JP2013111562A - Composition and method for manufacturing ammonia using the composition - Google Patents
Composition and method for manufacturing ammonia using the composition Download PDFInfo
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- JP2013111562A JP2013111562A JP2011262899A JP2011262899A JP2013111562A JP 2013111562 A JP2013111562 A JP 2013111562A JP 2011262899 A JP2011262899 A JP 2011262899A JP 2011262899 A JP2011262899 A JP 2011262899A JP 2013111562 A JP2013111562 A JP 2013111562A
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- Prior art keywords
- ammonia
- ruthenium
- composition
- catalyst
- mass
- Prior art date
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 66
- 239000000203 mixture Substances 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title abstract description 42
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 73
- 239000003054 catalyst Substances 0.000 claims abstract description 65
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 53
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 26
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 23
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
- 239000000956 alloy Substances 0.000 claims abstract description 10
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000011701 zinc Substances 0.000 claims abstract description 7
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 6
- 239000011777 magnesium Substances 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims abstract description 5
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 4
- 239000010941 cobalt Substances 0.000 claims abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 15
- 238000002360 preparation method Methods 0.000 description 35
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000004570 mortar (masonry) Substances 0.000 description 15
- 239000012702 metal oxide precursor Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 150000001340 alkali metals Chemical class 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 229910052783 alkali metal Inorganic materials 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000003446 ligand Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 7
- 239000005297 pyrex Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 5
- -1 lanthanoid sulfide Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 4
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 235000002597 Solanum melongena Nutrition 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 229910052792 caesium Inorganic materials 0.000 description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 238000004255 ion exchange chromatography Methods 0.000 description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 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 2
- 229910052798 chalcogen Inorganic materials 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910001998 lanthanoid nitrate Inorganic materials 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 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 2
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 2
- 150000003304 ruthenium compounds Chemical class 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- 238000009623 Bosch process Methods 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 1
- 239000013148 Cu-BTC MOF Substances 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000013178 MIL-101(Cr) Substances 0.000 description 1
- 239000013206 MIL-53 Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- YAGCJGCCZIARMJ-UHFFFAOYSA-N N1C(=NC=C1)C=O.[Zn] Chemical compound N1C(=NC=C1)C=O.[Zn] YAGCJGCCZIARMJ-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910002828 Pr(NO3)3·6H2O Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000013115 Zn-MOF-74 Substances 0.000 description 1
- PEIRNXHGNGIASB-UHFFFAOYSA-K [Ru](OC#N)(OC#N)OC#N.[K] Chemical compound [Ru](OC#N)(OC#N)OC#N.[K] PEIRNXHGNGIASB-UHFFFAOYSA-K 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 1
- 229910001964 alkaline earth metal nitrate Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 150000001787 chalcogens Chemical class 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- KFIKNZBXPKXFTA-UHFFFAOYSA-N dipotassium;dioxido(dioxo)ruthenium Chemical compound [K+].[K+].[O-][Ru]([O-])(=O)=O KFIKNZBXPKXFTA-UHFFFAOYSA-N 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- VMDTXBZDEOAFQF-UHFFFAOYSA-N formaldehyde;ruthenium Chemical compound [Ru].O=C VMDTXBZDEOAFQF-UHFFFAOYSA-N 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002601 lanthanoid compounds Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- FGHSTPNOXKDLKU-UHFFFAOYSA-N nitric acid;hydrate Chemical compound O.O[N+]([O-])=O FGHSTPNOXKDLKU-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 1
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
Description
本発明は窒素と水素からアンモニアを合成するのに適した組成物及び該組成物を用いたアンモニア製造方法に関するものである。 The present invention relates to a composition suitable for synthesizing ammonia from nitrogen and hydrogen, and an ammonia production method using the composition.
アンモニアは、長きにわたり、鉄系触媒を用いたハーバーボッシュ法により製造されてきた。しかしながらハーバーボッシュ法では、１５０気圧程度の高圧下で反応を行う必要があるため、設備投資及び消費電力の増大、製造工程の煩雑化等の問題を有する。 Ammonia has long been produced by the Harbor Bosch process using an iron-based catalyst. However, since the Harbor Bosch method requires the reaction to be performed under a high pressure of about 150 atm, it has problems such as equipment investment, increased power consumption, and complicated manufacturing processes.
上記問題に対して、近年では、ルテニウム触媒を用いて１０気圧程度の低圧条件下でアンモニアを製造する方法が報告されている。この触媒を用いることにより、低圧条件下でアンモニアが製造可能となるのみならず、一酸化炭素や水によるアンモニア合成阻害を低減することも可能となり、アンモニア収率が向上する（非特許文献１〜３）。 In recent years, a method for producing ammonia under a low pressure condition of about 10 atm using a ruthenium catalyst has been reported for the above problem. By using this catalyst, not only ammonia can be produced under low pressure conditions, but also ammonia synthesis inhibition by carbon monoxide and water can be reduced, and the ammonia yield is improved (Non-Patent Documents 1 to 3). 3).
ルテニウム触媒を用いるアンモニア製造では、ルテニウム触媒を担体に担持させたる場合がある。ルテニウムを担持させる担体としては、触媒の担体として一般的なアルミナが広く用いられている。最近では、アルミナに替えて希土類酸化物を担体として用いることにより、ルテニウムの使用量を低減でき、且つ、反応温度を低くできることが開示されている（特許文献１）。 In ammonia production using a ruthenium catalyst, the ruthenium catalyst may be supported on a carrier. As a carrier for supporting ruthenium, general alumina is widely used as a catalyst carrier. Recently, it has been disclosed that the amount of ruthenium used can be reduced and the reaction temperature can be lowered by using a rare earth oxide as a support instead of alumina (Patent Document 1).
しかしながら、上記のアンモニア製造方法では、より低圧条件下においてアンモニアを製造する場合のアンモニア収率が十分なものではなかった。 However, in the above ammonia production method, the ammonia yield when producing ammonia under a lower pressure condition is not sufficient.
本発明は、上記課題に鑑みてなされたものであって、低圧条件下において高収率でアンモニアを製造できる組成物、及び該組成物を用いたアンモニア製造方法を提供することを課題とする。 This invention is made | formed in view of the said subject, Comprising: It aims at providing the composition which can manufacture ammonia by a high yield under low-pressure conditions, and the ammonia manufacturing method using this composition.
本発明では以下の［１］〜［４］の組成物及び［５］のアンモニア製造方法を提供する。
［１］（１）ルテニウム、ルテニウムを含む合金又はルテニウムを含む化合物、
（２）ランタノイドを含む化合物、並びに、
（３）塩基性助触媒及び／又は多孔性金属錯体
を配合した組成物。
［２］前記ランタノイドを含む化合物が、ランタノイド酸化物である［１］に記載の組成物。
［３］前記塩基性助触媒が、アルカリ金属酸化物、アルカリ金属水酸化物、アルカリ土類金属酸化物又はアルカリ土類金属水酸化物である、［１］又は［２］に記載の組成物。
［４］前記多孔性金属錯体が、亜鉛、銅、マグネシウム、アルミニウム、マンガン、鉄、コバルト及びニッケルからなる群から選ばれる少なくとも１種の金属を有する、［１］〜［３］のいずれか一項に記載の組成物。
［５］［１］〜［４］のいずれか一項に記載の組成物を触媒として用い、窒素と水素とを反応させてアンモニアを製造する方法。
In the present invention, the following compositions [1] to [4] and an ammonia production method [5] are provided.
[1] (1) Ruthenium, an alloy containing ruthenium or a compound containing ruthenium,
(2) a compound containing a lanthanoid, and
(3) A composition containing a basic promoter and / or a porous metal complex.
[2] The composition according to [1], wherein the compound containing the lanthanoid is a lanthanoid oxide.
[3] The composition according to [1] or [2], wherein the basic promoter is an alkali metal oxide, an alkali metal hydroxide, an alkaline earth metal oxide, or an alkaline earth metal hydroxide. .
[4] Any one of [1] to [3], wherein the porous metal complex has at least one metal selected from the group consisting of zinc, copper, magnesium, aluminum, manganese, iron, cobalt, and nickel. The composition according to item.
[5] A method for producing ammonia by reacting nitrogen and hydrogen using the composition according to any one of [1] to [4] as a catalyst.
本発明によれば、低圧条件下においても高収率でアンモニアを製造することができる。また、低圧条件下においてアンモニアを製造することができることから、コンプレッサーなどの加圧装置が不要となり、設備投資だけでなく電力消費量を削減することができる。 According to the present invention, ammonia can be produced in high yield even under low pressure conditions. Further, since ammonia can be produced under low pressure conditions, a pressurizing device such as a compressor is not required, and not only capital investment but also power consumption can be reduced.
［組成物］
本発明の第一の態様の組成物は、
（１）ルテニウム、ルテニウムを含む合金又はルテニウムを含む化合物、
（２）ランタノイドを含む化合物、並びに、
（３）塩基性助触媒及び／又は多孔性金属錯体を配合したものである。
当該組成物は、アンモニアの製造において触媒として好適に用いることができる。
以下、各成分を順に説明する。以下、配合成分をそれぞれ、「成分（１）」、「成分（２）」、「成分（３）」という。
[Composition]
The composition of the first aspect of the present invention comprises:
(1) ruthenium, an alloy containing ruthenium or a compound containing ruthenium,
(2) a compound containing a lanthanoid, and
(3) A basic promoter and / or a porous metal complex is blended.
The composition can be suitably used as a catalyst in the production of ammonia.
Hereinafter, each component will be described in order. Hereinafter, the blending components are referred to as “component (1)”, “component (2)”, and “component (3)”, respectively.
（１）ルテニウム、ルテニウムを含む合金又はルテニウムを含む化合物
本発明の組成物において、成分（１）はアンモニア製造における触媒として機能しうる。
成分（１）がルテニウムを含む合金である場合、ルテニウム以外の金属元素としては、ルテニウムと共晶又は固溶体となりうるものであれば特に限定されるものではないが、アンモニア合成反応性を有し、触媒能を向上できることから、鉄、モリブデン及びニッケルからなる群から選ばれる少なくとも1種が好ましく、アンモニア合成に工業的に用いられている点から鉄がより好ましい。
(1) Ruthenium, an alloy containing ruthenium or a compound containing ruthenium In the composition of the present invention, the component (1) can function as a catalyst in ammonia production.
When component (1) is an alloy containing ruthenium, the metal element other than ruthenium is not particularly limited as long as it can be a eutectic or solid solution with ruthenium, but has ammonia synthesis reactivity. At least one selected from the group consisting of iron, molybdenum and nickel is preferable because the catalytic ability can be improved, and iron is more preferable because it is industrially used for ammonia synthesis.
ルテニウムを含む合金は、ルテニウム以外の金属元素を１種のみ含んでいてもよく、２種以上含んでいてもよい。また、ルテニウム及びルテニウム以外の金属元素に加えて、さらに炭素、ケイ素等の非金属元素を含んでいてもよい。 The alloy containing ruthenium may contain only one kind of metal element other than ruthenium, or may contain two or more kinds. Moreover, in addition to ruthenium and metal elements other than ruthenium, nonmetallic elements, such as carbon and silicon, may be included.
成分（１）がルテニウムを含む化合物である場合、該化合物がルテニウム以外に含む配位子としては特に限定されるものではなく、中性配位子であってもイオン性配位子であってもよい。 When component (1) is a compound containing ruthenium, the ligand contained in the compound other than ruthenium is not particularly limited, and even if it is a neutral ligand, it is an ionic ligand. Also good.
ルテニウムを含む化合物として具体的には、塩化ルテニウム、ルテニウムアセチルアセトナート、ルテニウムシアン酸カリウム、ルテニウム酸ナトリウム、ルテニウム酸カリウム、酸化ルテニウム、ドデカカルボニル三ルテニウム、硝酸ルテニウム等が挙げられる。 Specific examples of the compound containing ruthenium include ruthenium chloride, ruthenium acetylacetonate, potassium ruthenium cyanate, sodium ruthenate, potassium ruthenate, ruthenium oxide, dodecacarbonyltriruthenium, and ruthenium nitrate.
成分（１）としては、ルテニウム、ルテニウムを含む合金、ルテニウムを含む化合物のいずれか１種のみを用いてもよく、２種以上を組み合わせて用いてもよい。 As the component (1), only one of ruthenium, an alloy containing ruthenium, and a compound containing ruthenium may be used, or two or more kinds may be used in combination.
成分（１）がルテニウムを含む合金又はルテニウムを含む化合物である場合、該合金又は該化合物中のルテニウムの含有割合は１質量％〜９９質量％であることが好ましく、反応性を確保しやすいことから５０質量％〜９５質量％であることがより好ましい。 When component (1) is an alloy containing ruthenium or a compound containing ruthenium, the content of ruthenium in the alloy or the compound is preferably 1% by mass to 99% by mass, and it is easy to ensure the reactivity. To 50 mass% to 95 mass%.
組成物中の成分（１）の配合割合は、良好な触媒能を奏しうる割合であれば特に限定されるものではないが、０．０１〜１５質量％であることが好ましく、０．１〜１３質量％であることがより好ましく１〜１０質量％であることがさらに好ましい。
また、成分（１）がルテニウムである場合、ルテニウムの配合割合は、０．００５〜１５質量％であることが好ましく、０．０５〜１３質量％であることがより好ましく０．５〜１０質量％であることがさらに好ましい。
The blending ratio of component (1) in the composition is not particularly limited as long as it is a ratio capable of exhibiting good catalytic ability, but is preferably 0.01 to 15% by mass, More preferably, it is 13 mass%, and it is further more preferable that it is 1-10 mass%.
Moreover, when a component (1) is ruthenium, it is preferable that the mixture ratio of ruthenium is 0.005-15 mass%, It is more preferable that it is 0.05-13 mass%, 0.5-10 mass % Is more preferable.
また、成分（１）と後述する成分（２）との合計に対する、成分（１）の配合割合は、０．１〜１５質量％であることが好ましく、１〜１０質量％であることがより好ましい。０．１質量％以上とすることにより良好な触媒活性を得ることができ、１５質量％以下とすることにより触媒活性とコストとのバランスを取ることができる。 Moreover, it is preferable that the mixture ratio of a component (1) with respect to the sum total of a component (1) and the component (2) mentioned later is 0.1-15 mass%, and it is more preferable that it is 1-10 mass%. preferable. By setting it to 0.1% by mass or more, good catalytic activity can be obtained, and by setting it to 15% by mass or less, it is possible to balance catalyst activity and cost.
（２）ランタノイドを含む化合物
本発明の組成物において、成分（２）は前記成分（１）を担持する単体として機能しうる。ランタノイドを含む化合物としては特に限定されるものではなく、１５種のランタノイドのいずれを含む化合物であってもよい。
なかでも、ランタノイドとしてランタン、セリウム、プラセオジム、ネオジム、サマリウム、ガドリニウム、ジスプロシウムのいずれかを含む化合物であることが好ましく、強塩基性であるためルテニウムへの電子供給及びアンモニア合成が良好となることから、ランタン、セリウム、プラセオジムがより好ましい。
(2) Compound containing lanthanoid In the composition of the present invention, component (2) can function as a simple substance carrying component (1). The compound containing a lanthanoid is not particularly limited, and may be a compound containing any of 15 lanthanoids.
Among them, a compound containing any one of lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, and dysprosium is preferable, and since it is strongly basic, electron supply to ruthenium and ammonia synthesis are good. More preferred are lanthanum, cerium and praseodymium.
また、ランタノイドを含む化合物としては、ランタノイド酸化物、ランタノイド硫化物、ランタノイド水酸化物、ランタノイド硫酸塩等のランタノイドと第１６族元素（カルコゲン）とを含む化合物；
ランタノイド塩化物等のランタノイドと第１７族元素（ハロゲン）とを含む化合物等が挙げられ、
成分（１）を良好に担持できることから、ランタノイド酸化物が好ましい。即ち、成分（２）としては、ランタン酸化物、セリウム酸化物又はプラセオジム酸化物が好ましい。
Moreover, as a compound containing a lanthanoid, a compound containing a lanthanoid oxide such as a lanthanoid oxide, a lanthanoid sulfide, a lanthanoid hydroxide, a lanthanoid sulfate, and a group 16 element (chalcogen);
A compound containing a lanthanoid such as a lanthanoid chloride and a group 17 element (halogen), etc.
Since the component (1) can be favorably supported, a lanthanoid oxide is preferable. That is, as the component (2), lanthanum oxide, cerium oxide, or praseodymium oxide is preferable.
成分（２）としては、市販のものを用いてもよく、製造してもよい。ランタノイド酸化物である成分（２）を製造する場合、例えば、アルカリ溶液に市販のランタノイド化合物（ランタノイド硝酸塩、ランタノイド硝酸塩の水和物等）を分散し、沈殿法により固形物を得た後、得られた固形物を焼成することにより製造できる。このようにして得られたランタノイド酸化物は、結晶構造が安定しているため、良好に成分（１）を担持可能となる。 As component (2), a commercially available product may be used, or it may be produced. When the component (2) which is a lanthanoid oxide is produced, for example, a commercially available lanthanoid compound (lanthanoid nitrate, lanthanoid nitrate hydrate, etc.) is dispersed in an alkaline solution, and a solid is obtained by precipitation. It can manufacture by baking the obtained solid substance. Since the lanthanoid oxide thus obtained has a stable crystal structure, the component (1) can be favorably supported.
アルカリ溶液としては５〜５０質量％、より好ましくは１５〜３５質量％のアンモニア水が好ましい。
固形物は、沈殿物をろ過することにより得ることができる。
焼成は、２５０〜９００℃、より好ましくは３００〜７５０℃で行うことができる。また、該焼成前に、焼成より低温での仮焼成を行ってもよい。仮焼成の温度は、２００〜４００℃（但し、焼成より低温）が好ましい。
As an alkaline solution, 5-50 mass%, More preferably, 15-35 mass% ammonia water is preferable.
The solid can be obtained by filtering the precipitate.
Firing can be performed at 250 to 900 ° C, more preferably 300 to 750 ° C. Moreover, you may perform temporary baking at low temperature rather than baking before this baking. The calcination temperature is preferably 200 to 400 ° C. (however, lower temperature than calcination).
組成物中の成分（２）の配合割合は、成分（１）を良好に担持しうる割合であれば特に限定されるものではないが、４０〜９９．９８質量％であることが好ましく、５０〜９９．８質量％であることがより好ましく７０〜９８質量％であることがさらに好ましい。 The blending ratio of component (2) in the composition is not particularly limited as long as it is a ratio that can favorably support component (1), but it is preferably 40 to 99.98% by mass, and 50 More preferably, it is -99.8 mass%, and it is further more preferable that it is 70-98 mass%.
（３）塩基性助触媒及び／又は多孔性金属錯体
本発明の組成物において、成分（３）は、成分（１）による触媒効率を向上させるために用いられるものである。成分（３）としては、塩基性助触媒のみを用いてもよく、多孔性金属錯体のみを用いてもよく、両者を組み合わせて用いてもよい。
(3) Basic promoter and / or porous metal complex In the composition of the present invention, component (3) is used to improve the catalyst efficiency of component (1). As a component (3), only a basic promoter may be used, only a porous metal complex may be used, and both may be used in combination.
本発明において塩基性助触媒とは、電子供与性を有し、且つ、成分（１）と成分（２）と共に用いることにより触媒能を促進しうるものをいう。成分（３）は成分（１）のルテニウムに電子を供与することで反応を促進することができる。 In the present invention, the basic co-catalyst means one having an electron donating property and capable of promoting the catalytic ability when used together with the components (1) and (2). The component (3) can promote the reaction by donating an electron to the ruthenium of the component (1).
塩基性助触媒としては特に限定されるものではないが、
アルカリ金属を含む化合物及びアルカリ土類金属を含む化合物が好ましく、
アルカリ金属酸化物、アルカリ金属水酸化物、アルカリ土類金属酸化物及びアルカリ土類金属水酸化物がより好ましく、
アルカリ金属酸化物及びアルカリ金属水酸化物がより好ましい。
The basic promoter is not particularly limited,
Compounds containing alkali metals and compounds containing alkaline earth metals are preferred,
More preferred are alkali metal oxides, alkali metal hydroxides, alkaline earth metal oxides and alkaline earth metal hydroxides,
Alkali metal oxides and alkali metal hydroxides are more preferred.
アルカリ金属酸化物、アルカリ金属水酸化物、アルカリ土類金属酸化物及びアルカリ土類金属水酸化物の原料として用いることのできる前駆体として具体的には、アルカリ金属及びアルカリ土類金属の硝酸塩、硫酸塩、リン酸塩等が挙げられる。 Specific examples of precursors that can be used as raw materials for alkali metal oxides, alkali metal hydroxides, alkaline earth metal oxides, and alkaline earth metal hydroxides include alkali metal and alkaline earth metal nitrates, Examples thereof include sulfates and phosphates.
アルカリ金属及びアルカリ土類金属としては、リチウム、ナトリウム、カリウム、ルビジウム、セシウム、ベリリウム、マグネシウム、カルシウム、ストロンチウム及びバリウムが好ましく、成分（１）への電子供与性に優れることから、ナトリウム、カリウム、ルビジウム及びセシウムがより好ましく、セシウムが更に好ましい。 As the alkali metal and alkaline earth metal, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, and barium are preferable, and since they have excellent electron donating property to the component (1), sodium, potassium, Rubidium and cesium are more preferable, and cesium is still more preferable.
多孔性金属錯体としては特に限定されるものではなく、担体等の機能性材料として通常用いられるものを適宜選択することができる。成分（３）として多孔性金属錯体を用いることにより、多孔性金属錯体中に取り込まれたガスが、成分（１）による触媒効率を向上させうる。 The porous metal complex is not particularly limited, and those usually used as a functional material such as a carrier can be appropriately selected. By using a porous metal complex as the component (3), the gas taken into the porous metal complex can improve the catalyst efficiency of the component (1).
多孔性金属錯体としては例えば、文献１（Ｌｏｗら、「Ｊｏｕｒｎａｌ ｏｆ Ａｍｅｒｉｃａｎ Ｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔｒｙ」、２００９年、１３１号、ｐ．１５８３４−１５８４２）や、文献２（Ｓｃｈｒｏｄｅｒら、「Ｊｏｕｒｎａｌ ｏｆ Ａｍｅｒｉｃａｎ Ｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔｒｙ」、２００８年、１３０号、ｐ．６１１９−６１３０）に記載のものを用いることができる。 Examples of the porous metal complex include Reference 1 (Low et al., “Journal of American Chemical Society”, 2009, 131, p.15834-15842) and Reference 2 (Schroder et al., “Journal of American Chemical Chemistry,” 2008, 130, p.6119-6130) can be used.
なかでも、亜鉛、銅、マグネシウム、アルミニウム、マンガン、鉄、コバルト及びニッケルからなる群から選ばれる少なくとも１種の金属を有するものが好ましく、耐アンモニア性が確保しやすいと推測されることから、以下に示すものがより好ましい。
ＨＫＵＳＴ−１
（Ｃｕ３（Ｂｅｎｚｅｎｅｔｒｉｃａｒｂｏｘｙｌａｔｅ）２（Ｈ２Ｏ）３を表す。）、
Ｃｒ−ＭＩＬ−１０１
（Ｃｒ３Ｆ（Ｈ２Ｏ）Ｏ（Ｂｅｎｚｅｎｅｄｉｃａｒｂｏｘｙｌａｔｅ）３・ｎＨ２Ｏを表す。）、
Ａｌ−ＭＩＬ−１１０
（Ａｌ８（ＯＨ）１２｛（ＯＨ）３（Ｈ２Ｏ）３（Ｂｅｎｚｅｎｅｔｒｉｃａｒｂｏｘｙｌａｔｅ）３・ｎＨ２Ｏを表す。）、
Ｚｎ−ＭＯＦ−７４
（Ｚｎ２（ＤｉｏｘｉｄｏＢｅｎｚｅｎｅｄｉｃａｒｂｏｘｙｌａｔｅ）を表す。）、
Ａｌ−ＭＩＬ−５３
（Ａｌ（ＯＨ）（Ｂｅｎｚｅｎｅｄｉｃａｒｂｏｘｙｌａｔｅ）を表す。）、
Ａｌ−ＢＴＢ
（Ａｌ［ｂｅｎｚｅｎｅ−１，３，５−ｔｒｉｓ（ｐｈｅｎｙｌｃａｒｂｏｘｙｌａｔｅ）］を表す。）、
ＺＩＦ−８
（Ｚｎ（２−Ｍｅｔｈｙｌｉｍｉｄａｚｏｌａｔｅ）２・（Ｎ，Ｎ−ｄｉｍｅｔｈｙｌｆｏｒｍａｍｉｄｅ）・（Ｈ２Ｏ）３を表す。）、
ＺＩＦ−９０
（［Ｚｎ（ＩＣＡ）２］ｎ、Ｍｇ（ＨＣＯＯ）２を表す。）。
これらの中でも、３５０〜４００℃で安定して高活性を有することから、Ａｌ−ＢＴＢがさらに好ましい。
なお、上記の「ＩＣＡ」は「イミダゾレートー２−カルボキシアルデヒド」を表す。
Among them, those having at least one metal selected from the group consisting of zinc, copper, magnesium, aluminum, manganese, iron, cobalt and nickel are preferable, and it is estimated that ammonia resistance is easily secured. Those shown in FIG.
HKUST-1
(Represents Cu 3 (Benzenetricboxylate) 2 (H 2 O) 3 ),
Cr-MIL-101
(Represents Cr 3 F (H 2 O) O (Benzene dicarboxylicboxylate) 3 · nH 2 O).
Al-MIL-110
(Al 8 (OH) 12 {(OH) 3 (H 2 O) 3 (Benzenetricboxylate) 3 · nH 2 O is represented)],
Zn-MOF-74
(Represents Zn 2 (Dioxodobenzaldehyde)),
Al-MIL-53
(Al (OH) (represents Benzene dicarboxylate)),
Al-BTB
(Represents Al [benzene-1,3,5-tris (phenylcarboxylate)]).
ZIF-8
(Represents Zn (2-methylimidazolate) 2 · (N, N-dimethylformamide) · (H 2 O) 3 ),
ZIF-90
([Zn (ICA) 2 ] n represents Mg (HCOO) 2 ).
Among these, Al-BTB is more preferable because it has high activity stably at 350 to 400 ° C.
The above-mentioned “ICA” represents “imidazolate-2-carboxaldehyde”.
組成物中の成分（３）の配合割合は特に限定されるものではないが、０．０１〜１５質量％であることが好ましく、０．１〜１３質量％であることがより好ましく１〜１０質量％であることがさらに好ましい。 The blending ratio of component (3) in the composition is not particularly limited, but is preferably 0.01 to 15% by mass, more preferably 0.1 to 13% by mass. More preferably, it is mass%.
本発明の組成物は、成分（１）〜（３）以外のその他の成分が配合されたものであってもよい。その他の成分としては、本発明の効果を損なわないものであれば特に限定されるものではない。 The composition of the present invention may contain other components other than components (1) to (3). Other components are not particularly limited as long as the effects of the present invention are not impaired.
本発明において、成分（１）〜（３）を配合して組成物を調製する方法は特に限定されるものではないが、アンモニア製造触媒として用いる組成物（以下、「触媒組成物」ということがある。）を調製する場合の一例としては
（ｉ）成分（２）に成分（１）を担持させる工程、及び、
（ｉｉ）前記工程（ｉ）の生成物に、さらに成分（３）を配合し、触媒組成物を製造する工程、とを有する調製方法が挙げられる。
以下、各工程を説明する。
In the present invention, the method for preparing the composition by blending the components (1) to (3) is not particularly limited, but a composition used as an ammonia production catalyst (hereinafter referred to as “catalyst composition”). As an example in the case of preparing ()) (i) a step of supporting component (1) on component (2), and
(Ii) The preparation method which has a process of further mix | blending component (3) with the product of the said process (i), and manufacturing a catalyst composition is mentioned.
Hereinafter, each process will be described.
（工程（ｉ））
成分（２）に成分（１）を担持させる方法は特に限定されるものではないが、溶媒又は水中に成分（１）を分散させた後、成分（２）を添加することにより担持させる方法（含浸法）により行うことができる。
(Process (i))
The method of supporting the component (1) on the component (2) is not particularly limited, but the method of supporting the component (2) by adding the component (2) after dispersing the component (1) in a solvent or water ( Impregnation method).
溶媒としては特に限定されるものではないが、アセトン、テトラヒドロフラン等の極性溶媒、メタノール、エタノール等のアルコール系溶媒等が挙げられる。 Although it does not specifically limit as a solvent, Alcohol solvents, such as polar solvents, such as acetone and tetrahydrofuran, methanol, ethanol, etc. are mentioned.
成分（２）の添加後、必要に応じて、混合液の攪拌、溶媒又は水の留去、得られた生成物の乾燥等を行うことができる。 After the addition of component (2), the mixture can be stirred, the solvent or water can be distilled off, and the resulting product can be dried, if necessary.
また、成分（１）として用いるルテニウムがルテニウムを含む化合物である場合、該化合物に含まれる陰イオン又は配位子は、工程（ｉｉ）開始前に予め除去されることが好ましい。陰イオン又は配位子の除去は例えば、真空条件下又はＨｅ等の不活性ガスの存在下で、加熱処理することにより行うことができる。加熱は５０〜６００℃、好ましくは１５０〜５５０℃で、０．５〜２０時間行うことが好ましい。 Moreover, when the ruthenium used as the component (1) is a compound containing ruthenium, the anion or ligand contained in the compound is preferably removed in advance before the start of the step (ii). The anion or the ligand can be removed by, for example, heat treatment under vacuum conditions or in the presence of an inert gas such as He. Heating is preferably performed at 50 to 600 ° C, preferably 150 to 550 ° C for 0.5 to 20 hours.
（工程（ｉｉ））
・塩基性助触媒
成分（３）として塩基性助触媒を用いる場合、例えば、塩基性助触媒水溶液に工程（ｉ）で得られた生成物を添加し、塩基性助触媒を含浸させる含浸法により触媒組成物を調製することができる。
(Step (ii))
-Basic promoter When using a basic promoter as the component (3), for example, by an impregnation method in which the product obtained in step (i) is added to an aqueous basic promoter solution and impregnated with the basic promoter. A catalyst composition can be prepared.
塩基性助触媒の添加後、必要に応じて、混合液の攪拌、水の留去、得られた生成物の乾燥等を行うことができる。 After the addition of the basic promoter, the mixed solution can be stirred, water can be distilled off, and the resulting product can be dried as necessary.
塩基性助触媒の添加量は、成分（１）に対する原子比が０．０１〜２０質量％となる量であることが好ましい。上記下限値以上とすることにより触媒活性を特に向上させることができ、上記上限値以下とすることにより、過度の塩基性助触媒の存在による触媒活性の低下を防ぐことができる。 The addition amount of the basic promoter is preferably such that the atomic ratio with respect to component (1) is 0.01 to 20% by mass. By setting the lower limit value or more, the catalytic activity can be particularly improved, and by setting the upper limit value or less, it is possible to prevent a decrease in the catalytic activity due to the presence of an excessive basic promoter.
また、塩基性助触媒としてアルカリ金属を含む化合物又はアルカリ土類金属を含む化合物を用いる場合、該化合物に含まれる陰イオン又は配位子を除去することが好ましい。配位子の除去は前記ルテニウム化合物に含まれる陰イオン又は配位子の除去と同様に行うことができる。 When a compound containing an alkali metal or a compound containing an alkaline earth metal is used as the basic promoter, it is preferable to remove an anion or a ligand contained in the compound. The removal of the ligand can be performed in the same manner as the removal of the anion or ligand contained in the ruthenium compound.
・多孔性金属錯体
成分（３）として多孔性金属錯体を用いる場合、例えば、工程（ｉ）で得られた生成物と、多孔性金属錯体とを物理混合により複合化する方法により触媒組成物を調製することができる。物理混合の方法としては、乳鉢による混合、ボールミルによる混合等、公知の方法を用いることができる。
-Porous metal complex When using a porous metal complex as the component (3), for example, the catalyst composition is prepared by a method of complexing the product obtained in step (i) and the porous metal complex by physical mixing. Can be prepared. As the physical mixing method, a known method such as mixing with a mortar or ball mill can be used.
上記の様にして調製された触媒組成物に対して、さらに水素還元反応を行ってもよい。触媒であるルテニウムを金属状態に還元することにより、触媒能が向上する。水素還元反応は１００〜７００℃、好ましくは３００〜６００℃において、水素含有雰囲気中で０．５〜２０時間行うことが好ましい。 The catalyst composition prepared as described above may be further subjected to a hydrogen reduction reaction. Catalytic performance is improved by reducing ruthenium, which is a catalyst, to a metallic state. The hydrogen reduction reaction is preferably performed at 100 to 700 ° C., preferably 300 to 600 ° C., in a hydrogen-containing atmosphere for 0.5 to 20 hours.
なお、組成物の調製方法は上記方法に限定されるものではなく、例えば、含浸法により成分（２）に塩基性助触媒を含浸させた後に、含浸法によりさらに成分（１）を含浸させてもよい。
また、触媒組成物が塩基性助触媒と多孔性金属錯体との両者を配合したものである場合、工程（ｉ）の後、工程（ｉｉ）開始前に多孔性金属錯体と工程（ｉ）の生成物とを物理混合し、その後塩基性助触媒を含浸させてもよく、工程（ｉｉ）において塩基性助触媒を含浸させた後に、多孔性金属錯体を物理混合してもよい。
The method for preparing the composition is not limited to the above method. For example, after impregnating the component (2) with the basic promoter in the impregnation method, the component (1) is further impregnated in the impregnation method. Also good.
Further, when the catalyst composition is a combination of both a basic promoter and a porous metal complex, after step (i), before the start of step (ii), the porous metal complex and step (i) The product may be physically mixed and then impregnated with a basic promoter, or after impregnating the basic promoter in step (ii), the porous metal complex may be physically mixed.
［アンモニア製造方法］
本発明の第二の態様のアンモニア製造方法は、上記第一の態様の組成物を触媒として用いるものである。
アンモニアの製造方法は特に限定されるものではないが、例えば、第一の態様の組成物が充填された反応容器内に、水素ガスと窒素ガスとからなる原料ガスを供給することによりアンモニアを製造することができる。
[Ammonia production method]
The ammonia production method of the second aspect of the present invention uses the composition of the first aspect as a catalyst.
The method for producing ammonia is not particularly limited. For example, ammonia is produced by supplying a raw material gas composed of hydrogen gas and nitrogen gas into a reaction vessel filled with the composition of the first aspect. can do.
第一の態様の組成物は、予め粉砕、成型、整粒等を行った後にアンモニアの製造に用いてもよい。 The composition of the first aspect may be used for the production of ammonia after previously pulverizing, molding, sizing and the like.
反応温度は、２００℃〜６００℃が好ましく、２５０℃〜５００℃がより好ましく、３００℃〜４５０℃がさらに好ましい。本発明のアンモニア製造方法においては、第一の態様の組成物を用いることにより反応容器内が低圧条件下であってもアンモニアを高収率で製造することができる。そのため、反応容器内の圧力は、低圧である１〜２０気圧が好ましく、１〜１０気圧がより好ましく、１〜５気圧がさらに好ましい。 The reaction temperature is preferably 200 ° C to 600 ° C, more preferably 250 ° C to 500 ° C, and further preferably 300 ° C to 450 ° C. In the ammonia production method of the present invention, by using the composition of the first aspect, ammonia can be produced in a high yield even when the inside of the reaction vessel is under low pressure conditions. Therefore, the pressure in the reaction vessel is preferably 1 to 20 atm which is a low pressure, more preferably 1 to 10 atm, and further preferably 1 to 5 atm.
以下に実施例を示して本発明をさらに詳細に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
本実施例にて用いる反応装置について以下説明する。
アンモニア製造装置として、図１に示される固定床流通式装置を用いた。常圧実験の際には、内径７ｍｍの石英製のリアクターを使用した。
アンモニア製造の前処理として、検討に用いる組成物（触媒）をリアクターに充填し、５００℃、１時間の水素還元を行った。続けて、Ａｒパージを行いながら反応温度である３１０℃まで降温させ、温度が安定したところで反応ガスの供給を開始し、３５０℃まで昇温した。反応ガスはＮ２／Ｈ２＝１／３（ＳＶ＝１８０００ｍｌ／（ｈ・ｇ））とした。反応式は下に示す通りである。
Ｎ２＋３Ｈ２→２ＮＨ３
The reactor used in this example will be described below.
As the ammonia production apparatus, the fixed bed flow type apparatus shown in FIG. 1 was used. In a normal pressure experiment, a quartz reactor having an inner diameter of 7 mm was used.
As a pretreatment for ammonia production, the reactor was filled with the composition (catalyst) used for the study, and hydrogen reduction was performed at 500 ° C. for 1 hour. Subsequently, the temperature was lowered to 310 ° C. as the reaction temperature while performing Ar purge, and when the temperature was stabilized, supply of the reaction gas was started and the temperature was raised to 350 ° C. The reaction gas was N 2 / H 2 = 1/3 (SV = 18000 ml / (h · g)). The reaction formula is as shown below.
N 2 + 3H 2 → 2NH 3
（反応条件）
触媒量：０．２ｇ
活性化処理条件：Ｈ２流通下，１０ｍｌ／ｍｉｎ，５００℃，１ｈ．
反応温度：３５０℃
反応圧：０．１ＭＰａ（１気圧）
反応ガス：Ｎ２１５ｍｌ／分，Ｈ２４５ｍｌ／分
(Reaction conditions)
Catalyst amount: 0.2g
Activation treatment conditions: H 2 flow under, 10ml / min, 500 ℃, 1h.
Reaction temperature: 350 ° C
Reaction pressure: 0.1 MPa (1 atm)
Reaction gas: N 2 15 ml / min, H 2 45 ml / min
反応温度は３５０℃とし、３０分間のサンプリングを行った。アンモニアのサンプリング方法の模式図を図２に示す。反応菅の出口ガス（アンモニア、水素、窒素）をアンモニアトラップとして０．００１Ｍまたは０．０１Ｍ硫酸溶液に通し、アンモニアのみを捕集した。このときの反応式は下に示す通りである。
２ＮＨ３＋Ｈ２ＳＯ４→２ＮＨ４ ＋＋ＳＯ４ ２−
The reaction temperature was 350 ° C. and sampling was performed for 30 minutes. A schematic diagram of the ammonia sampling method is shown in FIG. The reactor outlet gas (ammonia, hydrogen, nitrogen) was passed through a 0.001 M or 0.01 M sulfuric acid solution as an ammonia trap to collect only ammonia. The reaction formula at this time is as shown below.
2NH 3 + H 2 SO 4 → 2NH 4 + + SO 4 2−
反応菅の出口ガス中のアンモニアとトラップの硫酸溶液から、アンモニウムイオンと硫酸イオンが生成する。この反応での電気伝導度の減少をモニターし、触媒のアンモニア合成への活性を測定した。 Ammonium ions and sulfate ions are produced from the ammonia in the outlet gas of the reaction tank and the sulfuric acid solution in the trap. The decrease in electrical conductivity in this reaction was monitored, and the activity of the catalyst for ammonia synthesis was measured.
さらに、電気伝導度値より計算を行ったアンモニア収率の確認として、イオンクロマトグラフィーでアンモニア濃度を測定した。イオンクロマトグラフィーには、アンモニア合成の各温度で捕集したアンモニアトラップ硫酸溶液を分取し、測定を行った。 Furthermore, as a confirmation of the ammonia yield calculated from the electrical conductivity value, the ammonia concentration was measured by ion chromatography. For ion chromatography, the ammonia trap sulfuric acid solution collected at each temperature of ammonia synthesis was collected and measured.
（イオンクロマトグラフィー分析条件）
カラム：ＳｈｏｄｅｘＩＣ ＹＫ−４２１
カラムサイズ：内径４．６ｍｍ，長さ１２５ｍｍ
充填剤：シリカゲルにカルボキシル基を持つポリマーを被覆した弱酸性の陽イオン交換体
溶離液：４ｍｍｏｌ／ｌリン酸溶液
(Ion chromatography analysis conditions)
Column: ShodexIC YK-421
Column size: inner diameter 4.6mm, length 125mm
Filler: Weakly acidic cation exchanger with silica gel coated with polymer having carboxyl group Eluent: 4 mmol / l phosphoric acid solution
なお，アンモニア収率の計算には窒素原子を内部標準として用いた．計算式は次式の通りである． The nitrogen yield was used as an internal standard for the calculation of ammonia yield. The calculation formula is as follows.
＜調製例１−１＞
５００ｍＬビーカー中で、０．１ｍｏｌ相当のＰｒ（ＮＯ３）３・６Ｈ２Ｏ（関東化学社製）を計り取り、イオン交換水４００ｍＬを加え攪拌し溶解した。また、別の１Ｌビーカーに２５％アンモニア水２００ｍＬを入れ、スターラーにて攪拌した。そして、マイクロチューブポンプを用い、上記硝酸塩水溶液を上記２５％アンモニア水に約４時間程度で滴下した後、一晩攪拌を続けた。その後、イオン交換水で濾過洗浄を繰り返した。得られた固形物は乾燥機での７０℃、１２時間以上の乾燥、排気焼成炉での大気中３００℃、３時間の仮焼成を経て、冷却後に乳鉢で粉砕した。さらにマッフル炉にて７００℃、３時間、大気中で本焼成し、Ｐｒ６Ｏ１１を得た。
<Preparation Example 1-1>
In 500mL beaker, 0.1 mol equivalent of Pr (NO 3) 3 · 6H 2 O ( manufactured by Kanto Chemical Co., Inc.) were weighed, and stirred and dissolved by adding ion-exchanged water 400 mL. Moreover, 200 mL of 25% ammonia water was put into another 1 L beaker and stirred with a stirrer. Then, using a microtube pump, the nitrate aqueous solution was dropped into the 25% aqueous ammonia in about 4 hours, and then stirring was continued overnight. Thereafter, filtration and washing with ion-exchanged water were repeated. The obtained solid matter was subjected to drying at 70 ° C. in a dryer for 12 hours or more, pre-baking at 300 ° C. in the air in an exhaust firing furnace for 3 hours, and pulverized in a mortar after cooling. Further, this was calcined in the atmosphere at 700 ° C. for 3 hours in a muffle furnace to obtain Pr 6 O 11 .
＜調製例１−２＞
５００ｍＬビーカー中で、０．１ｍｏｌ相当のＣｅ（ＮＯ３）３・６Ｈ２Ｏ（関東化学社製）を計り取り、イオン交換水４００ｍＬを加え攪拌し溶解した。また，別の１Ｌビーカーに２５％アンモニア水２００ｍＬを入れ、スターラーにて攪拌した。そして、マイクロチューブポンプを用い、上記硝酸塩水溶液を上記２５％アンモニア水に約４時間程度で滴下した後、一晩攪拌を続けた。その後、イオン交換水で濾過洗浄を繰り返した。得られた固形物は乾燥機での７０℃、１２時間以上の乾燥、排気焼成炉での大気中３００℃、３時間の仮焼成を経て、冷却後に乳鉢で粉砕した。さらにマッフル炉にて７００℃、３時間、大気中で本焼成し、ＣｅＯ２を得た。
<Preparation Example 1-2>
In 500mL beaker, 0.1 mol equivalent of Ce (NO 3) 3 · 6H 2 O ( manufactured by Kanto Chemical Co., Inc.) were weighed, and stirred and dissolved by adding ion-exchanged water 400 mL. Further, 200 mL of 25% aqueous ammonia was put into another 1 L beaker and stirred with a stirrer. Then, using a microtube pump, the nitrate aqueous solution was dropped into the 25% aqueous ammonia in about 4 hours, and then stirring was continued overnight. Thereafter, filtration and washing with ion-exchanged water were repeated. The obtained solid matter was subjected to drying at 70 ° C. in a dryer for 12 hours or more, pre-baking at 300 ° C. in the air in an exhaust firing furnace for 3 hours, and pulverized in a mortar after cooling. Further, this was calcined in the muffle furnace at 700 ° C. for 3 hours in the atmosphere to obtain CeO 2 .
＜調製例１−３＞
５００ｍＬビーカー中で、０．１ｍｏｌ相当のＬａ（ＮＯ３）３・６Ｈ２Ｏ（関東化学社製）を計り取り、イオン交換水４００ｍＬを加え攪拌し溶解した。また，別の１Ｌビーカーに２５％アンモニア水２００ｍＬを入れ、スターラーにて攪拌した。そして、マイクロチューブポンプを用い、上記硝酸塩水溶液を上記２５％アンモニア水に約４時間程度で滴下した後、一晩攪拌を続けた。その後、イオン交換水で濾過洗浄を繰り返した。得られた固形物は乾燥機での７０℃、１２時間以上の乾燥、排気焼成炉での大気中３００℃、３時間の仮焼成を経て、冷却後に乳鉢で粉砕した。さらにマッフル炉にて７００℃、３時間、大気中で本焼成し、Ｌａ２Ｏ３を得た。
<Preparation Example 1-3>
In 500mL beaker, 0.1 mol equivalent of La (NO 3) 3 · 6H 2 O ( manufactured by Kanto Chemical Co., Inc.) were weighed, and stirred and dissolved by adding ion-exchanged water 400 mL. Further, 200 mL of 25% aqueous ammonia was put into another 1 L beaker and stirred with a stirrer. Then, using a microtube pump, the nitrate aqueous solution was dropped into the 25% aqueous ammonia in about 4 hours, and then stirring was continued overnight. Thereafter, filtration and washing with ion-exchanged water were repeated. The obtained solid matter was subjected to drying at 70 ° C. in a dryer for 12 hours or more, pre-baking at 300 ° C. in the air in an exhaust firing furnace for 3 hours, and pulverized in a mortar after cooling. Further, this was calcined in the atmosphere at 700 ° C. for 3 hours in a muffle furnace to obtain La 2 O 3 .
＜調製例２−１＞
Ｒｕ３（ＣＯ）１２（和光純薬工業社製）５６５ｍｇ（０．８８ｍｍｏｌ）をナスフラスコにいれ、２００ｍｌのテトラヒドロフランに溶解させた後に、上記＜調製例１−１＞で得られた担体（Ｐｒ６Ｏ１１）５．０ｍｇ（４．９ｍｍｏｌ）を加え、１２時間常温でマグネットスターラーで攪拌した。その後，ロータリーエバポレーターを使用して溶媒を加熱除去した．このとき温浴の温度は７０℃まで徐々に上げた．得られた固形物はナスフラスコから焼成皿に移して７０℃の乾燥機で１日乾燥させた後、パイレックス（登録商標）ガラス（コーニング社製）のボートに入れ，Ｈｅ流通下の横型管状炉内で３５０℃，５時間加熱処理することで，ルテニウム化合物の配位子を除去した。このような手順で得られた生成物は、ルテニウムを５質量％担持した５質量％Ｒｕ／Ｐｒ６Ｏ１１であった。
<Preparation Example 2-1>
Ru 3 (CO) 12 (manufactured by Wako Pure Chemical Industries, Ltd.), 565 mg (0.88 mmol) was placed in an eggplant flask, dissolved in 200 ml of tetrahydrofuran, and then the carrier (Pr) obtained in <Preparation Example 1-1> above. 6 O 11 ) 5.0 mg (4.9 mmol) was added, and the mixture was stirred with a magnetic stirrer at room temperature for 12 hours. Thereafter, the solvent was removed by heating using a rotary evaporator. At this time, the temperature of the warm bath was gradually raised to 70 ° C. The obtained solid material was transferred from the eggplant flask to a baking dish and dried for one day with a dryer at 70 ° C., then placed in a Pyrex (registered trademark) glass (Corning) boat and a horizontal tubular furnace under He circulation. The ligand of the ruthenium compound was removed by heat treatment at 350 ° C. for 5 hours. The product obtained by such a procedure was 5 mass% Ru / Pr 6 O 11 carrying 5 mass% of ruthenium.
＜調製例２−２＞
＜調製例１−１＞で得られた担体に替えて、＜調製例１−２＞で得られた担体（ＣｅＯ２）５．０ｇ（２９ｍｍｏｌ）を用いた以外は上記＜調製例２−１＞と同様にして、ルテニウムを５質量％担持した５質量％Ｒｕ／ＣｅＯ２を調製した。
<Preparation Example 2-2>
<Preparation Example 2-1 above, except that 5.0 g (29 mmol) of the carrier (CeO 2 ) obtained in <Preparation Example 1-2> was used in place of the carrier obtained in <Preparation Example 1-1>. In the same manner as above, 5% by mass Ru / CeO 2 supporting 5% by mass of ruthenium was prepared.
＜調製例２−３＞
＜調製例１−１＞で得られた担体に替えて、＜調製例１−３＞で得られた担体（Ｌａ２Ｏ３）５．０ｇ（１５ｍｍｏｌ）を用いた以外は上記＜調製例２−１＞と同様にして、ルテニウムを５質量％担持した５質量％Ｒｕ／Ｌａ２Ｏ３を調製した。
<Preparation Example 2-3>
<Preparation Example 2> except that 5.0 g (15 mmol) of the carrier (La 2 O 3 ) obtained in <Preparation Example 1-3> was used in place of the carrier obtained in <Preparation Example 1-1>. -1> and was similarly prepared 5 wt% Ru / La 2 O 3 was 5 wt% supported ruthenium.
＜調製例２−４＞
担体には＜調製例１−３＞に準じて調製したＬａ２Ｏ３を用いた。
Ｒｕ３Ｃｌ３のｎ水和物を１５７ｍｇ、ポリビニルピロリドン６６６．６ｍｇ、エチレングリコール２９０ｍｌを、アルゴン雰囲気下２３℃にて５分間かけて攪拌した。２３℃で３０分、２２０℃で２時間攪拌した後、冷却、ろ別し、エタノール、アセトン、ジエチルエーテル、水で洗浄してＲｕナノ粒子を得た。
得られたＲｕナノ粒子８６９ｍｇを４０ｍｌエタノールに溶解し、Ｌａ２Ｏ３ ２．０ｇを加えて５分間超音波照射をした。水浴上でメタノールを蒸発させてＲｕナノ粒子担持触媒２．５４ｇを得た。
元素分析をＩＣＰ−ＡＥＳ（ＩＣＰＥ−９０００、島津製作所社製）にて行ったところ、３．０質量％のＲｕが担持されていることが判明した。以下、該触媒を３．０質量％Ｒｕ／Ｌａ２Ｏ３と呼称することがある。
<Preparation Example 2-4>
As the carrier, La 2 O 3 prepared according to <Preparation Example 1-3> was used.
157 mg of Ru 3 Cl 3 n hydrate, 666.6 mg of polyvinylpyrrolidone, and 290 ml of ethylene glycol were stirred at 23 ° C. for 5 minutes in an argon atmosphere. After stirring at 23 ° C. for 30 minutes and at 220 ° C. for 2 hours, the mixture was cooled, filtered, and washed with ethanol, acetone, diethyl ether, and water to obtain Ru nanoparticles.
869 mg of the obtained Ru nanoparticles were dissolved in 40 ml of ethanol, 2.0 g of La 2 O 3 was added, and ultrasonic irradiation was performed for 5 minutes. Methanol was evaporated on a water bath to obtain 2.54 g of Ru nanoparticle supported catalyst.
Elemental analysis was performed with ICP-AES (ICPE-9000, manufactured by Shimadzu Corporation), and it was found that 3.0% by mass of Ru was supported. Hereinafter, the catalyst may be referred to as 3.0 mass% Ru / La 2 O 3 .
＜調製例２−５＞
担体には＜調製例１−３＞に準じて調製したＬａ２Ｏ３を用いた。
ＲｕＣｌ３のｎ水和物を３１３ｍｇ、Ｆｅ［Ｃ３Ｈ８Ｏ２］３を４３ｍｇ、ポリビニルピロリドン２６６ｍｇ、水酸化ナトリウム１０ｍｇ、エチレングリコール３００ｍｌをナスフラスコに入れ、アルゴン雰囲気下１４０℃まで加熱攪拌した。水素化ホウ素ナトリウム４５４ｍｇを添加した後、１８０℃まで昇温し、１２０分間攪拌した。冷却、濾別し、エタノール、アセトン、ジエチルエーテル、水で洗浄して、ＲｕＦｅナノ粒子を２３０ｍｇ得た。
得られたＲｕＦｅナノ粒子１，０５０ｍｇを４０ｍｌメタノールに溶解し、Ｌａ２Ｏ３ ２．０ｇを加えて５分間超音波照射をした。水浴上でメタノールを蒸発させて、ＲｕＦｅナノ合金担持触媒２．３８ｇを得た。
元素分析をＩＣＰ−ＡＥＳにて行ったところ、４．７質量％のＲｕ及び０．３質量％のＦｅが担持されていることが判明した。以下、該触媒を４．７質量％Ｒｕ―０．３質量％Ｆｅ／Ｌａ２Ｏ３と呼称することがある。
<Preparation Example 2-5>
As the carrier, La 2 O 3 prepared according to <Preparation Example 1-3> was used.
RuCl 3 n-hydrate (313 mg), Fe [C 3 H 8 O 2 ] 3 (43 mg), polyvinylpyrrolidone (266 mg), sodium hydroxide (10 mg), and ethylene glycol (300 ml) were placed in an eggplant flask and heated and stirred to 140 ° C. under an argon atmosphere. . After adding 454 mg of sodium borohydride, the temperature was raised to 180 ° C. and stirred for 120 minutes. The mixture was cooled, filtered and washed with ethanol, acetone, diethyl ether and water to obtain 230 mg of RuFe nanoparticles.
1,050 mg of the obtained RuFe nanoparticles were dissolved in 40 ml of methanol, 2.0 g of La 2 O 3 was added, and ultrasonic irradiation was performed for 5 minutes. Methanol was evaporated on a water bath to obtain 2.38 g of a RuFe nanoalloy supported catalyst.
When elemental analysis was performed by ICP-AES, it was found that 4.7% by mass of Ru and 0.3% by mass of Fe were supported. Hereinafter sometimes referred to as 4.7 mass% Ru-0.3 wt% Fe / La 2 O 3 the catalyst.
＜調製例２−６＞
担体には＜調製例１−３＞に準じて調製したＬａ２Ｏ３を用いた。
ＲｕＣｌ３のｎ水和物５６４ｍｇ、Ｎｉ（ＣＨ３ＣＯ２）２６０ｍｇ、ポリビニルピロリドン１，３３３ｍｇ、エチレングリコール２００ｍｌを、ナスフラスコに入れ、アルゴン雰囲気下１７０℃まで加熱し、１５分間攪拌した。冷却、濾別し、エタノール、アセトン、ジエチルエーテル、水で洗浄して、ＲｕＮｉナノ粒子を８００ｍｇ得た。作製したＲｕＮｉナノ粒子８００ｍｇを４０ｍｌメタノールに溶解し、Ｌａ２Ｏ３ １．４ｇを加えて５分間超音波照射をした。水浴上でメタノールを蒸発させて、ＲｕＮｉナノ合金担持触媒を１．４２ｇ得た。
元素分析をＩＣＰ−ＡＥＳにて行ったところ、４．３質量％のＲｕ及び０．１質量％のＮｉが担持されていることが判明した。以下、該触媒を４．３質量％Ｒｕ―０．１質量％Ｎｉ／Ｌａ２Ｏ３と呼称することがある。
<Preparation Example 2-6>
As the carrier, La 2 O 3 prepared according to <Preparation Example 1-3> was used.
RuCl 3 n-hydrate 564 mg, Ni (CH 3 CO 2 ) 2 60 mg, polyvinylpyrrolidone 1,333 mg, and ethylene glycol 200 ml were placed in an eggplant flask, heated to 170 ° C. under an argon atmosphere, and stirred for 15 minutes. The mixture was cooled, filtered, and washed with ethanol, acetone, diethyl ether, and water to obtain 800 mg of RuNi nanoparticles. 800 mg of the prepared RuNi nanoparticles were dissolved in 40 ml of methanol, 1.4 g of La 2 O 3 was added, and ultrasonic irradiation was performed for 5 minutes. Methanol was evaporated on a water bath to obtain 1.42 g of a RuNi nanoalloy supported catalyst.
When elemental analysis was performed by ICP-AES, it was found that 4.3 mass% Ru and 0.1 mass% Ni were supported. Hereinafter, the catalyst may be referred to as 4.3 mass% Ru-0.1 mass% Ni / La 2 O 3 .
＜参考例１〜２、比較例１＞
表１に示す触媒を用い、上述した方法により３５０℃でのアンモニア合成活性（単位：％。Ｒｕ １ｇあたりの合成収率）を測定し、アンモニア収率を算出した。結果を表１に示す。なお、触媒は、乳鉢で充分に粉砕，混合し，ディスク成型にした後，再度，粉砕して２５０〜５００μｍに整粒して用いた。
<Reference Examples 1-2, Comparative Example 1>
Using the catalyst shown in Table 1, the ammonia synthesis activity (unit:%, synthesis yield per gram of Ru) at 350 ° C. was measured by the method described above, and the ammonia yield was calculated. The results are shown in Table 1. The catalyst was sufficiently pulverized and mixed in a mortar, formed into a disk, and then pulverized again to adjust the particle size to 250 to 500 μm.
上記結果から、Ｒｕに、Ｆｅ、Ｎｉのような卑金属を少量合金化し、ランタノイド担体に担持させた参考例１〜２の触媒は、Ｒｕ単独でランタノイド担体に担持させた比較例１の触媒に比べて、アンモニア合成活性が高まり、常圧においても高収率でアンモニアを製造できることがわかった。 From the above results, the catalysts of Reference Examples 1 and 2 in which a small amount of a base metal such as Fe and Ni was alloyed with Ru and supported on the lanthanoid carrier were compared with the catalyst of Comparative Example 1 in which Ru alone was supported on the lanthanoid carrier. As a result, it was found that ammonia synthesis activity was enhanced and ammonia could be produced in high yield even at normal pressure.
＜実施例１＞
Ａｌ−ＢＴＢと、上記＜調製例２−１＞で得られた５質量％Ｒｕ／Ｐｒ６Ｏ１１とを、質量比１：９で乳鉢を用いて物理混合した。このような手順でＡｌ−ＢＴＢ＋５質量％Ｒｕ／Ｐｒ６Ｏ１１を得た。得られた触媒を用いて、上述した方法によりアンモニアを製造し、アンモニア収率を算出したところ、０．１５％であった。結果を表２に示す。
なお、触媒は、参考例１〜２等と同様に粉砕、混合、成型、再粉砕、整粒した後に用いた。以下の実施例２〜１０及び比較例２も同様である。
<Example 1>
Al-BTB and 5 mass% Ru / Pr 6 O 11 obtained in the above <Preparation Example 2-1> were physically mixed using a mortar at a mass ratio of 1: 9. By such a procedure, Al-BTB + 5 mass% Ru / Pr 6 O 11 was obtained. Using the obtained catalyst, ammonia was produced by the method described above, and the ammonia yield was calculated to be 0.15%. The results are shown in Table 2.
The catalyst was used after being pulverized, mixed, molded, reground and sized in the same manner as in Reference Examples 1 and 2. The same applies to Examples 2 to 10 and Comparative Example 2 below.
＜実施例２＞
以下の手順で、５質量％Ｒｕ／Ｐｒ６Ｏ１１＜調製例２−１＞にアルカリ金属酸化物を配合した触媒を調製した。なお，触媒中のアルカリ金属とルテニウムの原子比は１．０となるようにした．
３００ｍｌビーカーに１５０ｍｌの蒸留水を入れ、アルカリ金属酸化物の前駆体であるＣｓＮＯ３（関東化学社製）を１９３ｍｇ（０．９９ｍｍｏｌ）加えてマグネットスターラーで撹拌し，溶解させた。
その後，上記＜調製例２−１＞で得られた５質量％Ｒｕ／Ｐｒ６Ｏ１１を２．０ｍｇ（Ｒｕ：０．９９ｍｍｏｌ）加えて常温で１２時間撹拌した。その後、ホットスターラ―上で加熱攪拌により水分を蒸発させ、ペースト状になったものを７０℃の乾燥機で充分に乾燥させ、乳鉢で粉砕混合した。
その後、パイレックス（登録商標）ガラス（コーニング社製）のボートにいれ、横型管状炉で１００％のＨ２流通下で５００℃、１時間加熱処理することで、アルカリ金属酸化物前駆体中の硝酸根を除去し、生成物を得た。
このような手順で得られた生成物は、Ｃｓ及び５質量％のルテニウムを担持したＣｓ／５質量％Ｒｕ／Ｐｒ６Ｏ１１であった。得られた生成物を触媒としてを用いて、上述した方法によりアンモニアを製造し、アンモニア収率を算出したところ、１．０１％であった。結果を表２に示す。
<Example 2>
In the following steps, a catalyst obtained by blending the alkali metal oxides were prepared in 5 wt% Ru / Pr 6 O 11 <Preparation Example 2-1>. The atomic ratio of alkali metal to ruthenium in the catalyst was set to 1.0.
150 ml of distilled water was put into a 300 ml beaker, and 193 mg (0.99 mmol) of CsNO 3 (manufactured by Kanto Chemical Co., Ltd.), which is an alkali metal oxide precursor, was added and stirred with a magnetic stirrer to dissolve.
Thereafter, 2.0 mg (Ru: 0.99 mmol) of 5 mass% Ru / Pr 6 O 11 obtained in the above <Preparation Example 2-1> was added and stirred at room temperature for 12 hours. Thereafter, the water was evaporated by heating and stirring on a hot stirrer, and the paste was sufficiently dried with a dryer at 70 ° C. and pulverized and mixed in a mortar.
Then, it is put into a boat made of Pyrex (registered trademark) glass (manufactured by Corning), and heated in a horizontal tubular furnace under 100% H 2 flow at 500 ° C. for 1 hour, so that nitric acid in the alkali metal oxide precursor. The roots were removed to give the product.
The product obtained by such a procedure was Cs / 5 wt% Ru / Pr 6 O 11 supporting Cs and 5 wt% ruthenium. Using the obtained product as a catalyst, ammonia was produced by the method described above, and the ammonia yield was calculated to be 1.01%. The results are shown in Table 2.
＜実施例３＞
以下の手順で、５質量％Ｒｕ／ＣｅＯ２＜調製例２−２＞にアルカリ金属酸化物を配合した触媒を調製した。なお、触媒中のアルカリ金属とルテニウムの原子比は０．５となるようにした。
３００ｍｌビーカーに１５０ｍｌの蒸留水を入れ、アルカリ金属酸化物の前駆体であるＣｓＮＯ３（関東化学社製）を９６ｍｇ（０．４９ｍｍｏｌ）加えてマグネットスターラーで撹拌し、溶解させた。
その後、上記＜調製例２−２＞で得られた所定量の５質量％Ｒｕ／ＣｅＯを２．０ｍｇ（Ｒｕ：０．９９ｍｍｏｌ）加えて常温で１２時間撹拌した。その後、ホットスターラ―上で加熱攪拌により水分を蒸発させ、ペースト状になったものを７０℃の乾燥機で充分に乾燥させ、乳鉢で粉砕混合した。
その後、パイレックス（登録商標）ガラス（コーニング社製）のボートにいれ、横型管状炉で１００％のＨ２流通下で５００℃、１時間加熱処理することで、アルカリ金属酸化物前駆体中の硝酸根を除去し、生成物を得た。
このような手順で得られた触媒は、Ｃｓ／５質量％Ｒｕ／ＣｅＯ２であった。得られた触媒を用いて、上述した方法によりアンモニアを製造し、アンモニア収率を算出したところ、０．７９％であった。結果を表２に示す。
<Example 3>
The following procedure was used to prepare a catalyst containing a combination of alkali metal oxide 5 wt% Ru / CeO 2 <Preparation Example 2-2>. The atomic ratio of alkali metal to ruthenium in the catalyst was set to 0.5.
150 ml of distilled water was put into a 300 ml beaker, and 96 mg (0.49 mmol) of CsNO 3 (manufactured by Kanto Chemical Co.), which is an alkali metal oxide precursor, was added and stirred with a magnetic stirrer to dissolve.
Thereafter, 2.0 mg (Ru: 0.99 mmol) of a predetermined amount of 5 mass% Ru / CeO obtained in the above <Preparation Example 2-2> was added and stirred at room temperature for 12 hours. Thereafter, the water was evaporated by heating and stirring on a hot stirrer, and the paste was sufficiently dried with a dryer at 70 ° C. and pulverized and mixed in a mortar.
Then, it is put into a boat made of Pyrex (registered trademark) glass (manufactured by Corning), and heated in a horizontal tubular furnace under 100% H 2 flow at 500 ° C. for 1 hour, so that nitric acid in the alkali metal oxide precursor. The roots were removed to give the product.
The catalyst obtained by such a procedure was Cs / 5 mass% Ru / CeO 2 . Using the obtained catalyst, ammonia was produced by the method described above, and the ammonia yield was calculated to be 0.79%. The results are shown in Table 2.
＜実施例４＞
以下の手順で５質量％Ｒｕ／Ｌａ２Ｏ３＜調製例２−３＞にアルカリ金属酸化物を配合した触媒を調製した。なお、触媒中のアルカリ金属とルテニウムの原子比は０．１となるようにした。
３００ｍｌビーカーに１５０ｍｌの蒸留水を入れ、アルカリ金属酸化物の前駆体であるＣｓＮＯ３（関東化学（株）製）を１９ｍｇ（０．０９７ｍｍｏｌ）加えてマグネットスターラーで撹拌し、溶解させた。
その後，上記＜調製例２−３＞で得られた所定量の５質量％Ｒｕ／Ｌａ２Ｏ３を２．０ｍｇ（Ｒｕ：０．９９ｍｍｏｌ）加えて常温で１２時間撹拌した。
その後、ホットスターラ―上で加熱攪拌により水分を蒸発させ、ペースト状になったものを７０℃の乾燥機で充分に乾燥させ、乳鉢で粉砕混合した。
その後、パイレックス（登録商標）ガラス製（コーニング社製）のボートにいれ、横型管状炉で１００％のＨ２流通下で５００℃、１時間加熱処理することで、アルカリ金属酸化物前駆体中の硝酸根を除去し、生成物を得た。
このような手順で得られた触媒は、Ｃｓ／５質量％Ｒｕ／Ｌａ２Ｏ３であった。得られた触媒を用いて、上述した方法によりアンモニアを製造し、アンモニア収率を算出したところ、０．７２％であった。結果を表２に示す。
<Example 4>
A catalyst was prepared by blending the alkali metal oxides in the following steps 5 wt% Ru / La 2 O 3 <Preparation Example 2-3>. The atomic ratio of alkali metal to ruthenium in the catalyst was set to 0.1.
150 ml of distilled water was put into a 300 ml beaker, 19 mg (0.097 mmol) of CsNO 3 (manufactured by Kanto Chemical Co., Ltd.), which is an alkali metal oxide precursor, was added and stirred with a magnetic stirrer to dissolve.
Thereafter, 2.0 mg (Ru: 0.99 mmol) of a predetermined amount of 5 mass% Ru / La 2 O 3 obtained in the above <Preparation Example 2-3> was added and stirred at room temperature for 12 hours.
Thereafter, the water was evaporated by heating and stirring on a hot stirrer, and the paste was sufficiently dried with a dryer at 70 ° C. and pulverized and mixed in a mortar.
Then, it is put into a boat made of Pyrex (registered trademark) glass (manufactured by Corning) and heated in a horizontal tubular furnace under a flow of 100% H 2 at 500 ° C. for 1 hour, so that the alkali metal oxide precursor The nitrate radical was removed to obtain the product.
The catalyst obtained by such a procedure was Cs / 5 mass% Ru / La 2 O 3 . Using the obtained catalyst, ammonia was produced by the method described above, and the ammonia yield was calculated to be 0.72%. The results are shown in Table 2.
＜実施例５＞
以下の手順で３質量％Ｒｕ／Ｌａ２Ｏ３＜調製例２−４＞にアルカリ金属酸化物を配合した触媒を調製する。なお，触媒中のアルカリ金属とルテニウムの原子比は０．１となるようにする。
３００ｍｌビーカーに１５０ｍｌの蒸留水を入れ、アルカリ金属酸化物の前駆体であるＣｓＮＯ３（関東化学（株）製）を加えてマグネットスターラーで撹拌し，溶解させる。
その後，上記＜調製例２−４＞で得られた所定量の３質量％Ｒｕ／Ｌａ２Ｏ３を加えて常温で１２時間撹拌する。
その後，ホットスターラ―上で加熱攪拌により水分を蒸発させ，ペースト状になったものを７０℃の乾燥機で充分に乾燥させ，乳鉢で粉砕混合する。
その後パイレックス（登録商標）ガラス製（コーニング社製）のボートにいれ，横型管状炉で１００％のＨ２流通下で５００℃，１時間加熱処理することで，アルカリ金属酸化物前駆体中の硝酸根を除去し、生成物を得る。
このような手順で得られる触媒は、Ｃｓ／３ｗｔ％Ｒｕ／Ｌａ２Ｏ３である。
<Example 5>
The following steps 3 wt% Ru / La 2 O 3 catalyst containing a combination of alkali metal oxide in <Preparation Example 2-4> is prepared. The atomic ratio of alkali metal to ruthenium in the catalyst is set to 0.1.
Add 150 ml of distilled water to a 300 ml beaker, add CsNO 3 (manufactured by Kanto Chemical Co., Inc.), which is an alkali metal oxide precursor, and stir with a magnetic stirrer to dissolve.
Thereafter, the predetermined amount of 3 mass% Ru / La 2 O 3 obtained in the above <Preparation Example 2-4> is added and stirred at room temperature for 12 hours.
Then, the water is evaporated by heating and stirring on a hot stirrer, and the paste is sufficiently dried with a dryer at 70 ° C. and pulverized and mixed in a mortar.
After that, it was put into a boat made of Pyrex (registered trademark) glass (Corning) and heated in a horizontal tube furnace under 100% H 2 flow at 500 ° C. for 1 hour, so that nitric acid in the alkali metal oxide precursor Remove the roots to obtain the product.
The catalyst obtained by such a procedure is Cs / 3 wt% Ru / La 2 O 3 .
＜実施例６＞
以下の手順で４．７質量％Ｒｕ−０．３質量％Ｆｅ／Ｌａ２Ｏ３＜調製例２−５＞にアルカリ金属酸化物を配合した触媒を調製する。なお，触媒中のアルカリ金属とルテニウムの原子比は０．１となるようにする。
３００ｍｌビーカーに１５０ｍｌの蒸留水を入れ、アルカリ金属酸化物の前駆体であるＣｓＮＯ３（関東化学（株）製）を加えてマグネットスターラーで撹拌し，溶解させる。
その後，上記＜調製例２−５＞で得られた所定量の４．７質量％Ｒｕ−０．３質量％Ｆｅ／Ｌａ２Ｏ３を加えて常温で１２時間撹拌する。
その後，ホットスターラ―上で加熱攪拌により水分を蒸発させ，ペースト状になったものを７０℃の乾燥機で充分に乾燥させ，乳鉢で粉砕混合する。
その後パイレックス（登録商標）ガラス製（コーニング社製）のボートにいれ，横型管状炉で１００％のＨ２流通下で５００℃，１時間加熱処理することで，アルカリ金属酸化物前駆体中の硝酸根を除去し、生成物を得る。
このような手順で得られる触媒は、Ｃｓ／４．７質量％Ｒｕ−０．３質量％Ｆｅ／Ｌａ２Ｏ３である。
<Example 6>
Preparing a catalyst obtained by blending alkali metal oxide of 4.7 wt% Ru-0.3 wt% Fe / La 2 O 3 <Preparation Example 2-5> by the following procedure. The atomic ratio of alkali metal to ruthenium in the catalyst is set to 0.1.
Add 150 ml of distilled water to a 300 ml beaker, add CsNO 3 (manufactured by Kanto Chemical Co., Inc.), which is an alkali metal oxide precursor, and stir with a magnetic stirrer to dissolve.
Thereafter, the predetermined amount of 4.7% by mass Ru-0.3% by mass Fe / La 2 O 3 obtained in the above <Preparation Example 2-5> is added and stirred at room temperature for 12 hours.
Then, the water is evaporated by heating and stirring on a hot stirrer, and the paste is sufficiently dried with a dryer at 70 ° C. and pulverized and mixed in a mortar.
After that, it was put into a boat made of Pyrex (registered trademark) glass (Corning) and heated in a horizontal tube furnace under 100% H 2 flow at 500 ° C. for 1 hour, so that nitric acid in the alkali metal oxide precursor Remove the roots to obtain the product.
Catalyst obtained by such a procedure is Cs / 4.7 wt% Ru-0.3 wt% Fe / La 2 O 3.
＜実施例７＞
以下の手順で４．３質量％Ｒｕ−０．１質量％Ｎｉ／Ｌａ２Ｏ３＜調製例２−６＞にアルカリ金属酸化物を配合した触媒を調製する。なお，触媒中のアルカリ金属とルテニウムの原子比は０．１となるようにする。
３００ｍｌビーカーに１５０ｍｌの蒸留水を入れアルカリ金属酸化物の前駆体（ＣｓＮＯ３（関東化学（株）製）を加えてマグネットスターラーで撹拌し，溶解させる。その後，上記＜調製例２−６＞で得られた所定量の４．３質量％Ｒｕ−０．１質量％Ｎｉ／Ｌａ２Ｏ３を加えて常温で１２時間撹拌する。その後，ホットスターラ―上で加熱攪拌により水分を蒸発させ，ペースト状になったものを７０℃の乾燥機で充分に乾燥させ，乳鉢で粉砕混合する。その後パイレックス（登録商標）ガラス製（コーニング社製）のボートにいれ，横型管状炉で１００％のＨ２流通下で５００℃，１時間加熱処理することで，アルカリ金属酸化物前駆体中の硝酸根を除去し、生成物を得る。
このような手順で得られた触媒は、Ｃｓ／４．３質量％Ｒｕ−０．１質量％Ｎｉ／Ｌａ２Ｏ３である。
<Example 7>
Preparing a catalyst obtained by blending alkali metal oxide of 4.3 wt% Ru-0.1 wt% Ni / La 2 O 3 <Preparation Example 2-6> by the following procedure. The atomic ratio of alkali metal to ruthenium in the catalyst is set to 0.1.
In a 300 ml beaker, 150 ml of distilled water is added, an alkali metal oxide precursor (CsNO 3 (manufactured by Kanto Chemical Co., Inc.)) is added and stirred and dissolved with a magnetic stirrer. It was added to the resultant 4.3 wt% Ru-0.1 wt% Ni / La 2 O 3 in a predetermined amount and stirred at room temperature for 12 hours then hot stirrer -. water is evaporated by heating and stirring on, the paste The resulting product is thoroughly dried in a dryer at 70 ° C. and pulverized and mixed in a mortar, then placed in a Pyrex (registered trademark) glass (Corning) boat and 100% H 2 in a horizontal tube furnace. The nitrate radical in the alkali metal oxide precursor is removed by heat treatment at 500 ° C. for 1 hour under flow to obtain a product.
The catalyst obtained in this procedure is a Cs / 4.3 wt% Ru-0.1 wt% Ni / La 2 O 3.
＜実施例８＞
Ａｌ−ＢＴＢと、上記＜調製例２−４＞で得られた３質量％Ｒｕ／Ｌａ２Ｏ３とを、質量比１：９で乳鉢を用いて物理混合する。
このような手順でＡｌ−ＢＴＢ＋３質量％Ｒｕ／Ｌａ２Ｏ３を得る。
<Example 8>
Al-BTB and 3 mass% Ru / La 2 O 3 obtained in the above <Preparation Example 2-4> are physically mixed using a mortar at a mass ratio of 1: 9.
Obtain Al-BTB + 3 wt% Ru / La 2 O 3 in such a procedure.
＜実施例９＞
Ａｌ−ＢＴＢと、上記＜調製例２−５＞で得られた４．７質量％Ｒｕ−０．３質量％Ｆｅ／Ｌａ２Ｏ３とを、質量比１：９で乳鉢を用いて物理混合する。
このような手順でＡｌ−ＢＴＢ＋４．７質量％Ｒｕ−０．３質量％Ｆｅ／Ｌａ２Ｏ３を得る。
<Example 9>
Physical mixing of Al-BTB and 4.7% by mass Ru-0.3% by mass Fe / La 2 O 3 obtained in the above <Preparation Example 2-5> using a mortar at a mass ratio of 1: 9 To do.
Obtain Al-BTB + 4.7 wt% Ru-0.3 wt% Fe / La 2 O 3 in such a procedure.
＜実施例１０＞
Ａｌ−ＢＴＢと、上記＜調製例２−６＞で得られた４．３質量％Ｒｕ−０．１質量％Ｎｉ／Ｌａ２Ｏ３とを、質量比１：９で乳鉢を用いて物理混合する。
このような手順でＡｌ−ＢＴＢ＋４．３質量％Ｒｕ−０．１質量％Ｎｉ／Ｌａ２Ｏ３を得る。
<Example 10>
And al-BTB, and 4.3 wt% Ru-0.1 wt% Ni / La 2 O 3 obtained in the above <Preparation Example 2-6>, a weight ratio of 1: 9 using a mortar in a physical mixture To do.
Obtain Al-BTB + 4.3 wt% Ru-0.1 wt% Ni / La 2 O 3 in such a procedure.
＜比較例２＞
上記比較例１において得られた触媒を用いて、上述した方法によりアンモニアを製造し、アンモニア収率を算出したところ、０．０６％であった。結果を表２に示す。
<Comparative example 2>
Ammonia was produced by the method described above using the catalyst obtained in Comparative Example 1, and the ammonia yield was calculated to be 0.06%. The results are shown in Table 2.
上記結果から、塩基性助触媒を配合した実施例２〜４の触媒、並びに多孔性金属錯体を配合した実施例１の触媒を用いた場合、塩基性助触媒及び多孔性金属錯体を配合していない比較例２の触媒に比べて、常圧においても高収率でアンモニアを製造できることがわかった。 From the above results, when using the catalyst of Examples 2 to 4 blended with the basic promoter and the catalyst of Example 1 blended with the porous metal complex, the basic promoter and the porous metal complex were blended. It was found that ammonia can be produced in a high yield even at normal pressure as compared with the catalyst of Comparative Example 2 that is not present.
Claims (5)
（２）ランタノイドを含む化合物、並びに、
（３）塩基性助触媒及び／又は多孔性金属錯体
を配合した組成物。 (1) ruthenium, an alloy containing ruthenium or a compound containing ruthenium,
(2) a compound containing a lanthanoid, and
(3) A composition containing a basic promoter and / or a porous metal complex.
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