JP2006272159A - Catalyst formed on surface of metal, and its forming method - Google Patents
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- 239000003054 catalyst Substances 0.000 title claims abstract description 119
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 78
- 239000002184 metal Substances 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims description 25
- 239000011148 porous material Substances 0.000 claims abstract description 44
- 239000000126 substance Substances 0.000 claims abstract description 36
- 238000005507 spraying Methods 0.000 claims abstract description 31
- 239000011368 organic material Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims description 40
- 239000011248 coating agent Substances 0.000 claims description 37
- 230000003197 catalytic effect Effects 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000005416 organic matter Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 description 26
- 229910052739 hydrogen Inorganic materials 0.000 description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 23
- 239000000843 powder Substances 0.000 description 19
- 239000000758 substrate Substances 0.000 description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 17
- 238000007751 thermal spraying Methods 0.000 description 16
- 239000004372 Polyvinyl alcohol Substances 0.000 description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 239000012528 membrane Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000010955 niobium Substances 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 4
- 229910052758 niobium Inorganic materials 0.000 description 4
- 229910052715 tantalum Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229910000484 niobium oxide Inorganic materials 0.000 description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910001252 Pd alloy Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 238000003466 welding Methods 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
- Y02E60/50—Fuel cells
Abstract
Description
本発明は、金属表面に形成させた触媒及びその形成方法に関するものであり、例えば、水素透過膜である金属の表面を触媒化することにより当該金属表面において水素の解離または結合を効率よく行うのに好適な金属表面に形成させた触媒及びその形成方法に係るものである。 The present invention relates to a catalyst formed on a metal surface and a method for forming the same. For example, by catalyzing a metal surface that is a hydrogen permeable membrane, hydrogen can be efficiently dissociated or bonded on the metal surface. The present invention relates to a catalyst formed on a suitable metal surface and a method for forming the catalyst.
水素透過膜は、水素ガスとその他のガスとの混合ガスの中から水素ガスのみを効率的に取り出せるものであり、特に、燃料電池での使用を主な用途として開発が進められている。例えば、固体高分子型燃料電池（ＰＥＦＣ）へ水素を供給するシステムにおいて、システムのコンパクト化を図るために、水蒸気改質器に水素透過膜によるＣＯ除去器を組み合わせた水素供給装置の開発が行われている。 The hydrogen permeable membrane is capable of efficiently extracting only hydrogen gas from a mixed gas of hydrogen gas and other gas, and is being developed mainly for use in a fuel cell. For example, in a system for supplying hydrogen to a polymer electrolyte fuel cell (PEFC), in order to make the system more compact, a hydrogen supply device that combines a steam reformer with a CO remover using a hydrogen permeable membrane has been developed. It has been broken.
水素透過膜としては、従来から、水素透過能や水素脆性の点で優れるＰｄやＰｄ合金が使用されてきた。しかしながら、貴金属であるＰｄは希少な金属であり、非常に高価な材料である。また、近年、電子部品等へＰｄが多用されていることから価格の上昇も予想され、Ｐｄ系水素透過膜に代わる安価な材料でなる水素透過膜が要請されている。そこで、例えば、下記特許文献１に開示されるようなＴａ、Ｎｂ又はそれらの合金など水素透過能のある材料で構成された水素透過膜の開発が進んでいる。
Conventionally, Pd and Pd alloys that are excellent in terms of hydrogen permeability and hydrogen embrittlement have been used as the hydrogen permeable membrane. However, Pd which is a noble metal is a rare metal and a very expensive material. In recent years, since Pd is frequently used in electronic parts and the like, the price is expected to rise, and a hydrogen permeable membrane made of an inexpensive material instead of the Pd-based hydrogen permeable membrane is demanded. Therefore, for example, development of a hydrogen permeable film made of a material having hydrogen permeability such as Ta, Nb, or an alloy thereof as disclosed in
しかしながら、非Ｐｄ系水素透過膜においても、水素の解離又は結合のために、当該水素透過膜の表面にはＰｄ又はＰｄ合金からなる触媒層を設ける必要がある。また、その触媒層は、水素解離（結合）を促進するために充分な触媒を担持可能な多孔質で比表面積の大きな触媒担体に触媒が担持されてなるものであることが望ましい。また、同様な要望が、燃料改質器等において燃焼用触媒となるステンレス等の金属表面に形成される触媒にも求められている。ここで、金属表面に多孔質な触媒担体を形成する方法としては、溶射法の他に、無電解メッキ法、陽極酸化法、溶着法、ディップコーティング法、ウォッシュコート法などが知られている。従来の溶射法は、緻密な溶射層を形成してしまうため、微細な空孔の形成が不十分で触媒担体の比表面積が小さく触媒としての活性が小さい。 However, even in a non-Pd-based hydrogen permeable membrane, it is necessary to provide a catalyst layer made of Pd or a Pd alloy on the surface of the hydrogen permeable membrane in order to dissociate or bond hydrogen. Further, the catalyst layer is preferably formed by supporting a catalyst on a porous catalyst carrier having a large specific surface area capable of supporting a catalyst sufficient to promote hydrogen dissociation (bonding). Similar demands are also being sought for catalysts formed on metal surfaces such as stainless steel, which serve as combustion catalysts in fuel reformers and the like. Here, as a method for forming a porous catalyst carrier on the metal surface, in addition to the spraying method, an electroless plating method, an anodic oxidation method, a welding method, a dip coating method, a wash coating method, and the like are known. Since the conventional thermal spraying method forms a dense thermal spray layer, formation of fine pores is insufficient, the specific surface area of the catalyst carrier is small, and the activity as a catalyst is small.
また、無電解めっき法で、下地の金属を直接触媒化する場合には下地の金属がニッケルやパラジウムに限定され、また、比較的触媒金属の粒子が大きくなり高い活性が期待できない。 Further, when the underlying metal is directly catalyzed by electroless plating, the underlying metal is limited to nickel or palladium, and the catalytic metal particles are relatively large, and high activity cannot be expected.
また、陽極酸化法では、数十μｍの多数の空孔を有し比表面積の大きな多孔質のアルミナ層を得ることができるが、下地の金属がアルミニウムに限定され、さらに、陽極酸化法、無電解メッキ法では、いずれもアルミニウムを使用するため、４００℃以上では使用しにくく、アルミニウムの融点である約６５０℃以上の高温では使用できない。 In addition, in the anodic oxidation method, a porous alumina layer having a large number of pores of several tens of μm and a large specific surface area can be obtained. However, the base metal is limited to aluminum. In any of the electrolytic plating methods, since aluminum is used, it is difficult to use at 400 ° C. or higher, and it cannot be used at a high temperature of about 650 ° C. or higher, which is the melting point of aluminum.
また、ディップコート法やウォッシュコート法により、金属上に厚い触媒層を直接形成した場合には、触媒層に高温が作用したときに触媒層が剥離する問題がある。また、ゾルゲル法では触媒として十分な量を金属上に被覆できない。これらの方法では、触媒層が緻密に形成されるため、比表面積が小さく触媒活性が乏しかった。さらに、アルミニウム合金などを溶射して後処理する場合は、被膜が緻密なため、表面のみしか活性化できなかった。
本発明は、上記の問題点に鑑みなされたものであり、多数の微細な細孔を有する比表面積の大きな触媒担体に触媒金属が担持されてなる触媒層を有する金属表面に形成された触媒を提供することを目的としている。 The present invention has been made in view of the above problems, and a catalyst formed on a metal surface having a catalyst layer in which a catalyst metal is supported on a catalyst carrier having a large number of fine pores and a large specific surface area. It is intended to provide.
かかる課題を解決する、本発明の第１発明は、有機物をコーティングした触媒金属を含む酸化物を金属表面に溶射して形成させた溶射被膜中の有機物からなる物質を燃焼させて空孔を形成させ、多孔質な酸化層となった溶射被膜を還元して微細な細孔を有する触媒層を形成させてなる金属表面に形成させた触媒である。ここで、有機物としてはポリビニルアルコール、ポリビニルブチラールなどで良く、触媒金属及び触媒担体である酸化物を分散させる溶媒に溶解するものであれば良い。また、触媒担体となる酸化物としてはジルコニア、アルミナ又は酸化ニオブ等種々の酸化物を利用することができる。 To solve this problem, the first invention of the present invention forms pores by burning an organic substance in a sprayed coating formed by spraying an oxide containing a catalytic metal coated with an organic substance on the metal surface. The catalyst is formed on the metal surface by reducing the sprayed coating formed into a porous oxide layer to form a catalyst layer having fine pores. Here, the organic substance may be polyvinyl alcohol, polyvinyl butyral, etc., as long as it dissolves in a solvent in which the catalyst metal and the oxide that is the catalyst carrier are dispersed. Various oxides such as zirconia, alumina or niobium oxide can be used as the oxide serving as the catalyst carrier.
かかる第１発明によれば、上記した触媒金属と酸化物とを、例えば有機物が溶解した溶媒中に均一に分散させてスラリー状にした後、溶媒分が揮発する温度で熱処理することにより、触媒金属を含む酸化物に有機物が被覆された溶射用粉末が得られる。この溶射用粉末を、金属表面に溶射することにより、金属表面には有機物からなる物質を含む溶射皮膜が形成される。 According to the first invention, the catalyst metal and the oxide described above are uniformly dispersed in, for example, a solvent in which an organic substance is dissolved to form a slurry, and then heat-treated at a temperature at which the solvent component volatilizes. A thermal spraying powder in which an organic substance is coated on an oxide containing a metal is obtained. By spraying this thermal spraying powder on the metal surface, a thermal spray coating containing a substance made of an organic substance is formed on the metal surface.
ここで、上記溶射皮膜に含まれる有機物からなる物質の一部とは、溶射時に溶射熱によって有機物が分解してなる炭素又は炭素、酸素及び水素からなる中間体である。それら有機物からなる物質を燃焼させることで、有機物からなる物質である炭素や中間体は分解し、微細な細孔を有し比表面積の大きな触媒担体である酸化層となった溶射皮膜が形成される。ここで、酸化物には触媒金属が含まれているので、多数の微細な細孔を有し比表面積の大きな触媒担体である溶射皮膜の該空孔に触媒金属が担持されてなる触媒層を有する金属表面に形成された触媒が提供される。 Here, a part of the substance made of an organic substance contained in the thermal spray coating is an intermediate made of carbon or carbon, oxygen, and hydrogen obtained by decomposing the organic substance by thermal spraying heat at the time of thermal spraying. By burning these organic substances, carbon and intermediates, which are organic substances, are decomposed to form a thermal spray coating that is an oxide layer that is a catalyst carrier with fine pores and a large specific surface area. The Here, since the oxide contains a catalyst metal, a catalyst layer in which the catalyst metal is supported in the pores of the thermal spray coating, which is a catalyst carrier having a large number of fine pores and a large specific surface area, is provided. A catalyst formed on a metal surface is provided.
本発明の第２発明は、有機物を被覆した触媒担体となる酸化物を金属表面に溶射して形成させた溶射被膜中の有機物からなる物質を燃焼させて空孔を形成させ、多孔質な酸化層となった溶射被膜に触媒金属を担持してなることを特徴とする金属表面に形成させた触媒である。かかる第２発明によれば、金属表面に形成された、微細な空孔と大きな比表面積を有する触媒担体である酸化層となった溶射皮膜に、触媒金属を担持させることにより、多数の微細な細孔を有し比表面積の大きな触媒担体である溶射皮膜の該細孔に触媒金属が担持されてなる触媒層を有する金属表面に形成された触媒が提供される。 According to the second aspect of the present invention, a porous oxide is formed by burning a substance made of organic matter in a sprayed coating formed by spraying an oxide serving as a catalyst carrier coated with an organic matter on a metal surface. A catalyst formed on a metal surface, characterized in that a catalytic metal is supported on a layered sprayed coating. According to the second invention, the catalyst metal is supported on the thermal spray coating formed on the metal surface and formed as an oxide layer which is a catalyst carrier having fine pores and a large specific surface area, whereby a large number of fine metals are supported. There is provided a catalyst formed on a metal surface having a catalyst layer in which a catalyst metal is supported on the pores of a thermal spray coating that is a catalyst carrier having pores and a large specific surface area.
本発明の第３発明は、有機物を被覆した触媒金属を含む酸化物を、金属表面に溶射して溶射被膜を形成させた後、熱処理により溶射被膜中の炭素を燃焼させて空孔を形成させ、ついで、多孔質な酸化層となった溶射被膜を還元して、微細な細孔を有する触媒金属の活性層を形成させる金属表面に触媒を形成させる方法である。本発明によれば、上記第１発明の触媒を好適に形成することができる。 According to a third aspect of the present invention, an oxide containing a catalytic metal coated with an organic substance is sprayed on a metal surface to form a sprayed coating, and then carbon in the sprayed coating is burned by heat treatment to form pores. Then, the thermal spray coating formed into a porous oxide layer is reduced to form a catalyst on the metal surface for forming a catalytic metal active layer having fine pores. According to the present invention, the catalyst of the first invention can be suitably formed.
本発明の第４発明は、有機物を被覆した触媒担体となる酸化物を、金属表面に溶射して溶射被膜を形成させた後、熱処理により溶射被膜中の有機物からなる物質を燃焼させて空孔を形成させ、ついで、多孔質な酸化層となった溶射被膜に触媒金属を担持することを特徴とする金属表面に触媒を形成させる方法である。本発明によれば、上記第２発明の触媒を好適に形成できる。 According to a fourth aspect of the present invention, an oxide serving as a catalyst support coated with an organic substance is sprayed on a metal surface to form a sprayed coating, and then a substance made of organic matter in the sprayed coating is burned by heat treatment to form pores. Then, the catalyst is formed on the metal surface, characterized in that the catalyst metal is supported on the sprayed coating formed into a porous oxide layer. According to the present invention, the catalyst of the second invention can be suitably formed.
ここで、上記の第４発明において得られた多孔質な触媒担体である溶射皮膜に触媒金属を担持させる方法としては、浸漬法、刷毛塗り法又はスプレー塗布法などを使用することができるが、特に含浸法又は析出沈殿法使用することが好ましい。また、上記発明において、熱処理により溶射被膜中の有機物からなる物質を燃焼させ、空孔径が１nm〜５００μmの範囲、望ましくは１ｎｍ〜１００μｍの範囲、さらに望ましくは１ｎｍ〜１０μｍの範囲の細孔を形成させることが好ましい。 また、上記発明において、有機物の被覆量を調整して、溶射被膜中の空隙率及び／又は空孔径を制御することが好ましい。 Here, as a method of supporting the catalyst metal on the thermal spray coating that is the porous catalyst support obtained in the fourth invention, a dipping method, a brush coating method, a spray coating method, or the like can be used. It is particularly preferable to use an impregnation method or a precipitation method. Further, in the above invention, a substance composed of an organic substance in the thermal spray coating is burned by heat treatment to form pores having a pore diameter in the range of 1 nm to 500 μm, preferably in the range of 1 nm to 100 μm, more preferably in the range of 1 nm to 10 μm. It is preferable to make it. Moreover, in the said invention, it is preferable to adjust the coating amount of organic substance and to control the porosity and / or hole diameter in a sprayed coating.
本発明は上記のように構成されているので、多数の微細な細孔を有する比表面積の大きな触媒担体に触媒金属が担持されてなる触媒層を有する金属表面に形成された触媒およびその形成方法を提供することが可能となる。 Since the present invention is configured as described above, a catalyst formed on a metal surface having a catalyst layer in which a catalyst metal is supported on a catalyst carrier having a large number of fine pores and a large specific surface area, and a method for forming the catalyst Can be provided.
以下、本発明の実施の形態について説明するが、本発明は下記の実施の形態に何ら限定されるものではなく、適宜変更して実施することが可能なものである。アルミニウム、ステンレス、銅、ニッケル、ニオブ、チタン、ジルコニウム又はタンタル等を含む金属などの板、チューブ、波板など様々な形状の金属の表面に、触媒金属を含む触媒担体となる酸化物に有機物が被覆された溶射用粉末を溶射して溶射皮膜を形成した後、熱処理により溶射被膜中の有機物からなる物質を燃焼させて、直径が１nm〜５００μｍ、望ましくは1ｎｍ〜１００μｍ、さらに望ましくは１ｎｍ〜１０μｍの空孔を形成させ、多孔質な酸化層である溶射皮膜を形成させる。このように、有機物を被覆した触媒金属を含む酸化物を金属板上に溶射した後、溶射被膜中の有機物からなる物質を分解して除去することにより、多孔質な触媒層あるいは触媒担体層を形成させることができ、耐熱性の高い金属上にも任意の厚さの多孔質な触媒層を形成させることが可能となる。また、多孔質層の厚さは溶射条件により任意に制御することができ、かつ、使用する有機物の種類や量を選ぶことで空隙率や細孔径も任意に制御することができる。 Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments, and can be implemented with appropriate modifications. An organic substance is present on the surface of a metal of various shapes such as a plate containing aluminum, stainless steel, copper, nickel, niobium, titanium, zirconium or tantalum, etc. After spraying the coated thermal spraying powder to form a thermal spray coating, a substance made of organic matter in the thermal spray coating is burned by heat treatment to have a diameter of 1 nm to 500 μm, preferably 1 nm to 100 μm, more preferably 1 nm to 10 μm. The thermal spray coating which is a porous oxide layer is formed. As described above, after the oxide containing the catalyst metal coated with the organic material is sprayed on the metal plate, the porous material layer or the catalyst carrier layer is formed by decomposing and removing the organic material in the sprayed coating. It is possible to form a porous catalyst layer of any thickness on a metal with high heat resistance. Further, the thickness of the porous layer can be arbitrarily controlled according to the spraying conditions, and the porosity and pore diameter can also be arbitrarily controlled by selecting the kind and amount of the organic substance to be used.
これを触媒として使用する際には、水素などにより触媒金属の酸化物を還元して微細な細孔を持つ活性層を形成させる。溶射被膜中の有機物からなる物質を分解させて空孔を形成させるための熱処理は、約２００〜約８００℃で１〜１０時間程度、望ましくは約４００〜約６００℃で２〜４時間程度行うことが好ましい。雰囲気は、完全に分解させる場合は酸化性雰囲気中が好ましいが、炭素が残存しても支障がない場合は非酸化性雰囲気中でも微細な細孔を形成させることができる。 When this is used as a catalyst, the catalytic metal oxide is reduced with hydrogen or the like to form an active layer having fine pores. The heat treatment for decomposing the organic substance in the thermal spray coating to form pores is performed at about 200 to about 800 ° C. for about 1 to 10 hours, preferably about 400 to about 600 ° C. for about 2 to 4 hours. It is preferable. The atmosphere is preferably an oxidizing atmosphere in the case of complete decomposition, but fine pores can be formed even in a non-oxidizing atmosphere if there is no problem even if carbon remains.
また、アルミニウム、ステンレス、銅、ニッケル、ニオブ、チタン、ジルコニウム又はタンタル等を含む金属などの板、チューブ、波板など様々な形状の金属の表面に、有機物が被覆された触媒担体となる酸化物を溶射し溶射皮膜を形成した、上記と同様の熱処理により溶射被膜中の有機物からなる物質を燃焼して分解し、直径が１nm〜５００μｍ、望ましくは１ｎｍ〜１００μｍ、さらに望ましくは１ｎｍ〜１０μｍの細孔を形成させ、多孔質な酸化層を形成させる。この酸化層に、浸漬、刷毛塗り、スプレー塗布、析出沈殿法などにより触媒金属又は担体物質をコーティングすることにより、微細な細孔と大きな比表面積を形成させた触媒又は触媒担体を得る。したがって、多孔質で比表面積の大きい触媒担体層を形成させ、後から既知の方法で触媒金属を担持することができるため、触媒金属の種類が限定されない。また、溶射膜の厚さは溶射条件により任意に制御することができ、かつ、有機物の種類やコーティングする有機物の量を選ぶことで空隙率や細孔径も任意に制御することができる。さらに、高温でも剥離することがない。 In addition, oxides serving as catalyst supports in which organic materials are coated on the surface of various shapes of metal such as aluminum, stainless steel, copper, nickel, niobium, titanium, zirconium or tantalum, etc. The material composed of organic matter in the sprayed coating is burned and decomposed by heat treatment similar to the above to form a sprayed coating, and the diameter is 1 nm to 500 μm, preferably 1 nm to 100 μm, more preferably 1 nm to 10 μm. Pores are formed, and a porous oxide layer is formed. By coating this oxide layer with a catalyst metal or a support material by dipping, brushing, spraying, precipitation or the like, a catalyst or catalyst support in which fine pores and a large specific surface area are formed is obtained. Therefore, since the catalyst carrier layer having a large specific surface area can be formed and supported on the catalyst metal by a known method later, the type of the catalyst metal is not limited. Further, the thickness of the sprayed film can be arbitrarily controlled according to the spraying conditions, and the porosity and pore diameter can be arbitrarily controlled by selecting the kind of organic substance and the amount of organic substance to be coated. Furthermore, it does not peel off even at high temperatures.
上記のいずれかの方法により、金属表面上に、水素、炭化水素、アルコール等と酸素を触媒上で反応させ酸化させる触媒燃焼用の燃焼触媒や、水素を解離または結合するための水素解離（結合）触媒を形成することができる。具体的には、燃焼触媒としては、Ｐｔ／Ａｌ2Ｏ3などであり、Ｐｔの代わりに、Ｆｅ、Ｎｉ、Ｃｏ、Ｒｕ、Ｐｄ、Ｒｈ、Ｃｕ、Ｎｂ、Ｚｒ又はＴａ等及びこれらの酸化物を用いることもできる。また、水素解離（結合）触媒としては、Pｄ／Ａｌ2Ｏ3などであり、Ｐｄの代わりに、Ｐｔ又はＮｉ及びこれらの酸化物を用いることもできる。 Using any of the above methods, a combustion catalyst for catalytic combustion that oxidizes hydrogen, hydrocarbons, alcohol, etc. with oxygen on the catalyst surface, or hydrogen dissociation (bonding) for dissociating or bonding hydrogen ) A catalyst can be formed. Specifically, the combustion catalyst is Pt / Al 2 O 3 or the like, and instead of Pt, Fe, Ni, Co, Ru, Pd, Rh, Cu, Nb, Zr, Ta or the like and oxides thereof Can also be used. The hydrogen dissociation (bonding) catalyst is Pd / Al 2 O 3 or the like, and Pt or Ni and oxides thereof can be used instead of Pd.
以下、本発明の実施例について説明する。 Examples of the present invention will be described below.
［実施例１］
ジルコニア粉末（粒子径０．１〜２μｍ）とポリビニルアルコールを重量比９０：１０で水を溶媒としボールミル混合した後、１００℃にて乾燥し、次いで造粒し、ポリビニルアルコールで被覆されたジルコニア粉末である溶射用粉末を作製した。次に、基板であるアルミニウム板の表面をサンドブラスト処理により粗面化した。溶射用粉末を大気中でプラズマ溶射し、基板上に７０μｍの厚みの溶射皮膜を形成した。図１に施工した被膜断面状況の模式図を示す。図１において、符号１０は基板、符号１２はポリビニルアルコールからなる物質、符号１４はジルコニア粒子、符号１５は触媒金属である。この後、大気中で５００℃にて４時間の熱処理を行い、ポリビニルアルコールからなる物質１２を燃焼して分解することにより多孔質な触媒担体である溶射被膜を得た。この溶射皮膜の細孔を測定したところ、直径１０ｎｍ〜１μｍの細孔が生成していた。これを基板Ａとする。
[Example 1]
Zirconia powder (particle diameter 0.1 to 2 μm) and polyvinyl alcohol are mixed in a weight ratio of 90:10 using water as a solvent in a ball mill, dried at 100 ° C., then granulated, and coated with polyvinyl alcohol. A thermal spraying powder was produced. Next, the surface of the aluminum plate as a substrate was roughened by sandblasting. The powder for thermal spraying was plasma sprayed in the atmosphere to form a sprayed coating having a thickness of 70 μm on the substrate. FIG. 1 shows a schematic diagram of the cross-sectional state of the applied film. In FIG. 1, reference numeral 10 is a substrate, reference numeral 12 is a substance made of polyvinyl alcohol, reference numeral 14 is zirconia particles, and reference numeral 15 is a catalyst metal. Thereafter, heat treatment was performed in the atmosphere at 500 ° C. for 4 hours to burn and decompose the substance 12 made of polyvinyl alcohol, thereby obtaining a sprayed coating as a porous catalyst carrier. When the pores of this thermal spray coating were measured, pores having a diameter of 10 nm to 1 μm were generated. This is called substrate A.
ポリビニルアルコールとアルミナ粉末（粒子径０．１〜２μｍ）を重量比で２０：８０にした水系スラリーとした後、乾燥し、次いで造粒して溶射用粉末を作成した。上記と同様に表面が調整された基板１０に、アルミナ粉末を含む溶射用粉末を上記と同様に溶射して溶射皮膜を形成した。その後、その溶射皮膜中の有機物からなる物質を熱処理で燃焼させて、多孔質な触媒担体である溶射皮膜を形成した。この溶射皮膜の細孔径は、直径１００ｎｍ〜１０μｍであった。これを基板Ｂとする。 A water-based slurry in which polyvinyl alcohol and alumina powder (particle diameter of 0.1 to 2 μm) were made to have a weight ratio of 20:80 was dried, and then granulated to prepare a thermal spraying powder. The thermal spraying powder containing alumina powder was sprayed in the same manner as above on the substrate 10 whose surface was adjusted in the same manner as described above to form a thermal spray coating. Thereafter, the organic material in the thermal spray coating was burned by heat treatment to form a thermal spray coating as a porous catalyst carrier. The pore diameter of this sprayed coating was 100 nm to 10 μm in diameter. This is called a substrate B.
ポリビニルブチラールと酸化ニオブ粉末（粒子径０．１〜２μｍ）を重量比で１０：９０にしたエタール系スラリーとした後、乾燥し、次いで造粒して溶射用粉末を作成した。その溶射用粉末を上記と同様に基板１０に溶射して溶射皮膜を形成し、当該溶射皮膜から有機物からなる物質を燃焼して分解してなる多孔質の触媒担体である溶射皮膜を形成した。その溶射皮膜の細孔径は、直径１０ｎｍ〜１００ｎｍであった。これを基板Ｃとする。 A polyvinyl butyral and niobium oxide powder (particle diameter 0.1 to 2 μm) was made into an etal slurry having a weight ratio of 10:90, dried, and then granulated to prepare a thermal spraying powder. The thermal spraying powder was sprayed onto the substrate 10 in the same manner as described above to form a thermal sprayed coating, and a thermal sprayed coating as a porous catalyst carrier formed by burning and decomposing a substance made of organic matter from the thermal sprayed coating was formed. The spray coating had a pore diameter of 10 nm to 100 nm. This is a substrate C.
基板Ａの溶射皮膜に、触媒金属１５であるＰｄを含むコロイド溶液を含浸法で塗布し、乾燥、４００℃にて熱処理し、触媒担体であるジルコニアの多孔層にＰｄ触媒が担持された触媒層が基板１０の上に形成された構造を持つ触媒を得た。この触媒を５００℃まで昇温し、ついで室温まで放冷しても、触媒層は剥離することなく、繰り返し使用することができた。 A catalyst layer in which a Pd catalyst is supported on a porous layer of zirconia as a catalyst carrier by applying a colloidal solution containing Pd as the catalyst metal 15 to the thermal spray coating of the substrate A by an impregnation method, drying and heat-treating at 400 ° C. A catalyst having a structure formed on the substrate 10 was obtained. Even when this catalyst was heated to 500 ° C. and then allowed to cool to room temperature, the catalyst layer could be used repeatedly without peeling.
基板Ｂを、触媒金属である塩化ルテニウムを５重量％含む水溶液に室温にて、１０時間浸漬後、４００℃にて３時間焼成し、触媒担体であるアルミナの多孔層にＲｕ触媒が担持された触媒層が基板１０の上に形成された構造を持つ触媒を得た。触媒として使用する際は、水素などでルテニウムを還元して使用した。この触媒を５００℃まで昇温し、ついで室温まで放冷しても、触媒層は剥離することなく、繰り返し使用することができた。 Substrate B was immersed in an aqueous solution containing 5% by weight of ruthenium chloride as a catalyst metal at room temperature for 10 hours, and then calcined at 400 ° C. for 3 hours. The Ru catalyst was supported on a porous layer of alumina as a catalyst carrier. A catalyst having a structure in which a catalyst layer was formed on the substrate 10 was obtained. When used as a catalyst, ruthenium was reduced with hydrogen or the like. Even when this catalyst was heated to 500 ° C. and then allowed to cool to room temperature, the catalyst layer could be used repeatedly without peeling.
［実施例２］
触媒金属であるＰｄ、ジルコニア粉末（粒子径０．１〜２μｍ）及びポリビニルアルコールを重量比５：８５：１０で水を溶媒としボールミル混合した後、１００℃にて乾燥し、次いで造粒して溶射用粉末を作製した。次に、水素透過膜であるＴａを主体とした基板１０（（株）ニラコ製、３Ｎグレード、板厚１ｍｍ）の表面に、溶射用粉末を真空中でプラズマ溶射し、基板上に７０μｍの厚みの溶射皮膜を形成した。この後、大気中で５００℃にて４時間の熱処理を行い、ポリビニルアルコールからなる物質を燃焼して分解することによりＰｄが担持された多孔質な溶射皮膜である触媒層が基板１０の上に形成された構造を持つ触媒を得た。この触媒層の空孔を測定したところ、直径１０ｎｍ〜１μｍの細孔が生成していた。この触媒を５００℃まで昇温し、ついで室温まで放冷しても、触媒層は剥離することなく、繰り返し使用することができた。
[Example 2]
Pd, which is a catalytic metal, zirconia powder (particle size: 0.1 to 2 μm) and polyvinyl alcohol are mixed at a weight ratio of 5:85:10 using water as a solvent in a ball mill, dried at 100 ° C., and then granulated. A powder for thermal spraying was prepared. Next, the powder for thermal spraying was plasma sprayed in vacuum on the surface of a substrate 10 (manufactured by Nilaco Co., Ltd., 3N grade,
［実施例３］
触媒金属であるＰｄ、酸化ニオブ粉末（粒子径０．１〜２μｍ）及びポリビニルアルコールを重量比５：８５：１０で水を溶媒としボールミル混合した後、１００℃にて乾燥し、次いで造粒して溶射用粉末を作製した。次に、水素透過膜であるＮｉ３０Ｔｉ３１Ｎｂ３９合金からなる基板１０（板厚１ｍｍ）の表面に、溶射用粉末を真空中でプラズマ溶射し、基板上に７０μｍの厚みの溶射皮膜を形成した。この後、大気中で５００℃にて４時間の熱処理を行い、ポリビニルアルコールからなる物質を燃焼して分解することによりＰｄが担持された多孔質な溶射皮膜である触媒層が基板１０の上に形成された構造を持つ触媒を得た。この触媒層の空孔を測定したところ、直径１０ｎｍ〜１μｍの細孔が生成していた。この触媒を５００℃まで昇温し、ついで室温まで放冷しても、触媒層は剥離することなく、繰り返し使用することができた。
[Example 3]
Pd, which is a catalytic metal, niobium oxide powder (particle size 0.1 to 2 μm) and polyvinyl alcohol are mixed at a weight ratio of 5:85:10 using water as a solvent in a ball mill, dried at 100 ° C., and then granulated. The powder for thermal spraying was produced. Next, the thermal spraying powder is plasma sprayed in vacuum on the surface of the substrate 10 (
１０ 基板
１２ 有機物からなる物質
１４ 酸化物
１５ 触媒金属
10 Substrate 12 Organic substance 14 Oxide 15 Catalytic metal
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007074689A1 (en) * | 2005-12-28 | 2007-07-05 | Hitachi, Ltd. | Catalyst having function of dehydrogenation or hydrogenation, fuel cell employing the catalyst, and apparatus for storing/supplying hydrogen |
| JP2008098069A (en) * | 2006-10-16 | 2008-04-24 | Inst Nuclear Energy Research Rocaec | Anode structure of nanochannel composite thin film, and manufacturing method of atmospheric plasma spraying system |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007074689A1 (en) * | 2005-12-28 | 2007-07-05 | Hitachi, Ltd. | Catalyst having function of dehydrogenation or hydrogenation, fuel cell employing the catalyst, and apparatus for storing/supplying hydrogen |
| JP2008098069A (en) * | 2006-10-16 | 2008-04-24 | Inst Nuclear Energy Research Rocaec | Anode structure of nanochannel composite thin film, and manufacturing method of atmospheric plasma spraying system |
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