JP2003047853A - Catalyst and method for reforming dimethyl ether - Google Patents
Catalyst and method for reforming dimethyl etherInfo
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- JP2003047853A JP2003047853A JP2001238657A JP2001238657A JP2003047853A JP 2003047853 A JP2003047853 A JP 2003047853A JP 2001238657 A JP2001238657 A JP 2001238657A JP 2001238657 A JP2001238657 A JP 2001238657A JP 2003047853 A JP2003047853 A JP 2003047853A
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- dimethyl ether
- reforming
- catalyst
- catalyst component
- reaction
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ジメチルエーテル
から効率的に水素を製造するためのジメチルエーテル改
質触媒およびジメチルエーテル改質方法に関するもので
ある。TECHNICAL FIELD The present invention relates to a dimethyl ether reforming catalyst and a dimethyl ether reforming method for efficiently producing hydrogen from dimethyl ether.
【０００２】[0002]
【従来の技術】燃料電池は、水素と酸素から水を得る電
池反応によって起電力を得ている。原料の水素は、原燃
料と水を改質触媒の存在下に反応させて得られる。この
ような燃料電池のうち、固体高分子型燃料電池（ＰＥＦ
Ｃ：Ｐｏｌｙｍｅｒ Ｅｌｅｃｔｒｏｌｙｔｅ Ｆｕｅ
ｌ Ｃｅｌｌ）が優れた性能を発揮できるものとして注
目されている。このような固体高分子型燃料電池では、
水素を燃料とし、アノード（燃料極）、カソード（空気
極）における電極反応によって起電力を得ている。2. Description of the Related Art Fuel cells obtain electromotive force by a cell reaction in which water is obtained from hydrogen and oxygen. Raw material hydrogen is obtained by reacting raw fuel and water in the presence of a reforming catalyst. Among such fuel cells, polymer electrolyte fuel cells (PEF)
C: Polymer Electrolyte Fue
l Cell) is attracting attention as a material capable of exhibiting excellent performance. In such a polymer electrolyte fuel cell,
Using hydrogen as fuel, electromotive force is obtained by electrode reaction at the anode (fuel electrode) and cathode (air electrode).
【０００３】上記原燃料としては、メタノール、エタノ
ールが用いられていたが、ジメチルエーテルも採用の選
択枝として採用されつつある。ジメチルエーテルでは、
メタネーション反応の副反応を抑制するために、７００
℃以上で改質反応を行なう。そして、副生するＣＯ（一
酸化炭素）を４５０℃付近のＣＯシフト反応によってＣ
Ｏを除去するようにしている。Although methanol and ethanol have been used as the above-mentioned raw fuel, dimethyl ether is being adopted as an option. With dimethyl ether,
In order to suppress side reactions of the methanation reaction, 700
Carry out a reforming reaction at a temperature above ℃. Then, CO (carbon monoxide), which is a by-product, is converted into C by a CO shift reaction near 450 ° C.
I try to remove O.
【０００４】しかし、このように温度域を変えて、改質
反応とＣＯシフト反応を行わせるためには、各々の反応
に合わせて触媒装置を設ける必要があり、ＰＥＦＣ装置
の大きさをコンパクト化するにあたって改善が望まれて
いた。However, in order to carry out the reforming reaction and the CO shift reaction by changing the temperature range in this way, it is necessary to provide a catalyst device for each reaction, and the size of the PEFC device is made compact. Improvement was desired in order to do so.
【０００５】[0005]
【発明が解決しようとする課題】本発明は上記事情に対
してなされたもので、ジメチルエーテルの改質反応と、
ＣＯシフト反応とを効率的に単一の触媒で、しかも低温
で行うことを可能とするジメチルエーテル改質触媒およ
びジメチルエーテルの改質方法を提供することを目的と
する。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances and includes a modification reaction of dimethyl ether,
An object of the present invention is to provide a dimethyl ether reforming catalyst and a method for reforming dimethyl ether, which can efficiently carry out the CO shift reaction with a single catalyst and at a low temperature.
【０００６】[0006]
【課題を解決するための手段】上記目的を達成するた
め、本発明に係るジメチルエーテル改質触媒は、ジメチ
ルエーテルと水から水素を得るためのジメチルエーテル
改質反応のための改質触媒成分と、副生するＣＯを除去
するＣＯシフト反応のためのＣＯシフト触媒成分とを含
む。本発明に係るジメチルエーテル改質触媒は、上記改
質触媒成分が白金を固体酸作用を有する担体に担持して
成る改質触媒成分とし、上記ＣＯシフト触媒成分がＣ
ｕ、Ｚｎ、Ｃｒ、ＦｅおよびＡｌの各々の酸化物から成
るグループから選択された少なくとも2種以上の複合酸
化物とすることをその実施の形態として含む。To achieve the above object, a dimethyl ether reforming catalyst according to the present invention comprises a reforming catalyst component for a dimethyl ether reforming reaction for obtaining hydrogen from dimethyl ether and water, and a by-product. CO shift catalyst component for a CO shift reaction to remove the CO that is generated. In the dimethyl ether reforming catalyst according to the present invention, the reforming catalyst component is a reforming catalyst component in which platinum is supported on a carrier having a solid acid action, and the CO shift catalyst component is C
Its embodiment includes forming at least two or more composite oxides selected from the group consisting of oxides of u, Zn, Cr, Fe and Al.
【０００７】上記改質触媒成分と上記ＣＯシフト触媒成
分とは、粉末混合することが好適である。また、その
他、改質触媒成分の粉末にＣＯシフト触媒成分を担持す
ることによっても本発明のジメチルエーテル改質触媒を
得ることができる。上記固体酸作用を有する担体として
は、γ−Ａｌ2Ｏ3、チタニア、ＺｒＯ2、ゼオライトお
よびメタロシリケートから成るグループから選ばれた少
なくとも1種が好適である。そして、固体酸作用を有す
る担体の固体酸量は、ピリジン吸着量で０．１ｍｍｏｌ
／ｇ以上とすることが好適である。The reforming catalyst component and the CO shift catalyst component are preferably powder-mixed. In addition, the dimethyl ether reforming catalyst of the present invention can also be obtained by supporting the CO shift catalyst component on the powder of the reforming catalyst component. As the carrier having a solid acid action, at least one selected from the group consisting of γ-Al 2 O 3 , titania, ZrO 2 , zeolite and metallosilicate is suitable. The solid acid amount of the carrier having a solid acid action is 0.1 mmol in terms of pyridine adsorption amount.
/ G or more is preferable.
【０００８】また、本発明は、別の側面において、上記
したジメチルエーテル改質触媒を用いたジメチルエーテ
ルの改質方法である。このようなジメチルエーテル改質
方法では、ジメチルエーテルに対し、水と酸素を加え、
部分酸化反応も生じさせるようにすることが好適であ
る。このように酸素をも加えることによって、ジメチル
エーテル改質反応と上記部分酸化反応とを併発させ、オ
ートサーマル反応を行うようにすることができる。In another aspect, the present invention is a method for reforming dimethyl ether using the above-mentioned dimethyl ether reforming catalyst. In such a dimethyl ether reforming method, water and oxygen are added to dimethyl ether,
It is preferable to cause a partial oxidation reaction. By thus adding oxygen as well, it is possible to cause the dimethyl ether reforming reaction and the above-mentioned partial oxidation reaction to occur simultaneously and to carry out the autothermal reaction.
【０００９】[0009]
【発明の実施の形態】以下、本発明に係るジメチルエー
テル改質触媒とジメチルエーテル改質方法をその実施の
形態等についてさらに詳細に説明する。本発明に係るジ
メチルエーテル改質触媒は、改質触媒成分として、白金
を固体酸作用を有する担体に担持して成るものを採用す
ることが好適である。このような、担体としてはγ−Ａ
ｌ2Ｏ3が一般的である。γ−Ａｌ2Ｏ3は固体酸性を有す
るためジメチルエーテルの加水分解作用を有し、メタノ
ールを中間体として活性金属の作用により、ＣＯ、Ｈ2
に分解することができる。なお、固体酸性を有するアナ
ターゼ型ＴｉＯ2等のチタニア、ジルコニア（Ｚｒ
Ｏ2）、ゼオライト、メタロシリケート等もγ−Ａｌ2Ｏ
3と同様な作用を有する。したがって、これらも本発明
に係るジメチルエーテルの改質触媒の担体として用いる
ことができる。また、これらの固体酸作用を有する担体
の固体酸量は、ピリジン吸着量で０．１ｍｍｏｌ／ｇ以
上であることが好適である。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the dimethyl ether reforming catalyst and the dimethyl ether reforming method according to the present invention will be described in more detail with reference to embodiments thereof. The dimethyl ether reforming catalyst according to the present invention preferably employs a reforming catalyst component in which platinum is supported on a carrier having a solid acid function. As such a carrier, γ-A
l 2 O 3 is common. Since γ-Al 2 O 3 has a solid acidity, it has a hydrolytic action on dimethyl ether, and CO, H 2
Can be decomposed into Incidentally, titania such as anatase type TiO 2 having solid acidity, zirconia (Zr
O 2 ), zeolite, metallosilicate, etc. are also γ-Al 2 O
Has the same effect as 3 . Therefore, these can also be used as a carrier for the dimethyl ether reforming catalyst according to the present invention. The solid acid amount of these carriers having a solid acid action is preferably 0.1 mmol / g or more in terms of pyridine adsorption amount.
【００１０】上記担体に担持される金属（改質触媒成分
の活性金属）としてはメタネーション作用が少ないＰｔ
が好ましい。もっとも、イリジウム、ロジウム、パラジ
ウム等であっても良い。すなわち、イリジウム、Ｐｔ、
ロジウムおよびパラジウム、さらにこれらに加えてこれ
らの化合物（酸化物、塩化物）から成るグループから選
択した少なくとも一の活性金属（活性金属化合物）であ
っても良い。As a metal (active metal of the reforming catalyst component) supported on the above carrier, Pt having a small methanation effect
Is preferred. However, it may be iridium, rhodium, palladium or the like. That is, iridium, Pt,
It may be at least one active metal (active metal compound) selected from the group consisting of rhodium and palladium, as well as these compounds (oxides, chlorides).
【００１１】さらに、ＣＯシフト能力を有する触媒成分
（ＣＯシフト触媒成分）としてＣｕ、Ｚｎ、Ｃｒ、Ｆｅ
およびＡｌの各々の酸化物から成るグループから選択さ
れた少なくとも2種以上の複合酸化物が好ましい。これ
らの複合酸化物は、主に共沈法等により調製される。ま
た、ＣＯシフト触媒成分は、含浸法によりジメチルエー
テル分解作用を有する触媒、すなわちジメチルエーテル
改質触媒成分に担持しても良い。Further, Cu, Zn, Cr, Fe are used as a catalyst component having a CO shift ability (CO shift catalyst component).
And at least two or more complex oxides selected from the group consisting of oxides of Al and Al are preferable. These complex oxides are mainly prepared by a coprecipitation method or the like. Further, the CO shift catalyst component may be supported on a catalyst having a dimethyl ether decomposition action by the impregnation method, that is, a dimethyl ether reforming catalyst component.
【００１２】ジメチルエーテル改質機能を持つ触媒とＣ
Ｏシフト機能を持つ触媒はおのおの１ｍｍ以下（好まし
くは０．５ｍｍ以下）の粒径が良く、好ましくは粉末粉
砕した触媒成分を混合させてペレット触媒化する方が良
い。各触媒成分の粒径が小さい方が好ましい理由は、ジ
メチルエーテルの改質で生じたＣＯが近接したＣＯシフ
ト機能を有する触媒に吸着されて、容易に拡散しＣＯシ
フト反応を進行させることができるためである。なお、
ジメチルエーテル改質機能を持つ触媒とＣＯシフト機能
を持つ触媒の配合比率は、（改質触媒成分）：（ＣＯシ
フト触媒成分）＝９５：５〜５：９５が好ましい。A catalyst having a dimethyl ether reforming function and C
Each of the catalysts having an O shift function has a particle size of 1 mm or less (preferably 0.5 mm or less), and it is preferable to mix powder-crushed catalyst components to form a pellet catalyst. The reason why the particle size of each catalyst component is preferably small is that CO generated by the reforming of dimethyl ether is adsorbed by a catalyst having a CO shift function in close proximity and can easily diffuse to advance the CO shift reaction. Is. In addition,
The mixing ratio of the catalyst having a dimethyl ether reforming function and the catalyst having a CO shift function is preferably (reforming catalyst component) :( CO shift catalyst component) = 95: 5 to 5:95.
【００１３】本発明に係るジメチルエーテル改質触媒を
用いることにより、ジメチルエーテルを４５０℃付近の
低温で分解し、さらに、ＣＯシフト反応も同時に行わせ
るため、水素濃度が高く、ＣＯ濃度が低いガスを製造す
ることが可能である。By using the dimethyl ether reforming catalyst according to the present invention, dimethyl ether is decomposed at a low temperature of around 450 ° C. and a CO shift reaction is also carried out at the same time, so that a gas having a high hydrogen concentration and a low CO concentration is produced. It is possible to
【００１４】ジメチルエーテルと水（水蒸気）とから
は、以下の反応によって、水素とＣＯを生成する。
ＣＨ3ＯＣＨ3＋Ｈ2Ｏ→２ＣＯ＋４Ｈ2 ・・・・（１）
従来は、メタネーション反応を抑制するために、７００
℃付近で行っていたが、本発明では、メタネーション反
応が少ない触媒を用いるので、４５０℃またはその付近
の低温で実施することができる。また、該温度で、次の
ＣＯシフト反応も同時に進行する。
ＣＯ＋Ｈ2Ｏ→ＣＯ2＋Ｈ2 ・・・・・（２）Hydrogen and CO are produced from dimethyl ether and water (steam) by the following reaction. CH 3 OCH 3 + H 2 O → 2CO + 4H 2 ... (1) Conventionally, in order to suppress the methanation reaction, 700
Although it was carried out at around 0 ° C., in the present invention, since a catalyst with less methanation reaction is used, it can be carried out at a low temperature of at or around 450 ° C. Further, at the temperature, the next CO shift reaction also proceeds at the same time. CO + H 2 O → CO 2 + H 2 (2)
【００１５】さらに、本発明に係るジメチルエーテル改
質方法では、ジメチルエーテルに対し、水と酸素（空
気）を加え、部分酸化反応も生じさせるようにすること
ができる。部分酸化反応をさらに適量に併発することに
よりオートサーマル反応として実施することができる。Furthermore, in the dimethyl ether reforming method according to the present invention, water and oxygen (air) can be added to dimethyl ether to cause a partial oxidation reaction. The partial oxidation reaction can be carried out as an autothermal reaction by further concurrently generating an appropriate amount.
【００１６】[0016]
【実施例】実施例１（触媒の調製）
（触媒１の調製）担体として比表面積１５０ｍ2／ｇの
γ型アルミナ粉末（以下γ−Ａｌ2Ｏ3（γアルミナ）と
もいう）を蒸発皿に入れ、塩化白金酸水溶液をγ−Ａｌ
2Ｏ3に滴下し、１００℃のホットプレート上にて滴下し
た水分を蒸発させた。粉末を攪拌させながら均一に白金
が担持されるようにし、このような含浸法にて担体に対
して１重量％の白金（Ｐｔ）を担持した。上記γ−Ａｌ
2Ｏ3担持Ｐｔ触媒粉末を１２０℃で１２時間乾燥させた
後、５５０℃で５時間空気雰囲気下にて焼成を行い、粉
末触媒成分１を得た。Example 1 (Preparation of catalyst) (Preparation of catalyst 1) γ-type alumina powder (hereinafter also referred to as γ-Al 2 O 3 (γ-alumina)) having a specific surface area of 150 m 2 / g was used as a carrier in an evaporation dish. Put chloroplatinic acid aqueous solution into γ-Al
2 O 3 was dropped, and the dropped water was evaporated on a hot plate at 100 ° C. While stirring the powder, platinum was uniformly loaded, and 1% by weight of platinum (Pt) was loaded on the carrier by such an impregnation method. Γ-Al
The 2 O 3 -supported Pt catalyst powder was dried at 120 ° C. for 12 hours and then calcined at 550 ° C. for 5 hours in an air atmosphere to obtain a powder catalyst component 1.
【００１７】また、硝酸銅、硝酸亜鉛、硝酸アルミニウ
ムを［Ｃｕ：Ｚｎ：Ａｌ＝５０：４０：１０（原子
比）］の割合で水に溶かし、０．０１モル／Ｌ溶液の酸
溶液（＝Ａ溶液）を得た。さらに、アルカリ溶液として
炭酸ナトリウム水溶液（＝Ｂ溶液）０．０１モル／Ｌ溶
液を調製した。Ａ溶液とＢ溶液を同時に別の容器にｐＨ
７の中性を一定に保ちながら注ぎ、４０℃において中和
沈殿を生成させた。Further, copper nitrate, zinc nitrate, and aluminum nitrate are dissolved in water in a ratio of [Cu: Zn: Al = 50: 40: 10 (atomic ratio)], and a 0.01 mol / L solution of an acid solution (= A solution) was obtained. Furthermore, a 0.01 mol / L solution of an aqueous sodium carbonate solution (= B solution) was prepared as an alkaline solution. PH of solution A and solution B in different containers at the same time
7 was poured while keeping the neutrality constant, and a neutralized precipitate was formed at 40 ° C.
【００１８】次に、沈殿物溶液を３時間熟成させなが
ら、洗浄濾過を行い、１１０℃で１２時間乾燥し、その
後、３００℃で５時間、空気雰囲気にて焼成を行い、粉
末触媒成分２を得た。粉末触媒成分１と粉末触媒成分２
を重量比にて１：１にてサンプリングし、めのう乳鉢に
て粉末混合を２時間行った。この場合各々の粉末成分は
５０μｍ以下になり、２つの混合物の粉末を得た。つぎ
にこの混合物に、にアルミナゾルバインダー２％と水を
添加して、３ｍｍφの粒状触媒を成型したのち、４００
℃で５時間焼成した。本粒状触媒を触媒１とした。Next, while aging the precipitate solution for 3 hours, it is washed and filtered, dried at 110 ° C. for 12 hours, and then calcined at 300 ° C. for 5 hours in an air atmosphere to obtain powder catalyst component 2. Obtained. Powder catalyst component 1 and powder catalyst component 2
Was sampled at a weight ratio of 1: 1 and powder mixing was carried out for 2 hours in an agate mortar. In this case, each powder component was 50 μm or less, and powders of two mixtures were obtained. Next, 2% of alumina sol binder and water were added to this mixture to mold a 3 mmφ granular catalyst, and then 400
Calcination was carried out for 5 hours. This granular catalyst was designated as catalyst 1.
【００１９】（触媒２〜６の調製）上記触媒１の粉末触
媒成分２の調製法において、Ａ溶液の調製において硝酸
銅の代わりに、硝酸クロム、硝酸鉄を同一の原子比にて
調製し、同様な方法により、粉末触媒成分３（Ｃｒ：Ｚ
ｎ：Ａｌ＝５０：４０：１０…原子比）、粉末触媒成分
４（Ｆｅ：Ｚｎ：Ａｌ＝５０：４０：１０…原子比）を
得た。さらに、Ａ溶液の調製法において、硝酸銅と硝酸
アルミニウムの代わりに、硝酸クロムまたは硝酸鉄を添
加し、Ｃｒ：Ｚｎ＝５０：５０（原子比）、Ｆｅ：Ｚｎ
＝５０：５０（原子比）を上記と同様な方法で得、粉末
触媒成分５、６を得た。粉末触媒成分１と粉末触媒成分
３〜６を、触媒１と同様にに粉砕混合及び粒状成型し、
触媒２〜５を得た。(Preparation of Catalysts 2 to 6) In the preparation method of the powder catalyst component 2 of the above catalyst 1, instead of copper nitrate in the preparation of the solution A, chromium nitrate and iron nitrate were prepared at the same atomic ratio, By the same method, powder catalyst component 3 (Cr: Z
n: Al = 50: 40: 10 ... atomic ratio), and powder catalyst component 4 (Fe: Zn: Al = 50: 40: 10 ... atomic ratio) was obtained. Further, in the method for preparing the solution A, chromium nitrate or iron nitrate is added instead of copper nitrate and aluminum nitrate, and Cr: Zn = 50: 50 (atomic ratio), Fe: Zn.
= 50: 50 (atomic ratio) was obtained in the same manner as above to obtain powder catalyst components 5 and 6. The powder catalyst component 1 and the powder catalyst components 3 to 6 are pulverized, mixed and granulated in the same manner as the catalyst 1.
Catalysts 2-5 were obtained.
【００２０】（触媒６、７の調製）上記触媒１の調製法
において、粉末触媒成分１（Ｐｔ／γ−Ａｌ2Ｏ3）に硝
酸銅と硝酸亜鉛と硝酸アルミニウム水溶液（溶液７）、
または硝酸クロム、硝酸亜鉛の水溶液（溶液８）を各々
含浸させ、攪拌して蒸発乾固後に３００℃で５時間焼成
を行い、粉末触媒６、７を得た。粉末触媒成分１に対す
る担持量は、粉末触媒６はＣｕ：５重量％、Ｚｎ：４重
量％、Ａｌ：１重量％、粉末触媒７は、Ｃｒ：５重量
％、Ｚｎ：５重量％であった。この粉末は触媒１と同様
と同様な方法に粒状触媒とし、触媒６、７を得た。(Preparation of catalysts 6 and 7) In the preparation method of the catalyst 1, the powder catalyst component 1 (Pt / γ-Al 2 O 3 ) was added to copper nitrate, zinc nitrate and an aqueous solution of aluminum nitrate (solution 7).
Alternatively, each of them was impregnated with an aqueous solution of chromium nitrate and zinc nitrate (solution 8), stirred, evaporated to dryness, and then baked at 300 ° C. for 5 hours to obtain powder catalysts 6 and 7. The supported amounts of the powder catalyst 6 on the powder catalyst component 1 were Cu: 5% by weight, Zn: 4% by weight, Al: 1% by weight, and the powder catalyst 7 was Cr: 5% by weight, Zn: 5% by weight. . This powder was made into a granular catalyst in the same manner as in Catalyst 1 to obtain Catalysts 6 and 7.
【００２１】（比較触媒１、２、３）上記触媒１の調製
法において、粉末触媒成分１のγ−Ａｌ2Ｏ3に担持する
触媒として、塩化白金酸の代わりに、塩化ルテニウム、
塩化ニッケルの各水溶液を各々含浸して粉末触媒化し、
各々金属でＲｕ：１％、Ｎｉ：１２％を担持させた。本
粉末触媒成分を比較粉末１、比較粉末２とした。さら
に、触媒１と同様な方法で３ｍｍφの粒状触媒を調製
し、比較触媒１、 ２を得た。さらに、粉末触媒成分１
のみにおいて、触媒１と同様に粒状触媒を調製し、比較
触媒３を得た。(Comparative Catalysts 1, 2, 3) In the preparation method of the above-mentioned catalyst 1, ruthenium chloride, instead of chloroplatinic acid, was used as the catalyst supported on γ-Al 2 O 3 of powder catalyst component 1.
Impregnated with each aqueous solution of nickel chloride to form a powder catalyst,
Ru: 1% and Ni: 12% were supported by the respective metals. The present powder catalyst components were designated as comparative powder 1 and comparative powder 2. Further, a 3 mmφ granular catalyst was prepared in the same manner as the catalyst 1, and comparative catalysts 1 and 2 were obtained. Furthermore, powder catalyst component 1
In the same manner, a granular catalyst was prepared in the same manner as catalyst 1 to obtain comparative catalyst 3.
【００２２】実施例２
（ジメチルエーテル水蒸気改質試験：反応条件１）上記
触媒１〜７、比較触媒１、２、３を用いて、以下の条件
においてジメチルエーテルの水蒸気改質試験を行った。
原料はジメチルエーテル（ＣＨ3ＯＣＨ3）と水蒸気、空
気を［水蒸気／ジメチルエーテル（Ｃ１ベース）］＝
４．０（モル比）の条件で混合させ、２０ｃｃ充填した
触媒層（３ｍｍφペレット充填：円筒形：径２６ｍｍ
φ、長さ２５ｍｍ）を触媒層平均温度４５０℃、５５０
℃に保持し、上記原料をＧＨＳＶ５０００ｈ-1（流量１
００Ｌ／ｈ）で供給した。Example 2 (Dimethyl ether steam reforming test: reaction condition 1) Using the above catalysts 1 to 7 and comparative catalysts 1, 2 and 3, a steam reforming test of dimethyl ether was conducted under the following conditions.
The raw materials are dimethyl ether (CH 3 OCH 3 ), steam, and air [steam / dimethyl ether (C1 base)] =
A catalyst layer (3 mmφ pellet filling: cylindrical: diameter 26 mm, which was mixed under conditions of 4.0 (molar ratio) and filled with 20 cc
φ, length 25 mm) is the catalyst layer average temperature 450 ℃, 550
The above raw materials were maintained at GHSV 5000h -1 (flow rate 1
00 L / h).
【００２３】反応管出口ガス組成の炭化水素はガスクロ
マトグラムで分析した。ジメチルエーテル転化率（η）
は＝［１−出口ジメチルエーテル／入口ジメチルエーテ
ル（Ｃ１ベース）］×１００にて求めた。また、生成物
の水素濃度、ＣＯ濃度、ＣＨ 4濃度（いずれもドライベ
ース）もガスクロマトグラフ法にて求めた。上記触媒の
活性評価試験結果を表１に示す。Hydrocarbons having a gas composition at the outlet of the reaction tube are
It was analyzed by a matogram. Dimethyl ether conversion (η)
== [1-outlet dimethyl ether / inlet dimethyl ether
(C1 base)] × 100. Also the product
Hydrogen concentration, CO concentration, CH FourConcentration (Dry
Was also determined by gas chromatography. Of the above catalyst
The results of the activity evaluation test are shown in Table 1.
【００２４】[0024]
【表１】 [Table 1]
【００２５】上記結果より、本発明に係る触媒１〜７は
いずれの反応温度においてもジメチルエーテル転化率９
０％以上、水素濃度６０％以上、ＣＨ4副生率５％以
下、ＣＯ濃度７％以下となり、低温で高効率にて水素を
製造でき、ＣＨ4やＣＯの副生物が少ないことを確認し
た。しかし、比較触媒１、２は何れも５５０℃以下にお
いてＣＨ4の副生が多く、さらに、比較触媒３はＣＯの
副生が多いことがわかる。なお、本発明の触媒１〜７に
おいて、十分な水素製造活性を有し、かつＣＨ4および
ＣＯが少ない理由として、メタネーション作用が低いＰ
ｔを活性金属に用いた粉末触媒成分１とＣＯシフト活性
を有するＢ成分のハイブリッド作用によると考えられ
る。From the above results, the catalysts 1 to 7 according to the present invention have a dimethyl ether conversion of 9 at any reaction temperature.
0% or more, hydrogen concentration 60% or more, CH 4 byproduct rate 5% or less, CO concentration 7% or less, it was confirmed that hydrogen can be produced with high efficiency at low temperature, and CH 4 and CO byproducts are small. . However, it can be seen that the comparative catalysts 1 and 2 both have a large amount of CH 4 by- products at 550 ° C. or lower, and the comparative catalyst 3 has a large amount of CO-by-products. In addition, in the catalysts 1 to 7 of the present invention, the reason for having sufficient hydrogen production activity and having a small amount of CH 4 and CO is P having a low methanation action.
It is considered that this is due to the hybrid action of the powder catalyst component 1 using t as an active metal and the component B having CO shift activity.
【００２６】実施例３
上記触媒１を用いて、実施例２で行った水蒸気改質条件
において、空気／ジメチルエーテル（Ｃ１ベース）：
１．５、２．５（モル比）の空気を供給し，オートサー
マル条件において活性評価を行った。さらに、水蒸気／
ジメチルエーテル（Ｃ１ベース）モル比の影響について
も検討を行った。表２に温度触媒温度４５０℃、５５０
℃の試験条件と活性評価結果を示す（Ｒｕｎ番号１１〜
１５）。Example 3 Using the above catalyst 1, under the steam reforming conditions carried out in Example 2, air / dimethyl ether (C1 based):
Air was supplied at 1.5 and 2.5 (molar ratio), and the activity was evaluated under autothermal conditions. In addition, steam /
The influence of the dimethyl ether (C1 base) molar ratio was also examined. Table 2 shows the temperature catalyst temperature 450 ° C., 550
C test conditions and activity evaluation results are shown (Run number 11 to
15).
【００２７】[0027]
【表２】 [Table 2]
【００２８】表２に示す試験結果より、本発明に係る触
媒１を用いて、空気を添加したオートサーマル条件や部
分酸化条件、および種々の空気、水蒸気分圧条件におい
ても４５０℃程度で十分なジメチルエーテル分解活性を
有し、さらにＣＨ4、ＣＯの副生もないことを確認し
た。From the test results shown in Table 2, using the catalyst 1 of the present invention, about 450 ° C. is sufficient even under autothermal conditions and partial oxidation conditions in which air is added, and various air and steam partial pressure conditions. It was confirmed that the compound has a dimethyl ether decomposition activity and that CH 4 and CO are not by-products.
【００２９】[0029]
【発明の効果】上記したところから明らかなように、本
発明によれば、ジメチルエーテルの改質反応と、ＣＯシ
フト反応とを効率的に単一の触媒で、しかも低温で行う
ことを可能とするジメチルエーテル改質触媒およびジメ
チルエーテルの改質方法が提供される。As is apparent from the above, according to the present invention, it is possible to efficiently carry out the dimethyl ether reforming reaction and the CO shift reaction with a single catalyst and at a low temperature. A dimethyl ether reforming catalyst and a method for reforming dimethyl ether are provided.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 渡辺 悟 広島県広島市西区観音新町四丁目６番22号 三菱重工業株式会社広島研究所内 (72)発明者 米村 将直 広島県広島市西区観音新町四丁目６番22号 三菱重工業株式会社広島研究所内 Ｆターム(参考） 4G040 EA01 EA06 EB32 EC01 EC02 EC03 EC05 4G069 AA03 AA08 BA01A BA01B BA04A BA05A BA07A BA45A BB02A BB02B BC16A BC16B BC31A BC31B BC35A BC35B BC58A BC58B BC66A BC66B BC75A BC75B CB81 CC25 EA02Y EB18Y EC27 EC28 FA01 FA02 FB07 FB14 FB19 ZA01A ZA37A ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Satoru Watanabe 4-6-22 Kannon Shinmachi, Nishi-ku, Hiroshima City, Hiroshima Prefecture Mitsubishi Heavy Industries Ltd. Hiroshima Research Center (72) Inventor Masanao Yonemura 4-6-22 Kannon Shinmachi, Nishi-ku, Hiroshima City, Hiroshima Prefecture Mitsubishi Heavy Industries Ltd. Hiroshima Research Center F term (reference) 4G040 EA01 EA06 EB32 EC01 EC02 EC03 EC05 4G069 AA03 AA08 BA01A BA01B BA04A BA05A BA07A BA45A BB02A BB02B BC16A BC16B BC31A BC31B BC35A BC35B BC58A BC58B BC66A BC66B BC75A BC75B CB81 CC25 EA02Y EB18Y EC27 EC28 FA01 FA02 FB07 FB14 FB19 ZA01A ZA37A
Claims (9)
めのジメチルエーテル改質反応のための改質触媒成分
と、副生するＣＯを除去するＣＯシフト反応のためのＣ
Ｏシフト触媒成分とを含むジメチルエーテル改質触媒。1. A reforming catalyst component for a dimethyl ether reforming reaction for obtaining hydrogen from dimethyl ether and water, and C for a CO shift reaction for removing CO as a by-product.
A dimethyl ether reforming catalyst containing an O shift catalyst component.
有する担体に担持して成る改質触媒成分であり、上記Ｃ
Ｏシフト触媒成分がＣｕ、Ｚｎ、Ｃｒ、ＦｅおよびＡｌ
の各々の酸化物から成るグループから選択された少なく
とも2種以上の複合酸化物であることを特徴とする請求
項１のジメチルエーテル改質触媒。2. The reforming catalyst component is a reforming catalyst component comprising platinum supported on a carrier having a solid acid function, and the above C
O shift catalyst component is Cu, Zn, Cr, Fe and Al
The dimethyl ether reforming catalyst according to claim 1, which is a composite oxide of at least two or more kinds selected from the group consisting of the respective oxides.
成分とを粉末混合して成ることを特徴とする請求項１ま
たは２のジメチルエーテル改質触媒。3. The dimethyl ether reforming catalyst according to claim 1, wherein the reforming catalyst component and the CO shift catalyst component are powder-mixed.
フト触媒成分を担持して成ることを特徴とするジメチル
エーテル改質触媒。4. A dimethyl ether reforming catalyst comprising a powder of the reforming catalyst component of claim 2 and a CO shift catalyst component supported on the powder.
2Ｏ3、チタニア、ＺｒＯ2、ゼオライトおよびメタロシ
リケートから成るグループから選ばれた少なくとも1種
の担体であることを特徴とする請求項２〜４のいずれか
のジメチルエーテル改質触媒。5. The carrier having a solid acid action is γ-Al.
The dimethyl ether reforming catalyst according to claim 2, which is at least one carrier selected from the group consisting of 2 O 3 , titania, ZrO 2 , zeolite and metallosilicate.
が、ピリジン吸着量で０．１ｍｍｏｌ／ｇ以上であるこ
とを特徴とする請求項２〜５のいずれかのジメチルエー
テル改質触媒。6. The dimethyl ether reforming catalyst according to claim 2, wherein the solid acid amount of the carrier having a solid acid action is 0.1 mmol / g or more in terms of pyridine adsorption amount.
テル改質触媒を用いてジメチルエーテルを改質すること
を特徴とするジメチルエーテル改質方法。7. A method for reforming dimethyl ether, which comprises reforming dimethyl ether using the catalyst for reforming dimethyl ether according to claim 1.
え、部分酸化反応も生じさせるようにしたことを特徴と
する請求項７のジメチルエーテル改質方法。8. The method for reforming dimethyl ether according to claim 7, wherein water and oxygen are added to dimethyl ether to cause a partial oxidation reaction.
おいて、ジメチルエーテル改質反応と上記部分酸化反応
とによって、オートサーマル反応を行うようにしたこと
を特徴とするジメチルエーテル改質方法。9. The dimethyl ether reforming method according to claim 8, wherein an autothermal reaction is performed by the dimethyl ether reforming reaction and the partial oxidation reaction.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004087566A1 (en) * | 2003-04-01 | 2004-10-14 | Haldor Topsøe A/S | Process for the preparation of a hydrogen-rich stream |
| JP2005095738A (en) * | 2003-09-24 | 2005-04-14 | Mitsubishi Gas Chem Co Inc | Catalyst for steam reforming of dimethyl ether having solid acid-containing coating layer |
| CN1331731C (en) * | 2003-04-01 | 2007-08-15 | 赫多特普索化工设备公司 | Process for the preparation of a hydrogen-rich stream. |
| JP2019193913A (en) * | 2018-05-01 | 2019-11-07 | 公立大学法人首都大学東京 | Hydrogen manufacturing catalyst |
-
2001
- 2001-08-07 JP JP2001238657A patent/JP4175452B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004087566A1 (en) * | 2003-04-01 | 2004-10-14 | Haldor Topsøe A/S | Process for the preparation of a hydrogen-rich stream |
| CN1331731C (en) * | 2003-04-01 | 2007-08-15 | 赫多特普索化工设备公司 | Process for the preparation of a hydrogen-rich stream. |
| US7517374B2 (en) | 2003-04-01 | 2009-04-14 | Haldor Topsoe A/S | Process for the preparation of a hydrogen-rich stream |
| JP2005095738A (en) * | 2003-09-24 | 2005-04-14 | Mitsubishi Gas Chem Co Inc | Catalyst for steam reforming of dimethyl ether having solid acid-containing coating layer |
| JP2019193913A (en) * | 2018-05-01 | 2019-11-07 | 公立大学法人首都大学東京 | Hydrogen manufacturing catalyst |
| JP7257019B2 (en) | 2018-05-01 | 2023-04-13 | 東京都公立大学法人 | Hydrogen production catalyst |
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