JP6381131B2 - Ammonia decomposition catalyst, method for producing the catalyst, and method for decomposing ammonia using the catalyst - Google Patents
Ammonia decomposition catalyst, method for producing the catalyst, and method for decomposing ammonia using the catalyst Download PDFInfo
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- JP6381131B2 JP6381131B2 JP2015038592A JP2015038592A JP6381131B2 JP 6381131 B2 JP6381131 B2 JP 6381131B2 JP 2015038592 A JP2015038592 A JP 2015038592A JP 2015038592 A JP2015038592 A JP 2015038592A JP 6381131 B2 JP6381131 B2 JP 6381131B2
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims description 188
- 229910021529 ammonia Inorganic materials 0.000 title claims description 91
- 239000003054 catalyst Substances 0.000 title claims description 84
- 238000000354 decomposition reaction Methods 0.000 title claims description 62
- 238000000034 method Methods 0.000 title claims description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 24
- 239000001095 magnesium carbonate Substances 0.000 claims description 24
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 229910052707 ruthenium Inorganic materials 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 17
- 150000002681 magnesium compounds Chemical class 0.000 claims description 16
- 239000011148 porous material Substances 0.000 claims description 15
- 150000003304 ruthenium compounds Chemical class 0.000 claims description 15
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 14
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 14
- 238000010304 firing Methods 0.000 claims description 14
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 13
- 230000009467 reduction Effects 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000000395 magnesium oxide Substances 0.000 claims description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 10
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 7
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 7
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 24
- 230000000694 effects Effects 0.000 description 24
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 20
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 20
- 229910052739 hydrogen Inorganic materials 0.000 description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 18
- 239000001257 hydrogen Substances 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 229910000027 potassium carbonate Inorganic materials 0.000 description 10
- 238000005470 impregnation Methods 0.000 description 8
- 230000001376 precipitating effect Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 6
- 229910001863 barium hydroxide Inorganic materials 0.000 description 6
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- VDRDGQXTSLSKKY-UHFFFAOYSA-K ruthenium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ru+3] VDRDGQXTSLSKKY-UHFFFAOYSA-K 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 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
- 229910052788 barium Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical group [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 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
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- -1 Alkali metal hydrogen carbonates Chemical class 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical group [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 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
- 238000005406 washing Methods 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-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
- 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
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Description
本発明は、アンモニアガスを効率よく分解し水素を製造するためのアンモニア分解触媒、及び該触媒の製造方法並びに該触媒を用いたアンモニアの分解方法に関するものである。 The present invention relates to an ammonia decomposition catalyst for efficiently decomposing ammonia gas to produce hydrogen, a method for producing the catalyst, and a method for decomposing ammonia using the catalyst.
近年、環境保護の観点から水素をクリーンエネルギー源として用いることが注目されており、例えば、水素を燃料とする燃料電池車の開発が活発に行われている。一方、水素は気体の状態では非常に軽いために、輸送することが困難であるという問題がある。解決策としては圧縮、または液化する方法があるが、エネルギー消費が大きく課題が残る。この課題を解決する方法として、液体アンモニアとして水素を貯蔵・輸送して、アンモニアの接触分解により水素を製造する試みがなされている。アンモニアから燃料電池の燃料として使用される水素を生成する場合には、アンモニアが電池を被毒することからほぼ完全に分解可能な高い性能をもつアンモニア分解触媒が必要となる。 In recent years, the use of hydrogen as a clean energy source has attracted attention from the viewpoint of environmental protection. For example, fuel cell vehicles using hydrogen as a fuel have been actively developed. On the other hand, since hydrogen is very light in a gaseous state, there is a problem that it is difficult to transport. As a solution, there is a method of compressing or liquefying, but energy consumption is a big problem. As a method for solving this problem, attempts have been made to produce hydrogen by catalytic decomposition of ammonia by storing and transporting hydrogen as liquid ammonia. In the case of producing hydrogen used as fuel for fuel cells from ammonia, ammonia poisons the cells, so an ammonia decomposing catalyst having high performance that can be almost completely decomposed is required.
従来、アンモニアを水素と窒素に分解する方法や触媒としては、以下の技術が知られている。
（１）シリカや酸化ランタンなどの無機質担体にニッケルやコバルトを含浸担持法等により担持した触媒を使用し、加熱下でアンモニアを接触させ、水素と窒素に分解する方法（特許文献１、非特許文献１、非特許文献２参照)。
（２）アルミナ、シリカ、酸化マグネシウムなどの無機質担体に、含浸担持法等により白金族(ルテニウム)を担持した触媒を使用し、加熱下でアンモニアを接触させ、水素と窒素に分解する方法(特許文献２〜５参照)。
Conventionally, the following techniques are known as methods and catalysts for decomposing ammonia into hydrogen and nitrogen.
(1) A method of using a catalyst in which nickel or cobalt is supported on an inorganic carrier such as silica or lanthanum oxide by an impregnation supporting method, etc., contacting ammonia under heating, and decomposing it into hydrogen and nitrogen (Patent Document 1, Non-patent) Reference 1 and Non-Patent Document 2).
(2) A method in which a catalyst in which a platinum group (ruthenium) is supported on an inorganic carrier such as alumina, silica, magnesium oxide or the like by an impregnation supporting method or the like is used, ammonia is brought into contact with heating and decomposed into hydrogen and nitrogen (patent) References 2-5).
中でもルテニウムを担持した触媒はアンモニアの分解に際して最も高い活性を示すが、実用化に際し、さらなる高活性化が望まれている。
しかし、従来の触媒では、ルテニウムを担体に均一に分散し、担持させることは難しく、触媒としての充分な機能が発揮し難いものであった。
Among them, a catalyst supporting ruthenium exhibits the highest activity when decomposing ammonia, but further high activation is desired for practical use.
However, with conventional catalysts, it is difficult to uniformly disperse and carry ruthenium on a carrier, and it is difficult to exhibit a sufficient function as a catalyst.
本発明は、活性種であるルテニウムを担体に均一に分散し、担持させることで極めて高い触媒活性を有するアンモニア分解触媒、および該触媒を用いたアンモニア分解方法を提供することを目的とするものである。 An object of the present invention is to provide an ammonia decomposition catalyst having extremely high catalytic activity by uniformly dispersing and supporting ruthenium, which is an active species, on a carrier, and an ammonia decomposition method using the catalyst. is there.
本発明者は、上記目的を達成すべく鋭意研究を重ねた結果、マグネシウム化合物とルテニウム化合物を、水溶液中でアルカリ金属炭酸塩により沈殿させ、乾燥、焼成、還元を経て作製されたルテニウム担持触媒が上記目的を達成できることを見出した。これは、アルカリ金属炭酸塩により沈殿したマグネシウム炭酸塩とルテニウム水酸化物が高度に分散した状態で緩く結びつき、さらに焼成条件を制御することで、高い比表面積を有し、３０Å付近に細孔径分布のピークを持つ塩基性炭酸マグネシウムを含む担体に、ルテニウム種を均一に高分散した状態とすることができるためである。また、該触媒に、活性助剤としてアルカリ金属もしくはアルカリ土類金属を添加することでさらに活性が向上することも合わせて見出した。 As a result of earnest research to achieve the above object, the present inventor obtained a ruthenium-supported catalyst prepared by precipitating a magnesium compound and a ruthenium compound with an alkali metal carbonate in an aqueous solution, drying, firing, and reduction. It has been found that the above object can be achieved. This is because the magnesium carbonate precipitated by the alkali metal carbonate and the ruthenium hydroxide are loosely tied in a highly dispersed state, and furthermore, by controlling the firing conditions, it has a high specific surface area and the pore size distribution in the vicinity of 30 mm. This is because the ruthenium species can be uniformly and highly dispersed in a carrier containing basic magnesium carbonate having a peak of. It has also been found that the activity is further improved by adding an alkali metal or an alkaline earth metal as an activity assistant to the catalyst.
本発明は、かかる知見に基づいて完成したものであり、以下の構成を要旨とするものである。
［１］塩基性炭酸マグネシウムを含む酸化マグネシウム担体と該記担体に担持されたルテニウムを含有することを特徴とするアンモニア分解触媒。
［２］３０Å付近に細孔径分布のピークを有することを特徴とする[１]に記載のアンモニア分解触媒。
［３］活性助剤として、アルカリ金属及びアルカリ土類金属から選ばれる少なくとも１つの金属を含有することを特徴とする[１]〜[２]のいずれかに記載のアンモニア分解触媒。
［４］マグネシウム化合物及びルテニウム化合物を含む水溶液中でアルカリ金属炭酸塩により沈殿させる工程、得られた沈殿を乾燥する工程、焼成する工程、及び還元する工程を含むことを特徴とするアンモニア分解触媒の製造方法。
［５］前記焼成を、４００℃を超え６００℃未満で行うことを特徴とする[４]に記載のアンモニア分解触媒の製造方法。
［６］前記還元を、還元性ガスを含む雰囲気中で行うことを特徴とする[４]又は[５]に記載のアンモニア分解触媒の製造方法。
［７］前記乾燥後の沈殿に、アルカリ金属化合物又はアルカリ土類金属化合物の水溶液を含浸させた後、乾燥させる工程を含むことを特徴とする[４]〜[６]のいずれかに記載のアンモニア分解触媒の製造方法。
［８］前記マグネシウム化合物及びルテニウム化合物を含む水溶液に、更にアルカリ金属化合物又はアルカリ土類金属化合物を含有させることを特徴とする[４]〜[６]のいずれかに記載のアンモニア分解触媒の製造方法。
［９］[４]〜[８]のいずれかに記載された方法で製造されたアンモニア分解触媒。
［１０］[１]〜[３]及び[９]のいずれかに記載のアンモニア分解触媒の存在下でアンモニアを分解することを特徴とするアンモニアの分解方法。
The present invention has been completed based on such findings, and has the following structure.
[1] An ammonia decomposition catalyst comprising a magnesium oxide carrier containing basic magnesium carbonate and ruthenium supported on the carrier.
[2] The ammonia decomposition catalyst according to [1], which has a pore size distribution peak in the vicinity of 30 mm.
[3] The ammonia decomposition catalyst according to any one of [1] to [2], which contains at least one metal selected from alkali metals and alkaline earth metals as an active auxiliary agent.
[4] An ammonia decomposition catalyst comprising a step of precipitation with an alkali metal carbonate in an aqueous solution containing a magnesium compound and a ruthenium compound, a step of drying the obtained precipitate, a step of firing, and a step of reducing. Production method.
[5] The method for producing an ammonia decomposition catalyst according to [4], wherein the calcination is performed at a temperature higher than 400 ° C. and lower than 600 ° C.
[6] The method for producing an ammonia decomposition catalyst according to [4] or [5], wherein the reduction is performed in an atmosphere containing a reducing gas.
[7] The method according to any one of [4] to [6], including a step of impregnating the precipitate after drying with an aqueous solution of an alkali metal compound or an alkaline earth metal compound and then drying the precipitate. A method for producing an ammonia decomposition catalyst.
[8] The ammonia decomposition catalyst according to any one of [4] to [6], wherein the aqueous solution containing the magnesium compound and the ruthenium compound further contains an alkali metal compound or an alkaline earth metal compound. Method.
[9] An ammonia decomposition catalyst produced by the method according to any one of [4] to [8].
[10] A method for decomposing ammonia, comprising decomposing ammonia in the presence of the ammonia decomposing catalyst according to any one of [1] to [3] and [9].
本発明によれば、活性種であるルテニウムを無機質担体に均一に分散し、担持させることで極めて高い触媒活性を有するアンモニア分解能を示す触媒が提供される。
また、本発明によれば、かかる触媒を使用することにより、低温でも非常に高い活性を示すアンモニアを水素と窒素に効率良く分解する方法、或いは、アンモニアから燃料電池用の水素と窒素とを効率的に製造する方法が提供される。
ADVANTAGE OF THE INVENTION According to this invention, the catalyst which shows the ammonia decomposition | disassembly which has very high catalyst activity is provided by disperse | distributing and carrying | supporting ruthenium which is an active species uniformly on an inorganic support | carrier.
In addition, according to the present invention, by using such a catalyst, ammonia that exhibits very high activity even at low temperatures can be efficiently decomposed into hydrogen and nitrogen, or hydrogen and nitrogen for fuel cells can be efficiently converted from ammonia. A method of manufacturing the same is provided.
本発明における担体を構成する成分である塩基性炭酸マグネシウムそのものは、アンモニア分解活性を全く示さない。また、市販の塩基性炭酸マグネシウムにルテニウムを含浸担持法により担持した触媒では、アンモニア分解活性を示すものの、その活性は低い。一方、マグネシウム化合物とルテニウム化合物を、水溶液中、アルカリ水酸化物、アンモニア、アンモニウム塩等による塩基性化合物で沈殿させ、これを乾燥、焼成、還元により調製したルテニウム担持触媒においてもアンモニア分解活性はさほど高くない。 Basic magnesium carbonate itself, which is a component constituting the carrier in the present invention, does not show any ammonia decomposing activity. Further, a catalyst in which ruthenium is supported on a commercially available basic magnesium carbonate by an impregnation supporting method shows ammonia decomposition activity, but its activity is low. Meanwhile, a ruthenium-supported catalyst prepared by precipitating a magnesium compound and a ruthenium compound with a basic compound such as an alkali hydroxide, ammonia, or an ammonium salt in an aqueous solution, and drying, calcining, or reducing the ammonia decomposition activity is not so much. not high.
これに対し、本発明の、マグネシウム化合物とルテニウム化合物を、水溶液中でアルカリ金属炭酸塩により沈殿させ、乾燥、焼成、還元を経て作製されたルテニウム担持触媒は、著しく高いアンモニア分解性能を有する。このような特異的な活性は、マグネシウム化合物とルテニウム化合物をアルカリ金属炭酸塩により沈殿させ調製することによって始めて発現するものである。 In contrast, a ruthenium-supported catalyst prepared by precipitating a magnesium compound and a ruthenium compound with an alkali metal carbonate in an aqueous solution and drying, calcining, and reducing the present invention has extremely high ammonia decomposition performance. Such specific activity is manifested only by preparing a magnesium compound and a ruthenium compound by precipitation with an alkali metal carbonate.
本発明における、触媒の調製における沈殿物作製の過程においては、マグネシウム化合物ならびにルテニウム化合物の混合溶液にアルカリ金属炭酸塩を後から添加する方法、もしくはアルカリ金属炭酸塩水溶液にマグネシウム化合物ならびにルテニウム化合物の混合溶液を添加する方法、もしくはアルカリ金属炭酸塩水溶液にマグネシウム化合物の溶液とルテニウム化合物の溶液を別々に同時あるいは逐次的に添加する方法等で行うことができる。この際、マグネシウム化合物の形態は水溶性の塩化物、硝酸塩、酢酸塩、アンミン錯体等が好ましく用いられる。特に好ましくは、残存陰イオンを空気中の焼成処理により比較的低温で分解できる硝酸マグネシウムが用いられる。また、ルテニウム化合物の形態は、水溶性の塩化物、硝酸塩、酢酸塩、アンミン錯体等が好ましく用いられる。特に好ましくは、安価な塩化ルテニウムが用いられる。 In the present invention, in the process of preparing the precipitate in the preparation of the catalyst, a method of adding an alkali metal carbonate to a mixed solution of a magnesium compound and a ruthenium compound later, or a mixing of a magnesium compound and a ruthenium compound in an aqueous alkali metal carbonate solution It can be carried out by a method of adding a solution, a method of adding a magnesium compound solution and a ruthenium compound solution separately or simultaneously to an alkali metal carbonate aqueous solution. In this case, water-soluble chlorides, nitrates, acetates, ammine complexes and the like are preferably used as the magnesium compound. Particularly preferably, magnesium nitrate that can decompose residual anions at a relatively low temperature by a calcination treatment in air is used. As the form of the ruthenium compound, water-soluble chlorides, nitrates, acetates, ammine complexes and the like are preferably used. Particularly preferably, inexpensive ruthenium chloride is used.
沈殿剤であるアルカリ金属炭酸塩の形態は炭酸リチウム、炭酸ナトリウム、炭酸カリウム、炭酸セシウム等が好ましく用いられる。また、アルカリ金属の炭酸水素塩も好ましく用いられる。特に好ましくは、炭酸カリウムが用いられる。例えば、炭酸カリウム水溶液中に硝酸マグネシウム水溶液、塩化ルテニウム水溶液を添加することにより、塩基性炭酸マグネシウムとルテニウム水酸化物からなる沈殿が得られる。この沈殿では、塩基性炭酸マグネシウムとルテニウム水酸化物が高度に分散した状態で緩く結びついた状態で存在している。 Lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate and the like are preferably used as the form of the alkali metal carbonate that is the precipitant. Alkali metal hydrogen carbonates are also preferably used. Particularly preferably, potassium carbonate is used. For example, by adding a magnesium nitrate aqueous solution and a ruthenium chloride aqueous solution to a potassium carbonate aqueous solution, a precipitate composed of basic magnesium carbonate and ruthenium hydroxide can be obtained. In this precipitation, basic magnesium carbonate and ruthenium hydroxide are present in a highly dispersed state and loosely bound.
得られた沈殿は、大気中静置して熟成させるのが好ましいが、熟成させなくてもよい。熟成は、常温〜８０℃で、１〜１４４時間で行うのが好ましい。その後、濾過、必要に応じて水洗を行い、乾燥し、空気中で焼成を行うことによって製造することができる。 The obtained precipitate is preferably allowed to stand in the atmosphere for aging, but may not be ripened. Aging is preferably performed at room temperature to 80 ° C. for 1 to 144 hours. Then, it can manufacture by performing filtration, washing with water as needed, drying, and baking in air.
活性助剤であるアルカリ金属、もしくはアルカリ土類金属の担持方法は、前記の手順に従って得られた沈殿物を乾燥したものに、アルカリ金属化合物もしくはアルカリ土類金属化合物からなる水溶液を含浸させた後、乾燥、焼成する。あるいは、沈殿作製時に、沈殿剤の水溶液中にアルカリ金属、もしくはアルカリ土類金属水溶液を混合した水溶液を供給し、沈殿を乾燥、焼成する方法を用いてもよい。 The method for supporting an alkali metal or alkaline earth metal as an active aid is obtained by impregnating an aqueous solution comprising an alkali metal compound or an alkaline earth metal compound into a dried precipitate obtained according to the above procedure. Dry and fire. Alternatively, a method may be used in which an aqueous solution obtained by mixing an aqueous alkali metal or alkaline earth metal solution in an aqueous solution of a precipitant is supplied at the time of preparing the precipitate, and the precipitate is dried and fired.
活性助剤であるアルカリ金属化合物の形態は水溶性の水酸化物、硝酸塩、塩化物等が好ましく用いられる。特に、水酸化物である水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化セシウム等が好ましく用いられる。特に好ましくは、水酸化セシウムが用いられる。また、アルカリ土類金属化合物の形態は水溶性の水酸化物、硝酸塩、塩化物等が好ましく用いられる。特に、水酸化物である水酸化カルシウム、水酸化ストロンチウム、水酸化バリウム等が好ましく用いられる。特に好ましくは、水酸化バリウムが用いられる。アルカリ金属化合物の含有量として、Ｒｕ含有量に対して原子比で１/１０〜１０、好ましくは１/２〜２の範囲で効果を示す。 As the form of the alkali metal compound which is the active auxiliary, water-soluble hydroxide, nitrate, chloride and the like are preferably used. In particular, hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide and the like are preferably used. Particularly preferably, cesium hydroxide is used. The alkaline earth metal compound is preferably water-soluble hydroxide, nitrate, chloride or the like. In particular, hydroxides such as calcium hydroxide, strontium hydroxide, and barium hydroxide are preferably used. Particularly preferably, barium hydroxide is used. As the content of the alkali metal compound, the effect is exhibited in the range of 1/10 to 10, preferably 1/2 to 2 in terms of atomic ratio with respect to the Ru content.
焼成は、酸素含有雰囲気、好ましくは大気中で、３００〜９００℃、好ましくは４００〜７００℃で、１〜１２時間で行い、低温、短時間であると、化合物の分解が十分に進行せず、高温、長時間であると、含有成分の凝集やシンタリングが起きて、触媒の活性が低下してしまう。焼成後には、塩基性炭酸マグネシウムは、焼成温度に従い塩基性炭酸マグネシウムのまま、もしくは一部あるいは全てが酸化マグネシウムとして存在すると考えられる。ルテニウムは、酸化物として存在すると考えられる。 Firing is performed in an oxygen-containing atmosphere, preferably in the air, at 300 to 900 ° C., preferably 400 to 700 ° C. for 1 to 12 hours. If the temperature is low and short, decomposition of the compound does not proceed sufficiently. If the temperature is high and the time is long, aggregation of components and sintering occur, and the activity of the catalyst decreases. After calcination, the basic magnesium carbonate is considered to remain as the basic magnesium carbonate or partially or entirely as magnesium oxide according to the calcination temperature. Ruthenium is considered to exist as an oxide.
本発明の触媒の形状は、特に制約はなく、粉状、粒状、球状、円柱状、リング状などのほか、特に、本発明の触媒は高い空間速度においても高い活性を示すことから、ハニカム状でも使用が可能である。 The shape of the catalyst of the present invention is not particularly limited, and is in the form of powder, granules, spheres, cylinders, rings, etc. In particular, the catalyst of the present invention exhibits high activity even at high space velocities. But it can be used.
上記触媒は還元処理を行うことにより、アンモニアガスから水素と窒素との生成をより高転化率で行うことができる。これは、主に、前記ルテニウムが、還元処理によって、還元処理前の酸化物の状態から活性状態である金属の状態に分散された状態で形成され、アンモニア分解触媒として機能するためである。 By performing a reduction treatment, the catalyst can generate hydrogen and nitrogen from ammonia gas at a higher conversion rate. This is mainly because the ruthenium is formed in a state of being dispersed from the oxide state before the reduction treatment to the active metal state by the reduction treatment, and functions as an ammonia decomposition catalyst.
この際、還元処理は、使用前に還元性ガスにより行ってもよく、また、使用中アンモニアガスによって行っても良い。還元処理は、還元性のガスの雰囲気に暴露することにより行うのが好ましい。還元性のガスとしては、特に制約はなく、水素ガス、アンモニアガス、ヒドラジンガス、一酸化炭素等が挙げられ、それだけで使用しても、また不活性ガスと混合して用いても良い。 In this case, the reduction treatment may be performed with a reducing gas before use or may be performed with ammonia gas during use. The reduction treatment is preferably performed by exposure to a reducing gas atmosphere. The reducing gas is not particularly limited, and examples thereof include hydrogen gas, ammonia gas, hydrazine gas, carbon monoxide, and the like. They may be used alone or in combination with an inert gas.
還元性ガスの還元処理時間は特に制限しないが、１〜２時間が好ましい。また、還元処理の温度は、３００〜９００℃が好ましい。 The reduction treatment time of the reducing gas is not particularly limited, but is preferably 1 to 2 hours. The reduction treatment temperature is preferably 300 to 900 ° C.
本発明のアンモニア分解触媒を用いることによりアンモニアを分解することができる。アンモニアの分解は、エネルギー源としての水素製造の観点からアンモニアを分解して水素と窒素を製造する場合や、公害防止などの観点から有害物としてのアンモニアを水素と窒素に分解する場合のいずれにも使用される。 Ammonia can be decomposed by using the ammonia decomposition catalyst of the present invention. Ammonia can be decomposed either in the case of decomposing ammonia from the viewpoint of hydrogen production as an energy source to produce hydrogen and nitrogen, or in the case of decomposing ammonia as a harmful substance into hydrogen and nitrogen from the viewpoint of pollution prevention. Also used.
本発明におけるアンモニア分解触媒を用いるアンモニアの分解反応は、温度が３００〜９００℃であるのが好ましく、４００〜６００℃がより好ましい。アンモニアの体積空間速度は１０００〜５００００ｈ-1であるのが好ましく、２０００〜２００００ｈ-1であるのがより好ましい。 In the ammonia decomposition reaction using the ammonia decomposition catalyst in the present invention, the temperature is preferably 300 to 900 ° C, more preferably 400 to 600 ° C. Is preferably a volume space velocity of ammonia is 1000~50000h -1, and more preferably 2000~20000h -1.
アンモニアの分解時の圧力は、適宜調整することができ、常圧であるのが特に好ましい。 The pressure at the time of decomposition of ammonia can be appropriately adjusted, and it is particularly preferable that the pressure be normal pressure.
アンモニア分解反応の反応装置の形式に特に制限はなく、バッチ式、流通式のいずれの装置も使用し得るが、流通式が効率も良いので好ましい。また、固定床方式、又は流動床方式のいずれも採用できるが、固定床方式が好ましい。 There is no particular limitation on the type of the ammonia decomposition reaction apparatus, and either a batch type or a flow type apparatus can be used, but the flow type is preferable because of its high efficiency. Moreover, although a fixed bed system or a fluidized bed system can be employed, a fixed bed system is preferable.
以下、実施例及び比較例により本発明を具体的に説明するが、本発明はこれらの実施例に限定して解釈されるべきではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention should not be limited and limited to these Examples.
（実施例１）
本実施例では、Ｒｕ出発原料は塩化ルテニウム(ＲｕＣｌ3・ｎＨ2Ｏ)とし、担体原料は硝酸マグネシウム(Ｍｇ(ＮＯ3)2・６Ｈ2Ｏ)(和光純薬工業、特級)とした。
焼成後のＲｕ担持触媒中のＲｕの量が３質量％となるように、塩化ルテニウム０.２９６ｇ及び硝酸マグネシウム２５.３４０ｇを計り取り、４００ｍＬの純水に溶解した。得られた混合溶液を激しく撹拌しながら、０.３ｍｏｌ／Ｌの炭酸カリウム溶液４００ｍＬを徐々に加え、沈殿物を作製した。沈殿物は常温で２４時間静置し、熟成させた。その後、濾過、洗浄し、１１０℃で２４時間乾燥した。これを空気中において５５０℃で２時間焼成しＲｕ担持触媒を得た。
Example 1
In this example, the Ru starting material was ruthenium chloride (RuCl 3 .nH 2 O), and the carrier material was magnesium nitrate (Mg (NO 3 ) 2 .6H 2 O) (Wako Pure Chemical Industries, special grade).
Ruthenium chloride (0.296 g) and magnesium nitrate (25.340 g) were weighed out and dissolved in 400 mL of pure water so that the amount of Ru in the Ru-supported catalyst after calcination was 3% by mass. While vigorously stirring the obtained mixed solution, 400 mL of a 0.3 mol / L potassium carbonate solution was gradually added to prepare a precipitate. The precipitate was left to stand at room temperature for 24 hours and aged. Then, it filtered, wash | cleaned, and dried at 110 degreeC for 24 hours. This was calcined in air at 550 ° C. for 2 hours to obtain a Ru-supported catalyst.
上記のようにして得られた本発明の触媒０．２gを常圧流通式反応装置に充填した。触媒床温度を測定するための熱電対を触媒床中心付近に配置した。
触媒は反応前に２０％Ｈ2／窒素気流中、５５０℃、１時間還元を施した。１００％アンモニアガスを反応ガスとし、反応温度４００℃、流量１００ｍｌ／ｍｉｎ(Ｗ／Ｆ ０.００２ｇ・ｍｉｎ／ｃｃ、ＳＶでは１５０００ｈ-1に相当)で触媒床に流通し、その生成ガスを、ガスクロマトグラフ(Ｎ2、Ｈ2、ＮＨ3分析)で分析した。
活性評価は、次式に示すＨ2収率により行い、その結果を表１に示した。
Ｈ2収率＝[３×Ｈ2濃度／２×ＮＨ3入口濃度]×１００(％)
The atmospheric pressure flow reactor was charged with 0.2 g of the catalyst of the present invention obtained as described above. A thermocouple for measuring the catalyst bed temperature was placed near the center of the catalyst bed.
The catalyst was subjected to reduction in a 20% H 2 / nitrogen stream at 550 ° C. for 1 hour before the reaction. 100% ammonia gas was used as the reaction gas, the reaction temperature was 400 ° C., the flow rate was 100 ml / min (W / F 0.002 g · min / cc, equivalent to 15000 h −1 for SV), and the product gas was circulated. Analysis was performed by gas chromatography (N 2 , H 2 , NH 3 analysis).
The activity was evaluated based on the H 2 yield represented by the following formula, and the results are shown in Table 1.
H 2 yield = [3 × H 2 concentration / 2 × NH 3 inlet concentration] × 100 (%)
（実施例２）
実施例１において、反応温度を４５０℃とした以外は、実施例１と同様にしてアンモニア分解反応を行い、その結果を表１に示した。
(Example 2)
In Example 1, the ammonia decomposition reaction was performed in the same manner as in Example 1 except that the reaction temperature was 450 ° C. The results are shown in Table 1.
（実施例３）
実施例１において、反応温度を５００℃とした以外は、実施例１と同様にしてアンモニア分解反応を行い、その結果を表１に示した。
(Example 3)
In Example 1, the ammonia decomposition reaction was performed in the same manner as in Example 1 except that the reaction temperature was 500 ° C. The results are shown in Table 1.
（実施例４）
実施例１において、反応温度を６００℃とした以外は、実施例１と同様にしてアンモニア分解反応を行い、その結果を表１に示した。
Example 4
In Example 1, the ammonia decomposition reaction was performed in the same manner as in Example 1 except that the reaction temperature was 600 ° C. The results are shown in Table 1.
（比較例１）
本比較例では、担体を酸化マグネシウム(和光純薬工業)としてＲｕを含浸法にて担持した以外は、実施例１と同様にしてＲｕ担持触媒を得た。すなわち、所定量の酸化マグネシウムに、焼成後のＲｕ担持触媒中のＲｕの量が３質量％となるように塩化ルテニウム(ＲｕＣｌ3・ｎＨ2Ｏ)を溶解した水溶液を加えて含浸させた後、１１０℃で２４時間乾燥し、これを空気中において５５０℃で２時間焼成した。
こうして得られたＲｕ担持触媒を用いて、実施例１と同様にアンモニア分解反応を行い、その結果を表１に示した。
(Comparative Example 1)
In this comparative example, a Ru-supported catalyst was obtained in the same manner as in Example 1, except that the support was magnesium oxide (Wako Pure Chemical Industries) and Ru was supported by the impregnation method. That is, after impregnating a predetermined amount of magnesium oxide with an aqueous solution in which ruthenium chloride (RuCl 3 · nH 2 O) is dissolved so that the amount of Ru in the Ru-supported catalyst after firing is 3% by mass, This was dried at 110 ° C. for 24 hours, and calcined in air at 550 ° C. for 2 hours.
Using the Ru-supported catalyst thus obtained, an ammonia decomposition reaction was carried out in the same manner as in Example 1, and the results are shown in Table 1.
（比較例２）
比較例１において、反応温度を４５０℃とした以外は、比較例１と同様にしてアンモニア分解反応を行い、その結果を表１に示した。
(Comparative Example 2)
In Comparative Example 1, the ammonia decomposition reaction was performed in the same manner as in Comparative Example 1 except that the reaction temperature was 450 ° C. The results are shown in Table 1.
（比較例３）
比較例１において、反応温度を５００℃とした以外は、比較例１と同様にしてアンモニア分解反応を行い、その結果を表１に示した。
(Comparative Example 3)
In Comparative Example 1, the ammonia decomposition reaction was performed in the same manner as in Comparative Example 1 except that the reaction temperature was 500 ° C. The results are shown in Table 1.
（比較例４）
比較例１において、反応温度を６００℃とした以外は、比較例１と同様にしてアンモニア分解反応を行い、その結果を表１に示した。
(Comparative Example 4)
In Comparative Example 1, an ammonia decomposition reaction was carried out in the same manner as in Comparative Example 1 except that the reaction temperature was 600 ° C. The results are shown in Table 1.
表１に示すように、実施例１〜４の本発明の触媒活性は、比較例１〜４に示す従来技術の含浸法で調製した触媒の活性に比べて著しく高く、反応温度が４５０℃以上では、ほぼ平衡値まで到達している。このことは、マグネシウム化合物とルテニウム化合物とをアルカリ金属炭酸塩にて沈殿させることで、これまでにないＲｕの触媒性能が現れることを示している。 As shown in Table 1, the catalytic activity of the present invention in Examples 1 to 4 is significantly higher than the activity of the catalyst prepared by the impregnation method of the prior art shown in Comparative Examples 1 to 4, and the reaction temperature is 450 ° C. or higher. Then, it has almost reached the equilibrium value. This indicates that an unprecedented Ru catalytic performance appears by precipitating a magnesium compound and a ruthenium compound with an alkali metal carbonate.
（比較例５）
硝酸マグネシウムを硝酸イットリアに代えた以外は、実施例２と同様にしてアンモニア分解反応を行い、その結果を表２に示した。
(Comparative Example 5)
An ammonia decomposition reaction was carried out in the same manner as in Example 2 except that magnesium nitrate was replaced with yttria nitrate. The results are shown in Table 2.
（比較例６）
硝酸マグネシウムを硝酸ランタンに代えた以外は、実施例２と同様にしてアンモニア分解反応を行い、その結果を表２に示した。
(Comparative Example 6)
The ammonia decomposition reaction was performed in the same manner as in Example 2 except that magnesium nitrate was replaced with lanthanum nitrate. The results are shown in Table 2.
（比較例７）
硝酸マグネシウムを硝酸セリウムに代えた以外は、実施例２と同様にしてアンモニア分解反応を行い、その結果を表２に示した。
(Comparative Example 7)
The ammonia decomposition reaction was performed in the same manner as in Example 2 except that magnesium nitrate was replaced with cerium nitrate. The results are shown in Table 2.
（比較例８）
硝酸マグネシウムを硝酸アルミニウムに代えた以外は、実施例２と同様にしてアンモニア分解反応を行い、その結果を表２に示した。
(Comparative Example 8)
The ammonia decomposition reaction was carried out in the same manner as in Example 2 except that magnesium nitrate was replaced with aluminum nitrate. The results are shown in Table 2.
（比較例９）
硝酸マグネシウムを硝酸カルシウムに代えた以外は、実施例２と同様にしてアンモニア分解反応を行い、その結果を表２に示した。
(Comparative Example 9)
The ammonia decomposition reaction was carried out in the same manner as in Example 2 except that magnesium nitrate was replaced with calcium nitrate. The results are shown in Table 2.
表２から、担体原料としてマグネシウム化合物を用いた本発明の触媒は、他の担体原料化合物を用いた場合よりも活性が著しく高いことがわかる。
このことから、マグネシウムを含む担体を用いることにより高い触媒性能が発揮されることがわかる。
From Table 2, it can be seen that the catalyst of the present invention using a magnesium compound as a carrier raw material has significantly higher activity than the case of using another carrier raw material compound.
From this, it can be seen that high catalyst performance is exhibited by using a carrier containing magnesium.
（実施例５）
炭酸カリウムを炭酸ナトリウムに代えた以外は、実施例２と同様にしてアンモニア分解反応を行い、その結果を表３に示した。
(Example 5)
The ammonia decomposition reaction was performed in the same manner as in Example 2 except that potassium carbonate was replaced with sodium carbonate. The results are shown in Table 3.
（比較例１０）
炭酸カリウムを水酸化ナトリウムに代えた以外は、実施例２と同様にしてアンモニア分解反応を行い、その結果を表３に示した。
(Comparative Example 10)
The ammonia decomposition reaction was performed in the same manner as in Example 2 except that potassium carbonate was replaced with sodium hydroxide. The results are shown in Table 3.
（比較例１１）
炭酸カリウムを水酸化カリウムに代えた以外は、実施例２と同様にしてアンモニア分解反応を行い、その結果を表３に示した。
(Comparative Example 11)
An ammonia decomposition reaction was carried out in the same manner as in Example 2 except that potassium carbonate was replaced with potassium hydroxide. The results are shown in Table 3.
（比較例１２）
炭酸カリウムをアンモニアに代えた以外は、実施例２と同様にしてアンモニア分解反応を行い、その結果を表３に示した。
(Comparative Example 12)
Ammonia decomposition reaction was carried out in the same manner as in Example 2 except that potassium carbonate was replaced with ammonia. The results are shown in Table 3.
表３から、沈殿剤としてアルカリ金属炭酸塩を用いた本発明の触媒は、水酸化物等の沈殿剤を用いた場合よりも活性が高くなっており、炭酸塩が高活性化に寄与していることが示される。特に沈殿剤に炭酸カリウムを用いることにより顕著に高い触媒性能が発揮されることがわかる。これは、沈殿生成時に炭酸カリウムにより塩基性炭酸マグネシウムとルテニウム水酸化物が生成するが、これらが高度に分散した状態で緩く結びついており、その結果、焼成後に塩基性炭酸マグネシウム上にルテニウム種が高分散した状態で担持されているためである。 From Table 3, the catalyst of the present invention using an alkali metal carbonate as a precipitating agent has higher activity than the case of using a precipitating agent such as a hydroxide, and the carbonate contributes to high activation. Is shown. In particular, it can be seen that remarkably high catalyst performance is exhibited by using potassium carbonate as the precipitant. This is because basic magnesium carbonate and ruthenium hydroxide are produced by potassium carbonate during precipitation, but they are loosely bound in a highly dispersed state, and as a result, the ruthenium species are formed on the basic magnesium carbonate after firing. This is because it is supported in a highly dispersed state.
（実施例６）
実施例２において、触媒の焼成温度を４００℃とした以外は、実施例２と同様にしてアンモニア分解反応を行い、その結果を表４に示した。
(Example 6)
In Example 2, the ammonia decomposition reaction was performed in the same manner as in Example 2 except that the calcination temperature of the catalyst was 400 ° C. The results are shown in Table 4.
（実施例７）
実施例２において、触媒の焼成温度を５００℃とした以外は、実施例２と同様にしてアンモニア分解反応を行い、その結果を表４に示した。
(Example 7)
In Example 2, the ammonia decomposition reaction was performed in the same manner as in Example 2 except that the calcination temperature of the catalyst was 500 ° C. The results are shown in Table 4.
（実施例８）
実施例２において、触媒の焼成温度を６００℃とした以外は、実施例２と同様にしてアンモニア分解反応を行い、その結果を表４に示した。
(Example 8)
In Example 2, the ammonia decomposition reaction was performed in the same manner as in Example 2 except that the calcination temperature of the catalyst was 600 ° C. The results are shown in Table 4.
（実施例９）
実施例２において、触媒の焼成温度を７００℃とした以外は、実施例２と同様にしてアンモニア分解反応を行い、その結果を表４に示した。
Example 9
In Example 2, the ammonia decomposition reaction was carried out in the same manner as in Example 2 except that the calcination temperature of the catalyst was 700 ° C. The results are shown in Table 4.
表４に示すように、４００℃から５５０℃までは活性はほとんどかわらず、焼成温度にはほとんど影響されないことがわかる。一方、焼成温度を６００℃、７００℃と高くした場合では温度が増加するにつれて活性が著しく低下する。硝酸マグネシウムと炭酸カリウムにより生成した沈殿物である塩基性炭酸マグネシウムは、６００℃付近で分解が終了し、酸化マグネシウムに変化することから、開発した触媒では、担体成分として塩基性炭酸マグネシウムが存在することによって高活性化されていると見なせる。 As shown in Table 4, it can be seen that there is almost no activity from 400 ° C. to 550 ° C., and it is hardly influenced by the firing temperature. On the other hand, when the firing temperature is increased to 600 ° C. and 700 ° C., the activity decreases remarkably as the temperature increases. Since the basic magnesium carbonate, which is a precipitate formed from magnesium nitrate and potassium carbonate, is decomposed at about 600 ° C. and changes to magnesium oxide, the developed catalyst has basic magnesium carbonate as a carrier component. It can be considered that it is highly activated.
実施例６、７及び８で調製した触媒について、比表面積、細孔容積、及び細孔容積を測定した。その結果を表５に示す。また、同触媒について、微分細孔容積分布の測定及びアンモニア分解反応前の触媒の粉末Ｘ線結晶構造解析を行った。その結果を、それぞれ図１及び図２に示す。 For the catalysts prepared in Examples 6, 7, and 8, the specific surface area, pore volume, and pore volume were measured. The results are shown in Table 5. Moreover, about the same catalyst, the measurement of differential pore volume distribution and the powder X-ray crystal structure analysis of the catalyst before ammonia decomposition reaction were performed. The results are shown in FIGS. 1 and 2, respectively.
表５より、焼成温度の増加に従い、比表面積、細孔容積とも低下することがわかる。
また、図１より、細孔径分布を比較すると、焼成温度が４００℃の場合では３０Å付近の細孔が多く見られるのに対し、焼成温度の増加に伴いこの３０Å付近の細孔は減少し、代わりに２００Å付近の細孔が増加するようになる。すなわち、塩基性炭酸マグネシウムが存在する状況では、マグネシウム担体は、細孔径が小さく表面積も高い状態であるが、塩基性炭酸マグネシウムの分解が進み酸化マグネシウムが増えてくるにつれ細孔径も大きくなり、比表面積も低下すると考えられる。さらに焼成温度と結晶構造の関係(図２)を比較すると、焼成温度が４００℃の場合では１５、３１°付近に塩基性炭酸マグネシウム由来のピークが存在し、酸化マグネシウム由来のピークは存在しない。焼成温度が５００℃においても、ピークは不明瞭であるが上記塩基性炭酸マグネシウム由来のピークが存在する。一方、焼成温度６００℃では、上記塩基性炭酸マグネシウム由来のピークは消失し、４２、６２°付近に酸化マグネシウム由来のピークが観察される。すなわち、表４の活性の結果と合わせて考えると、マグネシウム化合物とルテニウム化合物とをアルカリ金属炭酸塩にて沈殿する方法で調製された触媒では、塩基性炭酸マグネシウムが存在することにより、触媒の比表面積は高く、また、多くの小さな細孔が存在し、その結果、Ｒｕが従来にはない均一に高分散した状態で担持されており、これが高い活性を示した要因となっている。
Table 5 shows that both the specific surface area and the pore volume decrease as the firing temperature increases.
In addition, comparing the pore size distribution from FIG. 1, when the firing temperature is 400 ° C., many pores near 30% are seen, whereas as the firing temperature increases, the pores near 30% decrease, Instead, the number of pores around 200 mm increases. That is, in the situation where basic magnesium carbonate is present, the magnesium carrier is in a state where the pore diameter is small and the surface area is high, but as the decomposition of basic magnesium carbonate proceeds and magnesium oxide increases, the pore diameter increases and It is thought that the surface area also decreases. Further, comparing the relationship between the firing temperature and the crystal structure (FIG. 2), when the firing temperature is 400 ° C., there is a peak derived from basic magnesium carbonate at around 15 and 31 °, and no peak derived from magnesium oxide. Even at a calcination temperature of 500 ° C., the peak is unclear, but there is a peak derived from the basic magnesium carbonate. On the other hand, at a baking temperature of 600 ° C., the peak derived from the basic magnesium carbonate disappears, and a peak derived from magnesium oxide is observed in the vicinity of 42 and 62 °. That is, when considered together with the activity results in Table 4, the catalyst prepared by the method of precipitating the magnesium compound and the ruthenium compound with an alkali metal carbonate has a ratio of the catalyst due to the presence of basic magnesium carbonate. The surface area is high, and there are many small pores. As a result, Ru is supported in a uniformly and highly dispersed state, which is unprecedented, and this is a factor that shows high activity.
（比較例１３）
担体を塩基性炭酸マグネシウム(和光純薬工業)としてＲｕを含浸法にて担持した以外は、比較例１と同様にしてアンモニア分解反応を行い、その結果を表６に示した。
(Comparative Example 13)
The ammonia decomposition reaction was carried out in the same manner as in Comparative Example 1 except that the support was basic magnesium carbonate (Wako Pure Chemical Industries) and Ru was supported by the impregnation method. The results are shown in Table 6.
表６に示すように、実施例２の本発明の触媒活性は、比較例１３に示す塩基性炭酸マグネシウムに含浸担持した触媒の活性に比べて著しく高いことがわかる。このことは、担体が塩基性炭酸マグネシウムであっても、従来の含浸法では機能せず、本発明の触媒で用いているマグネシウム化合物とルテニウム化合物とをアルカリ金属炭酸塩にて沈殿させる方法により生成した塩基性炭酸マグネシウム担体によってのみ、ルテニウムの高い活性が現れることを示している。 As shown in Table 6, it can be seen that the catalytic activity of the present invention in Example 2 is significantly higher than that of the catalyst impregnated and supported on basic magnesium carbonate shown in Comparative Example 13. This means that even if the support is basic magnesium carbonate, it does not function in the conventional impregnation method, and is produced by a method of precipitating the magnesium compound and ruthenium compound used in the catalyst of the present invention with an alkali metal carbonate. It is shown that the high activity of ruthenium appears only by the basic magnesium carbonate support.
（実施例１０）
実施例２において調製したＲｕ担持触媒に、助触媒成分として水酸化セシウムをＣｓとＲｕの原子比が０.５となるように添加し含浸担持した触媒を用いた以外は、実施例２と同様にしてアンモニア分解反応を行い、その結果を表７に示した。なお、助触媒成分であるＣｓの担持方法は、実施例１に従って得られた沈殿物を乾燥したものに、水酸化セシウム水溶液を含浸させた後、実施例１と同様に乾燥、焼成を行った。
(Example 10)
Same as Example 2 except that the catalyst supported by impregnation with the addition of cesium hydroxide as a promoter component so that the atomic ratio of Cs and Ru is 0.5 is used for the Ru supported catalyst prepared in Example 2. The ammonia decomposition reaction was carried out and the results are shown in Table 7. The method for supporting Cs, which is a promoter component, was carried out in the same manner as in Example 1, after impregnating the precipitate obtained in accordance with Example 1 with a dried cesium hydroxide solution. .
（実施例１１）
水酸化セシウムをＣｓとＲｕの原子比が１.０となるように添加した以外は、実施例１０と同様にしてアンモニア分解反応を行い、その結果を表７に示した。
(Example 11)
The ammonia decomposition reaction was carried out in the same manner as in Example 10 except that cesium hydroxide was added so that the atomic ratio of Cs and Ru was 1.0. The results are shown in Table 7.
（実施例１２）
水酸化セシウムをＣｓとＲｕの原子比が２.０となるように添加した以外は、実施例１０と同様にしてアンモニア分解反応を行い、その結果を表７に示した。
(Example 12)
The ammonia decomposition reaction was performed in the same manner as in Example 10 except that cesium hydroxide was added so that the atomic ratio of Cs to Ru was 2.0. The results are shown in Table 7.
（実施例１３）
実施例２において調製したＲｕ担持触媒に、助触媒成分として水酸化バリウムをＢａとＲｕの原子比が０.５となるように添加し含浸担持した触媒を用いた以外は、実施例２と同様にしてアンモニア分解反応を行い、その結果を表７に示した。なお、実施例１０と同様に、助触媒成分であるＣｓの担持方法は、実施例１に従って得られた沈殿物を乾燥したものに、水酸化バリウム水溶液を含浸させた後、実施例１と同様に乾燥、焼成を行った。
(Example 13)
The same as Example 2 except that the Ru-supported catalyst prepared in Example 2 was added with a catalyst impregnated by adding barium hydroxide as a promoter component so that the atomic ratio of Ba and Ru was 0.5. The ammonia decomposition reaction was carried out and the results are shown in Table 7. As in Example 10, the method for supporting Cs as the promoter component is the same as in Example 1 after impregnating the precipitate obtained in Example 1 with a barium hydroxide aqueous solution. Then, drying and baking were performed.
（実施例１４）
水酸化バリウムをＢａとＲｕの原子比が１.０となるように添加した以外は、実施例１３と同様にしてアンモニア分解反応を行い、その結果を表７に示した。
(Example 14)
The ammonia decomposition reaction was performed in the same manner as in Example 13 except that barium hydroxide was added so that the atomic ratio of Ba and Ru was 1.0. The results are shown in Table 7.
（実施例１５）
水酸化バリウムをＢａとＲｕの原子比が２.０となるように添加した以外は、実施例１３と同様にしてアンモニア分解反応を行い、その結果を表７に示した。
(Example 15)
The ammonia decomposition reaction was performed in the same manner as in Example 13 except that barium hydroxide was added so that the atomic ratio of Ba and Ru was 2.0. The results are shown in Table 7.
表７に示すように、助触媒成分としてアルカリ金属であるＣｓはＣｓ／Ｒｕ原子比が０.５〜２.０に至るまで高い活性が得られ、特に原子比１.０においては収率が９９.６％に達し、ほぼ完全な分解が達成されている。また、アルカリ土類金属であるＢａの添加も有効であり、どの添加量においても収率が向上している。すなわち、アルカリ金属もしくはアルカリ土類金属の助触媒成分としての添加が、アンモニア分解活性の向上に有効であることが示されている。 As shown in Table 7, Cs, which is an alkali metal as a promoter component, has a high activity until the Cs / Ru atomic ratio reaches 0.5 to 2.0, and the yield is particularly high at an atomic ratio of 1.0. 99.6% is reached and almost complete degradation is achieved. In addition, addition of Ba, which is an alkaline earth metal, is also effective, and the yield is improved at any addition amount. That is, it has been shown that the addition of alkali metal or alkaline earth metal as a promoter component is effective for improving ammonia decomposition activity.
本発明のアンモニア分解触媒は、アンモニアから燃料電池用の水素と窒素とを効率的に製造する場合や、有害なアンモニアを水素と窒素に効率良く分解する場合などのアンモニアの分解に広く利用できる。 The ammonia decomposing catalyst of the present invention can be widely used for decomposing ammonia when efficiently producing hydrogen and nitrogen for fuel cells from ammonia or decomposing harmful ammonia efficiently into hydrogen and nitrogen.
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