JP4015390B2 - Hydrocarbon reforming catalyst and method for producing the same - Google Patents
Hydrocarbon reforming catalyst and method for producing the same Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明は、ガソリン、ナフサ、灯油、軽油等の炭化水素化合物を改質して水素を製造する際に使用される炭化水素改質触媒及びその製造方法に関する。
【０００２】
【従来の技術】
周知の如く、炭化水素を水蒸気によって改質する反応は、合成ガスあるいは水素を製造するための反応として知られている。従来、この反応には、一般に、Ｎｉ／Ａｌ２Ｏ３系触媒が用いられているが、炭素の析出（コーキング）が起こるという問題があった。
【０００３】
そこで、このコーキングを回避するために、上記反応にはＲｕ系触媒が提案されている（特開平７−８８３７６等）。しかし、Ｒｕ系触媒は還元状態で高性能を発揮するため、還元処理が必要とされる、また、Ｒｕ系触媒は容易に酸化されるため、大気暴露ができない等の使用制約がある。更に、従来のＲｕ系触媒は反応選択性向上のため、ＣａＯ、ＭｇＯ等の塩基性物質を混合するが、水蒸気改質時に徐々に溶出するため性能低下の一因と考えられている。更には、家庭用固体高分子型燃料電池（ＰＥＦＣ）用のプラント等での使用を目的とした場合、反応温度が６５０〜８５０℃と高温なため安全性面で不安があるとともに、起動時間がかかるという問題があった。
【０００４】
【発明が解決しようとする課題】
本発明は上記事情を考慮してなされたもので、耐酸化性を向上し使用制限を軽減できるとともに、担体塩基性付与効果により固体酸量を制御して反応選択性を維持し、耐久性向上を実現しうる炭化水素改質触媒を提供することを目的とする。
【０００５】
また、本発明は、４００〜６５０℃程度で炭化水素化合物を改質することができ、従来と比べ短時間起動を実現できると共に安全性の点で優れた炭化水素改質触媒の製造方法を提供することを目的とする。
【０００６】
【課題を解決するための手段】
本願第１の発明は、液系炭化水素化合物の改質により水素を製造する際に使用される炭化水素改質触媒において、二酸化ジルコニウムに酸化亜鉛あるいはアルミナ，シリカ，チタニア，セリアのいずれかを複合化して得られる塩基性担体に、アルコール還元法によってルテニウムを白金、パラジウム、ロジウムのいずれか一つ以上と合金化することにより得られる合金を活性種として含有させたことを特徴とする炭化水素改質触媒である。
【０００７】
本願第２の発明は、液化系炭化水素化合物の改質により水素を製造する際に使用される炭化水素改質触媒を製造する方法において、塩基性担体の前駆体となるハイドロタルサイト構造体を調製する工程と、前記ハイドロタルサイト構造体にアルコール還元法により得られるルテニウムと白金、パラジウム、ロジウムのいずれか一つ以上と合金化された合金活性種を担持させる工程と、前記ハイドロタルサイト構造体にルテニウム合金活性種が担持したものを焼成する工程とを具備し、塩基性担体にルテニウム合金活性種が担持された触媒を得ることを特徴とする炭化水素改質触媒の製造方法である。
【０００８】
【発明の実施の形態】
以下、本発明の炭化水素改質触媒及びその製造方法について更に詳しく説明する。本発明の炭化水素改質触媒において、担体としては二酸化ジルコニウム（ＺｒＯ２）に酸化亜鉛（ＺｎＯ）あるいはアルミナ（Ａｌ２Ｏ３）,シリカ（ＳｉＯ２）,チタニア（ＴｉＯ２）,セリア（ＣｅＯ２）等の酸化物を複合化した塩基性担体を用いる。これにより、担体固体酸量を制御し、高反応選択性触媒として長時間耐久性のある担体にすることができる。また、活性種としては、ルテニウム（Ｒｕ）にＰｄ，Ｐｔ等の貴金属をアルコール還元法により合金化して得られた合金を用いる。これにより、常にＲｕ金属状態を保ち、従来のようなＲｕ系触媒のように使用制限を軽減できるとともに、長時間耐久性のある活性種にすることができる。従って、本発明に係る炭化水素改質触媒によれば、耐酸化性が向上し、使用制限が軽減されると共に、固体酸量を制御することで反応選択性を維持しコーキングを抑制することで、耐久性向上を実現することができる。
【０００９】
本発明方法において、前記塩基性担体はハイドロタルサイト構造体を前駆体として調製した担体を用いることが好ましい。ここで、前駆体のハイドロタルサイト構造体とは、例えばジルコニアと亜鉛の組み合わせでは、Ｚｒ（ＣＯ３）ｘ（ＯＨ）ｙ・Ｚｎ（ＣＯ３）ｚ（ＯＨ）ｓのような示性式を持つ物質を意味する。これらを焼成することで、ＺｒＺｎＯ３の酸化物がアモルファス状に高表面積酸化物状態を維持する。例えば、ＺｒＯ（ＮＯ３）２とＺｎ（ＮＯ３）２を混合して焼成しただけでは焼成後の酸化物の表面積はもちろんジルコニアと亜鉛の混合状態も低い。
【００１０】
本発明方法によれば、４００〜６５０℃程度で炭化水素化合物を改質できるので、家庭用ＰＥＦＣ用のプラント等での使用を目的とした場合、従来と比べ短時間での起動を実現できるとともに、安全性にも優れた触媒を得ることができる。
【００１１】
また、ハイドロタルサイト構造体を前駆体として調製し、前記ハイドロタルサイト構造体を焼成することにより、二酸化ジルコニウムに酸化亜鉛あるいはアルミナ，シリカ，チタニア，セリア等の酸化物を塩基性の複合酸化物にでき、更に高表面積化が可能である。
【００１２】
【実施例】
以下、本発明の実施例について説明する。なお、下記実施例で述べる材料や数値等は一例を示すもので、本発明の権利範囲はこれにより限定されるものではない。
【００１３】
（実施例）
（１）まず、硝酸Ｒｕ溶液からＲｕ３ｇ相当量の溶液と硝酸Ｐｄ溶液からＲｕに対し同モル量のＰｄ３．１５ｇを秤量し、（１Ｎ）ＮａＯＨａｑで中和した。なお、Ｒｕは０．１〜１０ｗｔ％の範囲であればよく、Ｐｄの量はＲｕ量に対して０．１〜１０倍のモル量であればよい。また、Ｐｄ以外にも、Ｐｔ（塩化白金酸溶液を用いる）やＲｈ（硝酸ロジウム溶液）を用いてもよい。
【００１４】
（２）次に、（０．５Ｎ）Ｎａ２ＣＯ３ａｑを３．５Ｌ（リットル）上記（１）の溶液に加えた。なお、Ｎａ２ＣＯ３ａｑの濃度は０．０１〜２０Ｎの範囲でもよい。
（３）次に、硝酸亜鉛６水和物（Ｚｎ（ＮＯ３）２・６Ｈ２Ｏ）１３６．４５ｇとオキシ硝酸ジルコニル（ＺｒＯ（ＮＯ３）２・２Ｈ２Ｏ）１２２．５８ｇを蒸留水に溶解し、５００ｍｌに調製した硝酸塩溶液を上記（２）の溶液に滴下した。なお、硝酸亜鉛６水和物とオキシ硝酸ジルコニルは１：１のモル比で加えているが、０．１〜１０：０．１〜１０のモル比で加えても良い。
【００１５】
（４）次に、滴下終了後、液温を６０℃に昇温し、上記(３)の溶液にアルコール８００ｇを徐々に加え、２４時間保温及び攪拌すると、徐々に還元が進み微粒子のＲｕ−Ｐｄ合金が生成した。なお、液温は４０〜８０℃の範囲であればよい。その後、沈殿物を濾過し濾液がｐＨ＝７になるまで蒸留水で洗浄した。
【００１６】
（５）洗浄後、１１０℃で１２時間乾燥し、粉砕後、５００℃で３時間焼成した。なお、焼成温度は４００〜８００℃の範囲で、焼成時間１〜１０ｈの範囲でればよい。
【００１７】
以上の操作により、Ｒｕ−Ｐｄ／ＺｎＯ−ＺｒＯ２触媒が１００ｇ調製できる。調製された触媒の固体酸量の評価は、特に本触媒の場合、塩基性を示す為、ＣＯ２を用いた昇温脱離法により評価する。また、ハイドロタルサイト構造を前駆体とした担体調製法を用い、更にアルコール還元法を用いることにより、担体の高表面積を維持したまま、活性種であるＲｕ−Ｐｄ合金を坦持できるため、高表面積が生成し触媒活性が高い。
【００１８】
（比較例１）
（１）まず、（０．５Ｎ）Ｎａ２ＣＯ３ａｑを３．５Ｌ丸底フラスコに加えた。なお、濃度は０．０１〜２０の範囲でもよい。
（２）次に、硝酸亜鉛６水和物（Ｚｎ（ＮＯ３）２・６Ｈ２Ｏ）１３６．４５ｇとオキシ硝酸ジルコニル（ＺｒＯ（ＮＯ３）２・２Ｈ２Ｏ）１２２．５８ｇを蒸留水に溶解し、５００ｍｌに調製した硝酸塩溶液を上記（１）の溶液に滴下した。なお、硝酸亜鉛６水和物とオキシ硝酸ジルコニルは１：１のモル比で加えているが、０．１〜１０：０．１〜１０のモル比で加えても良い。
【００１９】
（３）滴下終了後、液温を４０℃で１２時間保温及び攪拌により沈殿物を熟成させた。その後、沈殿物を濾過し、濾液がｐＨ＝７になるまで蒸留水で洗浄した。
（４）洗浄後、１１０℃で１２時間乾燥し、粉砕後、５００℃で３時間焼成した。なお、焼成温度は４００〜８００℃の範囲で、焼成時間１〜１０時間の範囲であればよい。
【００２０】
（５）次に、硝酸Ｒｕ溶液（Ｒｕ３ｇ相当量の溶液）と硝酸Ｐｄ溶液（Ｒｕに対し同モル量の３．１５ｇ相当量の溶液を混合し、その溶液を（１Ｎ）ＮａＯＨａｑで中和した。なお、Ｒｕは０．１〜１０ｗｔ％の範囲であればよく、Ｐｄの量はＲｕ量に対して０．１〜１０倍のモル量であればよい。また、Ｐｄ以外にも、Ｐｔ（塩化白金酸溶液を用いる）やＲｈ（硝酸ロジウム溶液）を用いてもよい。
【００２１】
（６）次に、上記(５）の溶液を上記（４）で得られた粉体に混ぜ、スラリー状の液体を１６０℃のホットプレート上で蒸発乾固させた。なお、蒸発乾固の温度は１００〜２５０℃の範囲でもよい。
（７）次に、上記（６）で得られた粉体を蒸留水で濾過洗浄し、Ｎａイオンが１ｐｐｍ以下で濾液がｐＨ＝７になるまで洗浄した後、１１０℃で１２時間乾燥し、粉砕後５００℃で３時間焼成した。ここで、焼成温度は４００〜８００℃の範囲、焼成時間は１〜１０時間の範囲であればよい。
以上の操作により、Ｒｕ−Ｐｄ／ＺｎＯ−ＺｒＯ２触媒が１００ｇ調製できた。
【００２２】
（比較例２）
（１）まず、（０．５Ｎ）Ｎａ２ＣＯ３ａｑを３．５Ｌ丸底フラスコに加えた。なお、濃度は０．０１〜２０の範囲でもよい。
（２）次に、硝酸亜鉛６水和物（Ｚｎ（ＮＯ３）２・６Ｈ２Ｏ）１３６．４５ｇとオキシ硝酸ジルコニル（ＺｒＯ（ＮＯ３）２・２Ｈ２Ｏ）１２２．５８ｇを蒸留水に溶解し、５００ｍｌに調製した硝酸塩溶液を上記（１）の溶液に滴下した。なお、硝酸亜鉛６水和物とオキシ硝酸ジルコニルは１：１のモル比で加えているが、０．１〜１０：０．１〜１０のモル比で加えてもよい。
【００２３】
（３）滴下終了後、液温を４０℃で１２時間保温及び攪拌により沈殿物を熟成させた。その後、沈殿物を濾過し、濾液がｐＨ＝７になるまで蒸留水で洗浄した。
（４）洗浄後、１１０℃で１２時間乾燥し、粉砕後、５００℃で３時間焼成した。なお、焼成温度は４００〜８００℃の範囲で、焼成時間１〜１０時間の範囲であればよい。
【００２４】
（５）次に、硝酸Ｒｕ溶液（Ｒｕ３ｇ相当量の溶液）と硝酸Ｐｄ溶液（Ｒｕに対し同モル量の３．１５ｇ相当量の溶液を混合し、上記（４）で得られた粉体に混ぜ、スラリー状の液体を１６０℃のホットプレートで蒸発乾固させた。なお、Ｒｕは０．１〜１０ｗｔ％の範囲であればよく、Ｐｄの量はＲｕ量に対して０．１〜１０倍のモル量であればよい。また、Ｐｄ以外にも、Ｐｔ（塩化白金酸溶液を用いる）やＲｈ（硝酸ロジウム溶液）を用いてもよく、ホットプレートの温度は１００〜２５０℃の範囲で蒸発乾固させてもよい。
【００２５】
（６）次に、上記（５）で得られた粉体を蒸留水で濾過洗浄し、濾液がｐＨ＝７になるまで洗浄した後、１１０℃で１２時間乾燥後、粉砕し５００℃で３時間焼成した。ここで、焼成温度は４００〜８００℃の範囲、焼成時間は１〜１０時間の範囲であればよい。
以上の操作により、Ｒｕ−Ｐｄ／ＺｎＯ−ＺｒＯ２触媒が１００ｇ調製できた。
【００２６】
上記各実施例と比較例１，２により得られた触媒の物性(比表面積、塩基性度）は、下記表１のとおりである。
【００２７】
【表１】
また、上記実施例１により得られた触媒及び従来触媒の温度（℃）と転化率（％）との関係を調べたところ、図１に示す結果が得られた。また、同様にして、温度を一定（７５０℃）にして時間（ｈ）と転化率（％）との関係を調べたところ、図２に示す結果が得られた。図１より本発明の触媒が従来の触媒に比べて温度変化に対する（炭化水素から水素への）転化率が高いことが明らかである。また、図２より、従来の場合、時間の経過と共に転化率が低下するのに対し、本発明の時間が経過しても転化率がほとんど低下しないことが明らかである。以上より、本発明が従来と比べ優れていることが明らかである。
【００２９】
【発明の効果】
以上詳述したように本発明によれば、二酸化ジルコニウムに酸化亜鉛あるいはアルミナ，シリカ，チタニア，セリアのいずれかを複合化して得られる塩基性担体に、アルコール還元法によってルテニウムを白金、パラジウム、ロジウムのいずれか一つ以上と合金化することにより得られる合金を活性種として含有させたことにより、耐酸化性を向上し、使用制限を軽減できるとともに、固体酸素量を制御して反応選択性を維持しコーキング抑制することで、耐久性向上を実現しうる炭化水素改質触媒を提供できる。
【００３０】
また、本発明によれば、液化系炭化水素化合物の改質により水素を製造する際に使用される炭化水素改質触媒を製造する方法において、塩基性担体の前駆体となるハイドロタルサイト構造体を調製する工程と、前記ハイドロタルサイト構造体にアルコール還元法により得られるルテニウムと白金、パラジウム、ロジウムのいずれか一つ以上と合金化された合金活性種を担持させる工程と、前記ハイドロタルサイト構造体にルテニウム合金活性種が担持したものを焼成する工程とを具備し、塩基性担体にルテニウム合金活性種が担持された触媒を得ることにより、４００〜６５０℃程度で炭化水素化合物を改質することができ、従来と比べ短時間起動を実現できると共に安全性の点で優れ、特に家庭用ＰＥＦＣ用のプラント等での使用を目的とした場合に有用な炭化水素改質触媒の製造方法を提供できる。
【図面の簡単な説明】
【図１】本発明及び従来の触媒による温度と転化率との関係を示す特性図。
【図２】温度が一定の場合における本発明及び従来の触媒による時間と転化率との関係を示す特性図。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a hydrocarbon reforming catalyst used when hydrogen is produced by reforming a hydrocarbon compound such as gasoline, naphtha, kerosene, and light oil, and a method for producing the same.
[0002]
[Prior art]
As is well known, the reaction of reforming hydrocarbons with steam is known as a reaction for producing synthesis gas or hydrogen. Conventionally, Ni / Al 2 O 3 -based catalysts are generally used for this reaction, but there is a problem that carbon deposition (coking) occurs.
[0003]
In order to avoid this coking, a Ru-based catalyst has been proposed for the above reaction (Japanese Patent Laid-Open No. 7-88376, etc.). However, since the Ru-based catalyst exhibits high performance in a reduced state, a reduction treatment is required, and since the Ru-based catalyst is easily oxidized, there are restrictions on use such that exposure to the atmosphere is not possible. Further, conventional Ru-based catalysts are mixed with basic substances such as CaO and MgO to improve reaction selectivity, but are gradually eluted during steam reforming, which is considered to be a cause of performance degradation. Furthermore, when intended for use in household polymer electrolyte fuel cell (PEFC) plants, etc., the reaction temperature is as high as 650 to 850 ° C., so there are concerns about safety and startup time. There was a problem that it took.
[0004]
[Problems to be solved by the invention]
The present invention has been made in consideration of the above circumstances, and can reduce the use restriction to improve the oxidation resistance, by controlling the amount of solid acid by the support base-imparting effect maintaining the reaction selectivity, durability It aims at providing the hydrocarbon reforming catalyst which can implement | achieve.
[0005]
In addition, the present invention is a method for producing a hydrocarbon reforming catalyst that can reform a hydrocarbon compound at about 400 to 650 ° C., can achieve a shorter start-up time than conventional methods, and is excellent in safety. The purpose is to provide.
[0006]
[Means for Solving the Problems]
The first invention of the present application is a hydrocarbon reforming catalyst used when hydrogen is produced by reforming a liquid hydrocarbon compound. Zirconium dioxide is combined with zinc oxide or any of alumina, silica, titania, and ceria. basic carrier obtained turned into a platinum ruthenium by alcohol reduction method, palladium, hydrocarbons, characterized in that contained as the active species obtained alloy by one or more alloyed either rhodium It is a reforming catalyst.
[0007]
A second invention of the present application relates to a method for producing a hydrocarbon reforming catalyst used when producing hydrogen by reforming a liquefied hydrocarbon compound, wherein a hydrotalcite structure serving as a precursor of a basic support is provided. a step of preparing the hydrotalcite structure ruthenium and platinum obtained by an alcohol reduction method, palladium, a step of carrying any one or more alloyed with the alloy active species rhodium, the hydrotalcite A method for producing a hydrocarbon reforming catalyst, comprising: a step of firing a ruthenium alloy active species supported on a structure, and obtaining a catalyst having a ruthenium alloy active species supported on a basic support. .
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the hydrocarbon reforming catalyst of the present invention and the production method thereof will be described in more detail. In the hydrocarbon reforming catalyst of the present invention, the support is zirconium dioxide (ZrO 2 ), zinc oxide (ZnO), alumina (Al 2 O 3 ), silica (SiO 2 ), titania (TiO 2 ), ceria (CeO 2 ). ) Or the like is used. As a result, the amount of the carrier solid acid can be controlled, and a carrier having a long-term durability as a high reaction selective catalyst can be obtained. As the active species, an alloy obtained by alloying ruthenium (Ru) with a noble metal such as Pd or Pt by an alcohol reduction method is used. As a result, the Ru metal state can always be maintained, the use restriction can be reduced as in the case of a conventional Ru-based catalyst, and the active species can be made durable for a long time. Therefore, according to the hydrocarbon reforming catalyst according to the present invention, the oxidation resistance is improved, the use limitation is reduced, and the reaction selectivity is maintained by controlling the amount of solid acid, thereby suppressing coking. Durability improvement can be realized.
[0009]
In the method of the present invention, the basic carrier is preferably a carrier prepared using a hydrotalcite structure as a precursor. Here, the hydrotalcite structure of the precursor, for example, in the combination of zirconia and zinc, has a formula such as Zr (CO 3 ) x (OH) y · Zn (CO 3 ) z (OH) s. It means the substance you have. By baking these, the oxide of ZrZnO 3 maintains a high surface area oxide state in an amorphous state. For example, if only ZrO (NO 3 ) 2 and Zn (NO 3 ) 2 are mixed and fired, not only the surface area of the oxide after firing but also the mixed state of zirconia and zinc is low.
[0010]
According to the method of the present invention, the hydrocarbon compound can be reformed at about 400 to 650 ° C. Therefore, when it is intended for use in a plant for home PEFC, it can be started in a shorter time than conventional. Thus, a catalyst excellent in safety can be obtained.
[0011]
In addition, by preparing a hydrotalcite structure as a precursor and calcining the hydrotalcite structure, zinc oxide or oxides such as alumina, silica, titania and ceria are converted into basic composite oxides on zirconium dioxide. The surface area can be further increased.
[0012]
【Example】
Examples of the present invention will be described below. In addition, the material, numerical value, etc. which are described in the following Example show an example, and the right range of this invention is not limited by this.
[0013]
(Example)
(1) First, a solution corresponding to 3 g of Ru from a Ru nitrate solution and 3.15 g of Pd of the same molar amount relative to Ru from a Pd nitrate solution were weighed and neutralized with (1N) NaOHaq. In addition, Ru should just be the range of 0.1-10 wt%, and the quantity of Pd should just be a 0.1-10 times molar quantity with respect to Ru quantity. In addition to Pd, Pt (a chloroplatinic acid solution is used) or Rh (rhodium nitrate solution) may be used.
[0014]
(2) Next, (0.5 N) Na 2 CO 3 aq was added to the solution of (1) above in 3.5 L (liter). The concentration of Na 2 CO 3 aq may be in the range of 0.01 to 20N.
(3) Next, 136.45 g of zinc nitrate hexahydrate (Zn (NO 3 ) 2 .6H 2 O) and 122.58 g of zirconyl oxynitrate (ZrO (NO 3 ) 2 .2H 2 O) in distilled water A nitrate solution dissolved to 500 ml was added dropwise to the solution of (2) above. In addition, although zinc nitrate hexahydrate and zirconyl oxynitrate are added at a molar ratio of 1: 1, they may be added at a molar ratio of 0.1 to 10: 0.1 to 10.
[0015]
(4) Next, after completion of the dropwise addition, the liquid temperature was raised to 60 ° C., and 800 g of alcohol was gradually added to the solution of (3) above, and the mixture was kept warm and stirred for 24 hours. A Pd alloy was formed. In addition, liquid temperature should just be the range of 40-80 degreeC. Thereafter, the precipitate was filtered and washed with distilled water until the filtrate reached pH = 7.
[0016]
(5) After washing, dried at 110 ° C. for 12 hours, pulverized, and fired at 500 ° C. for 3 hours. The firing temperature may be in the range of 400 to 800 ° C. and the firing time may be in the range of 1 to 10 hours.
[0017]
By the above operation, 100 g of Ru—Pd / ZnO—ZrO 2 catalyst can be prepared. The solid acid amount of the prepared catalyst is evaluated by a temperature programmed desorption method using CO 2 in order to show basicity particularly in the case of this catalyst. In addition, by using a carrier preparation method using a hydrotalcite structure as a precursor and further using an alcohol reduction method, the Ru—Pd alloy which is an active species can be supported while maintaining a high surface area of the carrier. Surface area is generated and catalytic activity is high.
[0018]
(Comparative Example 1)
(1) First, (0.5N) Na 2 CO 3 aq was added to a 3.5 L round bottom flask. The concentration may be in the range of 0.01-20.
(2) Next, 136.45 g of zinc nitrate hexahydrate (Zn (NO 3 ) 2 .6H 2 O) and 122.58 g of zirconyl oxynitrate (ZrO (NO 3 ) 2 · 2H 2 O) in distilled water A nitrate solution dissolved to 500 ml was added dropwise to the solution of (1) above. In addition, although zinc nitrate hexahydrate and zirconyl oxynitrate are added at a molar ratio of 1: 1, they may be added at a molar ratio of 0.1 to 10: 0.1 to 10.
[0019]
(3) After completion of the dropwise addition, the precipitate was aged by keeping the liquid temperature at 40 ° C. for 12 hours and stirring. Thereafter, the precipitate was filtered and washed with distilled water until the filtrate reached pH = 7.
(4) After washing, dried at 110 ° C. for 12 hours, pulverized, and calcined at 500 ° C. for 3 hours. The firing temperature may be in the range of 400 to 800 ° C. and the firing time may be in the range of 1 to 10 hours.
[0020]
(5) Next, a Ru nitrate solution (a solution corresponding to 3 g of Ru) and a Pd nitrate solution (a solution corresponding to 3.15 g of the same molar amount with respect to Ru) were mixed, and the solution was neutralized with (1N) NaOHaq. In addition, Ru should just be the range of 0.1-10 wt%, and the quantity of Pd should just be 0.1-10 times the molar quantity with respect to Ru quantity. A chloroplatinic acid solution) or Rh (rhodium nitrate solution) may be used.
[0021]
(6) Next, the solution of the above (5) was mixed with the powder obtained in the above (4), and the slurry liquid was evaporated to dryness on a 160 ° C. hot plate. In addition, the range of 100-250 degreeC may be sufficient as the temperature of evaporation to dryness.
(7) Next, the powder obtained in (6) above is filtered and washed with distilled water, washed until Na ion is 1 ppm or less and the filtrate is pH = 7, and then dried at 110 ° C. for 12 hours, After pulverization, it was calcined at 500 ° C. for 3 hours. Here, the firing temperature may be in the range of 400 to 800 ° C., and the firing time may be in the range of 1 to 10 hours.
By the above operation, 100 g of Ru—Pd / ZnO—ZrO 2 catalyst was prepared.
[0022]
(Comparative Example 2)
(1) First, (0.5N) Na 2 CO 3 aq was added to a 3.5 L round bottom flask. The concentration may be in the range of 0.01-20.
(2) Next, 136.45 g of zinc nitrate hexahydrate (Zn (NO 3 ) 2 .6H 2 O) and 122.58 g of zirconyl oxynitrate (ZrO (NO 3 ) 2 · 2H 2 O) in distilled water A nitrate solution dissolved to 500 ml was added dropwise to the solution of (1) above. In addition, although zinc nitrate hexahydrate and zirconyl oxynitrate are added at a molar ratio of 1: 1, they may be added at a molar ratio of 0.1 to 10: 0.1 to 10.
[0023]
(3) After completion of the dropwise addition, the precipitate was aged by keeping the liquid temperature at 40 ° C. for 12 hours and stirring. Thereafter, the precipitate was filtered and washed with distilled water until the filtrate reached pH = 7.
(4) After washing, dried at 110 ° C. for 12 hours, pulverized, and calcined at 500 ° C. for 3 hours. The firing temperature may be in the range of 400 to 800 ° C. and the firing time may be in the range of 1 to 10 hours.
[0024]
(5) Next, a Ru nitrate solution (solution equivalent to 3 g of Ru) and a Pd nitrate solution (a solution equivalent to 3.15 g of the same molar amount with respect to Ru) are mixed, and the powder obtained in (4) above is mixed. The slurry liquid was evaporated to dryness on a hot plate at 160 ° C. Ru should be in the range of 0.1 to 10 wt%, and the amount of Pd was 0.1 to 10 relative to the Ru amount. In addition to Pd, Pt (using a chloroplatinic acid solution) or Rh (rhodium nitrate solution) may be used, and the temperature of the hot plate is in the range of 100 to 250 ° C. It may be evaporated to dryness.
[0025]
(6) Next, the powder obtained in the above (5) is filtered and washed with distilled water, washed until the filtrate reaches pH = 7, dried at 110 ° C. for 12 hours, pulverized, and pulverized at 500 ° C. for 3 hours. Baked for hours. Here, the firing temperature may be in the range of 400 to 800 ° C., and the firing time may be in the range of 1 to 10 hours.
By the above operation, 100 g of Ru—Pd / ZnO—ZrO 2 catalyst was prepared.
[0026]
The physical properties (specific surface area and basicity) of the catalysts obtained in the above Examples and Comparative Examples 1 and 2 are as shown in Table 1 below.
[0027]
[Table 1]
Further, when the relationship between the temperature (° C.) and the conversion rate (%) of the catalyst obtained in Example 1 and the conventional catalyst was examined, the result shown in FIG. 1 was obtained. Similarly, when the temperature was kept constant (750 ° C.) and the relationship between time (h) and conversion (%) was examined, the result shown in FIG. 2 was obtained. FIG. 1 clearly shows that the catalyst of the present invention has a higher conversion rate (from hydrocarbon to hydrogen) with respect to temperature change than the conventional catalyst. In addition, it is clear from FIG. 2 that in the conventional case, the conversion rate decreases with time, whereas the conversion rate hardly decreases even when the time of the present invention elapses. From the above, it is clear that the present invention is superior to the conventional one.
[0029]
【The invention's effect】
As described above in detail, according to the present invention, ruthenium is converted to platinum, palladium, rhodium by an alcohol reduction method on a basic support obtained by combining zirconium dioxide with zinc oxide or any of alumina, silica, titania, and ceria. by which contains an alloy obtained by one or more alloyed either beam as the active species, improving the oxidation resistance, it is possible to reduce use restrictions, reaction selectivity by controlling the solids oxygen content By maintaining coke and suppressing coking, a hydrocarbon reforming catalyst capable of realizing improved durability can be provided.
[0030]
Further, according to the present invention, in the method for producing a hydrocarbon reforming catalyst used when producing hydrogen by reforming a liquefied hydrocarbon compound, the hydrotalcite structure which is a precursor of a basic carrier a step of loading a step, ruthenium and platinum obtained by an alcohol reduction method in the hydrotalcite structure, palladium, any one or more alloyed with the alloy active species rhodium for preparing the hydrotalcite And a step of firing a ruthenium alloy active species supported on the site structure and obtaining a catalyst in which the ruthenium alloy active species is supported on a basic support, thereby improving the hydrocarbon compound at about 400 to 650 ° C. Compared to the conventional system, it can be started up in a shorter period of time and is safer, with the aim of being used in a home PEFC plant. Ru can provide a method for producing a useful hydrocarbon reforming catalyst when the.
[Brief description of the drawings]
FIG. 1 is a characteristic diagram showing the relationship between temperature and conversion rate according to the present invention and a conventional catalyst.
FIG. 2 is a characteristic diagram showing the relationship between time and conversion rate according to the present invention and the conventional catalyst when the temperature is constant.
Claims (2)
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| JP2006137651A (en) * | 2004-11-15 | 2006-06-01 | Toyota Central Res & Dev Lab Inc | Composite oxide and catalyst for purifying exhaust gas |
| ES2342814B1 (en) * | 2009-01-13 | 2011-05-23 | Hynergreen Technologies, S.A | CATALYST FOR A PROCESS FOR THE OBTAINING OF HYDROGEN BY REFORMED HYDROCARBONS WITH WATER VAPOR, PROCESS OF PREPARATION OF THE CATALYST AND USE OF THE SAME IN THE PROCESS. |
| EP2898945B1 (en) | 2012-09-18 | 2020-09-02 | Japan Science And Technology Agency | Catalyst using pd-ru solid-solution-type alloy particles |
| JP6481998B2 (en) * | 2015-02-28 | 2019-03-13 | 株式会社フルヤ金属 | Supported catalyst |
| KR102027964B1 (en) * | 2017-07-17 | 2019-10-04 | 한국과학기술원 | Catalyst for Hydrocarbon Reforming |
| JP6709557B2 (en) * | 2018-11-29 | 2020-06-17 | 株式会社フルヤ金属 | Supported catalyst |
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