addition of barium greatly improves the ammonia decomposition activity.
［実施例１０］
触媒として、触媒調製例１６で調製した５％BaO-Ni-La2O3-MgO：０．３０ｇを用いた以外は実施例１と同様にして、アンモニア分解の活性評価を行った。
アンモニア分解率は４５０℃で６２％、５００℃で９０％となった。
[Example 10]
The activity of ammonia decomposition was evaluated in the same manner as in Example 1 except that 5% BaO-Ni-La 2 O 3- MgO: 0.30 g prepared in Catalyst Preparation Example 16 was used as the catalyst.
The ammonia decomposition rate was 62% at 450 ° C. and 90% at 500 ° C.
［実施例１１］
触媒として、触媒調製例１８で調製した５％BaO-Ni-Nd2O3-MgO：０．３０ｇを用いた以外は実施例１と同様にして、アンモニア分解の活性評価を行った。
アンモニア分解率は４５０℃で６７％、５００℃で９４％となった。
[Example 11]
The activity of ammonia decomposition was evaluated in the same manner as in Example 1 except that 5% BaO-Ni-Nd 2 O 3- MgO: 0.30 g prepared in Catalyst Preparation Example 18 was used as the catalyst.
The ammonia decomposition rate was 67% at 450 ° C. and 94% at 500 ° C.
［実施例１２］
触媒として、触媒調製例２０で調製した５％BaO-Ni-Eu2O3-MgO：０．３０ｇを用いた以外は実施例１と同様にして、アンモニア分解の活性評価を行った。
アンモニア分解率は４５０℃で６３％、５００℃で９６％となった。
[Example 12]
The activity of ammonia decomposition was evaluated in the same manner as in Example 1 except that 5% BaO-Ni-Eu 2 O 3- MgO: 0.30 g prepared in Catalyst Preparation Example 20 was used as the catalyst.
The ammonia decomposition rate was 63% at 450 ° C. and 96% at 500 ° C.
［実施例１３］
触媒として、触媒調製例２２で調製した５％BaO-Ni-Gd2O3-MgO：０．３０ｇを用いた以外は実施例１と同様にして、アンモニア分解の活性評価を行った。
アンモニア分解率は４５０℃で７４％、５００℃で９７％となった。
[Example 13]
The activity of ammonia decomposition was evaluated in the same manner as in Example 1 except that 5% BaO-Ni-Gd 2 O 3- MgO: 0.30 g prepared in Catalyst Preparation Example 22 was used as the catalyst.
The ammonia decomposition rate was 74% at 450 ° C. and 97% at 500 ° C.
［実施例１４］
触媒として、触媒調製例２４で調製した５％BaO-Ni-Er2O3-MgO：０．３０ｇを用いた以外は実施例１と同様にして、アンモニア分解の活性評価を行った。
アンモニア分解率は４５０℃で７１％、５００℃で９６％となった。
[Example 14]
The activity of ammonia decomposition was evaluated in the same manner as in Example 1 except that 5% BaO-Ni-Er 2 O 3- MgO: 0.30 g prepared in Catalyst Preparation Example 24 was used as the catalyst.
The ammonia decomposition rate was 71% at 450 ° C and 96% at 500 ° C.
［比較例７］
触媒として、触媒調製例１５で調製した５％BaO-Ni-La2O3：０．３０ｇを用いた以外は実施例１と同様にして、アンモニア分解の活性評価を行った。
アンモニア分解率は４５０℃で３６％、５００℃で７３％となった。
[Comparative Example 7]
The activity of ammonia decomposition was evaluated in the same manner as in Example 1 except that 5% BaO-Ni-La 2 O 3 : 0.30 g prepared in Catalyst Preparation Example 15 was used as the catalyst.
The ammonia decomposition rate was 36% at 450 ° C. and 73% at 500 ° C.
［比較例８］
触媒として、触媒調製例１７で調製した５％BaO-Ni-Nd2O3：０．３０ｇを用いた以外は実施例１と同様にして、アンモニア分解の活性評価を行った。
アンモニア分解率は４５０℃で３８％、５００℃で８４％となった。
[Comparative Example 8]
The activity of ammonia decomposition was evaluated in the same manner as in Example 1 except that 5% BaO-Ni-Nd 2 O 3 : 0.30 g prepared in Catalyst Preparation Example 17 was used as the catalyst.
The ammonia decomposition rate was 38% at 450 ° C. and 84% at 500 ° C.
［比較例９］
触媒として、触媒調製例１９で調製した５％BaO-Ni-Eu2O3：０．３０ｇを用いた以外は実施例１と同様にして、アンモニア分解の活性評価を行った。
アンモニア分解率は４５０℃で４６％、５００℃で９２％となった。
[Comparative Example 9]
The activity of ammonia decomposition was evaluated in the same manner as in Example 1 except that 5% BaO-Ni-Eu 2 O 3 : 0.30 g prepared in Catalyst Preparation Example 19 was used as the catalyst.
The ammonia decomposition rate was 46% at 450 ° C. and 92% at 500 ° C.
［比較例１０］
触媒として、触媒調製例２１で調製した５％BaO-Ni-Gd2O3：０．３０ｇを用いた以外は実施例１と同様にして、アンモニア分解の活性評価を行った。
アンモニア分解率は４５０℃で４９％、５００℃で９６％となった。
[Comparative Example 10]
The activity of ammonia decomposition was evaluated in the same manner as in Example 1 except that 5% BaO-Ni-Gd 2 O 3 : 0.30 g prepared in Catalyst Preparation Example 21 was used as the catalyst.
The ammonia decomposition rate was 49% at 450 ° C and 96% at 500 ° C.
［比較例１１］
触媒として、触媒調製例２３で調製した５％BaO-Ni-Er2O3：０．３０ｇを用いた以外は実施例１と同様にして、アンモニア分解の活性評価を行った。
アンモニア分解率は４５０℃で４７％、５００℃で９３％となった。
[Comparative Example 11]
The activity of ammonia decomposition was evaluated in the same manner as in Example 1 except that 5% BaO-Ni-Er 2 O 3 : 0.30 g prepared in Catalyst Preparation Example 23 was used as the catalyst.
The ammonia decomposition rate was 47% at 450 ° C and 93% at 500 ° C.
実施例１０〜１４及び比較例７〜１１で用いた触媒の組成、及びその触媒によるアンモニア分解率を下記表２にまとめた。 The composition of the catalyst used in Examples 10 to 14 and Comparative Examples 7 to 11 and the ammonia decomposition rate by the catalyst are summarized in Table 2 below.
表２から明らかなように、実施例１０〜１４におけるいずれのアンモニア分解率も、比較例７〜１１におけるアンモニア分解率より高い。
このことから、元素（Ｂ）であるストロンチウム又はバリウムと、元素（Ａ）であるニッケルと、元素（Ｃ）と、マグネシウム（Ｄ）と、の組み合わせにおいて、元素（Ｃ）として、イットリウム及びサマリウム以外に、ランタン、ネオジム、ユウロピウム、ガドリニウム及びエルビウムがアンモニア分解活性の向上に効果があることが示された。
As is clear from Table 2, all the ammonia decomposition rates in Examples 10 to 14 are higher than the ammonia decomposition rates in Comparative Examples 7 to 11.
From this, in the combination of the element (B) strontium or barium, the element (A) nickel, the element (C), and the magnesium (D), the element (C) is other than yttrium and samarium. It was shown that lantern, neodymium, europium, gadolinium and erbium are effective in improving the ammonia decomposition activity.
＜モル元素比（元素（Ｃ）／マグネシウム（Ｄ））の算出＞
前述した触媒調製例にて得られた触媒について、元素（Ｃ）のモル数とマグネシウム（Ｄ）のモル数との比（モル元素比：元素（Ｃ）／マグネシウム（Ｄ））を、触媒の調製に用いた元素（Ｃ）の原料のモル数及びマグネシウム（Ｄ）の原料のモル数から算出した。
算出結果を表１及び２に示す。
この算出結果とアンモニア分解率の値から、実施例３〜実施例８の４５０℃でのアンモニア分解率を比較するに、実施例５〜７のアンモニア分解率（７２％〜７７％）が、実施例３、４及び８のアンモニア分解率（５８％〜６７％）よりも高い。触媒（Ｘ）の表面において、希土類酸化物（元素（Ｃ））に酸化マグネシウム（マグネシウム（Ｄ））が適度に覆われることが良好なアンモニア分解活性を得るためには重要と考えられる。このことから、元素（Ｃ）としてサマリウムを含有する触媒（Ｘ）では、実施例５〜７のモル元素比（元素（Ｃ）／マグネシウム（Ｄ））＝０．０２６〜０．０９９のときに、酸化サマリウムが酸化マグネシウムを適度に覆い、好ましい触媒（Ｘ）表面を形成し、特に良好なアンモニア分解活性を示すことが示唆された。
以上のことから、モル元素比（元素（Ｃ）／マグネシウム（Ｄ））の値が、アンモニア分解率に寄与していることが分かった。
<Calculation of molar element ratio (element (C) / magnesium (D))>
With respect to the catalyst obtained in the above-mentioned catalyst preparation example, the ratio of the number of moles of the element (C) to the number of moles of magnesium (D) (molar element ratio: element (C) / magnesium (D)) is determined by the catalyst. It was calculated from the number of moles of the raw material of the element (C) and the number of moles of the raw material of magnesium (D) used in the preparation.
The calculation results are shown in Tables 1 and 2.
From this calculation result and the value of the ammonia decomposition rate, when comparing the ammonia decomposition rates of Examples 3 to 8 at 450 ° C., the ammonia decomposition rates of Examples 5 to 7 (72% to 77%) were carried out. It is higher than the ammonia decomposition rate (58% to 67%) of Examples 3, 4 and 8. It is considered important that the rare earth oxide (element (C)) is appropriately covered with magnesium oxide (magnesium (D)) on the surface of the catalyst (X) in order to obtain good ammonia decomposition activity. From this, in the catalyst (X) containing samarium as the element (C), when the molar element ratio (element (C) / magnesium (D)) of Examples 5 to 7 is 0.026 to 0.099. It was suggested that samarium oxide moderately covers magnesium oxide, forms a preferable catalyst (X) surface, and exhibits particularly good ammonia decomposition activity.
From the above, it was found that the value of the molar element ratio (element (C) / magnesium (D)) contributes to the ammonia decomposition rate.
＜マグネシウム（Ｄ）の含有量の算出＞
前述した触媒調製例にて得られた触媒について、元素（Ａ）が単体金属であり、元素（Ｂ）と、元素（Ｃ）及びマグネシウム（Ｄ）が酸化物であると仮定したときの含有量を触媒の調製に用いた元素（Ａ）と、元素（Ｂ）と、元素（Ｃ）及びマグネシウム（Ｄ）の原料の質量から算出した。
算出結果を表１及び２に示す。
この算出結果とアンモニア分解率の値から、実施例１〜実施例８の４５０℃でのアンモニア分解率を比較するに、酸化マグネシウムを２７．５質量％〜５２．３質量％含む実施例１及び２と実施例４〜８はアンモニア分解率が６２％〜７７％であり、酸化マグネシウムを１６．５質量％含む実施例４のアンモニア分解率５８％よりも高い。このことは、一定以上の酸化マグネシウム（マグネシウム（Ｄ））を含む触媒（Ｘ）では、元素（Ａ）と元素（Ｂ）及び元素（Ｃ）が触媒（Ｘ）中に高分散して、各成分の添加効果をより効率的に活用できることを示唆している。
以上のことから、マグネシウム（Ｄ）の含有量がアンモニア分解率に寄与していることが分かった。
<Calculation of magnesium (D) content>
The content of the catalyst obtained in the above-mentioned catalyst preparation example when the element (A) is a simple substance metal and the element (B), the element (C) and the magnesium (D) are oxides. Was calculated from the masses of the raw materials of the element (A), the element (B), the element (C) and the magnesium (D) used in the preparation of the catalyst.
The calculation results are shown in Tables 1 and 2.
Comparing the ammonia decomposition rates of Examples 1 to 8 at 450 ° C. from this calculation result and the value of the ammonia decomposition rate, Examples 1 and Example 1 containing magnesium oxide in an amount of 27.5% by mass to 52.3% by mass. 2 and Examples 4 to 8 have an ammonia decomposition rate of 62% to 77%, which is higher than the ammonia decomposition rate of Example 4 containing 16.5% by mass of magnesium oxide. This means that in the catalyst (X) containing magnesium oxide (magnesium (D)) above a certain level, the element (A), the element (B) and the element (C) are highly dispersed in the catalyst (X). It is suggested that the effect of adding the components can be utilized more efficiently.
From the above, it was found that the content of magnesium (D) contributes to the ammonia decomposition rate.
水素を燃料などのエネルギー源として利用する分野に好適に適用することができる。 It can be suitably applied to the field where hydrogen is used as an energy source such as fuel.
Claims (14)
アンモニアを含有する原料ガスを分解して水素を製造することに用いられる水素製造用触媒。 One or more elements (A) selected from nickel, cobalt and iron, one or more elements (B) selected from strontium and barium, one or more elements (C) selected from rare earth elements, and magnesium. The content of magnesium (D) including (D) is 10% by mass to 65% by mass in terms of magnesium oxide with respect to the total mass of the catalyst for hydrogen production.
A catalyst for hydrogen production used to decompose a raw material gas containing ammonia to produce hydrogen.
The element (B) is, claims 9 to 1 3 of any one of hydrogen production catalyst according barium.
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