JP6789550B2 - Ammonia decomposition catalyst for microwave heating and its mixture - Google Patents
Ammonia decomposition catalyst for microwave heating and its mixture Download PDFInfo
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- JP6789550B2 JP6789550B2 JP2016157735A JP2016157735A JP6789550B2 JP 6789550 B2 JP6789550 B2 JP 6789550B2 JP 2016157735 A JP2016157735 A JP 2016157735A JP 2016157735 A JP2016157735 A JP 2016157735A JP 6789550 B2 JP6789550 B2 JP 6789550B2
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims description 422
- 229910021529 ammonia Inorganic materials 0.000 title claims description 210
- 238000010438 heat treatment Methods 0.000 title claims description 165
- 238000000354 decomposition reaction Methods 0.000 title claims description 151
- 239000003054 catalyst Substances 0.000 title claims description 145
- 239000000203 mixture Substances 0.000 title claims description 54
- 239000002923 metal particle Substances 0.000 claims description 54
- 229910021536 Zeolite Inorganic materials 0.000 claims description 22
- 239000010457 zeolite Substances 0.000 claims description 22
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 20
- 229910017052 cobalt Inorganic materials 0.000 claims description 20
- 239000010941 cobalt Substances 0.000 claims description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000003426 co-catalyst Substances 0.000 claims description 15
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052723 transition metal Inorganic materials 0.000 claims description 9
- 150000003624 transition metals Chemical group 0.000 claims description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 49
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 27
- 239000000126 substance Substances 0.000 description 25
- 239000001257 hydrogen Substances 0.000 description 23
- 229910052739 hydrogen Inorganic materials 0.000 description 23
- 238000000034 method Methods 0.000 description 19
- 230000000694 effects Effects 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 239000000969 carrier Substances 0.000 description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 5
- 229910010271 silicon carbide Inorganic materials 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 239000002738 chelating agent Substances 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004868 gas analysis Methods 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000007864 aqueous solution Substances 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- -1 cobalt (II) hexahydrate Chemical compound 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003860 storage Methods 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
- 238000005211 surface analysis Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910001233 yttria-stabilized zirconia Inorganic materials 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、マイクロ波加熱用アンモニア分解触媒及びマイクロ波加熱用アンモニア分解触媒混合物に関する。 The present invention relates to an ammonia decomposition catalyst for microwave heating and a mixture of ammonia decomposition catalysts for microwave heating.
水素は燃焼による熱エネルギーの生成時や燃料電池などによる電力の生成時に、環境汚染の原因となる有害物質や地球温暖化の原因となる二酸化炭素などを排出しない。そのため、近年、クリーンエネルギーとして、水素利用技術に関する研究開発が盛んに進められている。 Hydrogen does not emit harmful substances that cause environmental pollution or carbon dioxide that causes global warming when generating thermal energy by combustion or when generating electric power by fuel cells. Therefore, in recent years, research and development on hydrogen utilization technology has been actively promoted as clean energy.
しかし、水素ガスは天然にはほとんど存在しない。そのため、貯蔵輸送性に優れたアンモニアなどの水素原子含有物質を輸送・貯蔵し、必要な場所で水素ガスに転換することが検討されている。例えば、特許文献１では、アンモニア酸化触媒を有するアンモニア酸化部、及びアンモニア分解触媒を有するアンモニア分解部を有する水素生成装置が開示されている。
However, hydrogen gas is almost non-existent in nature. Therefore, it is being studied to transport and store hydrogen atom-containing substances such as ammonia, which have excellent storage and transportability, and convert them into hydrogen gas at necessary places. For example,
しかしながら、特許文献１の水素生成装置は、触媒に貴金属を必要とするため、コストが高くなるという課題があった。
However, the hydrogen generating apparatus of
本発明は、上記事情に鑑みてなされたものであり、貴金属を用いなくてもアンモニア分解活性の高いマイクロ波加熱用アンモニア分解触媒及びその混合物を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an ammonia decomposition catalyst for microwave heating having high ammonia decomposition activity and a mixture thereof without using a noble metal.
本発明の第１の態様に係るマイクロ波加熱用アンモニア分解触媒は、担体と、担体上に担持され、ニッケル、コバルト及び鉄からなる群より選択される少なくとも１種の遷移金属を主成分とする金属粒子と、を備える。 The ammonia decomposition catalyst for microwave heating according to the first aspect of the present invention contains a carrier and at least one transition metal supported on the carrier and selected from the group consisting of nickel, cobalt and iron as main components. With metal particles.
本発明の第２の態様に係るマイクロ波加熱用アンモニア分解触媒は、第１の態様のマイクロ波加熱用アンモニア分解触媒に関し、担体は、典型金属の多孔質酸化物及び遷移金属の多孔質酸化物の少なくともいずれか一方である。 The ammonia decomposition catalyst for microwave heating according to the second aspect of the present invention relates to the ammonia decomposition catalyst for microwave heating according to the first aspect, and the carrier is a porous oxide of a typical metal and a porous oxide of a transition metal. At least one of them.
本発明の第３の態様に係るマイクロ波加熱用アンモニア分解触媒は、第１又は第２の態様のマイクロ波加熱用アンモニア分解触媒に関し、担体は、酸化アルミニウム、酸化マグネシウム、酸化ジルコニウム、イットリア安定ジルコニア、ＮａＹ型ゼオライト、超安定化Ｙ型ゼオライト、ルチル型酸化チタン、アナターゼ型酸化チタン及びルチル−アナターゼ混晶型酸化チタンからなる群より選択される少なくとも１種の金属酸化物である。 The ammonia decomposition catalyst for microwave heating according to the third aspect of the present invention relates to the ammonia decomposition catalyst for microwave heating according to the first or second aspect, and the carriers are aluminum oxide, magnesium oxide, zirconium oxide, and itria stable zirconia. , NaY-type zeolite, ultra-stabilized Y-type zeolite, rutile-type titanium oxide, anatase-type titanium oxide, and rutile-anathase mixed crystal-type titanium oxide, which is at least one metal oxide selected from the group.
本発明の第４の態様に係るマイクロ波加熱用アンモニア分解触媒は、第１乃至第３のいずれかの態様のマイクロ波加熱用アンモニア分解触媒に関し、担体又は金属粒子上に、アルカリ金属及びアルカリ土類金属の少なくともいずれか一方を含む助触媒がさらに担持される。 The ammonia decomposition catalyst for microwave heating according to the fourth aspect of the present invention relates to the ammonia decomposition catalyst for microwave heating according to any one of the first to third aspects, and has alkali metal and alkaline soil on a carrier or metal particles. A co-catalyst containing at least one of the similar metals is further supported.
本発明の第５の態様に係るマイクロ波加熱用アンモニア分解触媒は、第１乃至第４のいずれかの態様におけるマイクロ波加熱用アンモニア分解触媒に関し、アンモニア前処理される。 The ammonia decomposition catalyst for microwave heating according to the fifth aspect of the present invention is subjected to ammonia pretreatment with respect to the ammonia decomposition catalyst for microwave heating according to any one of the first to fourth aspects.
本発明の第６の態様に係るマイクロ波加熱用アンモニア分解触媒は、第１乃至第５のいずれかの態様におけるマイクロ波加熱用アンモニア分解触媒に関し、担体は、キレート処理された担体である。 The ammonia decomposition catalyst for microwave heating according to the sixth aspect of the present invention relates to the ammonia decomposition catalyst for microwave heating according to any one of the first to fifth aspects, and the carrier is a chelated carrier.
本発明の第７の態様に係るマイクロ波加熱用アンモニア分解触媒混合物は、第１乃至第６のいずれかの態様におけるマイクロ波加熱用アンモニア分解触媒と、加熱助剤と、を備える。 The ammonia decomposition catalyst mixture for microwave heating according to the seventh aspect of the present invention includes the ammonia decomposition catalyst for microwave heating according to any one of the first to sixth aspects, and a heating aid.
本発明に係るマイクロ波加熱用アンモニア分解触媒及びこの触媒を含むマイクロ波加熱用アンモニア分解触媒混合物は、貴金属を用いなくてもマイクロ波加熱によるアンモニア分解活性が高い。 The ammonia decomposition catalyst for microwave heating and the ammonia decomposition catalyst mixture for microwave heating containing this catalyst according to the present invention have high ammonia decomposition activity by microwave heating even without using a noble metal.
以下、図面を用いて本発明の実施形態に係るマイクロ波加熱用アンモニア分解触媒及びマイクロ波加熱用アンモニア分解触媒混合物について詳細に説明する。なお、図面の寸法比率は説明の都合上誇張されており、実際の比率とは異なる場合がある。 Hereinafter, the ammonia decomposition catalyst for microwave heating and the ammonia decomposition catalyst mixture for microwave heating according to the embodiment of the present invention will be described in detail with reference to the drawings. The dimensional ratios in the drawings are exaggerated for convenience of explanation and may differ from the actual ratios.
［マイクロ波加熱用アンモニア分解触媒］
本実施形態のマイクロ波加熱用アンモニア分解触媒は、担体と、担体上に担持され、ニッケル、コバルト及び鉄からなる群より選択される少なくとも１種の遷移金属を主成分とする金属粒子と、を備える。
[Ammonia decomposition catalyst for microwave heating]
The ammonia decomposition catalyst for microwave heating of the present embodiment comprises a carrier and metal particles supported on the carrier and containing at least one transition metal as a main component selected from the group consisting of nickel, cobalt and iron. Be prepared.
（担体）
担体は、アンモニア分解反応において触媒作用を示す金属粒子を、安定かつ高分散に担持する物質である。ここで、高分散に担持するとは、担体の表面上における金属粒子の担持密度が担体の全表面にわたって均一又は均一に近い状態であることを意味する。担体に、金属粒子が高分散に担持されると、担体の表面上で隣接する金属粒子同士の間隔が均一又は均一に近い状態になる。
(Carrier)
The carrier is a substance that stably and highly disperses metal particles that act as a catalyst in an ammonia decomposition reaction. Here, supporting with high dispersion means that the loading density of metal particles on the surface of the carrier is uniform or nearly uniform over the entire surface of the carrier. When the metal particles are supported on the carrier in a highly dispersed manner, the distance between the adjacent metal particles on the surface of the carrier becomes uniform or nearly uniform.
担体は、典型金属の多孔質酸化物及び遷移金属の多孔質酸化物の少なくともいずれか一方であることが好ましい。例として、担体は、酸化アルミニウム（γ−Ａｌ２Ｏ３）、酸化マグネシウム（ＭｇＯ）、酸化ジルコニウム（ＺｒＯ２）、イットリア安定ジルコニア（ＹＳＺ）、ＮａＹ型ゼオライト、超安定化Ｙ型ゼオライト（ＵＳＹ型ゼオライト）、ルチル型酸化チタン（ルチル型ＴｉＯ２）、アナターゼ型酸化チタン（アナターゼ型ＴｉＯ２）及びルチル−アナターゼ混晶型酸化チタンからなる群より選択される少なくとも１種の金属酸化物であることが好ましい。担体として、このような金属酸化物を用いた場合、加熱助剤の共存下でマイクロ波の照射で加熱しやすいためである。なお、酸化アルミニウム（γ−Ａｌ２Ｏ３）とイットリア安定ジルコニア（ＹＳＺ）を担体として用いた場合は加熱助剤の添加が無くともマイクロ波の照射で加熱しやすい。 The carrier is preferably at least one of a porous oxide of a typical metal and a porous oxide of a transition metal. As an example, the carriers are aluminum oxide (γ-Al 2 O 3 ), magnesium oxide (MgO), zirconium oxide (ZrO 2 ), yttria-stable zirconia (YSZ), NaY-type zeolite, and ultra-stabilized Y-type zeolite (USY type). It is at least one metal oxide selected from the group consisting of (zeolite), rutyl-type titanium oxide (rutyl-type TiO 2 ), anatase-type titanium oxide (anatase-type TiO 2 ), and rutyl-anathase mixed-crystal titanium oxide. Is preferable. This is because when such a metal oxide is used as the carrier, it is easy to heat by irradiation with microwaves in the coexistence of a heating aid. When aluminum oxide (γ-Al 2 O 3) and yttria-stabilized zirconia (YSZ) are used as carriers, they can be easily heated by microwave irradiation even without the addition of a heating aid.
また、アンモニア分解活性を向上させるという観点から、担体は、酸化アルミニウム、イットリア安定ジルコニア及び超安定化Ｙ型ゼオライトからなる群より選択される少なくとも１種の金属酸化物であるとより好ましい。一方、加熱助剤の共存下でマイクロ波の照射で加熱しやすくするという観点から、担体は、酸化ジルコニウム、ＮａＹ型ゼオライト、超安定化Ｙ型ゼオライト、ルチル型酸化チタン、アナターゼ型酸化チタン及びルチル−アナターゼ混晶型酸化チタンからなる群より選択される少なくとも１種の金属酸化物であるとより好ましい。なお、アンモニア分解活性を向上させ、かつ、マイクロ波の照射で加熱しやすくするという観点から、担体が超安定化Ｙ型ゼオライトであることがさらに好ましい。 Further, from the viewpoint of improving the ammonia decomposition activity, the carrier is more preferably at least one metal oxide selected from the group consisting of aluminum oxide, yttria-stable zirconia and super-stabilized Y-zeolite. On the other hand, from the viewpoint of facilitating heating by irradiation with microwaves in the presence of a heating aid, the carriers used are zirconium oxide, NaY-type zeolite, ultra-stabilized Y-type zeolite, rutile-type titanium oxide, anatase-type titanium oxide and rutile. -It is more preferable that the metal oxide is at least one selected from the group consisting of anatase mixed crystal titanium oxide. It is more preferable that the carrier is a super-stabilized Y-type zeolite from the viewpoint of improving the ammonia decomposition activity and facilitating heating by irradiation with microwaves.
また、担体は、多孔質物質であると、担体の単位体積当たりの金属粒子の担持量が多くなりやすい点で好ましい。なお、担体は、イットリア安定ジルコニアの多孔質酸化物であると、マイクロ波の照射でさらに加熱しやすいためより好ましい。 Further, when the carrier is a porous substance, it is preferable that the amount of metal particles supported per unit volume of the carrier tends to be large. It is more preferable that the carrier is a porous oxide of yttria-stable zirconia because it is more easily heated by irradiation with microwaves.
担体のメディアン径は、１００〜６５０μｍであることが好ましく、２５０〜５００μｍであることがより好ましい。担体のメディアン径が上記範囲内にあると、マイクロ波加熱用アンモニア分解触媒がマイクロ波で制御性よく加熱され、かつ、アンモニアガスの流路に配置した場合に、圧力損失が生じにくくなるためである。 The median diameter of the carrier is preferably 100 to 650 μm, more preferably 250 to 500 μm. When the median diameter of the carrier is within the above range, the ammonia decomposition catalyst for microwave heating is heated with microwaves in a controllable manner, and when it is arranged in the flow path of ammonia gas, pressure loss is less likely to occur. is there.
（金属粒子）
金属粒子は、アンモニア分解反応において触媒作用を示す物質を含み、担体上に担持される粒子である。金属粒子は、ニッケル、コバルト及び鉄からなる群より選択される少なくとも１種の遷移金属を主成分とする。ここで、上記遷移金属を主成分とするとは、金属粒子中において、上記遷移金属の合計が５０質量％を超える量であることを意味する。ニッケル、コバルト及び鉄は、触媒作用が高くかつ安価であるため好ましい。なお、コスト低減の観点からは、金属粒子は貴金属を含まないことが好ましい。
(Metal particles)
Metal particles are particles that contain a substance that exhibits a catalytic action in an ammonia decomposition reaction and are supported on a carrier. The metal particles are mainly composed of at least one transition metal selected from the group consisting of nickel, cobalt and iron. Here, the fact that the transition metal is the main component means that the total amount of the transition metals exceeds 50% by mass in the metal particles. Nickel, cobalt and iron are preferred because they have high catalytic activity and are inexpensive. From the viewpoint of cost reduction, it is preferable that the metal particles do not contain a noble metal.
金属粒子は、粒径が担体よりも小さく、担体の表面に担持される。本実施形態に係るマイクロ波加熱用アンモニア分解触媒は、通常、担体の表面に、多数の金属粒子が担持されたものになっている。 The metal particles have a smaller particle size than the carrier and are supported on the surface of the carrier. The ammonia decomposition catalyst for microwave heating according to the present embodiment usually has a large number of metal particles supported on the surface of a carrier.
担体と金属粒子との組合せは、特に限定されず、上述した任意の担体と任意の金属粒子とを組み合わせて使用することができる。担体と金属粒子との好ましい組み合わせは、酸化アルミニウムとコバルトとの組み合わせ、酸化アルミニウムとニッケルとの組み合わせ、酸化アルミニウムと鉄との組み合わせ、イットリア安定ジルコニアとコバルトとの組み合わせ、イットリア安定ジルコニアとニッケルとの組み合わせ、イットリア安定ジルコニアと鉄との組み合わせ、超安定化Ｙ型ゼオライトとコバルトとの組み合わせ、超安定化Ｙ型ゼオライトとニッケルとの組み合わせ及び超安定化Ｙ型ゼオライトと鉄との組み合わせからなる群より選択される少なくとも１種である。これらの組み合わせは、アンモニア分解活性が高いためである。 The combination of the carrier and the metal particles is not particularly limited, and any of the above-mentioned carriers and any metal particles can be used in combination. Preferred combinations of carriers and metal particles are a combination of aluminum oxide and cobalt, a combination of aluminum oxide and nickel, a combination of aluminum oxide and iron, a combination of itria stable zirconia and cobalt, and a combination of itria stable zirconia and nickel. From the group consisting of combinations, a combination of itria-stable zirconia and iron, a combination of ultra-stabilized Y-type zeolite and cobalt, a combination of ultra-stabilized Y-type zeolite and nickel, and a combination of ultra-stabilized Y-type zeolite and iron At least one selected. This is because these combinations have high ammonia decomposition activity.
また、担体と金属粒子とのより好ましい組み合わせは、超安定化Ｙ型ゼオライトとコバルトとの組み合わせ、超安定化Ｙ型ゼオライトとニッケルとの組み合わせ及び超安定化Ｙ型ゼオライトと鉄との組み合わせである。これらの組み合わせは、アンモニア分解活性が高く、マイクロ波の照射でより加熱しやすいためである。なお、担体と金属粒子とのさらに好ましい組み合わせは、超安定化Ｙ型ゼオライトとコバルトとの組み合わせである。 More preferable combinations of the carrier and the metal particles are a combination of ultra-stabilized Y-zeolite and cobalt, a combination of ultra-stabilized Y-zeolite and nickel, and a combination of ultra-stabilized Y-zeolite and iron. .. This is because these combinations have high ammonia decomposition activity and are easier to heat by microwave irradiation. A more preferable combination of the carrier and the metal particles is a combination of ultra-stabilized Y-zeolite and cobalt.
担体への金属粒子の担持量は、担体と金属粒子との合計１００質量％に対して、１〜２０質量％であることが好ましい。担体への金属粒子の担持量が１質量％以上の場合、アンモニア分解活性が高く、担体への金属粒子の担持量が２０質量％以下の場合、マイクロ波の照射で加熱しやすいためである。なお、担体への金属粒子の担持量は、担体と金属粒子と合計１００質量％に対して、３〜１０質量％であることが好ましく、５〜１０質量％であることがさらに好ましい。担体への金属粒子の担持量がこのような範囲であることにより、さらにアンモニア分解活性が高く、マイクロ波の照射で加熱しやすいためである。 The amount of the metal particles supported on the carrier is preferably 1 to 20% by mass with respect to 100% by mass of the total of the carrier and the metal particles. This is because when the amount of metal particles supported on the carrier is 1% by mass or more, the ammonia decomposition activity is high, and when the amount of metal particles supported on the carrier is 20% by mass or less, it is easy to heat by irradiation with microwaves. The amount of the metal particles supported on the carrier is preferably 3 to 10% by mass, more preferably 5 to 10% by mass, based on 100% by mass of the total of the carrier and the metal particles. This is because when the amount of metal particles supported on the carrier is in such a range, the ammonia decomposition activity is further high and it is easy to heat by irradiation with microwaves.
担体は、キレート処理された担体であると、マイクロ波の照射で加熱しやすく、かつ、アンモニア分解活性が高くなるため好ましい。具体的には、マイクロ波加熱用アンモニア分解触媒は、担体にキレート剤を含浸させ、乾燥させた後、担体に金属粒子を担持して得られたものであると好ましい。その理由は、担体表面での金属粒子の分散性が高くなることに起因すると考えられる。キレート剤としては、例えば、エチレンジアミン四酢酸（ＥＤＴＡ）、ニトリロ三酢酸（ＮＴＡ）等を用いることができる。 It is preferable that the carrier is a chelated carrier because it is easily heated by irradiation with microwaves and has high ammonia decomposition activity. Specifically, the ammonia decomposition catalyst for microwave heating is preferably obtained by impregnating a carrier with a chelating agent, drying the catalyst, and then supporting metal particles on the carrier. The reason is considered to be that the dispersibility of the metal particles on the surface of the carrier is increased. As the chelating agent, for example, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA) and the like can be used.
キレート剤は、担体９５質量部に対して１〜１０質量部含浸させることが好ましく、３〜７質量部含浸させることがより好ましい。 The chelating agent is preferably impregnated with 1 to 10 parts by mass, more preferably 3 to 7 parts by mass with respect to 95 parts by mass of the carrier.
（助触媒）
マイクロ波加熱用アンモニア分解触媒は、担体又は金属粒子上に、アルカリ金属及びアルカリ土類金属の少なくともいずれか一方を含む助触媒がさらに担持されることが好ましい。マイクロ波の照射で加熱しやすく、かつ、アンモニア分解活性が高くなるためである。
(Co-catalyst)
In the ammonia decomposition catalyst for microwave heating, it is preferable that a co-catalyst containing at least one of an alkali metal and an alkaline earth metal is further supported on a carrier or metal particles. This is because it is easy to heat by irradiation with microwaves and the ammonia decomposition activity is increased.
助触媒を構成するアルカリ金属としては、例えば、ナトリウム、カリウム、ルビジウム及びセシウムからなる群より選択される少なくとも１種の元素を含む物質が用いられる。また、助触媒を構成するアルカリ土類金属としては、例えば、マグネシウム、カルシウム、ストロンチウム及びバリウムからなる群より選択される少なくとも１種の元素を含む物質が用いられる。このうち、助触媒が、カリウム及びルビジウムの少なくともいずれか一方の元素を含む物質である場合、マイクロ波加熱用アンモニア分解触媒がマイクロ波の照射でより加熱しやすく、かつ、アンモニア分解活性がより高くなるため好ましい。 As the alkali metal constituting the co-catalyst, for example, a substance containing at least one element selected from the group consisting of sodium, potassium, rubidium and cesium is used. Further, as the alkaline earth metal constituting the co-catalyst, for example, a substance containing at least one element selected from the group consisting of magnesium, calcium, strontium and barium is used. Of these, when the co-catalyst is a substance containing at least one element of potassium and rubidium, the ammonia decomposition catalyst for microwave heating is easier to heat by microwave irradiation and has higher ammonia decomposition activity. Therefore, it is preferable.
（アンモニア前処理）
マイクロ波加熱用アンモニア分解触媒は、アンモニア前処理されると、マイクロ波の照射で加熱しやすく、かつ、アンモニア分解活性が高くなるため好ましい。ここで、アンモニア前処理とは、マイクロ波加熱用アンモニア分解触媒を、触媒としての使用前に、高温のアンモニアで熱処理することを意味する。アンモニアでの熱処理温度は、通常、４００℃以上、好ましくは５００〜８００℃である。
(Ammonia pretreatment)
Ammonia decomposition catalyst for microwave heating is preferable because when it is pretreated with ammonia, it is easily heated by irradiation with microwaves and its ammonia decomposition activity is increased. Here, the ammonia pretreatment means that the ammonia decomposition catalyst for microwave heating is heat-treated with high-temperature ammonia before being used as a catalyst. The heat treatment temperature with ammonia is usually 400 ° C. or higher, preferably 500 to 800 ° C.
マイクロ波加熱用アンモニア分解触媒は、アンモニア前処理を行うと、マイクロ波加熱用アンモニア分解触媒における、担体及び金属粒子の少なくとも一方の表面に、窒素含有物質が形成される場合がある。窒素含有物質は一般的に誘電体材料として広く知られており、その窒素含有物質が形成されることで電気特性が変化しマイクロ波の照射で加熱しやすくなる可能性があり、かつ、アンモニアの分解反応が促進される場合があるため好ましい。 When the ammonia decomposition catalyst for microwave heating is subjected to ammonia pretreatment, a nitrogen-containing substance may be formed on at least one surface of the carrier and the metal particles in the ammonia decomposition catalyst for microwave heating. Nitrogen-containing substances are generally widely known as dielectric materials, and the formation of the nitrogen-containing substances may change the electrical characteristics and make it easier to heat by microwave irradiation. It is preferable because the decomposition reaction may be promoted.
本実施形態のマイクロ波加熱用アンモニア分解触媒は、アンモニア存在下でマイクロ波を照射すると、担体及び金属粒子がマイクロ波を良好に吸収し、迅速に加熱される。そのため、本実施形態のマイクロ波加熱用アンモニア分解触媒は、貴金属を用いなくてもアンモニア分解活性が高い。 When the ammonia decomposition catalyst for microwave heating of the present embodiment is irradiated with microwaves in the presence of ammonia, the carrier and metal particles absorb the microwaves well and are heated rapidly. Therefore, the ammonia decomposition catalyst for microwave heating of the present embodiment has high ammonia decomposition activity without using a noble metal.
［マイクロ波加熱用アンモニア分解触媒混合物］
本実施形態のマイクロ波加熱用アンモニア分解触媒混合物は、上述したマイクロ波加熱用アンモニア分解触媒と、加熱助剤と、を備える。マイクロ波加熱用アンモニア分解触媒は、マイクロ波の加熱に適した加熱助剤を介して加熱される。そのため、本実施形態のマイクロ波加熱用アンモニア分解触媒混合物は、マイクロ波の照射で加熱しやすくなるため好ましい。ここで、加熱助剤とは、マイクロ波の吸収性を向上させる物質を意味する。加熱助剤としては、例えば、炭化ケイ素、カーボン等が用いられる。このうち、炭化ケイ素は、マイクロ波の吸収性を向上させる度合いが大きく、かつ、マイクロ波加熱の制御性が優れているため好ましい。
[Ammonia decomposition catalyst mixture for microwave heating]
The ammonia decomposition catalyst mixture for microwave heating of the present embodiment includes the above-mentioned ammonia decomposition catalyst for microwave heating and a heating aid. The ammonia decomposition catalyst for microwave heating is heated via a heating aid suitable for microwave heating. Therefore, the ammonia decomposition catalyst mixture for microwave heating of the present embodiment is preferable because it is easily heated by irradiation with microwaves. Here, the heating aid means a substance that improves the absorption of microwaves. As the heating aid, for example, silicon carbide, carbon and the like are used. Of these, silicon carbide is preferable because it has a high degree of improving the absorption of microwaves and has excellent controllability of microwave heating.
マイクロ波加熱用アンモニア分解触媒混合物は、マイクロ波加熱用アンモニア分解触媒１００質量部に対して、加熱助剤の添加量が１〜３０質量部であることが好ましく、５〜２０質量部であることがより好ましく、８〜１５質量部であることがさらに好ましい。マイクロ波加熱用アンモニア分解触媒に対する加熱助剤の配合量がこの範囲内にあると、マイクロ波加熱用アンモニア分解触媒がマイクロ波の照射で加熱しやすく、かつ、制御が容易になるためである。 The amount of the heating aid added to the mixture of the ammonia decomposition catalyst mixture for microwave heating is preferably 1 to 30 parts by mass, and 5 to 20 parts by mass with respect to 100 parts by mass of the ammonia decomposition catalyst for microwave heating. Is more preferable, and 8 to 15 parts by mass is further preferable. This is because when the blending amount of the heating aid with respect to the ammonia decomposition catalyst for microwave heating is within this range, the ammonia decomposition catalyst for microwave heating can be easily heated by irradiation with microwaves and can be easily controlled.
本実施形態のマイクロ波加熱用アンモニア分解触媒混合物は、マイクロ波を照射すると、担体及び金属粒子がマイクロ波を吸収するのに加え、加熱助剤がより迅速に低い消費電力で加熱される。そのため、加熱助剤からの熱伝導により担体及び金属粒子が迅速に加熱される。そして、より迅速な加熱のため速やかに昇温した金属粒子は、アンモニア分解反応の反応速度を向上させてアンモニアから水素を製造することできる。このように、本実施形態のマイクロ波加熱用アンモニア分解触媒混合物によれば、マイクロ波加熱用アンモニア分解触媒の昇温時間が本実施形態のマイクロ波加熱用アンモニア分解触媒に比較してより短くなり、必要なマイクロ波に用いる電力も削減できる。 In the ammonia decomposition catalyst mixture for microwave heating of the present embodiment, when irradiated with microwaves, the carrier and metal particles absorb the microwaves, and the heating aid is heated more quickly with low power consumption. Therefore, the carrier and the metal particles are rapidly heated by heat conduction from the heating aid. Then, the metal particles whose temperature has been raised rapidly for faster heating can improve the reaction rate of the ammonia decomposition reaction to produce hydrogen from ammonia. As described above, according to the microwave heating ammonia decomposition catalyst mixture of the present embodiment, the temperature rise time of the microwave heating ammonia decomposition catalyst is shorter than that of the microwave heating ammonia decomposition catalyst of the present embodiment. , The power used for the required microwaves can also be reduced.
［水素製造装置］
本実施形態に係る水素製造装置１は、例えば図１で示すように、マイクロ波照射装置２と、導波管３と、円筒空胴共振器４と、反応管５と、マイクロ波加熱用アンモニア分解触媒６と、を備えることができる。本実施形態の水素製造装置１は、マイクロ波加熱用アンモニア分解触媒６を、マイクロ波を用いて加熱することができる。そのため、本実施形態の水素製造装置１は、一般的な電気炉などを用いて加熱した場合と比較し、速やかにマイクロ波加熱用アンモニア分解触媒６を加熱することができる。
[Hydrogen production equipment]
As shown in FIG. 1, for example, the
そして、円筒空胴共振器４は、マイクロ波照射装置２から発振されるマイクロ波をＴＭ０ｎ０モード（ｎは１以上の整数）で共振させることができる。この場合、円筒空胴共振器４内の電界強度は、円筒空胴共振器４内の円周方向に対して所定の位置に、軸方向に対する電界強度の極大値が一定となるように分布する。
Then, the cylindrical cavity resonator 4 can resonate the microwave oscillated from the
さらに、反応管５が、円筒空胴共振器４内の電界強度が極大となる位置に、円筒空胴共振器４の軸方向と平行に貫通して配置され、アンモニアガスを通過させることができる。そして、マイクロ波加熱用アンモニア分解触媒６は、反応管５内に充填することができる。このようにすると、マイクロ波が均一に効率よくマイクロ波加熱用アンモニア分解触媒６を加熱して、水素ガスを製造することができる。そのため、本実施形態の水素製造装置１は、機械的な調整が必要なく、簡易な操作で水素ガスを製造することができる。なお、本実施形態の水素製造装置１は、一例として円筒空胴共振器４を用いたが、これに限らず、矩形空胴共振器などを用いることもできる。
Further, the reaction tube 5 is arranged so as to penetrate parallel to the axial direction of the cylindrical cavity resonator 4 at a position where the electric field strength in the cylindrical cavity resonator 4 is maximized, and ammonia gas can pass therethrough. .. Then, the ammonia decomposition catalyst 6 for microwave heating can be filled in the reaction tube 5. In this way, the microwave can uniformly and efficiently heat the ammonia decomposition catalyst 6 for microwave heating to produce hydrogen gas. Therefore, the
本実施形態に係る水素製造装置１は、例えば、自動車用の水素製造装置として使用することもできる。
The
以下、本実施形態を実施例によりさらに詳細に説明するが、本実施形態はこれら実施例に限定されるものではない。 Hereinafter, the present embodiment will be described in more detail with reference to Examples, but the present embodiment is not limited to these Examples.
金属粒子及び加熱助剤の影響を調べるため、表１に示すように、マイクロ波加熱用アンモニア分解触媒及びマイクロ波加熱用アンモニア分解触媒混合物を調製し、アンモニア転化率を測定した。 In order to investigate the influence of the metal particles and the heating aid, as shown in Table 1, a mixture of an ammonia decomposition catalyst for microwave heating and an ammonia decomposition catalyst mixture for microwave heating was prepared, and the ammonia conversion rate was measured.
［実施例１］
含浸法（ｉｎｃｉｐｉｅｎｔ−ｗｅｔｎｅｓｓ法）にて、γ−アルミナにコバルトを担持させ、γ−アルミナを９５質量％、コバルトを５質量％含むコバルト担持γ−アルミナを調製した。具体的には、硝酸コバルト水溶液に、γ−アルミナを含浸させ、１１０℃で１２時間乾燥後、５００℃で３時間焼成した。焼成物は室温まで冷却させてペレット状に加圧成形した後粉砕し、２５０〜５００μｍになるようにふるい分けた。なお、γ−アルミナに担持させる金属粒子として、硝酸コバルト(和光純薬工業株式会社製 硝酸コバルト（ＩＩ)六水和物特級)を用いた。また、担体として、γ−アルミナ(住友化学株式会社製ＡＫＳ−ＧＴ００)を用いた。
[Example 1]
Cobalt-supported γ-alumina containing 95% by mass of γ-alumina and 5% by mass of cobalt was prepared by supporting cobalt on γ-alumina by an impregnation method (incipient-wetness method). Specifically, the cobalt nitrate aqueous solution was impregnated with γ-alumina, dried at 110 ° C. for 12 hours, and then calcined at 500 ° C. for 3 hours. The fired product was cooled to room temperature, pressure-molded into pellets, pulverized, and sieved to 250 to 500 μm. Cobalt nitrate (cobalt (II) hexahydrate special grade manufactured by Wako Pure Chemical Industries, Ltd.) was used as the metal particles supported on γ-alumina. Further, as a carrier, γ-alumina (AKS-GT00 manufactured by Sumitomo Chemical Co., Ltd.) was used.
このようにして得られたコバルト担持γ−アルミナを、６００℃、１気圧のＨ２雰囲気中で２時間放置する水素前処理を行い、マイクロ波加熱用アンモニア分解触媒を調製した。 The cobalt-supported γ-alumina thus obtained was subjected to hydrogen pretreatment by leaving it in an H 2 atmosphere at 600 ° C. and 1 atm for 2 hours to prepare an ammonia decomposition catalyst for microwave heating.
［実施例２］
硝酸コバルトに代え、硝酸ニッケル(和光純薬工業株式会社製 硝酸ニッケル（ＩＩ)六水和物 特級)を用いた以外は、実施例１と同様の方法にてマイクロ波加熱用アンモニア分解触媒を調製した。
[Example 2]
An ammonia decomposition catalyst for microwave heating was prepared in the same manner as in Example 1 except that nickel nitrate (nickel (II) nitrate hexahydrate special grade manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of cobalt nitrate. did.
［実施例３］
硝酸コバルトに代え、硝酸鉄(和光純薬工業株式会社製 硝酸鉄（ＩＩＩ）九水和物９９．９％)を用いた以外は、実施例１と同様の方法にてマイクロ波加熱用アンモニア分解触媒を調製した。
[Example 3]
Ammonia decomposition for microwave heating by the same method as in Example 1 except that iron nitrate (iron (III) nitrate 99.9% manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of cobalt nitrate. A catalyst was prepared.
［実施例４］
実施例１と同様の方法により得られた１００質量部のコバルト担持γ−アルミナと、１０質量部のＳｉＣ加熱助剤 (和光純薬工業株式会社製 粒径５０ｎｍ) とを混合した。このようにして得られた混合物を、６００℃、１気圧のＨ２雰囲気中で２時間放置する水素前処理を行い、マイクロ波加熱用アンモニア分解触媒混合物を調製した。
[Example 4]
100 parts by mass of cobalt-supported γ-alumina obtained by the same method as in Example 1 and 10 parts by mass of a SiC heating aid (particle size 50 nm manufactured by Wako Pure Chemical Industries, Ltd.) were mixed. The mixture thus obtained, 600 ° C., subjected to hydrogen pretreatment to stand for 2 hours in an H 2 atmosphere of 1 atm, to prepare a microwave heating ammonia decomposition catalyst mixture.
［実施例５］
硝酸コバルトに代え、硝酸ニッケル(和光純薬工業株式会社製 硝酸ニッケル（ＩＩ)六水和物 特級)を用いた以外は、実施例４と同様の方法にてマイクロ波加熱用アンモニア分解触媒混合物を調製した。
[Example 5]
Ammonia decomposition catalyst mixture for microwave heating was prepared in the same manner as in Example 4 except that nickel nitrate (nickel (II) nitrate hexahydrate special grade manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of cobalt nitrate. Prepared.
［実施例６］
硝酸コバルトに代え、硝酸鉄(和光純薬工業株式会社製 硝酸鉄（ＩＩＩ）九水和物９９．９％)を用いた以外は、実施例４と同様の方法にてマイクロ波加熱用アンモニア分解触媒混合物を調製した。
[Example 6]
Ammonia decomposition for microwave heating by the same method as in Example 4 except that iron nitrate (iron (III) nitrate 99.9% manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of cobalt nitrate. A catalyst mixture was prepared.
＜アンモニア転化率＞
各実施例のマイクロ波加熱用アンモニア分解触媒０．１ｇが充填された石英製反応管を、図１に示すような水素製造装置内に設置した。その後、石英製反応管に４０ｍＬ／分の流量でアンモニアを供給しながら、マイクロ波加熱用アンモニア分解触媒にマイクロ波を照射した。この時、温度を２５０℃から６００℃まで５０℃ごとに昇温して、所望の温度に達してから１０分後以降の生成ガスをサンプリングし、ガスクロマトグラフで定量した。この時のマイクロ波加熱用アンモニア分解触媒の温度（℃）とアンモニア転化率（％）との関係を図２に示す。なお、アンモニア転化率は、アンモニアが分解して生成した水素の割合を示し、アンモニアが完全に水素に分解した場合のアンモニア転化率を１００％とした。
<Ammonia conversion rate>
A quartz reaction tube filled with 0.1 g of the ammonia decomposition catalyst for microwave heating of each example was installed in a hydrogen production apparatus as shown in FIG. Then, while supplying ammonia to the quartz reaction tube at a flow rate of 40 mL / min, the ammonia decomposition catalyst for microwave heating was irradiated with microwaves. At this time, the temperature was raised from 250 ° C. to 600 ° C. in increments of 50 ° C., and the produced
図２の結果より、加熱助剤を混合した実施例４〜６のマイクロ波加熱用アンモニア分解触媒混合物は、実施例１〜３の加熱助剤を用いていないマイクロ波加熱用アンモニア分解触媒と比較して、アンモニア転化率が高いことが分かった。 From the results of FIG. 2, the mixture of the ammonia decomposition catalysts for microwave heating of Examples 4 to 6 mixed with the heating aid was compared with the ammonia decomposition catalyst for microwave heating of Examples 1 to 3 without the heating aid. It was found that the ammonia conversion rate was high.
次に、金属粒子の担持量の影響を調べるため、表２に示すように、マイクロ波加熱用アンモニア分解触媒を調製し、アンモニア転化率を測定した。 Next, in order to investigate the influence of the amount of metal particles supported, an ammonia decomposition catalyst for microwave heating was prepared and the ammonia conversion rate was measured, as shown in Table 2.
［実施例７］
γ−アルミナの含有量を９９質量％、コバルトの含有量を１質量％とした以外は、実施例１と同様の方法にてマイクロ波加熱用アンモニア分解触媒を調製した。
[Example 7]
An ammonia decomposition catalyst for microwave heating was prepared in the same manner as in Example 1 except that the content of γ-alumina was 99% by mass and the content of cobalt was 1% by mass.
［実施例８］
実施例１と同様の方法により、γ−アルミナの含有量が９５質量％、コバルトの含有量が５質量％のマイクロ波加熱用アンモニア分解触媒を調製した。
[Example 8]
An ammonia decomposition catalyst for microwave heating having a γ-alumina content of 95% by mass and a cobalt content of 5% by mass was prepared by the same method as in Example 1.
［実施例９］
γ−アルミナの含有量を９０質量％、コバルトの含有量を１０質量％とした以外は、実施例１と同様の方法にてマイクロ波加熱用アンモニア分解触媒を調製した。
[Example 9]
An ammonia decomposition catalyst for microwave heating was prepared in the same manner as in Example 1 except that the content of γ-alumina was 90% by mass and the content of cobalt was 10% by mass.
［実施例１０］
γ−アルミナの含有量を８０質量％、コバルトの含有量を２０質量％とした以外は、実施例１と同様の方法にてマイクロ波加熱用アンモニア分解触媒を調製した。
[Example 10]
An ammonia decomposition catalyst for microwave heating was prepared in the same manner as in Example 1 except that the content of γ-alumina was 80% by mass and the content of cobalt was 20% by mass.
実施例１と同様に、実施例７〜１０で得られたマイクロ波加熱用アンモニア分解触媒のアンモニア転化率（％）を測定した。結果を図３に示す。また、この時のマイクロ波出力（Ｗ）と、マイクロ波加熱用アンモニア分解触媒の温度（℃）との関係を図４に示す。 In the same manner as in Example 1, the ammonia conversion rate (%) of the ammonia decomposition catalyst for microwave heating obtained in Examples 7 to 10 was measured. The results are shown in FIG. Further, FIG. 4 shows the relationship between the microwave output (W) at this time and the temperature (° C.) of the ammonia decomposition catalyst for microwave heating.
図３の結果より、金属粒子の担持量が増加するほど、アンモニア転化率が高くなることが分かった。また、図４の結果より、マイクロ波出力が１００Ｗ未満であっても、金属粒子の担持量が1〜５質量％の場合は５５０℃まで、１０質量％の場合は６００℃まで加熱できることが分かった。一方、マイクロ波出力が１００Ｗ未満においては、金属粒子の担持量が２０質量％の場合、４５０℃までしか加熱できなかった。おそらく、金属粒子の担持量が増えて金属粒子が凝集することで、金属的な性質が増加し、マイクロ波の吸収効率が低下したためと考えられる。 From the results of FIG. 3, it was found that the ammonia conversion rate increases as the amount of metal particles supported increases. Further, from the results of FIG. 4, it was found that even if the microwave output is less than 100 W, it can be heated up to 550 ° C. when the amount of metal particles supported is 1 to 5% by mass and up to 600 ° C. when the amount of metal particles supported is 10% by mass. It was. On the other hand, when the microwave output was less than 100 W and the amount of metal particles supported was 20% by mass, it could only be heated to 450 ° C. This is probably because the amount of metal particles supported increases and the metal particles aggregate, which increases the metallic properties and reduces the microwave absorption efficiency.
次に、加熱方法の影響を調べるため、表３に示すように、マイクロ波加熱用アンモニア分解触媒及びマイクロ波加熱用アンモニア分解触媒混合物を調製し、アンモニア転化率を測定した。 Next, in order to investigate the influence of the heating method, as shown in Table 3, a mixture of an ammonia decomposition catalyst for microwave heating and an ammonia decomposition catalyst mixture for microwave heating was prepared, and the ammonia conversion rate was measured.
［実施例１１］
実施例１と同様の方法により、マイクロ波加熱用アンモニア分解触媒を調製し、アンモニア転化率を測定した。結果を図５に示す。
[Example 11]
An ammonia decomposition catalyst for microwave heating was prepared by the same method as in Example 1, and the ammonia conversion rate was measured. The results are shown in FIG.
［実施例１２］
実施例４と同様の方法により、マイクロ波加熱用アンモニア分解触媒を調製し、アンモニア転化率を測定した。結果を図５に示す。
[Example 12]
An ammonia decomposition catalyst for microwave heating was prepared by the same method as in Example 4, and the ammonia conversion rate was measured. The results are shown in FIG.
［実施例１３］
マイクロ波に代え、電気炉を用いて加熱した以外は、実施例１と同様の方法により、マイクロ波加熱用アンモニア分解触媒を調製し、アンモニア転化率を測定した。結果を図５に示す。
[Example 13]
An ammonia decomposition catalyst for microwave heating was prepared and the ammonia conversion rate was measured by the same method as in Example 1 except that the mixture was heated using an electric furnace instead of the microwave. The results are shown in FIG.
図５の結果より、同じコバルト担持γ−アルミナ触媒を用いた場合でも、一般的な電気炉による加熱より、マイクロ波加熱の方が、触媒の活性が著しく高くなることが分かった。また、ＳｉＣ加熱助剤を加えると、触媒の活性がより高くなることが分かった。 From the results of FIG. 5, it was found that even when the same cobalt-supported γ-alumina catalyst was used, the activity of the catalyst was significantly higher in the microwave heating than in the heating in a general electric furnace. It was also found that the activity of the catalyst became higher when the SiC heating aid was added.
次に、担体の影響を調べるため、表４に示すように、マイクロ波加熱用アンモニア分解触媒を調製し、アンモニア転化率を測定した。 Next, in order to investigate the influence of the carrier, as shown in Table 4, an ammonia decomposition catalyst for microwave heating was prepared, and the ammonia conversion rate was measured.
［実施例１４］
実施例１と同様の方法により、担体としてγ−アルミナを用いたマイクロ波加熱用アンモニア分解触媒を調製した。
[Example 14]
An ammonia decomposition catalyst for microwave heating using γ-alumina as a carrier was prepared by the same method as in Example 1.
［実施例１５］
γ−アルミナに代えて、イットリア安定ジルコニア（ＹＳＺ）(アルドリッチ社製 ｎａｎｏ ｐｏｗｄｅｒ)を用いた以外は、実施例１と同様の方法にてマイクロ波加熱用アンモニア分解触媒を調製した。
[Example 15]
An ammonia decomposition catalyst for microwave heating was prepared in the same manner as in Example 1 except that yttria-stable zirconia (YSZ) (nano powerer manufactured by Aldrich) was used instead of γ-alumina.
実施例１と同様に、実施例１４及び１５で得られたマイクロ波加熱用アンモニア分解触媒のアンモニア転化率（％）を測定した。結果を図６に示す。また、この時のマイクロ波加熱用アンモニア分解触媒の温度（℃）とマイクロ波出力（Ｗ）との関係を図７に示す。 In the same manner as in Example 1, the ammonia conversion rate (%) of the ammonia decomposition catalyst for microwave heating obtained in Examples 14 and 15 was measured. The results are shown in FIG. Further, FIG. 7 shows the relationship between the temperature (° C.) of the ammonia decomposition catalyst for microwave heating and the microwave output (W) at this time.
図６の結果より、γ−アルミナ担体を用いた場合と比較し、ＹＳＺ担体を用いた場合はアンモニア転化率が向上することが分かった。また、図７の結果より、γ−アルミナ担体を用いた場合は、マイクロ波出力を増加させるにつれマイクロ波加熱用アンモニア分解触媒の温度が高くなり、１００Ｗのマイクロ波出力で５５０℃まで達することが分かった。一方、ＹＳＺ担体を用いた場合は、温度が高くなるほど、必要なマイクロ波出力が小さくなり、２７Ｗ程度のマイクロ波出力で６００℃に達することが分かった。 From the results shown in FIG. 6, it was found that the ammonia conversion rate was improved when the YSZ carrier was used as compared with the case where the γ-alumina carrier was used. Further, from the results of FIG. 7, when the γ-alumina carrier is used, the temperature of the ammonia decomposition catalyst for microwave heating increases as the microwave output is increased, and the temperature reaches 550 ° C. at a microwave output of 100 W. Do you get it. On the other hand, when the YSZ carrier was used, it was found that the higher the temperature, the smaller the required microwave output, and the microwave output of about 27 W reached 600 ° C.
次に、加熱助剤を添加した場合の担体の影響を調べるため、表５に示すように、マイクロ波加熱用アンモニア分解触媒混合物を調製し、アンモニア転化率を測定した。 Next, in order to investigate the effect of the carrier when the heating aid was added, as shown in Table 5, an ammonia decomposition catalyst mixture for microwave heating was prepared, and the ammonia conversion rate was measured.
［実施例１６］
実施例４と同様の方法により、担体としてγ−アルミナを用いたマイクロ波加熱用アンモニア分解触媒混合物を調製した。
[Example 16]
An ammonia decomposition catalyst mixture for microwave heating using γ-alumina as a carrier was prepared by the same method as in Example 4.
［実施例１７］
γ−アルミナ担体に代えて、ＭｇＯ(宇部興産株式会社製 ５００Ａ)担体を用いた以外は、実施例４と同様にしてマイクロ波加熱用アンモニア分解触媒混合物を調製した。
[Example 17]
An ammonia decomposition catalyst mixture for microwave heating was prepared in the same manner as in Example 4 except that an MgO (500A manufactured by Ube Kosan Co., Ltd.) carrier was used instead of the γ-alumina carrier.
［実施例１８］
γ−アルミナ担体に代えて、ＺｒＯ２（和光純薬工業株式会社製 酸化ジルコニウム（ＩＶ）)担体を用いた以外は、実施例４と同様にしてマイクロ波加熱用アンモニア分解触媒混合物を調製した。
[Example 18]
An ammonia decomposition catalyst mixture for microwave heating was prepared in the same manner as in Example 4 except that a ZrO 2 (zirconium oxide (IV) oxide (IV) carrier manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of the γ-alumina carrier.
［実施例１９］
γ−アルミナ担体に代えて、イットリア安定ジルコニア（ＹＳＺ）(アルドリッチ社製 ｎａｎｏ ｐｏｗｄｅｒ)担体を用いた以外は、実施例４と同様にしてマイクロ波加熱用アンモニア分解触媒混合物を調製した。
[Example 19]
An ammonia decomposition catalyst mixture for microwave heating was prepared in the same manner as in Example 4 except that an yttria stable zirconia (YSZ) (nano powerer manufactured by Aldrich) carrier was used instead of the γ-alumina carrier.
［実施例２０］
γ−アルミナ担体に代えて、ＮａＹ型ゼオライト(東ソー株式会社製 ＨＳＺ−３２０ＡＡ)担体を用いた以外は、実施例４と同様にしてマイクロ波加熱用アンモニア分解触媒混合物を調製した。
[Example 20]
An ammonia decomposition catalyst mixture for microwave heating was prepared in the same manner as in Example 4 except that a NaY-type zeolite (HSZ-320AA manufactured by Tosoh Corporation) carrier was used instead of the γ-alumina carrier.
［実施例２１］
γ−アルミナ担体に代えて、超安定化Ｙ（ＵＳＹ）型ゼオライト(東ソー株式会社製 ＨＳＺ−３３０ＨＵＡ)担体を用いた以外は、実施例４と同様にしてマイクロ波加熱用アンモニア分解触媒混合物を調製した。
[Example 21]
An ammonia decomposition catalyst mixture for microwave heating was prepared in the same manner as in Example 4 except that an ultra-stabilized Y (USY) type zeolite (HSZ-330HUA manufactured by Tosoh Corporation) carrier was used instead of the γ-alumina carrier. did.
［実施例２２］
γ−アルミナ担体に代えて、Ｐ２５ＴｉＯ２(ルチル−アナターゼ混晶型ＴｉＯ２ アエロジル社製)担体を用いた以外は、実施例４と同様にしてマイクロ波加熱用アンモニア分解触媒混合物を調製した。
[Example 22]
An ammonia decomposition catalyst mixture for microwave heating was prepared in the same manner as in Example 4 except that a P25TiO 2 (rutile-anatase mixed crystal type TiO 2 manufactured by Aerodil) carrier was used instead of the γ-alumina carrier.
［実施例２３］
γ−アルミナ担体に代えて、ルチル型ＴｉＯ２(関東化学株式会社製 酸化チタン（ＩＶ）)担体を用いた以外は、実施例４と同様にしてマイクロ波加熱用アンモニア分解触媒混合物を調製した。
[Example 23]
A mixture of ammonia decomposition catalysts for microwave heating was prepared in the same manner as in Example 4 except that a rutile-type TiO 2 (titanium oxide (IV) oxide) carrier manufactured by Kanto Chemical Co., Inc. was used instead of the γ-alumina carrier.
［実施例２４］
γ−アルミナ担体に代えて、アナターゼ型ＴｉＯ２(和光純薬工業株式会社製 酸化チタン(IV)) 担体を用いた以外は、実施例４と同様にしてマイクロ波加熱用アンモニア分解触媒混合物を調製した。
[Example 24]
An ammonia decomposition catalyst mixture for microwave heating was prepared in the same manner as in Example 4 except that an anatase-type TiO 2 (titanium oxide (IV) oxide) carrier manufactured by Wako Pure Chemical Industries, Ltd. was used instead of the γ-alumina carrier. did.
実施例１１〜１３と同様に、実施例１６〜２４で得られたマイクロ波加熱用アンモニア分解触媒混合物を、マイクロ波で加熱した場合と、電気炉で加熱した場合のアンモニア転化率（％）を測定した。結果を図８に示す。なお、図８のアンモニア転化率は、５００℃で加熱した場合の結果を棒グラフで示している。また、この時のマイクロ波加熱用アンモニア分解触媒混合物の温度（℃）とマイクロ波出力（Ｗ）との関係を図９に示す。 Similar to Examples 11 to 13, the ammonia conversion rate (%) when the ammonia decomposition catalyst mixture for microwave heating obtained in Examples 16 to 24 was heated by microwaves and heated by an electric furnace was determined. It was measured. The results are shown in FIG. The ammonia conversion rate in FIG. 8 is a bar graph showing the result when heated at 500 ° C. Further, FIG. 9 shows the relationship between the temperature (° C.) of the ammonia decomposition catalyst mixture for microwave heating and the microwave output (W) at this time.
図８の結果より、電気炉で加熱するより、マイクロ波で加熱した方が、マイクロ波加熱用アンモニア分解触媒混合物のアンモニア転化率が高いことが分かった。特に、γ−アルミナ担体、ＹＳＺ担体、ＵＳＹ担体を用いた場合が、アンモニア転化率が高かった。また、図９の結果より、用いる担体によって、マイクロ波出力が異なることが分かった。この時、特にＺｒＯ２担体、ＮａＹ型ゼオライト担体、ＵＳＹ型ゼオライト担体、ＴｉＯ２担体を用いた場合に特に消費電力が低いことが分かった。 From the results of FIG. 8, it was found that the ammonia conversion rate of the ammonia decomposition catalyst mixture for microwave heating was higher when heated with microwaves than when heated with an electric furnace. In particular, when the γ-alumina carrier, YSZ carrier, and USY carrier were used, the ammonia conversion rate was high. Moreover, from the result of FIG. 9, it was found that the microwave output differs depending on the carrier used. At this time, it was found that the power consumption was particularly low when the ZrO 2 carrier, the NaY type zeolite carrier, the USY type zeolite carrier, and the TiO 2 carrier were used.
次に、キレート剤の影響を調べるため、表６に示すように、マイクロ波加熱用アンモニア分解触媒を調製し、アンモニア転化率を測定した。 Next, in order to investigate the effect of the chelating agent, as shown in Table 6, an ammonia decomposition catalyst for microwave heating was prepared, and the ammonia conversion rate was measured.
［実施例２５］
実施例１と同様の方法により、担体としてキレート処理をしていないγ−アルミナを用いてマイクロ波加熱用アンモニア分解触媒を調製した。
[Example 25]
An ammonia decomposition catalyst for microwave heating was prepared using γ-alumina which had not been chelated as a carrier by the same method as in Example 1.
［実施例２６］
キレート処理していないγ−アルミナ担体に代えて、キレート処理したγ−アルミナ担体を用いた以外は、実施例１と同様にしてマイクロ波加熱用アンモニア分解触媒を調製した。キレート処理は、含浸法（ｉｎｃｉｐｉｅｎｔ−ｗｅｔｎｅｓｓ法）にて行った。具体的には、γ−アルミナに、エチレンジアミン四酢酸（ＥＤＴＡ）(株式会社同仁化学研究所製 ＥＤＴＡ・２Ｎａ)を含浸させ、６０℃で予備乾燥後、さらに１１０℃で本乾燥を行った。得られたマイクロ波加熱用アンモニア分解触媒は、γ−アルミナを９５質量部、コバルトを５質量部、ＥＤＴＡの乾燥体を５質量部含んでいた。
[Example 26]
An ammonia decomposition catalyst for microwave heating was prepared in the same manner as in Example 1 except that a chelated γ-alumina carrier was used instead of the unchelated γ-alumina carrier. The chelation treatment was carried out by an impregnation method (incipient-wetness method). Specifically, γ-alumina was impregnated with ethylenediaminetetraacetic acid (EDTA) (EDTA, 2Na manufactured by Dojin Chemical Laboratory Co., Ltd.), pre-dried at 60 ° C, and then main-dried at 110 ° C. The obtained ammonia decomposition catalyst for microwave heating contained 95 parts by mass of γ-alumina, 5 parts by mass of cobalt, and 5 parts by mass of a dried product of EDTA.
実施例１と同様に、実施例２５及び２６で得られたマイクロ波加熱用アンモニア分解触媒のアンモニア転化率（％）を測定した。結果を図１０に示す。また、この時のマイクロ波加熱用アンモニア分解触媒の温度（℃）とマイクロ波出力（Ｗ）との関係を図１１に示す。 In the same manner as in Example 1, the ammonia conversion rate (%) of the ammonia decomposition catalyst for microwave heating obtained in Examples 25 and 26 was measured. The results are shown in FIG. Further, FIG. 11 shows the relationship between the temperature (° C.) of the ammonia decomposition catalyst for microwave heating and the microwave output (W) at this time.
図１０の結果より、キレート処理した実施例２６の触媒は、キレート処理していない実施例２５の触媒より、アンモニア転化率が向上することが分かった。おそらく、担体表面での金属粒子の分散性が高くなり、金属粒子の粒径が小さくなり、金属粒子の表面積が増えたためと考えられる。また、図１１の結果より、キレート処理した実施例２６の触媒は、キレート処理していない実施例２５の触媒より、必要なマイクロ波出力が大幅に低減することが分かった。 From the results of FIG. 10, it was found that the catalyst of Example 26 chelated had an improved ammonia conversion rate as compared with the catalyst of Example 25 not chelated. Probably because the dispersibility of the metal particles on the surface of the carrier became high, the particle size of the metal particles became small, and the surface area of the metal particles increased. Further, from the results of FIG. 11, it was found that the required microwave output of the chelated Example 26 catalyst was significantly reduced as compared with the non-chelated Example 25 catalyst.
次に、助触媒の影響を調べるため、表７に示すように、マイクロ波加熱用アンモニア分解触媒混合物を調製し、アンモニア転化率を測定した。 Next, in order to investigate the influence of the co-catalyst, as shown in Table 7, a mixture of ammonia decomposition catalysts for microwave heating was prepared, and the ammonia conversion rate was measured.
［実施例２７］
実施例４と同様の方法により、助触媒を担持しないマイクロ波加熱用アンモニア分解触媒混合物を調製した。
[Example 27]
An ammonia decomposition catalyst mixture for microwave heating, which does not support a co-catalyst, was prepared by the same method as in Example 4.
［実施例２８］
コバルトに加え、γ−アルミナにマグネシウムを助触媒として担持させた以外は、実施例４と同様の方法によりマイクロ波加熱用アンモニア分解触媒混合物を調製した。
[Example 28]
An ammonia decomposition catalyst mixture for microwave heating was prepared by the same method as in Example 4 except that magnesium was supported on γ-alumina as an auxiliary catalyst in addition to cobalt.
具体的には、実施例４と同様にしてコバルト担持γ−アルミナを準備した。そして、Ｍｇ（ＮＯ３）２・６Ｈ２Ｏ（和光純薬工業株式会社製 含量９９．５％）を用い、含浸法にて、コバルト担持γ−アルミナに担持させ、１１０℃で１２時間乾燥、５００℃で３時間焼成した。焼成物は室温まで冷却した後、ペレット状に加圧成形した。その後、ペレット状に加圧成形した焼成物を粉砕し、２５０〜５００μｍになるようにふるい分け、コバルト−マグネシウム担持γ−アルミナを得た。この時、コバルト−マグネシウム担持γ−アルミナは、γ−アルミナを９０質量％、コバルトを５質量％、マグネシウムを５質量％含んでいた。その後、実施例４と同様の方法にて、コバルト−マグネシウム担持γ−アルミナにＳｉＣ加熱助剤を加え、６００℃、１気圧のＨ２流通雰囲気中で２時間放置する水素前処理を行い、マイクロ波加熱用アンモニア分解触媒混合物を調製した。 Specifically, cobalt-supported γ-alumina was prepared in the same manner as in Example 4. Then, using the Mg (NO 3) 2 · 6H 2 O ( Wako Pure Chemical Industries, Ltd. content 99.5%) at an impregnation method, supported on cobalt supported γ- alumina, 12 hours drying at 110 ° C., It was calcined at 500 ° C. for 3 hours. The fired product was cooled to room temperature and then pressure-molded into pellets. Then, the calcined product pressure-molded into pellets was pulverized and sieved to 250 to 500 μm to obtain cobalt-magnesium-supported γ-alumina. At this time, the cobalt-magnesium-supported γ-alumina contained 90% by mass of γ-alumina, 5% by mass of cobalt, and 5% by mass of magnesium. Then, in the same manner as in Example 4, a SiC heating aid was added to the cobalt-magnesium-supported γ-alumina, and hydrogen pretreatment was performed by leaving it in an H 2 flow atmosphere at 600 ° C. and 1 atm for 2 hours. An ammonia decomposition catalyst mixture for wave heating was prepared.
［実施例２９］
Ｍｇ（ＮＯ３）２・６Ｈ２Ｏに代えて、ＫＮＯ３（和光純薬工業株式会社製 特級）を用いた以外は、実施例２８と同様にしてマイクロ波加熱用アンモニア分解触媒混合物を調製した。
[Example 29]
Instead of Mg (NO 3) 2 · 6H 2 O, except for using KNO 3 (produced by Wako Pure Chemical Industries, Ltd. special grade) was prepared microwave heating ammonia decomposition catalyst mixture in the same manner as in Example 28 ..
［実施例３０］
Ｍｇ（ＮＯ３）２・６Ｈ２Ｏに代えて、Ｃａ（ＮＯ３）２・４Ｈ２Ｏ（和光純薬工業株式会社製 含量９９．９％）を用いた以外は、実施例２８と同様にしてマイクロ波加熱用アンモニア分解触媒混合物を調製した。
[Example 30]
Mg (NO 3) in place of 2 · 6H 2 O, except for using Ca (NO 3) 2 · 4H 2 O ( Wako Pure Chemical Industries, Ltd. content 99.9%) are in the same manner as in Example 28 Ammonia decomposition catalyst mixture for microwave heating was prepared.
［実施例３１］
Ｍｇ（ＮＯ３）２・６Ｈ２Ｏに代えて、ＲｂＮＯ３（和光純薬工業株式会社製）を用いた以外は、実施例２８と同様にしてマイクロ波加熱用アンモニア分解触媒混合物を調製した。
[Example 31]
Instead of Mg (NO 3) 2 · 6H 2 O, except for using RbNO 3 (manufactured by Wako Pure Chemical Industries, Ltd.), to prepare a microwave heating ammonia decomposition catalyst mixture in the same manner as in Example 28.
実施例１と同様に、実施例２７〜３１で得られたマイクロ波加熱用アンモニア分解触媒混合物のアンモニア転化率（％）を測定した。結果を図１２に示す。なお、図１２のアンモニア転化率は、３５０℃及び４５０℃で加熱した場合の結果を棒グラフで示している。また、この時のマイクロ波加熱用アンモニア分解触媒混合物の温度（℃）とマイクロ波出力（Ｗ）との関係を図１３に示す。 In the same manner as in Example 1, the ammonia conversion rate (%) of the ammonia decomposition catalyst mixture for microwave heating obtained in Examples 27 to 31 was measured. The results are shown in FIG. The ammonia conversion rate in FIG. 12 is shown in a bar graph as a result of heating at 350 ° C. and 450 ° C. Further, FIG. 13 shows the relationship between the temperature (° C.) of the ammonia decomposition catalyst mixture for microwave heating and the microwave output (W) at this time.
図１２の結果より、アルカリ金属を含む助触媒を担持させることにより、アンモニア転化率が向上する場合があることが分かった。特にカリウムを助触媒として担持させた場合に、アンモニア転化率が向上することが分かった。また、図１３の結果より、アルカリ金属を含む助触媒を担持させることにより、加熱に必要なマイクロ波出力を低減させることが可能であることが分かった。この場合も、特にカリウムを助触媒として担持させた場合に、マイクロ波出力を低減できることが分かった。 From the results of FIG. 12, it was found that the ammonia conversion rate may be improved by supporting the co-catalyst containing an alkali metal. In particular, it was found that the ammonia conversion rate was improved when potassium was supported as a co-catalyst. Further, from the results of FIG. 13, it was found that it is possible to reduce the microwave output required for heating by supporting the co-catalyst containing an alkali metal. In this case as well, it was found that the microwave output can be reduced, especially when potassium is supported as a co-catalyst.
前処理の影響を調べるため、表８に示すように、マイクロ波加熱用アンモニア分解触媒混合物を調製した。 To investigate the effect of pretreatment, an ammonia decomposition catalyst mixture for microwave heating was prepared as shown in Table 8.
［実施例３２］
実施例４と同様の方法にて、６００℃、１気圧のＨ２流通雰囲気中で２時間放置する水素前処理を行い、マイクロ波加熱用アンモニア分解触媒混合物を調製した。
[Example 32]
In the same manner as in Example 4, 600 ° C., subjected to hydrogen pretreatment to stand 2 hours in H 2 flow atmosphere at 1 atm, to prepare a microwave heating ammonia decomposition catalyst mixture.
［実施例３３］
Ｈ２に代えて、ＮＨ３を用いて前処理した以外は、実施例４と同様の方法にてマイクロ波加熱用アンモニア分解触媒混合物を調製した。
[Example 33]
An ammonia decomposition catalyst mixture for microwave heating was prepared in the same manner as in Example 4 except that it was pretreated with NH 3 instead of H 2 .
［実施例３４］
実施例１と同様の方法にて、６００℃、１気圧のＨ２流通雰囲気中で２時間放置する水素前処理を行い、マイクロ波加熱用アンモニア分解触媒を調製した。
[Example 34]
In the same manner as in Example 1, 600 ° C., subjected to hydrogen pretreatment to stand 2 hours in H 2 flow atmosphere at 1 atm, to prepare a microwave heating ammonia decomposition catalyst.
［実施例３５］
Ｈ２に代えて、ＮＨ３を用いて前処理した以外は、実施例１と同様の方法にてマイクロ波加熱用アンモニア分解触媒を調製した。
[Example 35]
An ammonia decomposition catalyst for microwave heating was prepared in the same manner as in Example 1 except that it was pretreated with NH 3 instead of H 2 .
実施例１１〜１３と同様に、実施例３２及び３３で得られたマイクロ波加熱用アンモニア分解触媒混合物をマイクロ波で加熱した場合のアンモニア転化率（％）を測定した。同様に、実施例３４及び３５で得られたマイクロ波加熱用アンモニア分解触媒を電気炉で加熱した場合のアンモニア転化率（％）を測定した。結果を図１４に示す。 Similar to Examples 11 to 13, the ammonia conversion rate (%) when the ammonia decomposition catalyst mixture for microwave heating obtained in Examples 32 and 33 was heated by microwave was measured. Similarly, the ammonia conversion rate (%) when the ammonia decomposition catalyst for microwave heating obtained in Examples 34 and 35 was heated in an electric furnace was measured. The results are shown in FIG.
図１４の結果より、電気炉で加熱をした場合は、水素前処理に代えてアンモニア前処理をしても、アンモニア転化率に大きな差はなかった。しかし、マイクロ波で加熱した場合は、アンモニア前処理の方が、水素前処理よりもアンモニア転化率が向上することが分かった。 From the results shown in FIG. 14, when heating was performed in an electric furnace, there was no significant difference in the ammonia conversion rate even if ammonia pretreatment was performed instead of hydrogen pretreatment. However, it was found that the ammonia conversion rate was improved in the ammonia pretreatment than in the hydrogen pretreatment when heated with microwaves.
実施例３３のアンモニア転化率が向上した原因を調査するため、以下のような分析を行った。 In order to investigate the cause of the improvement in the ammonia conversion rate of Example 33, the following analysis was performed.
＜前処理後のマイクロ波加熱用アンモニア分解触媒の表面分析＞
実施例３２及び３３で得られたマイクロ波加熱用アンモニア分解触媒混合物の表面をＸＰＳで分析した。結果を表９に示す。
<Surface analysis of ammonia decomposition catalyst for microwave heating after pretreatment>
The surfaces of the ammonia decomposition catalyst mixture for microwave heating obtained in Examples 32 and 33 were analyzed by XPS. The results are shown in Table 9.
＜昇温脱離ガス分析＞
実施例３３で得られたマイクロ波加熱用アンモニア分解触媒混合物について、昇温脱離ガス分析を行った。結果を図１５に示す。図１５中、質量数２のスペクトルはＨ２、質量数１６のスペクトルはＮＨ２ ＋、質量数１７のスペクトルはＮＨ３とＯＨ−、質量数１８のスペクトルはＨ２Ｏ、質量数２８のスペクトルはＮ２に対応する。
<Analysis of heated desorption gas>
A warm desorption gas analysis was performed on the ammonia decomposition catalyst mixture for microwave heating obtained in Example 33. The results are shown in FIG. In Figure 15, the spectrum of
また、図１５中、２５０℃のピークは、マイクロ波加熱用アンモニア分解触媒混合物に、物理的に吸着したアンモニアの離脱によるものである。また、４００℃のピークは、窒素を含む表面吸着種の分解によるものである。これはアンモニア処理によって表面の窒素濃度が増加したＸＰＳの結果と一致する。 Further, in FIG. 15, the peak at 250 ° C. is due to the release of ammonia physically adsorbed on the ammonia decomposition catalyst mixture for microwave heating. The peak at 400 ° C. is due to the decomposition of surface-adsorbed species containing nitrogen. This is consistent with the result of XPS where the surface nitrogen concentration was increased by the ammonia treatment.
表９や図１５の結果より、マイクロ波加熱用アンモニア分解触媒混合物の表面に窒素を含む吸着種が存在し、これがアンモニア転化率向上に作用することが分かった。 From the results of Table 9 and FIG. 15, it was found that an adsorbed species containing nitrogen was present on the surface of the ammonia decomposition catalyst mixture for microwave heating, and this acted to improve the ammonia conversion rate.
以上、本発明を実施形態によって説明したが、本発明はこれらに限定されるものではなく、本発明の要旨の範囲内で種々の変形が可能である。 Although the present invention has been described above by embodiment, the present invention is not limited to these, and various modifications can be made within the scope of the gist of the present invention.
Claims (5)
担体と、
前記担体上に担持され、ニッケル、コバルト及び鉄からなる群より選択される少なくとも１種の遷移金属を主成分とする金属粒子と、
を備え、
前記担体への前記金属粒子の担持量は、前記担体と前記金属粒子との合計１００質量％に対して１〜５質量％であることを特徴とするマイクロ波加熱用アンモニア分解触媒。 Ammonia decomposition catalyst for microwave heating in TM 010 mode (n is an integer of 1 or more).
With the carrier
Metal particles supported on the carrier and containing at least one transition metal as a main component selected from the group consisting of nickel, cobalt and iron.
With
An ammonia decomposition catalyst for microwave heating, wherein the amount of the metal particles supported on the carrier is 1 to 5% by mass with respect to a total of 100% by mass of the carrier and the metal particles.
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| JP6604501B2 (en) * | 2014-09-16 | 2019-11-13 | 国立大学法人山梨大学 | Ammonia decomposition catalyst, method for producing the same, and apparatus using the same |
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