JP7161664B2 - Method for producing catalyst for hydrogen production - Google Patents
Method for producing catalyst for hydrogen production Download PDFInfo
- Publication number
- JP7161664B2 JP7161664B2 JP2019083120A JP2019083120A JP7161664B2 JP 7161664 B2 JP7161664 B2 JP 7161664B2 JP 2019083120 A JP2019083120 A JP 2019083120A JP 2019083120 A JP2019083120 A JP 2019083120A JP 7161664 B2 JP7161664 B2 JP 7161664B2
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- JP
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- Prior art keywords
- mass
- catalyst
- elements
- oxide
- hydrogen production
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims description 173
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 52
- 239000001257 hydrogen Substances 0.000 title claims description 52
- 238000004519 manufacturing process Methods 0.000 title claims description 52
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 46
- 150000001875 compounds Chemical class 0.000 claims description 57
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 50
- 239000011777 magnesium Substances 0.000 claims description 28
- 229910052749 magnesium Inorganic materials 0.000 claims description 27
- 239000012265 solid product Substances 0.000 claims description 25
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 24
- 229910052772 Samarium Inorganic materials 0.000 claims description 24
- 229910052759 nickel Inorganic materials 0.000 claims description 23
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 229910052788 barium Inorganic materials 0.000 claims description 19
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 19
- 239000000395 magnesium oxide Substances 0.000 claims description 17
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 17
- 229910017052 cobalt Inorganic materials 0.000 claims description 15
- 239000010941 cobalt Substances 0.000 claims description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 14
- 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
- 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
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 229910052691 Erbium Inorganic materials 0.000 claims description 9
- 229910052779 Neodymium Inorganic materials 0.000 claims description 9
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 9
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 9
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 9
- 229910052712 strontium Inorganic materials 0.000 claims description 8
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 114
- 229910021529 ammonia Inorganic materials 0.000 description 56
- 238000000034 method Methods 0.000 description 47
- 238000000354 decomposition reaction Methods 0.000 description 30
- 239000007789 gas Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 23
- 239000000126 substance Substances 0.000 description 23
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 22
- 239000000203 mixture Substances 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- 239000007787 solid Substances 0.000 description 19
- 239000002131 composite material Substances 0.000 description 17
- 239000002994 raw material Substances 0.000 description 16
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- 238000006243 chemical reaction Methods 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 230000009467 reduction Effects 0.000 description 11
- 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 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 229910002651 NO3 Inorganic materials 0.000 description 9
- -1 oxides Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 150000004767 nitrides Chemical class 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 150000004679 hydroxides Chemical class 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 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 5
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 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 4
- 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 4
- 229910000480 nickel oxide Inorganic materials 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 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 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 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
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 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
- 238000001914 filtration Methods 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
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 3
- 229910001954 samarium oxide Inorganic materials 0.000 description 3
- 229940075630 samarium oxide Drugs 0.000 description 3
- 238000005406 washing 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 239000003795 chemical substances by application Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 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
- 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 2
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 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
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 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
- 238000002156 mixing Methods 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
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- 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
- 230000008569 process Effects 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 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
- 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 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 239000004277 Ferrous carbonate Substances 0.000 description 1
- 238000009620 Haber process Methods 0.000 description 1
- 229910052689 Holmium 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- 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
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 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
- 239000002253 acid Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 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
- 230000008901 benefit Effects 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
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 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
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 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
- IUYLTEAJCNAMJK-UHFFFAOYSA-N cobalt(2+);oxygen(2-) Chemical compound [O-2].[Co+2] IUYLTEAJCNAMJK-UHFFFAOYSA-N 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
- 229910000335 cobalt(II) sulfate Inorganic materials 0.000 description 1
- PKSIZOUDEUREFF-UHFFFAOYSA-N cobalt;dihydrate Chemical compound O.O.[Co] PKSIZOUDEUREFF-UHFFFAOYSA-N 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-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
- 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 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
- 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 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
- MSNWSDPPULHLDL-UHFFFAOYSA-K ferric hydroxide Chemical compound [OH-].[OH-].[OH-].[Fe+3] MSNWSDPPULHLDL-UHFFFAOYSA-K 0.000 description 1
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 1
- 235000019268 ferrous carbonate Nutrition 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910001938 gadolinium oxide Inorganic materials 0.000 description 1
- 229940075613 gadolinium oxide Drugs 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
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 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
- 238000005470 impregnation Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- VYMHFSZGDLIMMG-UHFFFAOYSA-K iron(3+);diacetate;hydroxide Chemical compound [OH-].[Fe+3].CC([O-])=O.CC([O-])=O VYMHFSZGDLIMMG-UHFFFAOYSA-K 0.000 description 1
- 229910000015 iron(II) carbonate Inorganic materials 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- LNOZJRCUHSPCDZ-UHFFFAOYSA-L iron(ii) acetate Chemical compound [Fe+2].CC([O-])=O.CC([O-])=O LNOZJRCUHSPCDZ-UHFFFAOYSA-L 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
- 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
- 239000007788 liquid Substances 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
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides 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
- 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
- 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
- ATYNVYNPWGEMMI-UHFFFAOYSA-H nickel(2+);carbonate;tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Ni+2].[Ni+2].[Ni+2].[O-]C([O-])=O ATYNVYNPWGEMMI-UHFFFAOYSA-H 0.000 description 1
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical compound [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 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
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 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
- XSJBCHVBCBESFB-UHFFFAOYSA-N samarium;hexahydrate Chemical compound O.O.O.O.O.O.[Sm] XSJBCHVBCBESFB-UHFFFAOYSA-N 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
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 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
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 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、水素製造用触媒の製造方法に関する。 TECHNICAL FIELD The present invention relates to a method for producing 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、水素の貯蔵及び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際して大きな障害の一つとなっている。 Hydrogen is expected as a new energy source to solve problems such as the increase in 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.
水素と比べて低コストでの輸送及び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いる。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。アンモニアの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水素をより安価に製造することを可能とし、産業上非常に有益な技術である。 Ammonia, which can be transported and stored at a lower cost than hydrogen, is known to produce hydrogen relatively easily through a decomposition reaction. If this reaction can proceed efficiently, ammonia can be a promising substance as a hydrogen carrier. A technology for efficiently decomposing ammonia using a catalyst makes it possible to transport cheap ammonia produced overseas and produce hydrogen at a lower cost, and is a very useful technology for industry.
アンモニアの分解のための触媒は、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。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。 Catalysts for decomposing ammonia are broadly classified into catalysts containing ruthenium as noble metal-based catalysts and catalysts containing nickel, cobalt, and iron as non-noble metal-based catalysts. In general, noble metal catalysts are known to have higher activity, but less expensive non-noble metal catalysts are advantageous in terms of cost, and higher activity of non-noble metal catalysts is desired. Against this background, the following catalysts have been proposed as examples of non-noble metal-based ammonia decomposition catalysts.
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。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、さら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。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。本発明者らの発明にかかる特許文献５には、鉄系の元素、アルカリ土類金属及び希土類元素を含む触媒が開示されている。 For example, Patent Document 1 discloses a strontium oxide-lanthanum oxide-cobalt metal fine particle catalyst. Patent Document 2 discloses a catalyst in which cobalt or nickel is supported on a solid solution of ceria and zirconia (CeZrO x ), and an alkali metal or alkaline earth metal is added. Non-Patent Document 1, Patent Document 3, and Patent Document 4 disclose catalysts in which nickel and an alkaline earth metal are supported on rare earth oxides. Patent Document 5 according to the invention of the present inventors discloses a catalyst containing an iron-based element, an alkaline earth metal and a rare earth element.
特許文献５に開示された触媒の好適な製法として、ニッケル、コバルト及び鉄から選ばれる１種以上の元素を含む化合物、ストロンチウム及びバリウムから選ばれる１種以上の元素を含む化合物、希土類元素から選ばれる１種以上の元素を含む化合物、及びマグネシウムを含む化合物の水溶液を接触させて沈澱を得て、これを濾別し、乾燥させる方法がある。
本発明者らの検討の結果、この方法により得られる触媒の収量は理論収量を考慮すると改善の余地があることが判明した。
よって本発明は、収率に優れる水素製造用触媒の製造方法を提供することを課題としてなされたものである。
Preferred methods for producing the catalyst disclosed in Patent Document 5 include a compound containing at least one element selected from nickel, cobalt and iron, a compound containing at least one element selected from strontium and barium, and a rare earth element. There is a method of contacting an aqueous solution of a compound containing one or more elements and a compound containing magnesium to obtain a precipitate, which is filtered and dried.
As a result of studies by the present inventors, it has been found that the yield of the catalyst obtained by this method has room for improvement when considering the theoretical yield.
Accordingly, an object of the present invention is to provide a method for producing a hydrogen production catalyst with excellent yield.
本発明者らは上記の課題に鑑み鋭意検討した結果、収率に優れる水素製造用触媒の製造方法を提供することを課題とする。 As a result of intensive studies in view of the above problems, the inventors of the present invention have an object to provide a method for producing a catalyst for hydrogen production with excellent yield.
上記課題を解決するための手段には、以下の実施態様が含まれる。
＜１＞下記の元素（Ａ）を含む化合物、元素（Ｂ）を含む化合物、元素（Ｃ）を含む化合物及び元素（Ｄ）を含む化合物を水中で接触させて固体状生成物を得る接触工程を有し、前記接触工程の少なくとも一部は５０℃～９５℃の条件下で行われる、水素製造用触媒の製造方法。
（Ａ）ニッケル、コバルト及び鉄から選ばれる１種以上の元素
（Ｂ）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
（Ｃ）希土類元素から選ばれる１種以上の元素
（Ｄ）マグネシウム
＜２＞前記水素製造用触媒に含まれる元素（Ｄ）の含有率が、マグネシウムの酸化物換算で０．１質量％～８０質量％の範囲である、＜１＞に記載の水素製造用触媒の製造方法。＜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＞に記載の水素製造用触媒の製造方法。
＜４＞前記元素（Ｃ）が、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＞に記載の水素製造用触媒の製造方法。
＜５＞前記元素（Ａ）が、ニッケルである＜１＞～＜４＞のいずれか１項に記載の水素製造用触媒の製造方法。
＜６＞前記元素（Ｂ）が、バリウムである＜１＞～＜５＞のいずれか１項に記載の水素製造用触媒の製造方法。
＜７＞前記接触工程はｐＨが８～１３の条件下で行われる、＜１＞～＜６＞のいずれか１項に記載の水素製造用触媒の製造方法。
Means for solving the above problems include the following embodiments.
<1> A contacting step of contacting the following compound containing element (A), compound containing element (B), compound containing element (C) and compound containing element (D) in water to obtain a solid product. and at least part of the contacting step is carried out under conditions of 50°C to 95°C.
(A) one or more elements selected from nickel, cobalt and iron (B) one or more elements selected from strontium and barium (C) one or more elements selected from rare earth elements (D) magnesium <2> The method for producing a hydrogen production catalyst according to <1>, wherein the content of the element (D) contained in the hydrogen production catalyst is in the range of 0.1% by mass to 80% by mass in terms of magnesium oxide. . <3> Manufacture of the hydrogen production catalyst according to <1> or <2>, wherein the element (C) is one or more elements selected from yttrium, lanthanum, neodymium, samarium, europium, gadolinium and erbium. Method.
<4> The method for producing a hydrogen production catalyst according to <1> or <2>, wherein the element (C) is one or more elements selected from yttrium, neodymium, samarium, europium, gadolinium and erbium.
<5> The method for producing a hydrogen production catalyst according to any one of <1> to <4>, wherein the element (A) is nickel.
<6> The method for producing a hydrogen production catalyst according to any one of <1> to <5>, wherein the element (B) is barium.
<7> The method for producing a hydrogen production catalyst according to any one of <1> to <6>, wherein the contacting step is performed at a pH of 8 to 13.
本発明によれば、収率に優れる水素製造用触媒の製造方法が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the hydrogen production catalyst which is excellent in a yield is provided.
以下、本発明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。 An embodiment of the present invention will be described below. However, the present invention is by no means limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the purpose of the present invention.
本明細書において数値範囲を表す「～」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。
本明細書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。
本明細書において、「固体状生成物」という語は「固体状成分」と記す場合がある。沈澱は、固体状生成物の一形態と考えて差し支えない。
In this specification, "-" representing a numerical range represents a range including the upper and lower limits.
In the numerical ranges described stepwise in this specification, the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described stepwise.
In the numerical ranges described in this specification, upper or lower limits described in a certain numerical range may be replaced with values shown in Examples.
As used herein, the term "solid product" may be referred to as "solid component." Precipitation can be considered a form of solid product.
＜水素製造用触媒の製造方法＞
本開示の水素製造用触媒（以下、単に触媒ともいう）の製造方法は、下記の元素（Ａ）を含む化合物、元素（Ｂ）を含む化合物、元素（Ｃ）を含む化合物及び元素（Ｄ）を含む化合物を水中で接触させて固体状生成物を得る接触工程を有し、前記接触工程の少なくとも一部は５０℃～９５℃の条件下で行われる、水素製造用触媒の製造方法である。
（Ａ）ニッケル、コバルト及び鉄から選ばれる１種以上の元素
（Ｂ）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
（Ｃ）希土類元素から選ばれる１種以上の元素
（Ｄ）マグネシウム
なお前記の「接触」という語は、各成分が単に分子レベルも含めて接触する場合の他、接触して反応、化合、錯体形成する場合などを含む意味で使用される。
<Method for producing catalyst for hydrogen production>
The method for producing a catalyst for hydrogen production of the present disclosure (hereinafter also simply referred to as a catalyst) comprises the following compounds containing element (A), compounds containing element (B), compounds containing element (C) and element (D) A method for producing a catalyst for hydrogen production, comprising a contact step of obtaining a solid product by contacting a compound containing .
(A) one or more elements selected from nickel, cobalt and iron (B) one or more elements selected from strontium and barium (C) one or more elements selected from rare earth elements (D) magnesium The term "contact" is used to include the case where each component is in contact including the molecular level, as well as the case where the components are in contact to react, combine, form a complex, and the like.
本発明者らは、上述した元素（Ａ）～（Ｄ）を含む化合物を水中で接触させて固体状生成物を得る接触工程の少なくとも一部を特定の温度条件下で行うことで、得られる触媒の収率が向上することを見出し、本発明を完成させるに至った。 The present inventors have found that by performing at least part of the contacting step of obtaining a solid product by contacting the compound containing the above-described elements (A) to (D) in water under specific temperature conditions, The inventors have found that the yield of the catalyst is improved, and have completed the present invention.
本開示の方法により製造される触媒は、アンモニアを含有する原料ガスを用いる水素の製造方法に用いられる。より具体的には、アンモニアを含有する原料ガスと触媒とを接触させてアンモニアを窒素と水素に分解させることで水素を製造する方法に用いられる。 The catalyst produced by the method of the present disclosure is used in a method for producing hydrogen using a source gas containing ammonia. More specifically, it is used in a method of producing hydrogen by contacting a raw material gas containing ammonia with a catalyst to decompose ammonia into nitrogen and hydrogen.
本開示の方法において、接触工程を実施する手法は特に制限されない。例えば、溶液成分から固体成分を生成させる方法（所謂、沈澱法）により行ってもよい。 In the method of the present disclosure, the method of carrying out the contacting step is not particularly limited. For example, a method of forming a solid component from a solution component (so-called precipitation method) may be used.
沈澱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澱剤の添加により同カチオンの難溶性塩を沈澱させる一般的な沈澱法に加え、２種類以上のカチオンを含む溶液から沈澱剤の添加により複数の難溶性塩を同時に沈澱させる共沈法、溶液中の溶質を加水分解及び縮重合により沈澱させるゾルゲル法などが挙げられる。
アルカリ土類金属である元素（Ｂ）のカチオンを含むときは、このカチオンが一般に沈澱し難いため、クエン酸、シュウ酸等の多価カルボン酸を沈澱促進剤として加えてもよい。
Specifically, as a precipitation method, in addition to the general precipitation method of precipitating a sparingly soluble salt of the same cation from a solution containing one type of cation by adding a precipitant, a precipitant is added from a solution containing two or more types of cations. Examples include a coprecipitation method in which a plurality of sparingly soluble salts are simultaneously precipitated by addition, and a sol-gel method in which a solute in a solution is precipitated by hydrolysis and polycondensation.
When the cation of element (B), which is an alkaline earth metal, is contained, this cation is generally difficult to precipitate, so a polyvalent carboxylic acid such as citric acid or oxalic acid may be added as a precipitation accelerator.
接触工程で沈澱剤を用いる場合、沈澱剤としてアルカリ性化合物を用いることが好ましい。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て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。 When a precipitant is used in the contacting step, it is preferred to use an alkaline compound as the precipitant. Specific examples of alkaline compounds include ammonia, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, potassium carbonate, sodium carbonate, and aqueous solutions thereof. An alkaline compound may be added using a method of decomposing urea in a solution to generate ammonia.
本開示の方法において、元素（Ａ）～（Ｄ）を含む化合物を水中で接触させる手法は特に制限されない。例えば、元素（Ａ）～（Ｄ）を含む化合物をそのまま水に添加してもよく、元素（Ａ）～（Ｄ）を含む化合物の一部又はすべてを水溶液の状態にしてから混合してもよい。収率向上の観点からは、元素（Ａ）～（Ｄ）を含む化合物のすべてを水溶液の状態にしてから混合することが好ましい。 In the method of the present disclosure, the method of contacting the compound containing elements (A) to (D) in water is not particularly limited. For example, the compound containing the elements (A) to (D) may be added to water as it is, or a part or all of the compound containing the elements (A) to (D) may be made into an aqueous solution and then mixed. good. From the viewpoint of improving the yield, it is preferable to mix all the compounds containing the elements (A) to (D) after making them into an aqueous solution.
元素（Ａ）～（Ｄ）を含む化合物は、酸性金属塩等の水に可溶な化合物であることが好ましく、硝酸塩、塩化物、硫酸塩、カルボン酸塩、及びシュウ酸塩から選ばれる化合物であることがより好ましい。 The compound containing the elements (A) to (D) is preferably a water-soluble compound such as an acid metal salt, and is a compound selected from nitrates, chlorides, sulfates, carboxylates, and oxalates. is more preferable.
本開示の方法では、接触工程の少なくとも一部を５０℃～９５℃の条件下で行う。接触工程の少なくとも一部を５０℃以上で行うと、固体状生成物の生成反応が速やかに進行する傾向にある。その結果、溶液中の元素（特に、マグネシウム）が固体状生成物中に含有され易くなると推測される。一方、接触工程の少なくとも一部を９５℃以下で行うと、生成した固体状生成物が安定して水酸化物を主体とする構造を維持し易い傾向にある。 In the method of the present disclosure, at least part of the contacting step is performed under conditions of 50°C to 95°C. When at least part of the contacting step is carried out at 50° C. or higher, the reaction for producing a solid product tends to proceed rapidly. As a result, it is presumed that the elements (particularly magnesium) in the solution are likely to be contained in the solid product. On the other hand, when at least part of the contacting step is carried out at 95° C. or less, the produced solid product tends to be stable and tend to maintain a structure mainly composed of hydroxides.
上記温度の範囲は５５℃以上であることがより好ましく、６０℃以上であることがさらに好ましい。一方、上記温度の範囲は９０℃以下であることが好ましく、８５℃以下であることがより好ましい。 The above temperature range is more preferably 55° C. or higher, more preferably 60° C. or higher. On the other hand, the temperature range is preferably 90° C. or lower, more preferably 85° C. or lower.
本開示の方法では、接触工程のすべてを５０℃～９５℃の条件下で行ってもよく、一部を５０℃～９５℃以外の条件（例えば、２５℃付近）で行ってもよい。接触工程の一部を５０℃～９５℃以外の条件で行う場合、少なくともマグネシウムを含む化合物を他の元素を含む化合物と接触させた後の温度を５０℃～９５℃とすることが好ましい。 In the method of the present disclosure, all of the contacting steps may be performed under conditions of 50°C to 95°C, or some may be performed under conditions other than 50°C to 95°C (eg, around 25°C). When part of the contacting step is performed under conditions other than 50°C to 95°C, the temperature after contacting the compound containing at least magnesium with the compound containing another element is preferably 50°C to 95°C.
本開示の方法において、接触工程の少なくとも一部を上述した温度条件で行う時間は特に制限されない。充分な固体状生成物を得る観点からは１０分以上であることが好ましい。一方、成分の均一な固体状生成物を得る観点からは１８０分以下であることが好ましい。 In the method of the present disclosure, the time for performing at least part of the contacting step under the temperature conditions described above is not particularly limited. From the viewpoint of obtaining a sufficient solid product, the time is preferably 10 minutes or longer. On the other hand, from the viewpoint of obtaining a solid product with uniform components, the time is preferably 180 minutes or less.
上記時間の範囲は１５分以上であることが好ましく、２０分以上であることがより好ましい。一方、上記時間の範囲は１５０分以下であることがより好ましく、１２０分以下であることがさらに好ましい。 The time range is preferably 15 minutes or longer, more preferably 20 minutes or longer. On the other hand, the above time range is more preferably 150 minutes or less, and even more preferably 120 minutes or less.
接触工程を行うときの温度を上記範囲に制御する方法は、特に制限されない。例えば、（１）上記の各元素を含む化合物の接触を室温（２５℃付近）の水中で行った後、接触液を徐々にヒーターなどで加温して前記の温度範囲とする方法、（２）上記の各元素を含む化合物の水溶液と沈澱剤の水溶液を別々に加温して前記の温度範囲とした後、各水溶液を混合する方法、（３）上記の各元素を含む化合物の水溶液と沈澱剤の水溶液のいずれか一方を加温して前記の温度範囲とした後、もう一方の水溶液を混合する方法、などが挙げられる。 A method for controlling the temperature in the contacting step within the above range is not particularly limited. For example, (1) a method in which a compound containing each of the above elements is brought into contact with water at room temperature (around 25° C.), and then the contact liquid is gradually heated with a heater or the like to reach the above temperature range; ) A method of separately heating an aqueous solution of a compound containing each of the above elements and an aqueous solution of a precipitant to the above temperature range, and then mixing the respective aqueous solutions; For example, one of the precipitant aqueous solutions is heated to the above temperature range and then mixed with the other aqueous solution.
接触工程は、撹拌等の作業を伴っていてもよい。例えば、上記の各元素を含む化合物の水溶液と沈澱剤の水溶液をすべて混合した後、得られた溶液中での上記各元素を含む粒子を成長（熟成）させるために撹拌してもよい。 The contacting step may be accompanied by operations such as stirring. For example, after mixing the aqueous solution of the compound containing each of the above elements and the aqueous solution of the precipitant, the mixture may be stirred to grow (ripen) the particles containing each of the above elements in the resulting solution.
接触工程は、ｐＨが８～１３の条件下で行うことが好ましい。接触工程を行う際のｐＨが８以上であると、固体状生成物の生成反応が速やかに進行する傾向にある。一方、接触工程を行う際のｐＨが１３以下であると、得られる固体状生成物から沈澱剤を除去するために用いる水の量を少なくできる傾向にある。 The contacting step is preferably carried out under pH 8-13 conditions. When the pH is 8 or more when performing the contacting step, the reaction for producing a solid product tends to proceed rapidly. On the other hand, when the pH is 13 or less during the contacting step, the amount of water used to remove the precipitant from the resulting solid product tends to be reduced.
上記ｐＨの範囲は８．５以上であることがより好ましく、９以上であることがさらに好ましい。一方、上記ｐＨの範囲は１２以下であることがより好ましく、１１以下であることがさらに好ましい。 The above pH range is more preferably 8.5 or higher, and even more preferably 9 or higher. On the other hand, the above pH range is more preferably 12 or less, and even more preferably 11 or less.
接触工程において、元素（Ａ）～（Ｄ）を含む化合物の水中での濃度は特に制限されず、化合物の溶解性、撹拌しやすさ（粘度）、経済性等を考慮して設定できる。 In the contacting step, the concentration of the compound containing the elements (A) to (D) in water is not particularly limited, and can be set in consideration of the solubility of the compound, ease of stirring (viscosity), economic efficiency, and the like.
接触工程で得られる固体状生成物は、必要に応じて水で洗浄して沈澱剤を除去してもよい。洗浄の方法は特に制限されず、洗浄しながらろ過を行う方法、ろ過してケーキ状とした後に水中に再分散させてろ過を繰り返す方法など、種々の方法で行ってよい。 The solid product obtained in the contacting step may optionally be washed with water to remove the precipitant. The washing method is not particularly limited, and may be carried out by various methods such as a method of filtering while washing, a method of filtering to form a cake, redispersing it in water, and repeating filtration.
固体状生成物は、必要に応じて乾燥処理を行ってもよい。乾燥処理の温度は特に制限されないが、１００℃～１３０℃の温度条件で行うことが好ましい。乾燥処理の時間は特に制限されないが、３時間～４８時間の範囲が好ましく、５時間～２４時間の範囲がより好ましい。 The solid product may be dried if necessary. Although the temperature of the drying treatment is not particularly limited, it is preferably carried out under the temperature condition of 100°C to 130°C. Although the drying treatment time is not particularly limited, it is preferably in the range of 3 hours to 48 hours, more preferably in the range of 5 hours to 24 hours.
固体状生成物は、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いずれか一方又は両方を行ってもよい。焼成処理における酸化雰囲気としては、空気、酸素と窒素の混合ガス等が挙げられるが、特にこれらに限定されるものではない。還元処理における還元雰囲気としては、水素雰囲気、一酸化炭素雰囲気、一酸化窒素雰囲気等が挙げられるが、特にこれらに限定されるものではない。 The solid product may be subjected to one or both of firing treatment in an oxidizing atmosphere and reduction treatment in a reducing atmosphere, if necessary. The oxidizing atmosphere in the firing treatment includes air, a mixed gas of oxygen and nitrogen, and the like, but is not particularly limited to these. A reducing atmosphere for the reduction treatment includes, but is not limited to, a hydrogen atmosphere, a carbon monoxide atmosphere, a nitrogen monoxide atmosphere, and the like.
固体状生成物に対する焼成処理及び還元処理のそれぞれの処理条件は特に制限されないが、例えば、下記の条件としてもよい。
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。
The treatment conditions for the calcination treatment and the reduction treatment for the solid product are not particularly limited, but may be, for example, the following conditions.
The firing temperature is preferably in the range of 100°C to 1200°C, more preferably in the range of 400°C to 900°C.
The baking 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.
本開示の方法では、原料としての元素（Ａ）～（Ｄ）を含む化合物に対して焼成処理及び還元処理のいずれか一方又は両方を行ってもよい。また、触媒を用いて水素の製造を行う前に、触媒の焼成処理及び還元処理のいずれか一方又は両方を行ってもよい。
これらの焼成処理及び還元処理の処理条件は、上述した固体状生成物の処理条件と同様であってよい。
In the method of the present disclosure, either one or both of the calcination treatment and the reduction treatment may be performed on the compound containing the elements (A) to (D) as the raw material. Moreover, either one or both of the calcination treatment and the reduction treatment of the catalyst may be performed before the production of hydrogen using the catalyst.
The treatment conditions for these calcination treatment and reduction treatment may be the same as the treatment conditions for the solid product described above.
固体状生成物に対し、必要に応じて上述した洗浄、乾燥、酸化処理、還元処理等を行うことで、触媒が得られる。本開示の方法では、元素（Ａ）～（Ｄ）を含む化合物を水中で接触させて固体状生成物を得る手法（所謂 沈澱法）と他の手法（含浸法、蒸着法、固相合成法等）とを組み合わせてもよい。 A catalyst can be obtained by subjecting the solid product to the above-described washing, drying, oxidation treatment, reduction treatment, etc. as necessary. In the method of the present disclosure, a method of obtaining a solid product by contacting a compound containing elements (A) to (D) in water (so-called precipitation method) and other methods (impregnation method, vapor deposition method, solid phase synthesis method) etc.) may be combined.
触媒は、粉体の状態でもよく、粉体を所望の形状に成形してもよい。なお、触媒は、粉体又は成形体のいずれの場合であっても、アンモニア分解反応器内で触媒層を形成させて用いる。 The catalyst may be in powder form, and the powder may be formed into a desired shape. In addition, the catalyst is used after forming a catalyst layer in the ammonia decomposition reactor regardless of whether the catalyst is a powder or a compact.
粉体を成形して得られる成形触媒としては、粉体を圧縮して得られる凝集塊又はこの凝集塊を適当な粒径に破砕した圧縮成形体、粉体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、粉体を球状担体にコーティングした球状成形体、粉体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。 Molded catalysts obtained by molding powder include agglomerates obtained by compressing powder, compression moldings obtained by crushing this agglomerate to an appropriate particle size, and powder formed into a certain shape by a tableting machine. Compressed and solidified tablet moldings, spherical moldings in which powder is coated on a spherical carrier, honeycomb moldings in which powder is coated on a honeycomb carrier, extrusion moldings in which a binder is added to powder, kneaded and extruded, etc. However, it is not particularly limited to these.
成形触媒は、細孔を有していてもよい。細孔を有する成形触媒は、例えば、粉体に賦孔剤を加えて成形し、焼成処理を施すことにより得られる。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。 The shaped catalyst may have pores. A molded catalyst having pores can be obtained, for example, by adding a pore-forming agent to powder, molding the mixture, and subjecting the mixture to a calcination treatment. Examples of the pore-forming agent include carboxymethyl cellulose, polystyrene, etc., which are easily removed by a calcination treatment, but are not particularly limited to these.
本開示の方法では、元素（Ａ）を含む化合物を１種のみ使用してもよく、２種以上を併用してもよい。
元素（Ａ）としてニッケルを含む化合物としては、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。
元素（Ａ）としてコバルトを含む化合物としては、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。
元素（Ａ）として鉄を含む化合物としては、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。
In the method of the present disclosure, one type of compound containing element (A) may be used alone, or two or more types may be used in combination.
Compounds containing nickel as the element (A) include nickel (II) nitrate, nickel (II) oxide, nickel (II) chloride, nickel (II) hydroxide, nickel (II) sulfate, nickel (II) acetate, carbonate Nickel (II), basic nickel (II) carbonate, metallic nickel and the like.
Compounds containing cobalt as the element (A) include cobalt (II) nitrate, cobalt (II) oxide, cobalt (II) chloride, cobalt (II) hydroxide, cobalt (II) sulfate, cobalt (II) acetate, carbonate Cobalt (II), basic cobalt (II) carbonate, metallic cobalt, and the like.
Compounds containing iron as the element (A) include iron nitrate (II), iron nitrate (III), iron oxide (II), iron oxide (III), iron chloride (II), iron chloride (III), hydroxide Iron (II), iron (III) hydroxide, iron (II) sulfate, iron (III) sulfate, iron (II) acetate, basic iron (III) acetate, iron (II) carbonate, metallic iron, etc. .
本開示の方法では、元素（Ｂ）を含む化合物を１種のみ使用してもよく、２種以上を併用してもよい。
元素（Ｂ）としてストロンチウムを含む化合物としては、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。
元素（Ｂ）としてバリウムを含む化合物としては、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。
In the method of the present disclosure, one type of compound containing element (B) may be used alone, or two or more types may be used in combination.
Compounds containing strontium as element (B) include strontium nitrate, strontium oxide, strontium chloride, strontium hydroxide, strontium sulfate, strontium acetate, and strontium carbonate.
Compounds containing barium as element (B) include barium nitrate, barium oxide, barium chloride, barium hydroxide, barium sulfate, barium acetate, and barium carbonate.
本開示の方法では、元素（Ｃ）を含む化合物を１種のみ使用してもよく、２種以上を併用してもよい。
元素（Ｃ）としてイットリウムを含む化合物としては、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。
元素（Ｃ）としてランタンを含む化合物としては、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。
元素（Ｃ）としてネオジムを含む化合物としては、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。
元素（Ｃ）としてサマリウムを含む化合物としては、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。
元素（Ｃ）としてユウロピウムを含む化合物としては、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。
元素（Ｃ）としてガドリニウムを含む化合物としては、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。
元素（Ｃ）としてエルビウムを含む化合物としては、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。
In the method of the present disclosure, one type of compound containing element (C) may be used alone, or two or more types may be used in combination.
Examples of compounds containing yttrium as the element (C) include yttrium nitrate, yttrium oxide, yttrium chloride, yttrium sulfate, yttrium acetate, and yttrium carbonate.
Examples of compounds containing lanthanum as the element (C) include lanthanum nitrate, lanthanum oxide, lanthanum chloride, lanthanum hydroxide, lanthanum sulfate, lanthanum acetate, and lanthanum carbonate.
Compounds containing neodymium as the element (C) include neodymium nitrate, neodymium oxide, neodymium chloride, neodymium hydroxide, neodymium sulfate, neodymium acetate, and neodymium carbonate.
Examples of compounds containing samarium as the element (C) include samarium nitrate, samarium oxide, samarium chloride, samarium sulfate, samarium acetate, and samarium carbonate.
Examples of compounds containing europium as the element (C) include europium nitrate, europium oxide, europium chloride, europium sulfate, europium acetate, and europium carbonate.
Examples of compounds containing gadolinium as the element (C) include gadolinium nitrate, gadolinium oxide, gadolinium chloride, gadolinium sulfate, gadolinium acetate, and gadolinium carbonate.
Examples of compounds containing erbium as the element (C) include erbium nitrate, erbium oxide, erbium chloride, erbium sulfate, erbium acetate, and erbium carbonate.
本開示の方法では、元素（Ｄ）を含む化合物を１種のみ使用してもよく、２種以上を併用してもよい。
元素（Ｄ）を含む化合物としては、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。
In the method of the present disclosure, one type of compound containing the element (D) may be used alone, or two or more types may be used in combination.
Compounds containing the element (D) include magnesium nitrate, magnesium oxide, magnesium chloride, magnesium hydroxide, magnesium sulfate, magnesium acetate, magnesium carbonate, basic magnesium carbonate and the like.
本開示の方法により製造される触媒は、原料として用いる元素（Ａ）～（Ｄ）を含む化合物に含まれる元素（Ａ）～（Ｄ）を含む。触媒に含まれる元素（Ａ）～（Ｄ）は、それぞれ異なる化学的な形態を有していてもよく、これらの元素の２種以上が複合酸化物を形成していてもよい。
例えば、元素（Ａ）及び元素（Ｄ）からなる複合酸化物を形成していてもよい。複合酸化物の構造として具体的には、スピネル型酸化物が挙げられる。あるいは、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。複合酸化物の構造として具体的には、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 catalyst produced by the method of the present disclosure contains elements (A) to (D) contained in the compound containing elements (A) to (D) used as raw materials. Elements (A) to (D) contained in the catalyst may have different chemical forms, respectively, and two or more of these elements may form a composite oxide.
For example, a composite oxide consisting of element (A) and element (D) may be formed. A specific example of the structure of the composite oxide is a spinel-type oxide. Alternatively, a composite oxide composed of the element (B) and the element (C) may be formed. Specific examples of the structure of the composite oxide include perovskite-type oxides, fluorite-type oxides, spinel-type oxides, and the like.
［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種の元素である。中でも上記３つの元素より選ばれる１種又は２種の元素であることが好ましく、上記３つの元素より選ばれる１種の元素であることがより好ましい。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、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。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、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)]
Element (A) is at least one element selected from the three elements of nickel, cobalt and iron. Among them, one or two elements selected from the above three elements are preferable, and one element selected from the above three elements is more preferable. When the element (A) is one element selected from the above three elements, the element (A) is preferably nickel or cobalt, more preferably nickel. When element (A) is two elements selected from the above three elements, element (A) is preferably nickel and cobalt.
触媒に含まれる元素（Ａ）の化学的な形態は特に制限されず、元素（Ａ）を含んでいれば他の元素を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る。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、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）及び窒化コバルト（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) contained in the catalyst is not particularly limited, and as long as the element (A) is contained, it may exist in a form containing other elements.
Specific chemical forms of the element (A) include elemental metals, alloys, nitrides, oxides, composite oxides, carbides, hydroxides and mixtures thereof. Among them, single metals, alloys, nitrides, oxides, composite oxides and mixtures thereof are preferred, and single metals, alloys, nitrides, oxides, composite oxides and mixtures thereof are more preferred.
More specifically, the chemical forms of the element (A) include nickel metal, nickel oxide (NiO), nickel nitride (Ni 3 N), cobalt metal, cobalt oxide (CoO, Co 3 O 4 ) and cobalt nitride ( Co x N y ), among which nickel metal and cobalt metal are preferred.
［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種の元素である。中でも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)]
Element (B) is at least one element selected from strontium and barium. Among them, it preferably contains barium, and more preferably contains only barium.
触媒に含まれる元素（Ｂ）の化学的な形態は特に制限されず、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) contained in the catalyst is not particularly limited, and as long as the element (B) is contained, it may exist in a form containing other elements at the same time.
Preferred chemical forms of the element (B) specifically include oxides and composite oxides, among which strontium oxide (SrO), barium oxide (BaO) and mixtures thereof are preferred.
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。
The element (B) may exist as a mixture of multiple chemical forms, but 30% by mass to 100% by mass of all the elements (B) contained in the catalyst are oxides or composite oxides. Preferably.
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種の元素である。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さらに好ましく、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 them, at least one element selected from scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium is preferable, and yttrium and lanthanum , neodymium, samarium, europium, gadolinium and erbium, more preferably at least one element selected from yttrium, samarium, europium and gadolinium, and samarium. is particularly preferred.
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さらに好ましい。
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さらに好ましい。
As a combination of the element (B) and the element (C), the following are preferred.
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 element selected from samarium and gadolinium. Elements are more preferred, and samarium is even more preferred.
When the element (B) contains barium, the element (C) is preferably at least one element selected from yttrium, lanthanum, neodymium, samarium, europium, gadolinium and erbium, and yttrium, neodymium, It is more preferably at least one element selected from samarium, europium, gadolinium and erbium, and more preferably at least one element selected from yttrium, samarium and gadolinium.
触媒に含まれる元素（Ｃ）の化学的な形態は特に制限されず、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。
元素（Ｃ）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。
The chemical form of the element (C) contained in the catalyst is not particularly limited, and as long as the element (C) is contained, it may exist in a form containing other elements at the same time.
Preferred chemical forms of element (C) 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.
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 element (C) may exist as a mixture of multiple forms, but 30% by mass to 100% by mass of all the elements (C) contained in the catalyst form oxides or composite oxides. preferably. Specific examples of forms other than oxides or composite oxides include nitrides, hydroxides, and carbonates.
［元素（Ｄ）］
触媒に含まれる元素（Ｄ）であるマグネシウムの化学的な形態は特に制限されず、マグネシウム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（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。
[Element (D)]
The chemical form of magnesium, which is the element (D) contained in the catalyst, is not particularly limited.
Preferred chemical forms of the element (D) include oxides and composite oxides, among which magnesium oxide (MgO) is preferred.
元素（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、触媒に含まれる全ての元素（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。 The element (D) may exist as a mixture of multiple chemical forms, but 30% by mass to 100% by mass of all the elements (D) contained in the catalyst are oxides or composite oxides. It is particularly preferred to have Specific examples of chemical forms other than oxides or composite oxides include nitrides, hydroxides, and carbonates.
［その他の元素］
触媒は、元素（Ａ）～（Ｄ）以外の元素を含んでいてもよい。
触媒に含まれる元素（Ａ）～（Ｄ）以外の元素として具体的には、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、酸素などが挙げられる。
これらの元素の化学的な形態及び触媒中の含有量は、触媒のアンモニア分解の活性を低減させない範囲であることが好ましい。
[Other elements]
The catalyst may contain elements other than elements (A) to (D).
Specific examples of elements other than the elements (A) to (D) contained in the catalyst include alkali metal elements, alkaline earth metal elements excluding magnesium, strontium and barium, Group 4 elements, Group 8 elements other than iron, Examples include group 9 elements other than cobalt, group 10 elements other than nickel, aluminum, carbon, silicon, nitrogen, and oxygen.
The chemical form of these elements and the content in the catalyst are preferably within a range that does not reduce the ammonia decomposition activity of the catalyst.
触媒中の元素（Ａ）～（Ｄ）及びこれら以外の元素の化学的な形態は、Ｘ線回折法（ＸＲＤ）等の公知の方法を用いて確認することができる。 The chemical forms of the elements (A) to (D) and other elements in the catalyst can be confirmed using known methods such as X-ray diffraction (XRD).
触媒に含まれる元素（Ａ）～（Ｄ）の量は、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。さらに、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。 The amounts of elements (A) to (D) contained in the catalyst are calculated in terms of single metals for element (A) and in terms of oxides for element (B), element (C) and magnesium (D). The ranges shown below are preferred. Further, a method for calculating each content will be described in detail below.
触媒に含まれる元素（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％がさらに好ましく、３０質量％～５０質量％が特に好ましい。
The amount of element (A) contained in the catalyst is calculated on the assumption that all contained elements (A) are present as elemental metals.
The total amount of the element (A) is not particularly limited, but it is preferably 0.01% by mass to 80% by mass, and 1% by mass to It is more preferably 70% by mass, more preferably 10% by mass to 60% by mass, more preferably 20% by mass to 60% by mass, more preferably 30% by mass to 55% by mass, and 30% by mass. % to 50% by weight is particularly preferred.
触媒に含まれる元素（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さらに好ましく、３質量％～７質量％の範囲が特に好ましい。
The amount of element (B) contained in the catalyst is calculated on the assumption that all contained elements (B) are present as oxides.
The total amount of the element (B) is not particularly limited, but it is preferably in the range of 0.1% by mass to 15% by mass as an oxide of the element (B) with respect to the total mass of the catalyst, and 1 mass % to 15% by mass, more preferably 2% to 15% by mass, more preferably 2% to 12% by mass, 2% by mass to It is more preferably in the range of 9% by mass, more preferably in the range of 2% to 7% by mass, and particularly preferably in the range of 3% to 7% by mass.
触媒に含まれる元素（Ｂ）がバリウムを含む場合には、触媒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％であることがさらに好ましく、４質量％～６質量％の範囲が特に好ましい。 When the element (B) contained in the catalyst contains barium, the amount of barium relative to the total mass of the catalyst is preferably 0.1% by mass to 15% by mass as barium oxide, and 1% by mass. It is more preferably 15% by mass, more preferably 2% by mass to 12% by mass, more preferably 2% by mass to 9% by mass, and 3% by mass to 7% by mass. More preferably, the range of 4% by mass to 6% by mass is particularly preferred.
触媒に含まれる元素（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％であることがさらに好ましく、２質量％～３０質量％であることが特に好ましい。
The amount of element (C) contained in the catalyst is calculated on the assumption that all contained elements (C) exist as oxides.
The total amount of the element (C) is not particularly limited, but it is preferably 0.1% by mass to 60% by mass, and 1% by mass to It is more preferably 40% by mass, even more preferably 1% to 35% by mass, and particularly preferably 2% to 30% by mass.
前記の元素（Ｃ）量を算出する酸化物とは、前記の酸化環境での焼成工程によって得られる酸化物と考えてよい。即ち、具体例としては、前記した酸化イットリウム（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）等、三価の金属の酸化物を挙げることが出来る。 The oxide for which the amount of element (C) is calculated may be considered to be the oxide obtained by the firing process in the oxidizing environment. That is, specific examples include 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 trivalent metal oxides.
触媒に含まれる元素（Ｃ）がサマリウムを含む場合には、触媒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％であることがさらに好ましく、７質量％～２０質量％であることが特に好ましい。 When the element (C) contained in the catalyst contains samarium, the amount of samarium relative to the total mass of the catalyst is preferably 0.1% by mass to 60% by mass as samarium oxide, and 1% by mass. It is more preferably 40% by mass, more preferably 1% by mass to 35% by mass, more preferably 2% by mass to 30% by mass, and 2% by mass to 25% by mass. It is more preferably 2% by mass to 20% by mass, even more preferably 4% by mass to 20% by mass, and particularly preferably 7% by mass to 20% by mass.
触媒に含まれる元素（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がさらに好ましく、０．０４～０．１が特に好ましい。
触媒が元素（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がさらに好ましく、０．０２～０．０８が特に好ましい。
The ratio of the number of moles of the element (B) and the number of moles of the element (A) contained in the catalyst (element (B)/element (A)) is preferably 0.01 to 0.21, more preferably 0.01 to 0. 0.15 is more preferred, 0.02 to 0.15 is more preferred, 0.02 to 0.12 is more preferred, 0.02 to 0.1 is more preferred, 0.025 to 0.1 is more preferred, 0.03 to 0.1 is more preferred, and 0.04 to 0.1 is particularly preferred.
When the catalyst contains barium as the element (B), the ratio of the number of moles of barium to the number of moles of the element (A) (barium/element (A)) is preferably 0.01 to 0.21. 0.01 to 0.15 is more preferred, 0.02 to 0.15 is more preferred, 0.02 to 0.12 is more preferred, 0.02 to 0.1 is even more preferred, and 0.02 to 0.1 is more preferred. 08 is particularly preferred.
触媒に含まれる元素（Ｄ）の量は、含まれる全ての元素（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。
元素（Ｄ）の量は、触媒の全質量に対して、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％であることがさらに好ましく、２０質量％～５５質量％であることが特に好ましい。
The amount of element (D) contained in the catalyst is calculated on the assumption that all contained elements (D) are present as oxides (that is, magnesium oxide).
The amount of the element (D) is preferably 0.1% by mass to 80% by mass, preferably 1% by mass to 70% by mass, in terms of oxide (as magnesium oxide) with respect to the total mass of the catalyst. more preferably 10% by mass to 65% by mass, more preferably 15% by mass to 65% by mass, even more preferably 20% by mass to 60% by mass, 20% by mass % to 55% by weight is particularly preferred.
触媒に含まれる元素（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がさらに好ましく、０．０１～０．４０が特に好ましい。
触媒が元素（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がさらに好ましく、０．０１５～０．２０が特に好ましい。
The ratio between the number of moles of element (C) and the number of moles of magnesium (D) contained in the catalyst, that is, the molar element ratio (element (C)/magnesium (D)) is preferably 0.005 to 8.00, 0.010 to 1.00 is more preferred, 0.010 to 0.60 is more preferred, 0.010 to 0.50 is even more preferred, and 0.01 to 0.40 is particularly preferred.
When the catalyst contains samarium as the element (C), the ratio between the number of moles of samarium and the number of moles of magnesium (D) (samarium/magnesium (D)) is preferably 0.005 to 8.00. 0.010 to 1.00 is more preferred, 0.010 to 0.60 is more preferred, 0.010 to 0.50 is more preferred, 0.01 to 0.40 is more preferred, and 0.010 to 0.01 is more preferred. 25 is more preferred, 0.013 to 0.22 is even more preferred, and 0.015 to 0.20 is particularly preferred.
触媒に含まれる元素（Ａ）～（Ｄ）のそれぞれ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）及び元素（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、以下の範囲であることが好ましい。
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さらに好ましく、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％及び元素（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 respective amounts of the elements (A) to (D) contained in the catalyst is calculated by converting all the elements (A) as single metals, and oxidizing the elements (B), the elements (C) and the elements (D). The following range is preferable when converted as a substance and calculated so that the sum of them is 100% by mass.
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 magnesium (D) is 2% by mass to A combination of 76% by mass is preferred, with 30% to 50% by mass of element (A), 3% to 7% by mass of element (B), 2% to 35% by mass of element (C), 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. % to 30% by mass and magnesium (D) is more preferably 13% to 65% by mass, element (A) is 35% to 50% by mass, and element (B) is 4% to 7% by mass. , A combination in which the element (C) is 2% by mass to 30% by mass and magnesium (D) is 13% by mass to 59% by mass is more preferable, the element (A) is 35% by mass to 45% by mass, and the element (B) is 4% to 6% by weight, element (C) is 2% to 30% by weight and element (D) is 19% to 59% by weight.
触媒が元素（Ｃ）としてサマリウムを含む場合には、触媒に含まれる元素（Ａ）と元素（Ｂ）と元素（Ｃ）と元素（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）及び元素（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。 When the catalyst contains samarium as the element (C), the combination of the amounts of the element (A), the element (B), the element (C) and the element (D) contained in the catalyst is equal to all the elements (A) is converted into a single metal, the element (B), the element (C) and the element (D) are all converted into oxides, and the total is 100% by mass. .
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％及び元素（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％及び元素（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％及び元素（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％及び元素（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％及び元素（Ｄ）が２３質量％～５６質量％である組み合わせがさらに好ましく、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％及び元素（Ｄ）が２９質量％～５６質量％である組み合わせが特に好ましい。 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 element (D) is 2% by mass to A combination of 76% by mass is preferred, with 30% to 50% by mass of element (A), 3% to 7% by mass of element (B), 2% to 35% by mass of element (C) and element ( 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. % to 30% by mass and 13% to 65% by mass of element (D) is more preferable, with 30% to 50% by mass of element (A) and 3% to 7% by mass of element (B). , A combination in which the element (C) is 2% by mass to 25% by mass and 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. % to 7% by mass, 3% to 20% by mass of element (C) and 23% to 64% by mass of element (D), and 35% to 50% by mass of element (A). , A 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 element (D) is 23% by mass to 56% by mass is more preferable, and the element (A) is 35% to 45% by mass, element (B) is 4% to 6% by mass, element (C) is 5% to 20% by mass, and element (D) is 29% to 56% by mass. is particularly preferred.
触媒中の各元素の量は、各元素を含む原料の質量から計算して求めることもできるが、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 in the catalyst can be determined by calculating from the mass of the raw material containing each element. It can also be measured by a known method such as (XRF).
＜水素の製造方法＞
本開示の方法で製造される触媒は、水素の製造に用いられる。具体的には、アンモニアを含有する原料ガスと触媒とを接触させると起こるアンモニア分解反応を利用して水素が製造される。以下、触媒を用いた水素の製造方法について説明する。
<Method for producing hydrogen>
The catalyst produced by the method of the present disclosure is used for hydrogen production. Specifically, hydrogen is produced using an ammonia decomposition reaction that occurs when a source gas containing ammonia is brought into contact with a catalyst. A method for producing hydrogen using a catalyst will be described below.
〔原料ガス〕
アンモニアを含む原料ガスは特に制限されず、アンモニアのみを含んでいても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は特に制限されず、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さらに好ましく、９０体積％～１００体積％の範囲内であることが特に好ましい。
原料ガスがアンモニア以外の成分を含む場合、アンモニア以外の成分として具体的には、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、ヘリウム、窒素及びアルゴンが好ましい。
[Raw material gas]
The raw material gas containing ammonia is not particularly limited, and may contain only ammonia or components other than ammonia.
The ammonia concentration in the raw material gas is not particularly limited, and is preferably in the range of 1% by volume to 100% by volume, more preferably in the range of 20% by volume to 100% by volume, and 50% by volume to 100% by volume. It is more preferably within the range of vol%, and particularly preferably within the range of 90% to 100% by volume.
When the source gas contains a component other than ammonia, specific examples of the component other than ammonia include helium, nitrogen, argon, water vapor, carbon dioxide, carbon monoxide, hydrogen, and hydrocarbons. Among them, helium, nitrogen and argon are preferred.
〔反応様式〕
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観点からは、固定床式が好適である。
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、具体的に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。
反応器を加熱する方法は特に制限されず、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。
触媒は、反応器内で触媒層を形成していることが好ましい。
[Reaction mode]
The reaction mode for carrying out the hydrogen production method is not particularly limited, such as a fixed bed type, a fluidized bed type, a moving bed type, etc., but the equipment can be simplified, the space can be saved, and the equipment cost can be reduced. From a practical point of view, the fixed bed type is preferable.
As the fixed bed type reactor, any known type of reactor can be used, and specific examples include a catalyst packed bed reactor, a catalyst membrane reactor, and the like.
The method of heating the reactor is not particularly limited, and any known method such as heating with an electric heater, heating with a burner, or heating with a heating medium such as kerosene or molten salt can be used.
The catalyst preferably forms a catalyst layer within the reactor.
反応器に供給される原料ガスは、特に制限されない。例えば、精製ガスを用いてもよく、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. For example, a purified gas may be used, or a product gas from a process that produces ammonia, such as an ammonia synthesis plant by the Haber-Bosch process, an organic waste treatment plant containing ammonia in exhaust gas, etc., may be used directly.
〔反応条件〕
触媒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際の反応条件は、特に制限されない。例えば、以下の条件で行ってもよい。
[Reaction conditions]
There are no particular restrictions on the reaction conditions when bringing the ammonia-containing source gas into contact with the catalyst to cause the ammonia decomposition reaction. For example, it may be carried out under the following conditions.
（反応温度）
触媒に原料ガスを接触させる際の反応温度（触媒の温度）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。
触媒が反応器内で触媒層を形成している場合、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 reaction temperature (catalyst temperature) when the raw material gas is brought into contact with the catalyst 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 It is particularly preferred to be in the range of 800°C.
When the catalyst forms a catalyst layer in the reactor, the temperature of the catalyst layer preferably satisfies the above range.
（反応ガス）
アンモニア分解反応は、原料ガスのみを触媒に接触させて生じさせてもよいが、必要に応じて、その他のガス（反応ガス）とともに触媒に接触させてもよい。反応ガスとしては、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。
(Reactive gas)
The ammonia decomposition reaction may be caused by bringing only the raw material gas into contact with the catalyst, but if necessary, it may be brought into contact with the catalyst together with other gases (reactant gas). Reactive gases include, but are not limited to, nitrogen, argon, helium, hydrogen, carbon monoxide, water vapor, and the like.
（反応圧力）
反応器内の原料ガス（反応ガスを併用する場合はこれらの混合ガス）の圧力は、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さらに好ましい。
反応器内の原料ガス（反応ガスを併用する場合はこれらの混合ガス）の全圧は、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さらに好ましい。
(reaction pressure)
The pressure of the raw material gas (the mixed gas when the reaction gas is used together) 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, as ammonia partial pressure. and more preferably within the range of 0.05 MPa to 0.2 MPa.
The total pressure of the source gas in the reactor (the mixed gas when the reaction gas is used together) is preferably within the range of 0.001 MPa to 3 MPa, and preferably within the range of 0.05 MPa to 1 MPa. More preferably, it is in the range of 0.05 MPa to 0.2 MPa.
（接触時間）
原料ガスと触媒とを接触させる時間は特に制限されないが、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 time for contacting the raw material gas with the catalyst is not particularly limited, but the weight hourly space velocity (SV) per catalyst mass defined by the following formula (1) is 1000 [Ncc/g/h] to 100000 [Ncc/g/h]. h], and more preferably 3000 [Ncc/g/h] to 100000 [Ncc/g/h]. The raw material supply amount is expressed as the volume (Ncc) of ammonia gas in standard conditions supplied per unit time.
(SV [Ncc/g/h])=(raw material supply amount [Ncc/h])/(catalyst mass [g]) Equation (1)
〔生成物〕
アンモニア分解反応の結果得られる生成物は水素を含むものであれば特に制限されず、水素のみからなっていても水素と水素以外の成分とを含んでいてもよい。
生成物中の水素濃度は特に制限されないが、一般的なアンモニア分解反応ではアンモニア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。
生成物はアンモニアを含んでいてもよい。この場合、生成物中のアンモニア含有量は、生成物全体の８０体積％以下であることが好ましく、５０体積％以下であることがより好ましく、１０体積％以下であることがさらに好ましい。
[Product]
The product obtained as a result of the ammonia decomposition reaction is not particularly limited as long as it contains hydrogen, and may consist of only hydrogen or may contain hydrogen and components other than hydrogen.
The concentration of hydrogen in the product is not particularly limited, but in a general ammonia decomposition reaction, 3 molecules of hydrogen and 1 molecule of nitrogen are produced from 2 molecules of ammonia, so if the source gas does not contain nitrogen and hydrogen, It can be generally said that the product contains nitrogen and hydrogen in a volume ratio of 1:3.
The product may contain ammonia. In this case, the content of ammonia in the product is preferably 80% by volume or less, more preferably 50% by volume or less, and even more preferably 10% by volume or less of the entire product.
以下、実施例によって本発明をさら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。 The present invention will be described in more detail below with reference to Examples, but the present invention is not limited in any way by these Examples. In addition, "%" represents "% by mass" unless otherwise specified. Further, regarding the compounds shown below, it is assumed that the source of acquisition is the same as long as the compounds are the same.
＜触媒の調製＞
［実施例１］
１５．７ｇの無水炭酸ナトリウム（富士フイルム和光純薬株式会社製）を蒸留水に溶解して、炭酸ナトリウム水溶液を調製した。また、０．５１ｇの硝酸バリウム（富士フイルム和光純薬株式会社製）、１１．９ｇの硝酸ニッケル六水和物（富士フイルム和光純薬株式会社製）、１．６８ｇの硝酸サマリウム六水和物（富士フイルム和光純薬株式会社製）及び１６．８ｇの硝酸マグネシウム六水和物（富士フイルム和光純薬株式会社製）を蒸留水に溶解して、成分（Ａ）～（Ｄ）を含む化合物の硝酸塩水溶液を別途調製した。
<Preparation of catalyst>
[Example 1]
An aqueous sodium carbonate solution was prepared by dissolving 15.7 g of anhydrous sodium carbonate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) in distilled water. Also, 0.51 g of barium nitrate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 11.9 g of nickel nitrate hexahydrate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 1.68 g of samarium nitrate hexahydrate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) and 16.8 g of magnesium nitrate hexahydrate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) are dissolved in distilled water to form a compound containing components (A) to (D). was prepared separately.
次に、炭酸ナトリウム水溶液を加熱して５５℃として激しく撹拌しながら、硝酸塩水溶液を添加して、固体状成分を生成させた。前記固体状生成物を含む懸濁液を５５℃で３０分撹拌し、熟成させた。その後、ろ過して、得られた固形成分を蒸留水で洗浄して、空気下１２０℃で１５時間乾燥した。乾燥させた固形成分を空気下６００℃で５時間焼成を行い、５％ＢａＯ－Ｎｉ－Ｓｍ２Ｏ３－ＭｇＯの組成からなる触媒を調製した。得られた触媒の収量は６．０６ｇであった。 Next, the aqueous sodium carbonate solution was heated to 55° C. with vigorous stirring while the aqueous nitrate solution was added to form a solid component. The suspension containing the solid product was stirred at 55° C. for 30 minutes and aged. Then, it was filtered, and the resulting solid component was washed with distilled water and dried in the air at 120° C. for 15 hours. The dried solid component was calcined in air at 600° C. for 5 hours to prepare a catalyst having a composition of 5% BaO—Ni—Sm 2 O 3 —MgO. The yield of catalyst obtained was 6.06 g.
触媒の組成をＢａＣＯ３／ＮｉＯ／Ｓｍ２Ｏ３／ＭｇＯと仮定して、用いた原料の量から算出した理論収量を以下の式を用いて算出したところ、６．７４ｇとなった。
理論収量（ｇ）＝（硝酸バリウムの量／硝酸バリウムの式量×炭酸バリウムの式量＋硝酸ニッケル六水和物の量／硝酸ニッケル六水和物の式量×酸化ニッケルの式量＋硝酸サマリウム六水和物の量／硝酸サマリウム六水和物の式量×酸化サマリウムの式量／２＋硝酸マグネシウム六水和物の量／硝酸マグネシウム六水和物の式量×酸化マグネシウムの式量）
Assuming that the composition of the catalyst is BaCO 3 /NiO/Sm 2 O 3 /MgO, the theoretical yield calculated from the amounts of raw materials used was 6.74 g as calculated using the following formula.
Theoretical yield (g) = (amount of barium nitrate / formula weight of barium nitrate × formula weight of barium carbonate + amount of nickel nitrate hexahydrate / formula weight of nickel nitrate hexahydrate × formula weight of nickel oxide + nitric acid Amount of samarium hexahydrate / formula weight of samarium nitrate hexahydrate × formula weight of samarium oxide / 2 + amount of magnesium nitrate hexahydrate / formula weight of magnesium nitrate hexahydrate × formula weight of magnesium oxide)
触媒の収率を以下の式で算出したところ、８９．９％であった。
触媒の収率（％）＝触媒の収量／理論収量×１００
When the yield of the catalyst was calculated by the following formula, it was 89.9%.
Catalyst Yield (%) = Catalyst Yield/Theoretical Yield x 100
［実施例２］
炭酸ナトリウム水溶液を加熱して７０℃とした後、硝酸塩水溶液を添加して固体状成分を生成させ、懸濁液を７０℃で３０分撹拌し、熟成させたこと以外は実施例１と同様にして、５％ＢａＯ－Ｎｉ－Ｓｍ２Ｏ３－ＭｇＯの組成からなる触媒を調製した。触媒の収量は６．６７ｇであった。算出した理論収量は６．７４ｇであり、触媒の収率は９９．０％であった。
[Example 2]
The same as Example 1 except that the aqueous sodium carbonate solution was heated to 70° C., then the aqueous nitrate solution was added to form a solid component, and the suspension was stirred at 70° C. for 30 minutes and aged. A catalyst having a composition of 5% BaO--Ni--Sm 2 O 3 --MgO was prepared. The yield of catalyst was 6.67 g. The calculated theoretical yield was 6.74 g and the catalyst yield was 99.0%.
［実施例３］
炭酸ナトリウム水溶液を加熱して８０℃とした後、硝酸塩水溶液を添加して固体状成分を生成させ、懸濁液を８０℃で３０分撹拌し、熟成させたこと以外は実施例１と同様にして、５％ＢａＯ－Ｎｉ－Ｓｍ２Ｏ３－ＭｇＯの組成からなる触媒を調製した。触媒の収量は６．５９ｇであった。理論収量は６．７４ｇであり、触媒の収率は９７．８％であった。
[Example 3]
The same as Example 1 except that the aqueous sodium carbonate solution was heated to 80° C., then the aqueous nitrate solution was added to form a solid component, and the suspension was stirred at 80° C. for 30 minutes and aged. A catalyst having a composition of 5% BaO--Ni--Sm 2 O 3 --MgO was prepared. The yield of catalyst was 6.59 g. The theoretical yield was 6.74 g and the catalyst yield was 97.8%.
［実施例４］
無水炭酸ナトリウムの量を１８．１ｇに変えて得た炭酸ナトリウム水溶液を激しく撹拌しながら、室温（２５℃付近、以下同じ）で硝酸塩水溶液を添加して、固体状成分を生成させ、懸濁液を加熱して８０℃とした。その後３０分撹拌し、熟成させた。それ以外は実施例１と同様にして、５％ＢａＯ－Ｎｉ－Ｓｍ２Ｏ３－ＭｇＯの組成からなる触媒を調製した。触媒の収量は６．０３ｇであった。理論収量は６．７４ｇであり、触媒の収率は８９．５％であった。
[Example 4]
While vigorously stirring an aqueous sodium carbonate solution obtained by changing the amount of anhydrous sodium carbonate to 18.1 g, an aqueous nitrate solution is added at room temperature (approximately 25° C., hereinafter the same) to form a solid component and form a suspension. was heated to 80°C. After that, the mixture was stirred for 30 minutes and aged. A catalyst having a composition of 5% BaO-Ni-Sm 2 O 3 -MgO was prepared in the same manner as in Example 1 except for the above. The yield of catalyst was 6.03 g. The theoretical yield was 6.74 g and the catalyst yield was 89.5%.
［比較例１］
７．８６ｇの無水炭酸ナトリウムを蒸留水に溶解して炭酸ナトリウム水溶液を調製した。また、０．２６ｇの硝酸バリウム、５．９４ｇの硝酸ニッケル六水和物、０．８４ｇの硝酸サマリウム六水和物及び８．４０ｇの硝酸マグネシウム六水和物を蒸留水に溶解して硝酸塩水溶液を別途調製した。
[Comparative Example 1]
An aqueous sodium carbonate solution was prepared by dissolving 7.86 g of anhydrous sodium carbonate in distilled water. Also, 0.26 g of barium nitrate, 5.94 g of nickel nitrate hexahydrate, 0.84 g of samarium nitrate hexahydrate and 8.40 g of magnesium nitrate hexahydrate were dissolved in distilled water to prepare an aqueous nitrate solution. was prepared separately.
次に、炭酸ナトリウム水溶液を激しく撹拌しながら、室温で硝酸塩水溶液を添加して、固体状成分を生成させた。前記固体状生成物を含む懸濁液を室温で３０分撹拌し、熟成させた。それ以外は実施例１と同様にして、５％ＢａＯ－Ｎｉ－Ｓｍ２Ｏ３－ＭｇＯの組成からなる触媒を調製した。触媒の収量は２．７５ｇであった。理論収量は３．３７ｇであり、触媒の収率は８１．６％であった。 Next, while vigorously stirring the aqueous sodium carbonate solution, an aqueous nitrate solution was added at room temperature to form a solid component. The suspension containing the solid product was stirred at room temperature for 30 minutes and aged. A catalyst having a composition of 5% BaO-Ni-Sm 2 O 3 -MgO was prepared in the same manner as in Example 1 except for the above. The yield of catalyst was 2.75 g. The theoretical yield was 3.37 g and the catalyst yield was 81.6%.
［比較例２］
無水炭酸ナトリウムの量を２４．２ｇ、硝酸バリウムの量を０．５１ｇ、硝酸ニッケル六水和物の量を１１．９ｇ、硝酸サマリウム六水和物の量を１．６８ｇ、及び硝酸マグネシウム六水和物の量を１６．８ｇにそれぞれ変えたこと以外は比較例１と同様にして、５％ＢａＯ－Ｎｉ－Ｓｍ２Ｏ３－ＭｇＯの組成からなる触媒を調製した。触媒の収量は５．４１ｇであった。理論収量は６．７４ｇであり、触媒の収率は８０．２％であった。
[Comparative Example 2]
24.2 g of anhydrous sodium carbonate, 0.51 g of barium nitrate, 11.9 g of nickel nitrate hexahydrate, 1.68 g of samarium nitrate hexahydrate, and magnesium nitrate hexahydrate. A catalyst having a composition of 5% BaO--Ni--Sm 2 O 3 --MgO was prepared in the same manner as in Comparative Example 1, except that the amount of the solute was changed to 16.8 g. The yield of catalyst was 5.41 g. The theoretical yield was 6.74 g and the catalyst yield was 80.2%.
［比較例３］
無水炭酸ナトリウムの量を４８．３ｇに変えたこと以外は比較例２と同様にして、５％ＢａＯ－Ｎｉ－Ｓｍ２Ｏ３－ＭｇＯの組成からなる触媒を調製した。触媒の収量は５．７８ｇであった。理論収量は６．７４ｇであり、触媒の収率は８５．８％であった。
[Comparative Example 3]
A catalyst having a composition of 5% BaO--Ni--Sm 2 O 3 --MgO was prepared in the same manner as in Comparative Example 2, except that the amount of anhydrous sodium carbonate was changed to 48.3 g. The yield of catalyst was 5.78 g. The theoretical yield was 6.74 g and the catalyst yield was 85.8%.
［比較例４］
無水炭酸ナトリウムの量を９．０６ｇに変え、懸濁液の撹拌時間を３０分から２４時間に変えたこと以外は比較例１と同様にして、５％ＢａＯ－Ｎｉ－Ｓｍ２Ｏ３－ＭｇＯの組成からなる触媒を調製した。触媒の収量は２．７８ｇであった。理論収量は３．３７ｇであり、触媒の収率は８２．５％であった。
[Comparative Example 4]
5% BaO—Ni—Sm 2 O 3 —MgO was prepared in the same manner as in Comparative Example 1 except that the amount of anhydrous sodium carbonate was changed to 9.06 g and the suspension stirring time was changed from 30 minutes to 24 hours. A catalyst of the composition was prepared. The yield of catalyst was 2.78 g. The theoretical yield was 3.37 g and the catalyst yield was 82.5%.
実施例１～４及び比較例１～４において固体状成分を生成したときの温度、撹拌時間、炭酸イオン／硝酸イオンのモル比、撹拌終了後の固体状成分を含む懸濁液のｐＨ、理論収量、触媒の収量、及び触媒の収率を下記表１にまとめた。 In Examples 1 to 4 and Comparative Examples 1 to 4, the temperature, stirring time, molar ratio of carbonate ions/nitrate ions, pH of the suspension containing the solid components after stirring, theoretical The yield, catalyst yield, and catalyst yield are summarized in Table 1 below.
表１から明らかなように、実施例１～４におけるいずれの触媒の収率も、比較例１～４における触媒の収率より高く、固体状生成物を生じるときの温度を５０℃～９５℃とすることは触媒の収率の向上に効果があることが示された。 As is clear from Table 1, the yields of any of the catalysts in Examples 1-4 are higher than those of the catalysts in Comparative Examples 1-4, and the temperature at which solid products are produced is 50°C to 95°C. It was shown that it is effective in improving the yield of the catalyst.
特に、実施例１～３と比較例１の触媒の収率を比較すると、炭酸イオン／硝酸イオンのモル比を０．６５に統一したときに、固体状成分生成時の温度を５５℃、７０℃、８０℃としたときの方が、室温としたときよりも触媒の収率が向上することがわかる。 In particular, when comparing the yields of the catalysts of Examples 1 to 3 and Comparative Example 1, when the molar ratio of carbonate ions/nitrate ions was unified at 0.65, the temperature at which the solid components were produced was 55°C and 70°C. C. and 80.degree. C. improve the yield of the catalyst more than room temperature.
また、実施例１と比較例１～３の触媒の収率を比較すると、炭酸イオン／硝酸イオンのモル比を０．６５～２として、撹拌終了時の懸濁液のｐＨを高めても、固体状成分生成時の温度が室温である場合は触媒の収率を向上させる効果は小さいが、固体状成分生成時の温度を５５℃に高めた方が触媒の収率が向上し、固体状成分生成時の温度を室温よりも高くすることが触媒の収率を向上させる効果があることがわかる。 Further, when comparing the catalyst yields of Example 1 and Comparative Examples 1 to 3, even if the molar ratio of carbonate ions/nitrate ions is set to 0.65 to 2 and the pH of the suspension at the end of stirring is increased, When the temperature at which the solid component is produced is room temperature, the effect of improving the yield of the catalyst is small. It can be seen that raising the temperature at the time of component production above room temperature has the effect of improving the yield of the catalyst.
また、実施例４と比較例１、４の触媒の収率の比較から、固体状成分生成時の温度が室温では撹拌時間を３０分から２４時間に延ばしても触媒の収率を向上させる効果は小さいが、室温で固体状成分を生成させてから温度を上げると、さらに固体状成分が生成して触媒の収率が向上することがわかる。 Further, from the comparison of the catalyst yields of Example 4 and Comparative Examples 1 and 4, when the temperature at which the solid component was generated was room temperature, even if the stirring time was extended from 30 minutes to 24 hours, the effect of improving the yield of the catalyst was not observed. Although it is small, it can be seen that when the temperature is raised after the solid component is produced at room temperature, the solid component is further produced and the yield of the catalyst is improved.
＜触媒組成の検討＞
実施例２と比較例１で調製した触媒を誘導結合プラズマ原子発光法（ＩＣＰ－ＡＥＳ）で分析し、触媒に含まれるＮｉのモル数に対するＢａ、Ｓｍ、Ｍｇのそれぞれのモル数の比（Ｎｉ／Ｎｉ、Ｂａ／Ｎｉ、Ｓｍ／Ｎｉ、Ｍｇ／Ｎｉ）を算出した結果を表２にまとめた。ここで、理論値とは、触媒を調製するときに用いた原料の質量から算出したモル数の比である。
<Study of catalyst composition>
The catalysts prepared in Example 2 and Comparative Example 1 were analyzed by inductively coupled plasma atomic emission spectroscopy (ICP-AES), and the ratio of the number of moles of Ba, Sm, and Mg to the number of moles of Ni contained in the catalyst (Ni /Ni, Ba/Ni, Sm/Ni, Mg/Ni) are summarized in Table 2. Here, the theoretical value is the ratio of the number of moles calculated from the mass of raw materials used when preparing the catalyst.
表２から明らかなように、実施例２と比較例１のＢａ／Ｎｉ、Ｓｍ／Ｎｉ、Ｍｇ／Ｎｉの値をそれぞれの理論値と比較すると、実施例２はいずれも理論値と同等であって各元素が固体状生成物として充分に析出したことがわかる。一方、比較例１ではＢａ／Ｎｉ、Ｓｍ／Ｎｉは理論値と同等であるが、Ｍｇ／Ｎｉの値が小さく、マグネシウム成分が固体状生成物に不足していることがわかる。 As is clear from Table 2, when the Ba/Ni, Sm/Ni, and Mg/Ni values of Example 2 and Comparative Example 1 are compared with their respective theoretical values, Example 2 is equivalent to the theoretical values. It can be seen that each element was sufficiently precipitated as a solid product. On the other hand, in Comparative Example 1, the Ba/Ni and Sm/Ni values are equivalent to the theoretical values, but the Mg/Ni value is small, indicating that the magnesium component is insufficient in the solid product.
以上の結果は、固体状成分を生じるときの温度を５０℃～９５℃とすることは触媒に含まれるマグネシウム量を増大させ、これが触媒の収率の向上に寄与することを示唆している。その理由は、下記のように考えられる。 The above results suggest that setting the temperature at which the solid component is produced to 50° C. to 95° C. increases the amount of magnesium contained in the catalyst, which contributes to the improvement of the yield of the catalyst. The reason is considered as follows.
固体状成分を生成させる工程において、バリウム、ニッケル、サマリウム、マグネシウムをそれぞれ含む成分が均一に微分散した粒子を形成し、粒子の成長により溶媒である水に難溶性の固体状成分を生成する。室温ではこの粒子の成長が遅く、特にマグネシウムを含む成分は、粒子に取り込まれて難溶性の安定な粒子を形成し終える前に水に再度溶解してしまうと考えられる。固体状成分が生成するときの温度を５０℃～９５℃としたときは、（１）粒子の成長が速いこと、（２）そのため、水に比較的溶解し難いバリウム、ニッケル、サマリウムをそれぞれ含む成分によってマグネシウムを含む成分が覆われること、等の理由によりマグネシウムの水への溶解が抑制され、触媒の収率が向上したと考えられる。 In the step of producing the solid component, particles are formed in which the components containing barium, nickel, samarium, and magnesium are uniformly finely dispersed, and the growth of the particles produces a solid component that is sparingly soluble in the solvent, water. At room temperature, the growth of the particles is slow, and it is believed that the magnesium-containing component in particular dissolves again in water before it has been incorporated into the particles to form stable, sparingly soluble particles. When the temperature at which the solid component is generated is 50° C. to 95° C., (1) the growth of particles is rapid, and (2) it contains barium, nickel, and samarium, which are relatively difficult to dissolve in water. It is thought that the dissolution of magnesium in water was suppressed because the component containing magnesium was covered with the component, and the yield of the catalyst was improved.
＜アンモニア分解活性の評価＞
［実施例５］
実施例１で調製した触媒について、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、０．３０ｇの触媒を反応管に充填し、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時間流通させて還元処理を行った。還元処理後、流通ガスを１００体積％アルゴンに切り替え、５００℃に降温して、触媒層の温度を５００℃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、５Ｎｃｃ／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。アンモニア分解率を以下の式を用いて算出したところ、９８．４％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
<Evaluation of ammonia decomposition activity>
[Example 5]
The catalyst prepared in Example 1 was subjected to an ammonia decomposition reaction using a fixed bed flow reactor, and the ammonia decomposition activity was evaluated.
Specifically, 0.30 g of catalyst was filled in a reaction tube and heated to 600° C. under argon flow. Next, while 50% by volume hydrogen diluted with argon was passed through the reaction tube at a flow rate of 50 Ncc/min, the temperature of the catalyst layer was 600° C. and the total pressure was 0.10 MPa for 2 hours to perform reduction treatment. After the reduction treatment, the circulating gas was switched to 100% by volume argon, the temperature was lowered to 500° C., the temperature of the catalyst layer was set to 500° C., and the total pressure was 0.10 MPa, and the circulating gas was switched to 100% by volume ammonia gas at 5 Ncc/min. was passed through the reaction tube for 20 minutes at a flow rate of , and the ammonia decomposition reaction was carried out. When the ammonia decomposition rate was calculated using the following formula, it was 98.4%.
Ammonia decomposition rate (%) = (hydrogen generation amount + nitrogen generation amount) / (2 x ammonia supply amount) x 100
［実施例６］
触媒として、実施例２で調製した触媒を用いたこと以外は実施例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、５００℃で９８．８％となった。
[Example 6]
Ammonia decomposition activity was evaluated in the same manner as in Example 1, except that the catalyst prepared in Example 2 was used as the catalyst. The ammonia decomposition rate was 98.8% at 500°C.
［実施例７］
触媒として、実施例３で調製した触媒を用いたこと以外は実施例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、５００℃で９８．８％となった。
[Example 7]
Ammonia decomposition activity was evaluated in the same manner as in Example 1, except that the catalyst prepared in Example 3 was used as the catalyst. The ammonia decomposition rate was 98.8% at 500°C.
［実施例８］
触媒として、実施例４で調製した触媒を用いたこと以外は実施例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、５００℃で９８．０％となった。
[Example 8]
Ammonia decomposition activity was evaluated in the same manner as in Example 1, except that the catalyst prepared in Example 4 was used as the catalyst. The ammonia decomposition rate was 98.0% at 500°C.
［比較例５］
触媒として、比較例１で調製した触媒を用いたこと以外は実施例５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、５００℃で９８．１％となった。
[Comparative Example 5]
Ammonia decomposition activity was evaluated in the same manner as in Example 5 except that the catalyst prepared in Comparative Example 1 was used as the catalyst. The ammonia decomposition rate was 98.1% at 500°C.
［比較例６］
触媒として、比較例２で調製した触媒を用いたこと以外は実施例５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、５００℃で９８．０％となった。
[Comparative Example 6]
Ammonia decomposition activity was evaluated in the same manner as in Example 5, except that the catalyst prepared in Comparative Example 2 was used as the catalyst. The ammonia decomposition rate was 98.0% at 500°C.
［比較例７］
触媒として、比較例３で調製した触媒を用いたこと以外は実施例５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、５００℃で９８．７％となった。
[Comparative Example 7]
Ammonia decomposition activity was evaluated in the same manner as in Example 5, except that the catalyst prepared in Comparative Example 3 was used as the catalyst. The ammonia decomposition rate was 98.7% at 500°C.
実施例１～４で得た触媒を用いた実施例５～８のアンモニア分解率は、比較例１～３で得た触媒を用いた比較例５～７のアンモニア分解率と同等であり、同等のアンモニア分解活性が示された。
以上の結果から、本発明の触媒の製造方法によればアンモニア分解活性の良好な触媒を高い収率で得られることがわかった。
The ammonia decomposition rates of Examples 5-8 using the catalysts obtained in Examples 1-4 are equivalent to the ammonia decomposition rates of Comparative Examples 5-7 using the catalysts obtained in Comparative Examples 1-3. was shown to decompose ammonia.
From the above results, it was found that a catalyst having good ammonia decomposition activity can be obtained at a high yield according to the method for producing a catalyst of the present invention.
Claims (7)
（Ａ）ニッケル、コバルト及び鉄から選ばれる１種以上の元素
（Ｂ）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
（Ｃ）希土類元素から選ばれる１種以上の元素
（Ｄ）マグネシウム A contacting step of contacting the following compound containing element (A), compound containing element (B), compound containing element (C) and compound containing element (D) in water to obtain a solid product. , a method for producing a catalyst for hydrogen production, wherein at least part of the contacting step is performed under conditions of 50°C to 95°C.
(A) one or more elements selected from nickel, cobalt and iron (B) one or more elements selected from strontium and barium (C) one or more elements selected from rare earth elements (D) magnesium
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