JP2010069453A - Catalyst for reforming dimethyl ether - Google Patents

Catalyst for reforming dimethyl ether Download PDF

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JP2010069453A
JP2010069453A JP2008242189A JP2008242189A JP2010069453A JP 2010069453 A JP2010069453 A JP 2010069453A JP 2008242189 A JP2008242189 A JP 2008242189A JP 2008242189 A JP2008242189 A JP 2008242189A JP 2010069453 A JP2010069453 A JP 2010069453A
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dimethyl ether
catalyst
reforming catalyst
steam reforming
methanol steam
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Kaoru Takeishi
薫 武石
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst for reforming dimethyl ether, which is used for obtaining hydrogen from dimethyl ether by a steam reforming method and exhibits higher activity. <P>SOLUTION: The catalyst for reforming dimethyl ether is obtained by dispersing a catalyst for steam-reforming methanol in a gel particle of a catalyst for hydrolyzing dimethyl ether. The gel particle of the catalyst for hydrolyzing dimethyl ether is normally an alumina-based particle. The catalyst for steam-reforming methanol is a catalyst fine particle which is based on a copper element and preferably contains an element selected from the group consisting of zinc, manganese, iron, chromium and cobalt or an element selected from the group consisting of cerium, praseodymium, terbium, zirconium, lanthanum, yttrium and neodymium. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は、ジメチルエーテル改質触媒に関する。 The present invention relates to a dimethyl ether reforming catalyst.

ジメチルエーテル〔ＣＨ3−Ｏ−ＣＨ3〕は、小出力の燃料電池システムにおいて水素〔Ｈ2〕を製造するための原料としての利用が期待されている。かかるジメチルエーテルから水素を製造する方法としては、ジメチルエーテルを気相でジメチルエーテル改質触媒の存在下に水蒸気〔Ｈ2Ｏ〕と反応させる水蒸気改質法が知られている。 Dimethyl ether [CH 3 —O—CH 3 ] is expected to be used as a raw material for producing hydrogen [H 2 ] in a low-power fuel cell system. As a method for producing hydrogen from such dimethyl ether, there is known a steam reforming method in which dimethyl ether is reacted in a gas phase with steam [H 2 O] in the presence of a dimethyl ether reforming catalyst.

ジメチルエーテル改質触媒として、特許文献１には、アルミナ粉末を成形したアルミナ粉末成形体に、含浸法により、銅元素を担持させたジメチルエーテル改質触媒が開示されている。 As a dimethyl ether reforming catalyst, Patent Document 1 discloses a dimethyl ether reforming catalyst in which a copper element is supported by an impregnation method on an alumina powder molded body obtained by molding an alumina powder.

かかるジメチルエーテル改質触媒としては、より高い活性を示すものが求められている。 As such a dimethyl ether reforming catalyst, a catalyst having higher activity is required.

特開２００１−９６１５９号公報JP 2001-96159 A

そこで本発明者は、より高い活性を示すジメチルエーテル改質触媒を開発するべく鋭意検討した結果、本発明に至った。 Therefore, the present inventors have intensively studied to develop a dimethyl ether reforming catalyst exhibiting higher activity, and as a result, have reached the present invention.

すなわち本発明は、ジメチルエーテルから水蒸気改質法により水素を得るために用いられるジメチルエーテル改質触媒であって、ジメチルエーテル加水分解触媒ゲル粒子に、メタノール水蒸気改質触媒が分散されてなることを特徴とするジメチルエーテル改質触媒を提供するものである。 That is, the present invention is a dimethyl ether reforming catalyst used for obtaining hydrogen from dimethyl ether by a steam reforming method, wherein the methanol steam reforming catalyst is dispersed in dimethyl ether hydrolysis catalyst gel particles. A dimethyl ether reforming catalyst is provided.

本発明のジメチルエーテル改質触媒は高活性であるので、高い水素生成速度で、ジメチルエーテルから水蒸気改質法により水素を製造することができる。 Since the dimethyl ether reforming catalyst of the present invention is highly active, hydrogen can be produced from dimethyl ether by a steam reforming method at a high hydrogen production rate.

〔ジメチルエーテル加水分解触媒ゲル粒子〕
本発明のジメチルエーテル改質触媒を構成するジメチルエーテル加水分解触媒ゲル粒子は、ジメチルエーテルを加水分解してメタノールを生成させる際に使用されるジメチルエーテル加水分解触媒のゲル粒子である。ジメチルエーテル改質触媒としては、例えばアルミナ、ゼオライト、シリカ−アルミナなどのような固体酸が挙げられ、高活性のジメチルエーテル改質触媒が容易に得られる点で、好ましくはアルミナである。 [Dimethyl ether hydrolysis catalyst gel particles]
The dimethyl ether hydrolysis catalyst gel particles constituting the dimethyl ether reforming catalyst of the present invention are gel particles of a dimethyl ether hydrolysis catalyst used when dimethyl ether is hydrolyzed to produce methanol. Examples of the dimethyl ether reforming catalyst include solid acids such as alumina, zeolite, silica-alumina and the like, and alumina is preferable because a highly active dimethyl ether reforming catalyst can be easily obtained.

〔メタノール水蒸気改質触媒〕
メタノール水蒸気改質触媒は、メタノールを水蒸気と反応させて水素を生成させる際に用いられる触媒であって、通常は銅元素を主成分とする触媒微粒子が用いられ、好ましくは銅元素を主成分とし、亜鉛、マンガン、鉄、クロムおよびコバルトからなる群から選ばれた元素を含むもの、銅元素を主成分とし、セリウム、プラセオジウム、テルビウム、ジルコニウム、ランタン、イットリウムおよびネオジウムからなる群から選ばれた元素を含むもの、さらに好ましくは銅元素を主成分とし、亜鉛を含む触媒微粒子、銅元素を主成分とし、セリウムを含む触媒微粒子であり、特に好ましくは銅元素を主成分とし、亜鉛およびセリウムを含む触媒微粒子である。触媒微粒子において、これらの元素は通常、酸化物として含まれている。 [Methanol steam reforming catalyst]
The methanol steam reforming catalyst is a catalyst used when hydrogen is produced by reacting methanol with steam, and usually catalyst fine particles mainly composed of copper element are used, and preferably copper element is mainly composed of copper element. Containing an element selected from the group consisting of zinc, manganese, iron, chromium and cobalt, an element selected from the group consisting of cerium, praseodymium, terbium, zirconium, lanthanum, yttrium and neodymium based on copper Catalyst fine particles containing copper as a main component and containing zinc, catalyst fine particles containing copper element as a main component and containing cerium, particularly preferably containing copper element as a main component and containing zinc and cerium Catalyst fine particles. In the catalyst fine particles, these elements are usually contained as oxides.

メタノール水蒸気改質触媒は、ジメチルエーテル加水分解触媒ゲル粒子の表面に分散されていてもよいし、内部に分散されていてもよく、表面および内部の両方に分散されていてもよい。 The methanol steam reforming catalyst may be dispersed on the surface of the dimethyl ether hydrolysis catalyst gel particles, may be dispersed inside, or may be dispersed both on the surface and inside.

〔ジメチルエーテル改質触媒〕
本発明のジメチルエーテル改質触媒の好ましい例としては、アルミナゲル粒子に、銅元素を主成分とする微粒子が担持されたものが挙げられる。かかる改質触媒における元素の組成は、質量比で通常、Ａｌ2Ｏ3が３０質量％〜９０質量％であり、Ｃｕが７０質量％〜１０質量％である。さらに好ましいジメチルエーテル改質触媒の例として、アルミナゲル粒子に、銅元素を主成分とし、亜鉛元素またはセリウム元素を含む微粒子が担持されたものが挙げられ、その元素組成比は通常、Ａｌ2Ｏ3が３０質量％〜９０質量％であり、Ｃｕが７０質量％〜１０質量％であり、ＺｎＯが５０質量％以下、ＣｅＯ2が５０質量％以下である。 [Dimethyl ether reforming catalyst]
Preferable examples of the dimethyl ether reforming catalyst of the present invention include those in which fine particles mainly containing copper element are supported on alumina gel particles. The composition of elements in such a reforming catalyst is usually 30% by mass to 90% by mass of Al 2 O 3 and 70% by mass to 10% by mass of Cu in terms of mass ratio. Examples of more preferred dimethylether reforming catalyst, an alumina gel particles, elemental copper as a main component include those particles containing zinc element or cerium element is supported, the element composition ratio is usually, Al 2 O 3 Is 30% by mass to 90% by mass, Cu is 70% by mass to 10% by mass, ZnO is 50% by mass or less, and CeO 2 is 50% by mass or less.

〔ジメチルエーテル改質触媒の製造方法〕
かかる本発明のジメチルエーテル改質触媒は、揮発性溶媒中にジメチルエーテル加水分解触媒ゲル粒子前駆体が分散され、メタノール水蒸気改質触媒前駆体が溶解した分散液を溶媒留去する方法により製造することができる。 [Method for producing dimethyl ether reforming catalyst]
Such a dimethyl ether reforming catalyst of the present invention can be produced by a method in which a dimethyl ether hydrolysis catalyst gel particle precursor is dispersed in a volatile solvent, and the dispersion in which the methanol steam reforming catalyst precursor is dissolved is distilled off. it can.

〔揮発性溶媒〕
揮発性溶媒としては通常、水を主成分とする水性媒体が用いられ、エチレングリコール、プロパノール、エタノールメタノールなどのアルコール類や、ジメチルホルムアミドなどのような、水溶性有機溶媒と水との混合溶媒であってもよい。 (Volatile solvent)
As the volatile solvent, an aqueous medium containing water as a main component is usually used. Alcohols such as ethylene glycol, propanol, and ethanolmethanol, and a mixed solvent of a water-soluble organic solvent such as dimethylformamide and water are used. There may be.

〔ジメチルエーテル加水分解触媒ゲル粒子前駆体〕
ジメチルエーテル加水分解触媒ゲル粒子前駆体としては、ジメチルエーテル加水分解触媒としてアルミナを用いる場合には、通常、加水分解性アルミナ化合物を水性媒体中で加水分解して得られるゾルが挙げられる。加水分解性アルミナ化合物として通常はアルミニウムイソプロポキシド、アルミニウムエトキシド、アルミニウムブトキシドなどのアルミニウムアルコキシドが挙げられる。 [Dimethyl ether hydrolysis catalyst gel particle precursor]
Examples of the dimethyl ether hydrolysis catalyst gel particle precursor include a sol obtained by hydrolyzing a hydrolyzable alumina compound in an aqueous medium when alumina is used as the dimethyl ether hydrolysis catalyst. Examples of the hydrolyzable alumina compound include aluminum alkoxides such as aluminum isopropoxide, aluminum ethoxide, and aluminum butoxide.

加水分解性アルミナ化合物の加水分解は通常の方法、例えば加水分解性アルミニウム化合物としてアルミニウムアルコキシドを用いる場合には、これを含む水性媒体の水素イオン濃度を通常ｐＨ３以下、さらにはｐＨ２以下、通常はｐＨ０以上とすることにより行われる。水素イオン濃度を上記範囲とするには、例えば硝酸、塩酸、硫酸などの無機酸を水性媒体に加えればよい。また、水性媒体の水素イオン濃度を通常ｐＨ９以上、通常はｐＨ１４以下とする方法により、アルミニウムアルコキシドの加水分解を行ってもよい。水素イオン濃度を上記範囲とするには、例えばアンモニア水、炭酸ナトリウム、水酸化ナトリウムなどの無機塩基を水性媒体に加えればよい。好ましくは無機酸を加えることにより、水性媒体の水素イオン濃度を通常ｐＨ３以下とする方法である。 Hydrolysis of the hydrolyzable alumina compound is carried out by an ordinary method, for example, when aluminum alkoxide is used as the hydrolyzable aluminum compound, the hydrogen ion concentration of the aqueous medium containing this is usually pH 3 or less, further pH 2 or less, usually pH 0. This is done as described above. In order to set the hydrogen ion concentration within the above range, for example, an inorganic acid such as nitric acid, hydrochloric acid, or sulfuric acid may be added to the aqueous medium. Alternatively, the aluminum alkoxide may be hydrolyzed by a method in which the hydrogen ion concentration in the aqueous medium is usually pH 9 or higher, usually pH 14 or lower. In order to make the hydrogen ion concentration within the above range, for example, an inorganic base such as aqueous ammonia, sodium carbonate or sodium hydroxide may be added to the aqueous medium. Preferably, the method is such that the hydrogen ion concentration of the aqueous medium is usually adjusted to pH 3 or less by adding an inorganic acid.

かくして、加水分解性アルミナ化合物の加水分解物が水性媒体中に分散されたゾル状の分散液を得ることができる。 Thus, a sol-like dispersion in which the hydrolyzate of the hydrolyzable alumina compound is dispersed in the aqueous medium can be obtained.

〔メタノール水蒸気改質触媒前駆体〕
メタノール水蒸気改質触媒前駆体としては、例えば銅塩が挙げられ、具体的には硝酸銅、炭酸銅などの無機銅塩、酢酸銅などの有機銅塩およびアルコキシドなどが挙げられる。また、メタノール水蒸気改質触媒として、銅元素を主成分とし、亜鉛、マンガン、鉄、クロムおよびコバルトからなる群から選ばれた元素や、セリウム、プラセオジウム、テルビウム、ジルコニウム、ランタン、イットリウムおよびネオジウムからなる群から選ばれた元素を含むものを用いる場合には、亜鉛、マンガン、鉄、クロム、コバルト、セリウム、プラセオジウム、テルビウム、ジルコニウム、ランタン、イットリウム、ネオジウムの硝酸塩、炭酸塩、ハロゲン化物、硫酸塩などの無機塩、酢酸塩などの有機塩およびアルコキシドなども挙げられる。 [Methanol steam reforming catalyst precursor]
Examples of the methanol steam reforming catalyst precursor include copper salts, specifically, inorganic copper salts such as copper nitrate and copper carbonate, organic copper salts such as copper acetate, and alkoxides. Further, as a methanol steam reforming catalyst, an element selected from the group consisting of zinc, manganese, iron, chromium, and cobalt, and cerium, praseodymium, terbium, zirconium, lanthanum, yttrium, and neodymium are mainly composed of copper element. When using an element selected from the group, zinc, manganese, iron, chromium, cobalt, cerium, praseodymium, terbium, zirconium, lanthanum, yttrium, neodymium nitrate, carbonate, halide, sulfate, etc. Inorganic salts, organic salts such as acetates, and alkoxides are also included.

〔溶媒留去〕
かかる揮発性溶媒中にジメチルエーテル加水分解触媒ゲル粒子前駆体が分散され、メタノール水蒸気改質触媒前駆体が溶解した分散液を溶媒留去することにより、固形物を得る。得られた固形物は通常、焼成され、次いで還元処理が施される。 (Solvent distillation)
A dimethyl ether hydrolysis catalyst gel particle precursor is dispersed in such a volatile solvent, and the solid solution is obtained by distilling off the solvent in which the methanol steam reforming catalyst precursor is dissolved. The obtained solid is usually fired and then subjected to a reduction treatment.

〔焼成〕
溶媒留去により得られた固形物の焼成は通常、空気中で行われ、焼成温度は通常３００℃〜７００℃、焼成時間は通常３時間〜７時間である。 [Baking]
The solid obtained by distilling off the solvent is usually fired in air, the firing temperature is usually 300 ° C. to 700 ° C., and the firing time is usually 3 hours to 7 hours.

〔還元処理〕
還元処理は、例えば水素ガスなどの還元性ガス雰囲気中に２５０℃〜４５０℃で１時間以上、好ましくは３時間以上、通常は２４時間以下保持することにより行われる。 [Reduction treatment]
The reduction treatment is performed, for example, by holding in a reducing gas atmosphere such as hydrogen gas at 250 ° C. to 450 ° C. for 1 hour or longer, preferably 3 hours or longer, usually 24 hours or shorter.

〔ジメチルエーテル改質触媒〕
かくして得られる本発明のジメチルエーテル改質触媒は粉末状であり、そのままジメチルエーテルの改質に用いてもよいが、通常は顆粒状、球状、円柱状、円筒状の形状に成形して用いられる。また、基材上に担持して用いてもよい。基材としては、改質の際に発生する反応熱を速やかに放散し得る点で、金属銅、ステンレスなどの金属材料、セラミックス材料などのような伝熱性に優れた伝熱性材料が好ましく用いられる。基材の形状としては、例えば板状、網状、ハニカム状が挙げられる。 [Dimethyl ether reforming catalyst]
The dimethyl ether reforming catalyst of the present invention thus obtained is in powder form and may be used as it is for reforming dimethyl ether, but is usually used after being molded into a granular, spherical, cylindrical or cylindrical shape. Moreover, you may carry | support and use on a base material. As the substrate, a heat transfer material having excellent heat transfer properties such as metal materials such as metallic copper and stainless steel and ceramic materials is preferably used in that the reaction heat generated during the modification can be quickly dissipated. . Examples of the shape of the substrate include a plate shape, a net shape, and a honeycomb shape.

〔水素の製造〕
本発明のジメチルエーテル改質触媒は、高い活性を示すので、本発明のジメチルエーテル改質触媒の存在下にジメチルエーテルを水蒸気と反応させることにより、高い生成速度で水素を製造することができる。反応は通常、気相中で行われ、反応温度は通常１５０℃〜４５０℃、反応圧力は通常０．１ＭＰａ〜１０ＭＰａ（絶対圧）である。反応に用いる反応器としては、例えば固定床反応器、流動床反応器、移動床反応器が挙げられる。 [Production of hydrogen]
Since the dimethyl ether reforming catalyst of the present invention exhibits high activity, hydrogen can be produced at a high production rate by reacting dimethyl ether with steam in the presence of the dimethyl ether reforming catalyst of the present invention. The reaction is usually carried out in the gas phase, the reaction temperature is usually 150 ° C. to 450 ° C., and the reaction pressure is usually 0.1 MPa to 10 MPa (absolute pressure). Examples of the reactor used for the reaction include a fixed bed reactor, a fluidized bed reactor, and a moving bed reactor.

本発明のジメチルエーテル改質触媒によるジメチルエーテル〔ＣＨ3−Ｏ−ＣＨ3〕の改質の機構は必ずしも明確ではないが、ジメチルエーテル〔ＣＨ3−Ｏ−ＣＨ3〕は、改質触媒中のジメチルエーテル加水分解触媒ゲル粒子により化学反応式（１）
ＣＨ3−Ｏ−ＣＨ3 ＋ Ｈ2Ｏ → ２ＣＨ3ＯＨ ・・・（１）
に従い水蒸気〔Ｈ2Ｏ〕による加水分解を起してメタノール〔ＣＨ3ＯＨ〕となり、この加水分解により生成したメタノールは、メタノール水蒸気改質触媒により化学反応式（２）
２ＣＨ3ＯＨ ＋ Ｈ2Ｏ → ３Ｈ2 ＋ ＣＯ2 ・・・（２）
に従い、さらに水蒸気〔Ｈ2Ｏ〕と反応して水素〔Ｈ2〕が生成するものと考えられる。 Although the mechanism of reforming of dimethyl ether [CH 3 —O—CH 3 ] by the dimethyl ether reforming catalyst of the present invention is not necessarily clear, dimethyl ether [CH 3 —O—CH 3 ] is used for hydrolysis of dimethyl ether in the reforming catalyst. Chemical reaction formula with catalyst gel particles (1)
CH 3 -O-CH 3 + H 2 O → 2CH 3 OH ··· (1)
In accordance with the above, hydrolysis with steam [H 2 O] is performed to form methanol [CH 3 OH]. Methanol generated by this hydrolysis is represented by the chemical reaction formula (2) by the methanol steam reforming catalyst.
2CH 3 OH + H 2 O → 3H 2 + CO 2 (2)
Accordingly, it is considered that hydrogen [H 2 ] is generated by further reacting with water vapor [H 2 O].

以下、実施例により本発明をより詳細に説明するが、本発明は、かかる実施例によって限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by this Example.

実施例１
〔ジメチルエーテル製造用触媒の製造〕
７０℃の水１００ｍＬに、乳鉢で磨り潰したアルミニウムイソプロポキシド粉末〔Ａｌ[ＯＣＨ(ＣＨ3)2]3、和光純薬工業社製、第一級、純度９５％〕９．０７９ｇおよびエチレングリコール〔和光純薬工業社製、特級〕６．４ｍＬ（７．１ｇ）を加え、同温度で１５分以上撹拌して分散させた。次いで、希硝酸を少しずつ加えて水素イオン濃度ｐＨ１〜ｐＨ２に調整して、分散液（アルミナクリアゾル）を得た。この分散液に、硝酸銅３水和物〔和光純薬工業社製、特級、純度９９％〕３．４７５ｇ、硝酸亜鉛６水和物〔和光純薬工業社製、特級、純度９９％〕０．１４３ｇおよび硝酸セリウム６水和物〔和光純薬工業社製、特級、純度９８％〕０．０８０ｇを純水に溶解させた銅・亜鉛・セリウム水溶液〔２０ｍＬ〕を加え、同温度でさらに１５分間撹拌し、その後、エバポレーターにより溶媒留去を行って固形分〔ゲル〕を得た。この固形分を粉砕したのち、大気中、５００℃で５時間の焼成を行い、得られた焼成物に、水素雰囲気中４５０℃で１０時間の還元処理を施してジメチルエーテル改質触媒３．１ｇを得た。 Example 1
[Production of catalyst for dimethyl ether production]
Aluminum isopropoxide powder [Al [OCH (CH 3 ) 2 ] 3 , Wako Pure Chemical Industries, first grade, purity 95%] 9.079 g and ethylene glycol in 100 mL of water at 70 ° C. [Special grade of Wako Pure Chemical Industries, Ltd.] 6.4 mL (7.1 g) was added, and the mixture was stirred and dispersed at the same temperature for 15 minutes or more. Next, dilute nitric acid was added little by little to adjust the hydrogen ion concentration to pH 1 to pH 2 to obtain a dispersion (alumina clear sol). To this dispersion, copper nitrate trihydrate (manufactured by Wako Pure Chemical Industries, special grade, purity 99%) 3.475 g, zinc nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, special grade, purity 99%) 0 .143 g and a cerium nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd., special grade, purity 98%) 0.080 g of copper / zinc / cerium aqueous solution [20 mL] dissolved in pure water was added, and further 15 at the same temperature. After stirring for a minute, the solvent was distilled off with an evaporator to obtain a solid [gel]. After this solid content is pulverized, it is calcined at 500 ° C. for 5 hours in the air, and the obtained calcined product is subjected to reduction treatment at 450 ° C. for 10 hours in a hydrogen atmosphere to obtain 3.1 g of a dimethyl ether reforming catalyst. Obtained.

〔ジメチルエーテル製造用触媒〕
この改質触媒の元素の質量組成は、Ａｌ2Ｏ3が６９質量％、Ｃｕが２９質量％、ＺｎＯが１質量％、ＣｅＯ2が１質量％である。この改質触媒にピリジンを吸着させ、赤外線分光光度計で赤外線吸収スペクトルを測定したところ、１４５０ｃｍ-1近傍に吸収ピークが見られたことから、Ｌｅｗｉｓ酸などの酸が存在する固体酸であることを確認できた。 [Dimethyl ether production catalyst]
The mass composition of the elements of the reforming catalyst is 69% by mass for Al 2 O 3 , 29% by mass for Cu, 1% by mass for ZnO, and 1% by mass for CeO 2 . Pyridine was adsorbed on this reforming catalyst, and when an infrared absorption spectrum was measured with an infrared spectrophotometer, an absorption peak was observed in the vicinity of 1450 cm −1 . Therefore, the acid was a solid acid in which an acid such as Lewis acid was present. Was confirmed.

〔ジメチルエーテルの水蒸気改質〕
上記で得た改質触媒０．１ｇを反応管に充填し、反応温度３００℃、３２５℃または３５０℃に保ちながら、この反応管に、モル比でガス状ジメチルエーテルおよび水蒸気を１：３で含み、アルゴンで希釈された原料ガスを供給した。原料ガスの供給量は、改質触媒１ｇあたり、１分あたり、ジメチルエーテル１２ミリモルおよび水蒸気３６ミリモルとした。反応管の出口から得られた反応ガス中に含まれる水素ガスの濃度から、水素生成速度を求めたところ、触媒１ｇあたり１時間あたり、反応温度３００℃では０．１００モル、３２５℃では０．１０９モル、３５０℃では０．１１１モルであった。また、供給したジメチルエーテルのうち、消費されたものの割合を示すジメチルエーテル転化率を求めたところ、反応温度３００℃では８１．４％、３２５℃では９２．８％、３５０℃では９８．０％であった。結果を第１表に示す。 [Steam reforming of dimethyl ether]
The reaction tube was filled with 0.1 g of the reforming catalyst obtained above, and the reaction tube contained gaseous dimethyl ether and water vapor at a molar ratio of 1: 3 while maintaining the reaction temperature at 300 ° C., 325 ° C. or 350 ° C. The raw material gas diluted with argon was supplied. The supply amount of the raw material gas was 12 mmol of dimethyl ether and 36 mmol of water vapor per minute per 1 g of the reforming catalyst. The hydrogen production rate was determined from the concentration of the hydrogen gas contained in the reaction gas obtained from the outlet of the reaction tube. It was 0.111 mol at 109 mol and 350 ° C. Further, when the conversion rate of dimethyl ether indicating the ratio of consumed dimethyl ether was calculated, it was 81.4% at a reaction temperature of 300 ° C, 92.8% at 325 ° C, and 98.0% at 350 ° C. It was. The results are shown in Table 1.

実施例２
〔ジメチルエーテル製造用触媒の製造〕
実施例１と同様に操作して得た分散液（アルミナクリアゾル）に、硝酸銅３水和物〔和光純薬工業社製、特級、純度９９％〕３．４７５ｇおよび硝酸亜鉛６水和物〔和光純薬工業社製、特級、純度９９％〕０．１４３ｇを純水に溶解させた銅・亜鉛水溶液〔２０ｍＬ〕を加え、その後、実施例１と同様に操作して、固形分〔ゲル〕を得、焼成物を得、ジメチルエーテル改質触媒３．１ｇを得た。この改質触媒の元素の質量組成は、Ａｌ2Ｏ3が７０質量％、Ｃｕが２９質量％、ＺｎＯが１質量％である。実施例１と同様にして、この改質触媒はＬｅｗｉｓ酸などの酸が存在する固体酸であることを確認できた。 Example 2
[Production of catalyst for dimethyl ether production]
In a dispersion (alumina clear sol) obtained by operating in the same manner as in Example 1, copper nitrate trihydrate (manufactured by Wako Pure Chemical Industries, Ltd., special grade, purity 99%) 3.475 g and zinc nitrate hexahydrate [Wako Pure Chemical Industries, Ltd., special grade, purity 99%] A copper / zinc aqueous solution [20 mL] in which 0.143 g was dissolved in pure water was added. To obtain 3.1 g of a dimethyl ether reforming catalyst. The mass composition of the elements of the reforming catalyst is 70% by mass for Al 2 O 3 , 29% by mass for Cu, and 1% by mass for ZnO. In the same manner as in Example 1, it was confirmed that the reforming catalyst was a solid acid in which an acid such as Lewis acid was present.

〔ジメチルエーテルの水蒸気改質〕
実施例１で得たジメチルエーテル改質触媒に代えて、上記で得た改質触媒を用いた以外は実施例１と同様に操作して、ジメチルエーテルの改質を行った。結果を第１表に示す。 [Steam reforming of dimethyl ether]
The dimethyl ether was reformed in the same manner as in Example 1 except that the reforming catalyst obtained above was used instead of the dimethyl ether reforming catalyst obtained in Example 1. The results are shown in Table 1.

比較例１
〔ジメチルエーテル製造用触媒の製造〕
７０℃の水１００ｍＬに、乳鉢で磨り潰したアルミニウムイソプロポキシド粉末〔Ａｌ[ＯＣＨ(ＣＨ3)2]3、和光純薬工業社製、第一級、純度９５％〕９．０７９ｇを加え、同温度で１５分以上撹拌して分散させ、実施例１で用いたと同じ銅・亜鉛・セリウム水溶液〔２０ｍＬ〕を加え、さらにエチレングリコール〔和光純薬工業社製、特級〕６．４ｍＬ（７．１ｇ）を加え、次いで、希硝酸を少しずつ加えて水素イオン濃度ｐＨ１〜ｐＨ２に調整して、分散液（アルミナクリアゾル）を得た。その後、実施例１と同様に操作して固形分〔ゲル〕を得、焼成物を得、ジメチルエーテル改質触媒３．１ｇを得た。この改質触媒の元素の質量組成は、Ａｌ2Ｏ3が６９質量％、Ｃｕが２９質量％、ＺｎＯが１質量％、ＣｅＯ2が１質量％である。 Comparative Example 1
[Production of catalyst for dimethyl ether production]
To 100 mL of water at 70 ° C., 9.079 g of aluminum isopropoxide powder [Al [OCH (CH 3 ) 2 ] 3 , manufactured by Wako Pure Chemical Industries, Ltd., first grade, purity 95%] ground in a mortar, The same copper / zinc / cerium aqueous solution [20 mL] used in Example 1 was added by stirring at the same temperature for 15 minutes or more, and ethylene glycol (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) 6.4 mL (7. 1 g) was added, and then dilute nitric acid was added little by little to adjust the hydrogen ion concentration to pH 1 to pH 2 to obtain a dispersion (alumina clear sol). Thereafter, the same operation as in Example 1 was performed to obtain a solid [gel], a fired product was obtained, and 3.1 g of a dimethyl ether reforming catalyst was obtained. The mass composition of the elements of the reforming catalyst is 69% by mass for Al 2 O 3 , 29% by mass for Cu, 1% by mass for ZnO, and 1% by mass for CeO 2 .

〔ジメチルエーテルの水蒸気改質〕
実施例１で得たジメチルエーテル改質触媒に代えて、上記で得た改質触媒を用いた以外は実施例１と同様に操作して、ジメチルエーテルの改質を行った。結果を第１表に示す。 [Steam reforming of dimethyl ether]
The dimethyl ether was reformed in the same manner as in Example 1 except that the reforming catalyst obtained above was used instead of the dimethyl ether reforming catalyst obtained in Example 1. The results are shown in Table 1.

比較例２
〔ジメチルエーテル製造用触媒の製造〕
銅・亜鉛・セリウム水溶液に代えて、実施例２で用いた銅・亜鉛水溶液〔２０ｍＬ〕を用いた以外は比較例１と同様に操作して分散液（アルミナクリアゾル）を得、ジメチルエーテル改質触媒３．１ｇを得た。この改質触媒の元素の質量組成は、Ａｌ2Ｏ3が７０質量％、Ｃｕが２９質量％、ＺｎＯが１質量％である。 Comparative Example 2
[Production of catalyst for dimethyl ether production]
A dispersion (alumina clear sol) was obtained in the same manner as in Comparative Example 1 except that the copper / zinc aqueous solution [20 mL] used in Example 2 was used in place of the copper / zinc / cerium aqueous solution. 3.1 g of catalyst was obtained. The mass composition of the elements of the reforming catalyst is 70% by mass for Al 2 O 3 , 29% by mass for Cu, and 1% by mass for ZnO.

〔ジメチルエーテルの水蒸気改質〕
実施例１で得たジメチルエーテル改質触媒に代えて、上記で得た改質触媒を用いた以外は実施例１と同様に操作して、ジメチルエーテルの改質を行った。結果を第１表に示す。 [Steam reforming of dimethyl ether]
The dimethyl ether was reformed in the same manner as in Example 1 except that the reforming catalyst obtained above was used instead of the dimethyl ether reforming catalyst obtained in Example 1. The results are shown in Table 1.

第 １ 表
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
例 組成（質量％） 反応温度 水素生成速度 転化率
Al2O3 Cu ZnO CeO2 （℃） （モル／触媒ｇ／時間） （％）
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
実施例１ ６９ ２９ １ １ ３００ ０．１００ ８１．４
３２５ ０．１０９ ９２．８
３５０ ０．１１１ ９８．０
────────────────────────────────────────
実施例２ ７０ ２９ １ ０ ３００ ０．０７６ ７９．８
３２５ ０．０８４ ８８．８
３５０ ０．０８７ ９３．２
────────────────────────────────────────
比較例１ ６９ ２９ １ １ ３００ ０．０５０ ６７．１
３２５ ０．０６２ ８３．６
３５０ ０．０６９ ９３．３
────────────────────────────────────────
比較例２ ７０ ２９ １ ０ ３００ ０．０５５ ７２．４
３２５ ０．０６６ ８６．１
３５０ ０．０７４ ９３．９
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 1
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Example Composition (% by mass) Reaction temperature Hydrogen production rate Conversion
Al 2 O 3 Cu ZnO CeO 2 (° C) (mol / g catalyst / hour) (%)
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Example 1 69 29 1 1 300 0.100 81.4
325 0.109 92.8
350 0.111 98.0
────────────────────────────────────────
Example 2 70 29 1 0 300 0.076 79.8
325 0.084 88.8
350 0.087 93.2
────────────────────────────────────────
Comparative Example 1 69 29 1 1 300 0.050 67.1
325 0.062 83.6
350 0.069 93.3
────────────────────────────────────────
Comparative Example 2 70 29 1 0 300 0.055 72.4
325 0.066 86.1
350 0.074 93.9
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

Claims (9)

ジメチルエーテルから水蒸気改質法により水素を得るために用いられるジメチルエーテル改質触媒であって、ジメチルエーテル加水分解触媒ゲル粒子に、メタノール水蒸気改質触媒が分散されてなることを特徴とするジメチルエーテル改質触媒。 A dimethyl ether reforming catalyst used for obtaining hydrogen from dimethyl ether by a steam reforming method, wherein a methanol steam reforming catalyst is dispersed in dimethyl ether hydrolysis catalyst gel particles. ジメチルエーテル加水分解触媒ゲル粒子がアルミナを主成分とする粒子であり、メタノール水蒸気改質触媒が、銅元素を主成分とする触媒微粒子である請求項１に記載のジメチルエーテル改質触媒。 The dimethyl ether reforming catalyst according to claim 1, wherein the dimethyl ether hydrolysis catalyst gel particles are particles mainly composed of alumina, and the methanol steam reforming catalyst is catalyst fine particles mainly composed of copper element. メタノール水蒸気改質触媒が、銅元素を主成分とし、亜鉛、マンガン、鉄、クロムおよびコバルトからなる群から選ばれた元素を含む触媒微粒子である請求項２に記載のジメチルエーテル改質触媒。 The dimethyl ether reforming catalyst according to claim 2, wherein the methanol steam reforming catalyst is a catalyst fine particle containing an element selected from the group consisting of zinc, manganese, iron, chromium, and cobalt containing copper as a main component. メタノール水蒸気改質触媒が、銅元素を主成分とし、セリウム、プラセオジウム、テルビウム、ジルコニウム、ランタン、イットリウムおよびネオジウムからなる群から選ばれた元素を含む触媒微粒子である請求項２または請求項３に記載のジメチルエーテル改質触媒。 The methanol steam reforming catalyst is a catalyst fine particle containing copper as a main component and containing an element selected from the group consisting of cerium, praseodymium, terbium, zirconium, lanthanum, yttrium and neodymium. Dimethyl ether reforming catalyst. 揮発性溶媒中にジメチルエーテル加水分解触媒ゲル粒子前駆体が分散され、メタノール水蒸気改質触媒前駆体が溶解した分散液を溶媒留去することを特徴とする請求項１に記載のジメチルエーテル改質触媒の製造方法。 2. The dimethyl ether reforming catalyst according to claim 1, wherein the dimethyl ether hydrolysis catalyst gel particle precursor is dispersed in a volatile solvent, and the dispersion in which the methanol steam reforming catalyst precursor is dissolved is distilled off. Production method. ジメチルエーテル加水分解触媒ゲル粒子前駆体がアルミナゲルであり、メタノール水蒸気改質触媒前駆体が銅塩を主成分とするものであり、溶媒留去により得られた固形物を焼成し、得られた焼成物に還元処理を施す請求項５に記載の製造方法。 The dimethyl ether hydrolysis catalyst gel particle precursor is alumina gel, the methanol steam reforming catalyst precursor is mainly composed of a copper salt, the solid obtained by distilling off the solvent is fired, and the fired obtained The production method according to claim 5, wherein the product is subjected to a reduction treatment. メタノール水蒸気改質触媒前駆体が、銅塩を主成分とし、亜鉛、マンガン、鉄、クロムおよびコバルトからなる群から選ばれた元素の塩を含むものである請求項６に記載の製造方法。 The method according to claim 6, wherein the methanol steam reforming catalyst precursor contains a salt of an element selected from the group consisting of zinc, manganese, iron, chromium and cobalt, the main component of which is a copper salt. メタノール水蒸気改質触媒前駆体が、銅塩を主成分とし、セリウム、プラセオジウム、テルビウム、ジルコニウム、ランタン、イットリウムおよびネオジウムからなる群から選ばれた元素の塩を含むものである請求項６または請求項７に記載の製造方法。 The methanol steam reforming catalyst precursor contains a salt of an element selected from the group consisting of cerium, praseodymium, terbium, zirconium, lanthanum, yttrium and neodymium as a main component. The manufacturing method as described. 請求項１〜請求項４に記載のジメチルエーテル改質触媒の存在下にジメチルエーテルを水蒸気と反応させることを特徴とする水素の製造方法。 A method for producing hydrogen, comprising reacting dimethyl ether with water vapor in the presence of the dimethyl ether reforming catalyst according to claim 1.
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