JP2007268453A - Catalyst for reforming methanol with steam and method for preparing the same - Google Patents
Catalyst for reforming methanol with steam and method for preparing the same Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 137
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000002407 reforming Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title abstract description 25
- 238000007747 plating Methods 0.000 claims abstract description 123
- 229910052751 metal Inorganic materials 0.000 claims abstract description 95
- 239000002184 metal Substances 0.000 claims abstract description 95
- 239000011701 zinc Substances 0.000 claims abstract description 62
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000010949 copper Substances 0.000 claims abstract description 61
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 61
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052802 copper Inorganic materials 0.000 claims abstract description 60
- 238000007772 electroless plating Methods 0.000 claims abstract description 49
- 238000001651 catalytic steam reforming of methanol Methods 0.000 claims description 57
- 238000006243 chemical reaction Methods 0.000 claims description 46
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 238000006073 displacement reaction Methods 0.000 claims description 11
- 238000010304 firing Methods 0.000 claims description 11
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims 1
- 238000001354 calcination Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 20
- 239000001257 hydrogen Substances 0.000 description 19
- 229910052739 hydrogen Inorganic materials 0.000 description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000758 substrate Substances 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000000151 deposition Methods 0.000 description 5
- 238000009713 electroplating Methods 0.000 description 5
- 238000006057 reforming reaction Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000000629 steam reforming Methods 0.000 description 3
- 239000002918 waste heat Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 2
- 229940074439 potassium sodium tartrate Drugs 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical group [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- -1 aluminum ions Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000012764 semi-quantitative analysis Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Catalysts (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Fuel Cell (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
Description
本発明は、メタノール水蒸気改質触媒およびその製造方法に関し、特に金属表面に銅−亜鉛系触媒のめっき層を形成したメタノール水蒸気改質触媒に関するものである。 The present invention relates to a methanol steam reforming catalyst and a method for producing the same, and more particularly to a methanol steam reforming catalyst in which a plating layer of a copper-zinc catalyst is formed on a metal surface.
通常、触媒反応は、容器に粒状の触媒を充填して行われることが多いが、近年、より効率の良い触媒反応装置としてマイクロリアクタが注目されている。この触媒反応用のマイクロリアクタは、反応場である微小な（１ｍｍ程度以下）流路の壁面に触媒を担持させたものである。
このマイクロリアクタは、流路幅が微小であるため、単位体積当たりの伝熱面積が大きく、精密な反応温度の制御が可能、理想的な押し出し流れに近く反応時間が厳密に制御できるなどの特徴がある。この特徴により、マイクロリアクタは、高い反応転化率が得られ、また副反応が抑制されるため目的の反応だけを促進することができる、つまり反応選択率を向上させることができる。
また、マイクロリアクタは、微小な流路を集積した構造であるため、従来の触媒反応容器と比較して、装置の大幅なコンパクト化が可能である。
Usually, the catalytic reaction is often performed by filling a granular catalyst in a container, but in recent years, a microreactor has attracted attention as a more efficient catalytic reaction apparatus. This microreactor for catalytic reaction is one in which a catalyst is supported on the wall surface of a minute (about 1 mm or less) flow path as a reaction field.
This microreactor has features such as a small flow path width, large heat transfer area per unit volume, precise control of reaction temperature, close to ideal extrusion flow, and precise control of reaction time. is there. With this feature, the microreactor can obtain a high reaction conversion rate and suppress side reactions, so that only the desired reaction can be promoted, that is, the reaction selectivity can be improved.
In addition, since the microreactor has a structure in which minute flow paths are integrated, the apparatus can be greatly downsized as compared with a conventional catalytic reaction vessel.
一方、近年、次世代のクリーン燃料として水素が注目されている。水素は天然ガス、ガソリン等種々の原料から製造できるが、メタノールの水蒸気改質で水素を製造する方法は、安全性が高く、また、比較的低温（２００〜３００℃）の反応であるため、中低温排熱の利用が可能であるという利点を有する。
メタノール水蒸気改質反応は吸熱反応であり、温度が厳密に制御可能なマイクロリアクタを利用することで、反応効率を向上させることができるため、メタノール水蒸気改質反応は、マイクロリアクタのメリットが活かせる反応である。
メタノール水蒸気改質の触媒は銅−亜鉛系触媒である。従って、メタノール水蒸気改質反応により水素を製造するためのマイクロリアクタを実現するためには、微小な流路表面に触媒成分である亜鉛と銅を被着させることが必要である。
触媒成分を金属表面に被着させる方法として無電解めっき法が知られている。無電解めっきは、電気めっきと比較して緻密なめっきが可能であり、それにより電気めっきよりも単位面積当たりの触媒成分の担持量を多くすることができるという特徴を有している。
また、電気めっきは、電流密度の不均一性によりめっき厚さが場所によって不均一となり、均一な性能の触媒層を形成させるのが難しい。一方、無電解めっきは、ほぼ均一な厚さのめっき層が容易に形成できるという利点がある。
On the other hand, in recent years, hydrogen has attracted attention as a next-generation clean fuel. Hydrogen can be produced from various raw materials such as natural gas and gasoline, but the method of producing hydrogen by steam reforming of methanol is highly safe and is a reaction at a relatively low temperature (200 to 300 ° C.). There is an advantage that it is possible to use mid- and low-temperature exhaust heat.
The methanol steam reforming reaction is an endothermic reaction, and the reaction efficiency can be improved by using a microreactor whose temperature can be strictly controlled. Therefore, the methanol steam reforming reaction is a reaction that can take advantage of the microreactor. is there.
The catalyst for methanol steam reforming is a copper-zinc catalyst. Therefore, in order to realize a microreactor for producing hydrogen by a methanol steam reforming reaction, it is necessary to deposit zinc and copper as catalyst components on the surface of a minute channel.
An electroless plating method is known as a method for depositing a catalyst component on a metal surface. Electroless plating has a feature that it can be denser than electroplating, and thereby can carry a larger amount of catalyst component per unit area than electroplating.
In addition, in electroplating, the plating thickness becomes nonuniform depending on the location due to nonuniformity of current density, and it is difficult to form a catalyst layer with uniform performance. On the other hand, electroless plating has an advantage that a plating layer having a substantially uniform thickness can be easily formed.
無電解めっき法で触媒成分を担持する方法が次の２つの特許文献に記載されている。
特許文献１は、アルミニウムを含有する金属部材にニッケルを含有する金属を担持させて表面を触媒化する方法である。ニッケルを含有する金属を担持させる方法として無電解めっき法が好適であるとしている。このニッケル系触媒は、メタノールの改質反応に用いられる。この反応は水蒸気改質反応ではなく、水を使わずにメタノールのみを原料とし、比較的高温（５００℃程度）でメタノールから水素を生成する反応である。なお、このニッケル担持法は、アルミニウム部材の表面に無電解めっきでニッケルを被着させる方法であり、一般的に知られている方法である。
特許文献２は、伝導加熱区域と被加熱改質区域とを持った改質ガス製造装置であり、被加熱改質区域側の面に改質ガス製造用触媒成分を無電解めっきにより被着する。触媒成分の無電解めっきによる被着の方法については、具体的には、アルミニウム材の表面に、亜鉛置換めっきにより亜鉛を被着した後、無電解めっきによりニッケルを被着させて触媒層を形成させる方法が提示されている。
Methods for supporting a catalyst component by electroless plating are described in the following two patent documents.
Patent Document 1 is a method of catalyzing a surface by supporting a metal containing nickel on a metal member containing aluminum. The electroless plating method is suitable as a method for supporting a metal containing nickel. This nickel catalyst is used for the reforming reaction of methanol. This reaction is not a steam reforming reaction, but a reaction that uses only methanol as a raw material without using water and generates hydrogen from methanol at a relatively high temperature (about 500 ° C.). In addition, this nickel carrying | support method is a method of depositing nickel on the surface of an aluminum member by electroless plating, and is a generally known method.
Patent Document 2 is a reformed gas manufacturing apparatus having a conductive heating zone and a heated reforming zone, and deposits a reforming gas manufacturing catalyst component on the surface of the heated reforming zone by electroless plating. . Regarding the method of depositing the catalyst components by electroless plating, specifically, after zinc is deposited on the surface of the aluminum material by zinc displacement plating, nickel is deposited by electroless plating to form a catalyst layer A way to do it is presented.
上記２つの従来技術は、いずれも無電解めっき法により金属表面にニッケル系触媒を形成させる方法を提示したものであるが、銅−亜鉛系触媒層の形成方法については述べられていない。
特許文献２には、亜鉛置換めっきにより亜鉛を被着させた後、ニッケルを無電解めっきにより被着させる方法、即ちニッケル−亜鉛系触媒層の形成方法が提示されているが、この方法を銅−亜鉛系触媒層の形成に適用することはできない。
また、ニッケル無電解めっきは、ｐＨ５〜７程度の弱酸性〜中性のｐＨ条件で行われるため、亜鉛めっきの上からニッケルめっきをすることが可能であるが、銅無電解めっきは、ｐＨ１２前後のアルカリ条件で行われるため、亜鉛置換めっき後に銅無電解めっきを行うと亜鉛がアルカリで溶出してしまい、亜鉛めっきが殆ど残らないという問題があった。
従って、特許文献２の方法は、銅−亜鉛系触媒層の形成には適用できなかった。
Both of the above two prior arts present a method for forming a nickel-based catalyst on a metal surface by an electroless plating method, but a method for forming a copper-zinc-based catalyst layer is not described.
Patent Document 2 proposes a method of depositing zinc by electroless plating after zinc is deposited by zinc displacement plating, that is, a method of forming a nickel-zinc catalyst layer. -It cannot be applied to the formation of a zinc-based catalyst layer.
In addition, since nickel electroless plating is performed under weakly acidic to neutral pH conditions of about pH 5 to 7, nickel plating can be performed from above zinc plating, but copper electroless plating is about pH 12 Therefore, when copper electroless plating is performed after zinc displacement plating, zinc is eluted with alkali, and there is a problem that almost no zinc plating remains.
Therefore, the method of Patent Document 2 cannot be applied to the formation of a copper-zinc catalyst layer.
本発明は、このような事情に鑑みてなされたものであり、亜鉛めっき層を溶出させることなく、金属表面に銅−亜鉛系触媒成分を、均一且つ多量に担持させたメタノール水蒸気改質触媒とその製造方法を提供することを課題とする。 The present invention has been made in view of such circumstances, and a methanol steam reforming catalyst in which a copper-zinc based catalyst component is uniformly and abundantly supported on a metal surface without eluting a galvanized layer. It is an object to provide a manufacturing method thereof.
前記課題を解決するために、請求項１に記載の発明は、金属板の片面または両面に複数のめっき層を形成したメタノール水蒸気改質触媒であって、前記金属板の表面に、亜鉛の無電解めっきによる第一のめっき層と、前記第一のめっき層の直上に、銅のフラッシュめっきによる第二のめっき層と、前記第二のめっき層の直上に、銅の無電解めっきによる第三のめっき層とを形成し、焼成処理により前記亜鉛および前記銅を表面に露出させたことを特徴としている。 In order to solve the above-mentioned problem, the invention according to claim 1 is a methanol steam reforming catalyst in which a plurality of plating layers are formed on one side or both sides of a metal plate, the surface of the metal plate being free of zinc. A first plating layer by electrolytic plating, a second plating layer by copper flash plating directly on the first plating layer, and a third by copper electroless plating directly on the second plating layer. And the zinc and the copper are exposed on the surface by a baking treatment.
この構成により、金属板の表面に形成された触媒は、めっき被膜を緻密にして触媒成分の担持量を多くすることができ、また、めっき厚さが金属板全体に均一であるため、場所による触媒性能のバラツキを少なくすることができる。 With this configuration, the catalyst formed on the surface of the metal plate can increase the loading of the catalyst component by making the plating film dense, and the plating thickness is uniform throughout the metal plate, so it depends on the location. Variations in catalyst performance can be reduced.
請求項２に記載のメタノール水蒸気改質触媒は、前記金属板が、さらに、ガスケットと交互に積層され、メタノールが流通する少なくとも１つの空間層を設けて、反応容器に装着可能に固定されたことを特徴としている。また、請求項３に記載のメタノール水蒸気改質触媒は、前記金属板が、波型の金属板であることを特徴としている。 The methanol steam reforming catalyst according to claim 2, wherein the metal plates are further laminated alternately with gaskets, and provided with at least one space layer through which methanol circulates, and is fixed so as to be attachable to a reaction vessel. It is characterized by. The methanol steam reforming catalyst according to claim 3 is characterized in that the metal plate is a corrugated metal plate.
この構成により、金属板の特性を活かして、よりコンパクトで、温度制御が可能な触媒として提供でき、また反応容器に装着容易な形状とすることができる。 With this configuration, the characteristics of the metal plate can be utilized to provide a more compact and temperature-controllable catalyst, and the shape can be easily mounted on the reaction vessel.
請求項４に記載の発明は、ハニカム状または格子状金属筒の内壁に複数のめっき層を形成したメタノール水蒸気改質触媒であって、前記内壁の表面に、亜鉛の無電解めっきによる第一のめっき層と、前記第一のめっき層の直上に、銅のフラッシュめっきによる第二のめっき層と、前記第二のめっき層の直上に、銅の無電解めっきによる第三のめっき層とを形成し、焼成処理により前記亜鉛および前記銅を表面に露出させたことを特徴としている。 The invention according to claim 4 is a methanol steam reforming catalyst in which a plurality of plating layers are formed on the inner wall of a honeycomb-like or lattice-like metal cylinder, and a first electroless plating of zinc is performed on the surface of the inner wall. Forming a plating layer, a second plating layer by copper flash plating directly on the first plating layer, and a third plating layer by copper electroless plating directly on the second plating layer The zinc and the copper are exposed on the surface by a baking treatment.
この構成により、金属筒の表面に形成された触媒は、めっき被膜を緻密にして触媒成分の担持量を多くすることができ、また、めっき厚さが金属筒の内壁全体に均一であるため、場所による触媒性能のバラツキを少なくすることができる。また、金属筒の特性を活かして、よりコンパクトで、温度制御が可能な触媒として提供でき、また反応容器に装着容易な形状とすることができる。 With this configuration, the catalyst formed on the surface of the metal cylinder can make the plating film dense to increase the amount of the catalyst component supported, and the plating thickness is uniform over the entire inner wall of the metal cylinder. Variations in catalyst performance due to location can be reduced. Further, by making use of the characteristics of the metal cylinder, the catalyst can be provided as a more compact and temperature-controllable catalyst and can be easily mounted in the reaction vessel.
請求項５に記載の発明は、金属管の内面、外面または両面に複数のめっき層を形成したメタノール水蒸気改質触媒であって、前記金属管の表面に、亜鉛の無電解めっきによる第一のめっき層と、前記第一のめっき層の直上に、銅のフラッシュめっきによる第二のめっき層と、前記第二のめっき層の直上に、銅の無電解めっきによる第三のめっき層とを形成し、焼成処理により前記亜鉛および前記銅を表面に露出させたことを特徴としている。また、請求項６に記載のメタノール水蒸気改質触媒は、前記金属管が、さらに、径の異なる多重管として形成され、メタノールが流通する少なくとも一つの空間を設けたことを特徴としている。 The invention according to claim 5 is a methanol steam reforming catalyst in which a plurality of plating layers are formed on the inner surface, outer surface, or both surfaces of a metal tube, wherein the first surface is formed by electroless plating of zinc on the surface of the metal tube. Forming a plating layer, a second plating layer by copper flash plating directly on the first plating layer, and a third plating layer by copper electroless plating directly on the second plating layer The zinc and the copper are exposed on the surface by a baking treatment. The methanol steam reforming catalyst according to claim 6 is characterized in that the metal pipe is further formed as a multiple pipe having different diameters and provided with at least one space through which methanol flows.
この構成により、金属管の表面に形成された触媒層は、めっき被膜を緻密にして触媒成分の担持量を多くすることができ、また、めっき厚さが金属管全体に均一であるため、場所による触媒性能のバラツキを少なくすることができる。また、金属管の特性を活かして、よりコンパクトで、温度制御が可能な触媒として提供でき、また他の排熱を利用する熱交換型反応容器とすることもできる。 With this configuration, the catalyst layer formed on the surface of the metal tube can make the plating film dense to increase the amount of the catalyst component supported, and the plating thickness is uniform throughout the metal tube. The variation in the catalyst performance due to can be reduced. Further, by utilizing the characteristics of the metal tube, the catalyst can be provided as a more compact and temperature-controllable catalyst, and a heat exchange reaction vessel using other exhaust heat can be provided.
請求項７に記載のメタノール水蒸気改質触媒は、前記金属板、前記金属筒または前記金属管の表面に、同一方向に複数の凹状または波状の溝を設けたことを特徴としている。
この構成により、触媒の接触面積をさらに大きくできるので、よりコンパクトで、温度制御が可能な触媒として提供できる。
The methanol steam reforming catalyst according to claim 7 is characterized in that a plurality of concave or corrugated grooves are provided in the same direction on the surface of the metal plate, the metal tube or the metal tube.
With this configuration, since the contact area of the catalyst can be further increased, the catalyst can be provided as a more compact and temperature-controllable catalyst.
請求項８に記載のメタノール水蒸気改質触媒は、前記金属がアルミニウムであり、且つ、前記第一のめっき層が、亜鉛の置換めっきによる無電解めっき層であることを特徴としている。この構成により、加工性および伝熱性に優れ、軽量・コンパクトで温度制御が容易な触媒が提供できる。 The methanol steam reforming catalyst according to claim 8 is characterized in that the metal is aluminum and the first plating layer is an electroless plating layer by displacement plating of zinc. With this configuration, it is possible to provide a catalyst that is excellent in processability and heat transfer property, is lightweight and compact, and can be easily temperature controlled.
請求項９に記載の発明は、金属表面に複数のめっき層を形成したメタノール水蒸気改質触媒の製造方法であって、前記金属表面に、亜鉛の無電解めっきによる第一のめっき層と、前記第一のめっき層の直上に、銅のフラッシュめっきによる第二のめっき層と、前記第二のめっき層の直上に、銅の無電解めっきによる第三のめっき層とを形成し、焼成処理により前記亜鉛および前記銅を表面に露出させたことを特徴としている。また、請求項１０に記載のメタノール水蒸気改質触媒の製造方法は、前記金属はアルミニウムであり、且つ、前記第一のめっき層は、亜鉛の置換めっきによる無電解めっき層であることを特徴としている。 Invention of Claim 9 is a manufacturing method of the methanol steam reforming catalyst which formed the several plating layer on the metal surface, Comprising: The said 1st plating layer by the electroless plating of zinc on the said metal surface, and the said A second plating layer formed by flash plating of copper is formed directly on the first plating layer, and a third plating layer formed by electroless plating of copper is formed directly on the second plating layer. The zinc and the copper are exposed on the surface. The method for producing a methanol steam reforming catalyst according to claim 10 is characterized in that the metal is aluminum, and the first plating layer is an electroless plating layer by displacement plating of zinc. Yes.
この構成により、めっき被膜を緻密にして触媒成分の担持量を多くすることができ、また、めっき厚さが金属表面全体に均一であるため、場所による触媒性能のバラツキを少なくする触媒の製造方法が提供できる。また、加工性および伝熱性に優れた軽量なアルミニウム基材の触媒が製造できる。 With this configuration, the plating film can be made dense to increase the amount of the catalyst component supported, and the plating thickness is uniform over the entire metal surface, so that the catalyst manufacturing method can reduce variation in catalyst performance depending on the location. Can be provided. In addition, a lightweight aluminum-based catalyst excellent in processability and heat conductivity can be produced.
本発明に係るメタノール水蒸気改質触媒は、金属表面に銅−亜鉛系触媒成分を、均一且つ多量に担持させることができるため、よりコンパクトで、温度制御が可能となり、また金属基材の特性を活かした加工性（形状）および伝熱性にも優れた触媒とすることができる。
また本発明に係るメタノール水蒸気改質触媒の製造方法は、めっき被膜を緻密にして触媒成分の担持量を多くすることができ、また、場所による触媒性能のバラツキが少ない。
The methanol steam reforming catalyst according to the present invention can support a copper-zinc based catalyst component uniformly and in a large amount on the metal surface, so that it is more compact and temperature control is possible, and the characteristics of the metal substrate are improved. It is possible to make the catalyst excellent in processability (shape) and heat transfer performance.
Further, the method for producing a methanol steam reforming catalyst according to the present invention can increase the amount of the catalyst component supported by making the plating film dense, and there is little variation in catalyst performance depending on the location.
以下、本発明を実施するための最良の形態について説明する。
本発明に係るメタノール水蒸気改質触媒は、メタノールと水（水蒸気）を触媒反応させて水素を得るものである。この水素は燃料電池に供給されて電気となり、自動車やパソコン・携帯電話、そして家庭用等のクリーンなエネルギー源として注目されている。そのため、本メタノール水蒸気改質触媒においても、高反応効率（高水素転化率）は無論のこと、小型化、軽量化、加工性、そして高伝熱性なども求められ、マイクロリアクタ（超小型反応容器）の主要構成部品としても重要な位置づけとなっている。
Hereinafter, the best mode for carrying out the present invention will be described.
The methanol steam reforming catalyst according to the present invention is a catalyst for reacting methanol with water (steam) to obtain hydrogen. This hydrogen is supplied to fuel cells to become electricity, and is attracting attention as a clean energy source for automobiles, personal computers, mobile phones, and homes. For this reason, this methanol steam reforming catalyst not only has high reaction efficiency (high hydrogen conversion), but also requires miniaturization, weight reduction, processability, and high heat transfer. It is also positioned as an important component of
また、本発明に係るメタノール水蒸気改質触媒は、銅−亜鉛系触媒を金属基材に担持させるもので、無電解めっきによる第一の亜鉛めっき層、フラッシュめっきによる第二の銅めっき層、そして無電解めっきによる第三の銅めっき層を形成し、焼成処理により亜鉛と銅の両方を表面に露出させる。ここで、銅のフラッシュめっきを行うのは、亜鉛被膜を溶出させないための処理である。 Further, the methanol steam reforming catalyst according to the present invention is a catalyst in which a copper-zinc catalyst is supported on a metal substrate, a first zinc plating layer by electroless plating, a second copper plating layer by flash plating, and A third copper plating layer is formed by electroless plating, and both zinc and copper are exposed to the surface by baking treatment. Here, the copper flash plating is performed to prevent the zinc coating from being eluted.
（金属基材の構造）
まず、図面を用いて本実施形態に係る金属基材の構造と、メタノール水蒸気改質触媒（以下、改質触媒とも言う）の形状の例について説明する。
図１（ａ）はメタノール水蒸気改質触媒１の平面図、図１（ｂ）は、（ａ）のＡ−Ａ断面とした断面図である。図１に示すように、金属板２の片面に、同一方向に複数の凹溝を設けてメタノールと水蒸気の流路とし、その表面にめっきと焼成処理による銅−亜鉛系触媒層を形成し（図示なし）、メタノール水蒸気改質触媒１とした。ここで、金属板２は一辺の長さ１００ｍｍの正方形で、厚さは３ｍｍである。流路は、幅０．５ｍｍ、深さ２ｍｍの溝を９０本設けた（図１では流路の一部を表示）。この程度の大きさの溝であれば、溝加工、各めっき層形成、焼成処理および流路での改質反応効率のいずれにおいても問題はない。
(Metal base material structure)
First, the structure of the metal substrate according to the present embodiment and an example of the shape of a methanol steam reforming catalyst (hereinafter also referred to as a reforming catalyst) will be described with reference to the drawings.
FIG. 1A is a plan view of the methanol steam reforming catalyst 1, and FIG. 1B is a cross-sectional view taken along the line AA of FIG. As shown in FIG. 1, a plurality of concave grooves are provided in the same direction on one surface of a metal plate 2 to form a methanol and water vapor channel, and a copper-zinc catalyst layer is formed on the surface by plating and firing treatment ( Methanol steam reforming catalyst 1 was obtained. Here, the metal plate 2 is a square with a side length of 100 mm and a thickness of 3 mm. The channel was provided with 90 grooves having a width of 0.5 mm and a depth of 2 mm (FIG. 1 shows a part of the channel). If the groove has such a size, there is no problem in any of the groove processing, the formation of each plating layer, the firing treatment, and the reforming reaction efficiency in the flow path.
図２は、改質触媒１を装着する平行四辺形の反応ケースを真上から見た図である。図２（ａ）は、反応ケースのフタ３であり、メタノールと水蒸気からなるガスのガス入口５と、生成ガス（水素）のガス出口６の２つの貫通孔が設けられている。このフタ３の下側の面は、流路の一部を構成するので、前記と同様のめっきと焼成処理により触媒層を形成している。図２（ｂ）は反応ケース４の本体であり、深さ３ｍｍの窪みを設けて、改質触媒１（金属板２）を収納し、かつ、ガスがガス入口５からガス出口６へ流通できる空間を形成している。なお、フタ３および反応ケース４の形状は、平行四辺形以外でも構わない。
図２（ｃ）は、反応ケース４の窪みに、改質触媒１（金属板２）を収納した図を示している。
FIG. 2 is a view of a parallelogram reaction case in which the reforming catalyst 1 is mounted as seen from directly above. FIG. 2A shows a reaction case lid 3, which is provided with two through holes, a gas inlet 5 for a gas composed of methanol and water vapor, and a gas outlet 6 for a product gas (hydrogen). Since the lower surface of the lid 3 constitutes a part of the flow path, the catalyst layer is formed by the same plating and baking treatment as described above. FIG. 2 (b) shows the main body of the reaction case 4, which is provided with a recess having a depth of 3 mm to accommodate the reforming catalyst 1 (metal plate 2), and gas can flow from the gas inlet 5 to the gas outlet 6. A space is formed. The shapes of the lid 3 and the reaction case 4 may be other than the parallelogram.
FIG. 2 (c) shows a view in which the reforming catalyst 1 (metal plate 2) is accommodated in the recess of the reaction case 4.
図３は、前記した反応ケース４に改質触媒１を収納したものを、フタ３とともにボルト締め７で固定した反応容器の断面図であり、コンパクトなマイクロリアクタとしての一形態を示している。 FIG. 3 is a cross-sectional view of a reaction vessel in which the reforming catalyst 1 is housed in the reaction case 4 and fixed with bolts 7 together with the lid 3, and shows one form of a compact microreactor.
図４は、金属板２の加工の変形例であり、図４（ａ）はＶ字波状の溝、図４（ｂ）は、Ｕ字波状の溝を示した図である。このように金属板の加工容易性を活かして、金属表面積を大きくし、且つ伝熱性の良い構造の変形例が可能である。 FIG. 4 is a modified example of the processing of the metal plate 2. FIG. 4 (a) shows a V-shaped groove, and FIG. 4 (b) shows a U-shaped groove. As described above, a modification of the structure having a large metal surface area and good heat conductivity is possible by taking advantage of the ease of processing of the metal plate.
また、複数の改質触媒１（金属板２）を組み合わせた例を図５に示す。
図５（ａ）は、４枚の金属板２と、３対のガスケット１１とを交互に積層し、３層の空間層１０（ガス流路）を形成して、ボルト締め７で固定し、メタノール水蒸気改質触媒１の触媒エレメントとした図である。このとき、中間の２枚の金属板２は、その両面に触媒層を形成し、一番上と下の金属板２は、内側（片面）のみに触媒層を形成する。このように構成された触媒エレメントを、燃料電池の反応容器（図示なし）に着脱自在となるように装着すれば、触媒の活性が落ちたときに、その交換が容易である。
Moreover, the example which combined the some reforming catalyst 1 (metal plate 2) is shown in FIG.
5A, four metal plates 2 and three pairs of gaskets 11 are alternately laminated to form a three-layer space layer 10 (gas flow path), and are fixed with bolts 7. 1 is a view showing a catalytic element of a methanol steam reforming catalyst 1. FIG. At this time, the two intermediate metal plates 2 form catalyst layers on both sides thereof, and the uppermost and lower metal plates 2 form catalyst layers only on the inner side (one side). If the thus configured catalyst element is detachably attached to a reaction vessel (not shown) of the fuel cell, it can be easily replaced when the activity of the catalyst falls.
同様に、図５（ｂ）は、波型の金属板２を用いた例として、３枚の平らな金属板２と、２枚の波型の金属板２とを交互に配置して、多数のガス流路を形成した触媒エレメントである。この変形例として、金属板２の積層数を増やしたり、渦巻き状に巻いて円筒形の触媒エレメントとすることも可能である。また波型の形状は、図５（ｂ）に示す丸型以外にも、例えば台形、Ｖ字状、または凹凸状の波型であってもよい。 Similarly, FIG. 5B shows an example in which the corrugated metal plate 2 is used, in which three flat metal plates 2 and two corrugated metal plates 2 are alternately arranged, and many This is a catalyst element in which a gas flow path is formed. As a modified example, it is possible to increase the number of stacked metal plates 2 or to form a cylindrical catalyst element by spirally winding the metal plate 2. In addition to the round shape shown in FIG. 5B, the wave shape may be, for example, a trapezoidal shape, a V shape, or an uneven wave shape.
次に、図６は、金属筒８に複数の貫通孔１２を設けて、その内壁に触媒層を形成したメタノール水蒸気改質触媒１である。この複数の貫通孔１２は、ハニカム状か、格子状のものがよい。かかる形状のものであっても、めっき浴でのめっき層形成や、電気炉での焼成処理には、問題はない。 Next, FIG. 6 shows the methanol steam reforming catalyst 1 in which a plurality of through holes 12 are provided in the metal cylinder 8 and a catalyst layer is formed on the inner wall thereof. The plurality of through holes 12 preferably have a honeycomb shape or a lattice shape. Even if it is the thing of this shape, there is no problem in the plating layer formation in a plating bath, and the baking process in an electric furnace.
図７は、金属管９の表面に触媒層を形成して、二重管構造のメタノール水蒸気改質触媒１とした例である。ここでは、２つの空間１０（流路）が設けられており、両方を改質反応のための流路としてもよいし、または一方を、廃熱を持つ流体の流路としてもよい。例えば溶融塩型燃料電池のように、高温で発電する場合に、その高温・中温の廃熱を持つ蒸気を、図７の内側の空間１０（流路）に流通させ、外側の空間１０（流路）では、その内壁と外壁に形成された改質触媒で改質反応を行わせることができる。前記したように改質反応は吸熱反応であるため、このように廃熱との熱交換を好適に行うことにより、効率のよい温度制御（反応制御）が可能となる。 FIG. 7 is an example in which a catalyst layer is formed on the surface of the metal tube 9 to form a methanol steam reforming catalyst 1 having a double tube structure. Here, two spaces 10 (flow paths) are provided, and both may be used as the flow paths for the reforming reaction, or one of them may be a flow path for fluid having waste heat. For example, when power is generated at a high temperature, such as a molten salt fuel cell, the steam having the waste heat of high / medium temperature is circulated through the inner space 10 (flow path) in FIG. In the road), the reforming reaction can be performed by the reforming catalyst formed on the inner wall and the outer wall. Since the reforming reaction is an endothermic reaction as described above, efficient temperature control (reaction control) is possible by appropriately performing heat exchange with waste heat in this way.
（各めっき層の形成）
次に、各めっき層の形成について説明する。
最初に、金属表面に形成する亜鉛の無電解めっきは、金属基材のアルカリ脱脂、酸処理などの前処理を行ってから、酸化亜鉛などの溶液を含む無電解めっき浴で、無電解めっきを行う。これにより、金属表面に亜鉛被膜が形成されるが、この被膜は０．１μｍから５０μｍの膜厚とするのがよい。亜鉛の無電解めっき処理の後は、水洗を行ってから、次に銅のフラッシュめっきを行う。
(Formation of each plating layer)
Next, formation of each plating layer will be described.
First, in the electroless plating of zinc formed on the metal surface, the pretreatment such as alkali degreasing and acid treatment of the metal substrate is performed, and then electroless plating is performed in an electroless plating bath containing a solution such as zinc oxide. Do. As a result, a zinc coating is formed on the metal surface, and this coating should have a thickness of 0.1 to 50 μm. After the zinc electroless plating treatment, washing with water is performed, and then flash plating of copper is performed.
フラッシュめっきとは、高電流密度で短時間のめっきにより素早く０．０１〜１μｍ程度の薄いめっき膜を形成させるめっき法である。本実施形態における銅フラッシュめっきとしては、数秒〜数分の短時間の電気めっきを好適に用いることができる。銅フラッシュめっきは短時間で完了するため、銅の無電解めっきのように長時間アルカリ条件に曝露されることに起因する亜鉛皮膜の溶出が殆ど起こらない。また、銅のフラッシュめっきはアルカリ条件で行うこともあるが、亜鉛皮膜の溶出を抑制するためにｐＨが中性付近のめっき浴を用いることが好ましい。 Flash plating is a plating method in which a thin plating film of about 0.01 to 1 μm is rapidly formed by high-current density and short-time plating. As the copper flash plating in the present embodiment, electroplating for a short time of several seconds to several minutes can be suitably used. Since the copper flash plating is completed in a short time, the zinc film is hardly eluted due to being exposed to alkaline conditions for a long time like the electroless plating of copper. Moreover, although the copper flash plating may be performed under alkaline conditions, it is preferable to use a plating bath having a neutral pH in order to suppress elution of the zinc film.
銅のフラッシュめっきをすることにより、その後の銅の無電解めっきを行う際には、亜鉛の溶出は起こらない。これは、亜鉛のめっき被膜をごく薄い銅のフラッシュめっき被膜で覆うことができるためである。これにより、亜鉛と銅をそれぞれ無電解めっき法により金属基材に被着させてメタノール水蒸気改質用の銅−亜鉛系触媒層を形成させることができる。 By performing copper flash plating, no elution of zinc occurs during the subsequent electroless plating of copper. This is because the zinc plating film can be covered with a very thin copper flash plating film. Thereby, zinc and copper can each be deposited on a metal substrate by electroless plating to form a copper-zinc based catalyst layer for methanol steam reforming.
用いる金属基材は特に限定しないが、加工性、伝熱性等からアルミニウムが好ましい。アルミニウムを金属基材として用いる場合は、亜鉛の無電解めっき法として、亜鉛の置換めっきを用いることができる。亜鉛の置換めっきの原理は、アルミニウムの溶解（アルミニウムイオンの溶出）とそれに伴う亜鉛イオンのアルミニウム表面への置換還元析出である。 Although the metal base material to be used is not particularly limited, aluminum is preferable from the viewpoint of workability and heat conductivity. When aluminum is used as the metal substrate, zinc displacement plating can be used as the electroless plating method for zinc. The principle of zinc displacement plating is dissolution of aluminum (elution of aluminum ions) and accompanying displacement reduction deposition of zinc ions on the aluminum surface.
前記の銅のフラッシュめっきの後に、銅の無電解めっきを行う。これは、還元剤を用いた一般的な化学還元めっきを用いればよい。形成する銅の被膜の厚さは、０．５μｍから５０μｍとするのがよい。 After the copper flash plating, electroless plating of copper is performed. For this, general chemical reduction plating using a reducing agent may be used. The thickness of the copper film to be formed is preferably 0.5 μm to 50 μm.
本実施形態では、亜鉛被膜の上に銅被膜を形成させており、最表面は銅被膜で覆われて、亜鉛が最表面には出ていない状態であるため、めっき処理後に焼成処理を行う。この焼成処理により亜鉛が表面に移行し、表面に銅と亜鉛が露出した良好な状態の銅−亜鉛系触媒層となる。焼成温度は、２００〜７００℃程度とすればよい。２００℃より低温では亜鉛の表面への移行が十分ではなく、７００℃より高温では触媒成分が剥離する恐れがある。 In the present embodiment, a copper coating is formed on the zinc coating, the outermost surface is covered with the copper coating, and zinc is not exposed on the outermost surface. Therefore, the baking treatment is performed after the plating treatment. By this firing treatment, zinc is transferred to the surface, and a copper-zinc-based catalyst layer in a good state in which copper and zinc are exposed on the surface is obtained. The firing temperature may be about 200 to 700 ° C. If the temperature is lower than 200 ° C., the migration of zinc to the surface is not sufficient, and if the temperature is higher than 700 ° C., the catalyst component may be peeled off.
焼成処理を行った後は、銅と亜鉛が表面に露出した状態にあるが、これらは主に金属酸化物の形態になっており、そのままでは触媒の活性が低いため、本実施形態の改質触媒１は、反応容器に装着して改質反応の運転を行う前に、還元処理により金属酸化物の一部または全部を還元して触媒を活性化させることが好ましい。 After performing the firing treatment, copper and zinc are in a state of being exposed on the surface, but these are mainly in the form of metal oxides, and since the activity of the catalyst is low as it is, the modification of this embodiment Before the catalyst 1 is mounted in the reaction vessel and the reforming operation is performed, the catalyst is preferably activated by reducing part or all of the metal oxide by reduction treatment.
図８は、本実施形態に係るメタノール水蒸気改質触媒１の製造と運転までの工程の例を示したフローチャートである。
前記したように、まず金属基材を、反応容器の形状や寸法に合せた加工、または凹溝形成のための加工を行い（ステップＳ８１）、アルカリ脱脂、酸処理など、めっき層形成のための前処理を行う（ステップＳ８２）。次に、その金属表面に、無電解めっきにより、亜鉛のめっき層を形成させる（ステップＳ８３）。水洗などを適宜行った後に、銅のフラッシュめっきを行い（ステップＳ８４）、さらに、無電解めっきにより銅のめっき層を形成する（ステップＳ８５）。金属基材がアルミニウムの場合は、亜鉛の置換めっきがよい。そして焼成処理を行って、亜鉛と銅の両方の元素を金属基材の表面に露出させる（ステップＳ８６）。
FIG. 8 is a flowchart showing an example of steps up to the manufacture and operation of the methanol steam reforming catalyst 1 according to this embodiment.
As described above, first, the metal base material is processed according to the shape and dimensions of the reaction vessel or processed for forming a groove (step S81), and is used for forming a plating layer such as alkali degreasing and acid treatment. Pre-processing is performed (step S82). Next, a zinc plating layer is formed on the metal surface by electroless plating (step S83). After performing water washing etc. suitably, copper flash plating is performed (step S84), and a copper plating layer is further formed by electroless plating (step S85). When the metal substrate is aluminum, zinc displacement plating is preferable. A firing process is then performed to expose both zinc and copper elements on the surface of the metal substrate (step S86).
得られた改質触媒１は、反応ケース４に収納したり、触媒エレメントとして反応容器（マイクロリアクタ）に装着する（ステップＳ８７）。そして還元ガスを用いて改質触媒１の還元処理を行えば（ステップＳ８８）、メタノール水蒸気改質反応の運転が可能となる（ステップＳ８９）。 The obtained reforming catalyst 1 is accommodated in the reaction case 4 or mounted in a reaction vessel (microreactor) as a catalyst element (step S87). When the reducing gas is used to reduce the reforming catalyst 1 (step S88), the methanol steam reforming reaction can be operated (step S89).
以上のように、本実施形態のメタノール水蒸気改質触媒１は、加工性、伝熱性に優れた金属基材、特にアルミニウムの表面に、銅−亜鉛系触媒成分を均一に多量に担持させることができるため、形状自在、コンパクト、且つ温度制御が可能な触媒エレメントとすることができる。 As described above, the methanol steam reforming catalyst 1 of the present embodiment can uniformly and abundantly support a copper-zinc catalyst component on the surface of a metal substrate, particularly aluminum, which is excellent in workability and heat conductivity. Therefore, the catalyst element can be formed freely, compactly, and can be controlled in temperature.
図１に示すアルミニウム製の金属板２（縦１００ｍｍ×横１００ｍｍ×厚さ３ｍｍの純アルミニウム板に、幅０．５ｍｍ、深さ２ｍｍの流路を機械加工で９０本作成したもの）の表面に以下の条件で銅−亜鉛系触媒層を形成させた。 1 on the surface of an aluminum metal plate 2 shown in FIG. 1 (90 mm long, 100 mm wide x 3 mm thick pure aluminum plate made by machining 90 channels with a width of 0.5 mm and a depth of 2 mm). A copper-zinc catalyst layer was formed under the following conditions.
＜触媒形成方法＞
アルカリ脱脂、酸処理により、アルミニウム金属板２表面を洗浄した。
以下の亜鉛置換めっき浴にアルミニウム金属板２を３０秒間浸漬し、膜厚０．６μｍの亜鉛被膜を形成させた。
・酸化亜鉛：２０ｇ／Ｌ
・水酸化ナトリウム：１２０ｇ／Ｌ
・塩化第二鉄：２ｇ／Ｌ
・酒石酸カリウムナトリウム：５０ｇ／Ｌ
・硝酸ナトリウム：１ｇ／Ｌ
・温度：２０℃
<Catalyst formation method>
The surface of the aluminum metal plate 2 was washed by alkali degreasing and acid treatment.
The aluminum metal plate 2 was immersed in the following zinc substitution plating bath for 30 seconds to form a zinc film having a thickness of 0.6 μm.
・ Zinc oxide: 20 g / L
・ Sodium hydroxide: 120 g / L
・ Ferric chloride: 2g / L
・ Potassium sodium tartrate: 50 g / L
・ Sodium nitrate: 1g / L
・ Temperature: 20 ℃
次に、水洗後、以下の条件で銅のフラッシュめっきを行って、膜厚０．１μｍの銅被膜を形成させた。
・シアン化銅：１５ｇ／Ｌ
・シアン化ナトリウム：３０ｇ／Ｌ
・遊離シアン化ナトリウム：１０ｇ／Ｌ
・温度：４０℃
・電流密度：８Ａ／ｄｍ２
・時間：３０秒
Next, after washing with water, copper flash plating was performed under the following conditions to form a copper film having a thickness of 0.1 μm.
・ Copper cyanide: 15 g / L
・ Sodium cyanide: 30 g / L
・ Free sodium cyanide: 10 g / L
・ Temperature: 40 ℃
・ Current density: 8A / dm2
・ Time: 30 seconds
次に、水洗後、以下の条件で銅の無電解めっきを行って、膜厚２μｍの銅被膜を形成させた。
・硝酸銅：１５ｇ／Ｌ
・炭酸水素ナトリウム：１０ｇ／Ｌ
・酒石酸カリウムナトリウム：３０ｇ／Ｌ
・水酸化ナトリウム：２０ｇ／Ｌ
・３７％ホルムアルデヒド：１００ｍＬ／Ｌ
・温度：２４℃
・時間：３０分
Next, after washing with water, electroless plating of copper was performed under the following conditions to form a copper film having a thickness of 2 μm.
・ Copper nitrate: 15g / L
・ Sodium bicarbonate: 10 g / L
・ Potassium sodium tartrate: 30 g / L
・ Sodium hydroxide: 20 g / L
・ 37% formaldehyde: 100mL / L
・ Temperature: 24 ℃
・ Time: 30 minutes
次に、水洗後、処理品を自然乾燥し、電気炉にて４００℃、空気下で２時間の焼成処理を行い、メタノール水蒸気改質触媒１を作成した。 Next, after washing with water, the treated product was naturally dried and subjected to a firing treatment in an electric furnace at 400 ° C. for 2 hours in the air to prepare a methanol steam reforming catalyst 1.
この改質触媒１の切断試料を作成し、ＳＥＭ観察および元素分析した結果を、図９に示す。
ＳＥＭ観察は、試料の切断面を、日立製作所製Ｓ−４０００電界放射型走査顕微鏡（ＦＥ−ＳＥＭ）を用いて７００倍で観察を行った（上側の画像）。
また、元素分析は、試料の切断面を、堀場製作所製ＥＭＡＸ−５７７０Ｗエネルギー分散型Ｘ線分析装置（ＥＤＸ）を用いて、加速電圧２０ｋＶ、測定時間１００ｓｅｃで行った（下側の画像）。各元素（アルミニウムＡｌ、酸素Ｏ、銅Ｃｕ、亜鉛Ｚｎ）について半定量分析を行い、カラーマッピングで各元素の濃度を色別に表示して、銅、亜鉛ともに試料表面に露出されていることが確認できた。
A cut sample of the reforming catalyst 1 is prepared, and the results of SEM observation and elemental analysis are shown in FIG.
In the SEM observation, the cut surface of the sample was observed at 700 times using a Hitachi S-4000 field emission scanning microscope (FE-SEM) (upper image).
Elemental analysis was performed on the cut surface of the sample using an EMAX-5770W energy dispersive X-ray analyzer (EDX) manufactured by HORIBA, Ltd. with an acceleration voltage of 20 kV and a measurement time of 100 sec (lower image). Semi-quantitative analysis is performed on each element (aluminum Al, oxygen O, copper Cu, zinc Zn), and the concentration of each element is displayed by color mapping, confirming that both copper and zinc are exposed on the sample surface. did it.
このようにして得られたメタノール水蒸気改質触媒１を図３に示すような反応ケース４に収納して、フタ３をし、周りをボルト締め７で固定した後、２５０℃のオイルバスに入れた。２５０℃に予熱したガス（水素５％＋アルゴン９５％）をガス入口５より供給し、４時間流通させて触媒の還元処理を行った。 The methanol steam reforming catalyst 1 thus obtained is housed in a reaction case 4 as shown in FIG. 3, the lid 3 is covered, the periphery is fixed with bolts 7, and then placed in an oil bath at 250 ° C. It was. A gas preheated to 250 ° C. (hydrogen 5% + argon 95%) was supplied from the gas inlet 5 and circulated for 4 hours to reduce the catalyst.
＜メタノール水蒸気改質実験＞
還元処理後、ガス入口５より２５０℃に予熱したメタノールガス（２０．０ミリモル／分）と水蒸気（４０．０ミリモル／分）を流通させ、ガス出口６の水素濃度をガスクロマトグラフィーで測定し、水素ガス量を求めた。
<Methanol steam reforming experiment>
After the reduction treatment, methanol gas (20.0 mmol / min) and water vapor (40.0 mmol / min) preheated to 250 ° C. from the gas inlet 5 are circulated, and the hydrogen concentration at the gas outlet 6 is measured by gas chromatography. The amount of hydrogen gas was determined.
メタノールの水蒸気改質による水素生成反応は、次の反応式で表される。
ＣＨ３ＯＨ ＋ Ｈ２Ｏ → ３Ｈ２ ＋ ＣＯ２
従って、メタノールが１００％水素に転化されれば、１モルのメタノールから３モルの水素が生成する。よって、この反応の水素転化率は次式で表される。
水素転化率（％）＝ １００ × Ｈ ／（３ × Ｍ）
Ｈ：生成した水素のモル数、Ｍ：使用したメタノールのモル数
The hydrogen generation reaction by steam reforming of methanol is represented by the following reaction formula.
CH 3 OH + H 2 O → 3H 2 + CO 2
Thus, if methanol is converted to 100% hydrogen, 3 moles of hydrogen are produced from 1 mole of methanol. Therefore, the hydrogen conversion rate of this reaction is expressed by the following equation.
Hydrogen conversion rate (%) = 100 × H / (3 × M)
H: moles of hydrogen produced, M: moles of methanol used
本実施例で、ガス出口６の水素ガス量は５８．８ミリモル／分であったので、水素転化率は９８．０％であり、高い水素転化率のメタノール水蒸気改質触媒１が得られた。 In this example, since the amount of hydrogen gas at the gas outlet 6 was 58.8 mmol / min, the hydrogen conversion rate was 98.0%, and the methanol steam reforming catalyst 1 having a high hydrogen conversion rate was obtained. .
１ メタノール水蒸気改質触媒（改質触媒）
２ 金属板
３ フタ
４ 反応ケース
５ ガス入口
６ ガス出口
７ ボルト締め
８ 金属筒
９ 金属管
１０ 空間層（空間）
１１ ガスケット
1 Methanol steam reforming catalyst (reforming catalyst)
2 Metal plate 3 Lid 4 Reaction case 5 Gas inlet 6 Gas outlet 7 Bolt tightening 8 Metal cylinder 9 Metal tube 10 Space layer (space)
11 Gasket
Claims (10)
前記金属板の表面に、亜鉛の無電解めっきによる第一のめっき層と、
前記第一のめっき層の直上に、銅のフラッシュめっきによる第二のめっき層と、
前記第二のめっき層の直上に、銅の無電解めっきによる第三のめっき層と
を形成し、焼成処理により前記亜鉛および前記銅を表面に露出させたことを特徴とするメタノール水蒸気改質触媒。 A methanol steam reforming catalyst in which a plurality of plating layers are formed on one side or both sides of a metal plate,
On the surface of the metal plate, a first plating layer by electroless plating of zinc,
A second plating layer by flash plating of copper, directly above the first plating layer,
A methanol steam reforming catalyst, characterized in that a third plating layer by electroless plating of copper is formed directly on the second plating layer, and the zinc and the copper are exposed on the surface by a firing treatment. .
前記内壁の表面に、亜鉛の無電解めっきによる第一のめっき層と、
前記第一のめっき層の直上に、銅のフラッシュめっきによる第二のめっき層と、
前記第二のめっき層の直上に、銅の無電解めっきによる第三のめっき層と
を形成し、焼成処理により前記亜鉛および前記銅を表面に露出させたことを特徴とするメタノール水蒸気改質触媒。 A methanol steam reforming catalyst in which a plurality of plating layers are formed on the inner wall of a honeycomb-like or lattice-like metal cylinder,
On the surface of the inner wall, a first plating layer by electroless plating of zinc,
A second plating layer by flash plating of copper, directly above the first plating layer,
A methanol steam reforming catalyst, characterized in that a third plating layer by electroless plating of copper is formed directly on the second plating layer, and the zinc and the copper are exposed on the surface by a firing treatment. .
前記金属管の表面に、亜鉛の無電解めっきによる第一のめっき層と、
前記第一のめっき層の直上に、銅のフラッシュめっきによる第二のめっき層と、
前記第二のめっき層の直上に、銅の無電解めっきによる第三のめっき層と
を形成し、焼成処理により前記亜鉛および前記銅を表面に露出させたことを特徴とするメタノール水蒸気改質触媒。 A methanol steam reforming catalyst in which a plurality of plating layers are formed on the inner surface, outer surface or both surfaces of a metal tube,
On the surface of the metal tube, a first plating layer by electroless plating of zinc,
A second plating layer by flash plating of copper, directly above the first plating layer,
A methanol steam reforming catalyst, characterized in that a third plating layer by electroless plating of copper is formed directly on the second plating layer, and the zinc and the copper are exposed on the surface by a firing treatment. .
前記第一のめっき層は、亜鉛の置換めっきによる無電解めっき層
であることを特徴とする請求項１から請求項７のいずれか一項に記載のメタノール水蒸気改質触媒。 The metal is aluminum, and
The methanol steam reforming catalyst according to any one of claims 1 to 7, wherein the first plating layer is an electroless plating layer formed by zinc displacement plating.
前記金属表面に、亜鉛の無電解めっきによる第一のめっき層と、
前記第一のめっき層の直上に、銅のフラッシュめっきによる第二のめっき層と、
前記第二のめっき層の直上に、銅の無電解めっきによる第三のめっき層と
を形成し、焼成処理により前記亜鉛および前記銅を表面に露出させたことを特徴とするメタノール水蒸気改質触媒の製造方法。 A method for producing a methanol steam reforming catalyst having a plurality of plating layers formed on a metal surface,
A first plating layer by electroless plating of zinc on the metal surface;
A second plating layer by flash plating of copper, directly above the first plating layer,
A methanol steam reforming catalyst, characterized in that a third plating layer by electroless plating of copper is formed directly on the second plating layer, and the zinc and the copper are exposed on the surface by a firing treatment. Manufacturing method.
前記第一のめっき層は、亜鉛の置換めっきによる無電解めっき層
であることを特徴とする請求項９に記載のメタノール水蒸気改質触媒の製造方法。 The metal is aluminum, and
The method for producing a methanol steam reforming catalyst according to claim 9, wherein the first plating layer is an electroless plating layer by displacement plating of zinc.
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| JP2005098089A (en) * | 2003-08-27 | 2005-04-14 | Toto Ltd | Header unit |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007268459A (en) * | 2006-03-31 | 2007-10-18 | Kobe Steel Ltd | Catalyst for reforming methanol with steam and method for preparing the same |
| JP2013212988A (en) * | 2008-01-08 | 2013-10-17 | Tokyo Gas Co Ltd | Cylindrical steam reformer |
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