JP2010269239A - Catalyst for oxidation/decomposition of ammonia - Google Patents

Catalyst for oxidation/decomposition of ammonia Download PDF

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JP2010269239A
JP2010269239A JP2009122792A JP2009122792A JP2010269239A JP 2010269239 A JP2010269239 A JP 2010269239A JP 2009122792 A JP2009122792 A JP 2009122792A JP 2009122792 A JP2009122792 A JP 2009122792A JP 2010269239 A JP2010269239 A JP 2010269239A
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ammonia
oxidation
metal
oxide
catalyst
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JP5352343B2 (en
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Sadao Araki
貞夫 荒木
Susumu Hizuya
進 日数谷
Takuma Mori
匠磨 森
Akira Taniguchi
晃 谷口
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Hitachi Zosen Corp
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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    • Y02E60/36Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst for oxidation/decomposition of ammonia, which is obtained by supporting a catalytically-active metal on a carrier consisting of an oxidizable/reducible metal oxide. <P>SOLUTION: Ammonia and air are brought into contact with the catalyst for oxidation/decomposition of ammonia, which is obtained by supporting the catalytically-active metal on the carrier consisting of the oxidizable/reducible metal oxide, at normal temperature, to allow the carrier in a reduced state to react with oxygen, to generate oxidation heat to raise the temperature of a catalyst layer instantaneously. Once the temperature of the catalyst layer reaches the temperature at which ammonia reacts with oxygen, an ammonia oxidation reaction is advanced independently after that. The heat generated by an exothermal reaction being the ammonia oxidation reaction is used at a step of decomposing ammonia in the presence of the catalytically-active metal to produce hydrogen. As a result, the production cost of hydrogen can be reduced since the preheating using an electric heater or the like is not required. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

本発明は、アンモニアから水素を生成する反応に供されるアンモニア酸化・分解触媒に関する。本明細書および特許請求の範囲において、「金属」とはケイ素のような半金属も含むこととする。   The present invention relates to an ammonia oxidation / decomposition catalyst used in a reaction for producing hydrogen from ammonia. In the present specification and claims, the term “metal” includes metalloids such as silicon.

アンモニア分解触媒の存在下にアンモニアを分解して水素を製造するためには、反応温度350℃以上で、下記式(I)の反応を進行させる必要がある。   In order to produce hydrogen by decomposing ammonia in the presence of an ammonia decomposing catalyst, it is necessary to proceed the reaction of the following formula (I) at a reaction temperature of 350 ° C. or higher.

2NH → 3H + N(吸熱反応)
・・・(I)
式(I)の反応はルテニウム系触媒を使用し反応温度400℃以上で進行させることが可能であるが、この反応は吸熱反応であるため、安定したアンモニア分解率を得るためには反応系に熱を与える必要がある。
2NH 3 → 3H 2 + N 2 (endothermic reaction)
... (I)
The reaction of formula (I) can be carried out using a ruthenium catalyst at a reaction temperature of 400 ° C. or higher. However, since this reaction is an endothermic reaction, in order to obtain a stable ammonia decomposition rate, a reaction system is used. It is necessary to give heat.

アンモニアが100%分解した場合の温度降下は約900℃であり、触媒層下流域でガス温度を例えば350℃以上にするには入口ガス温度を1250℃以上にする必要があり、現実的でない。そこで、吸熱反応によるガス温度降下を抑制するために従来は外部から熱を供給していたが、この方法では伝熱速度が反応速度より遅いため十分な伝熱速度を得るには伝熱面積を大きくせざるをえず、装置のコンパクト化が難しい。   The temperature drop when ammonia is 100% decomposed is about 900 ° C., and in order to increase the gas temperature to 350 ° C. or higher, for example, in the downstream region of the catalyst layer, the inlet gas temperature needs to be 1250 ° C. or higher. Therefore, in the past, heat was supplied from the outside in order to suppress the gas temperature drop due to endothermic reaction, but in this method the heat transfer rate is slower than the reaction rate, so a heat transfer area is required to obtain a sufficient heat transfer rate. It must be large and it is difficult to make the device compact.

また、外部からの熱供給の熱源としてアンモニアエンジンの排ガスを利用する方法も考えられるが、この方法ではエンジン排ガスの温度が350℃以下である場合は触媒が作動する温度より低いため、熱供給を行うことができず、所定量の水素を製造することができないという難点がある。   In addition, a method of using the exhaust gas of an ammonia engine as a heat source for supplying heat from the outside is conceivable. However, in this method, when the temperature of the engine exhaust gas is 350 ° C. or lower, the temperature is lower than the temperature at which the catalyst operates. There is a disadvantage that it cannot be performed and a predetermined amount of hydrogen cannot be produced.

熱供給の熱源としては、外部からの供給以外に下記式(II)に示されるように、アンモニアと酸素との反応により熱を発生させ、この熱を利用する方法がある。   As a heat source for heat supply, there is a method of generating heat by reaction of ammonia and oxygen and using this heat as shown in the following formula (II) in addition to external supply.

NH + 3/4O → 1/2N + 3/2HO (発熱反応)
・・・(II)
式(I)と式(II)の反応を同一の反応管内で起こさせると式(I)の吸熱分を式(II)で発生する熱で補うことが可能となる。また、式(II)の酸素量を制御することで触媒層温度を制御することができる。例えば、エンジン排ガスの廃熱を熱交換して予熱された供給ガス温度が変動する場合において、安定して水素を製造することが可能となる。
NH 3 + 3 / 4O 2 → 1 / 2N 2 + 3 / 2H 2 O (exothermic reaction)
... (II)
When the reactions of formula (I) and formula (II) are caused in the same reaction tube, the endothermic component of formula (I) can be supplemented with the heat generated by formula (II). Further, the temperature of the catalyst layer can be controlled by controlling the amount of oxygen in the formula (II). For example, when the supply gas temperature preheated by exchanging waste heat of engine exhaust gas fluctuates, hydrogen can be stably produced.

アンモニア酸化用触媒としては、通常、白金系触媒が用いられる。例えば特許文献1には、耐火性金属酸化物、この耐火性金属酸化物上に設けられた白金層、およびこの白金上に設けられたバナジア層を含んでなる多層化アンモニア酸化触媒が提案されている。   A platinum-based catalyst is usually used as the ammonia oxidation catalyst. For example, Patent Document 1 proposes a multilayered ammonia oxidation catalyst comprising a refractory metal oxide, a platinum layer provided on the refractory metal oxide, and a vanadia layer provided on the platinum. Yes.

しかし、この触媒の作動温度は200℃程度であり、それ以下の温度では酸化反応を進行することができず、電気ヒータ等でガス温度を200℃程度まで上げる必要がある。   However, the operating temperature of this catalyst is about 200 ° C., and the oxidation reaction cannot proceed at a temperature lower than that, and it is necessary to raise the gas temperature to about 200 ° C. with an electric heater or the like.

特許文献2には、セリウム及びプラセオジムから選択される少なくとも1種の元素の酸化物と、イットリウムを含む原子価非可変性希土類元素から選択される少なくとも1種の元素の酸化物と、コバルトの酸化物を含むアンモニア酸化触媒が提案され、また特許文献3には、本質的に白金、ロジウム、随時パラジウムからなるフィラメントを含み、該フィラメントが白金コーティングを有するアンモニア酸化触媒が提案されているが、これらも特許文献1と同じ問題を有する。   Patent Document 2 discloses an oxide of at least one element selected from cerium and praseodymium, an oxide of at least one element selected from valence-nonvariable rare earth elements including yttrium, and oxidation of cobalt. In addition, Patent Document 3 proposes an ammonia oxidation catalyst that includes a filament consisting essentially of platinum, rhodium, and optionally palladium, and the filament has a platinum coating. Also have the same problem as Patent Document 1.

特表2007-504945号公報Special Table 2007-504945 特許4165661号公報Japanese Patent No. 4165661 特開昭63-72344号公報JP 63-72344 JP

本発明は、上記のような問題を解消することができるアンモニア酸化・分解触媒を提供することを目的とする。   An object of this invention is to provide the ammonia oxidation and decomposition catalyst which can eliminate the above problems.

本発明は、酸化還元可能な金属酸化物からなる担体に触媒活性金属(担持金属ともいう)が担持されてなるアンモニア酸化・分解触媒に関する。   The present invention relates to an ammonia oxidation / decomposition catalyst in which a catalytically active metal (also referred to as a supported metal) is supported on a support composed of a metal oxide capable of redox.

金属酸化物は複合酸化物であってもよい。   The metal oxide may be a complex oxide.

金属酸化物は、好ましくは希土類金属酸化物である。   The metal oxide is preferably a rare earth metal oxide.

酸化還元可能な金属酸化物とは、酸化状態と還元状態を可逆的に変換しうる金属をいう。   The metal oxide capable of redox refers to a metal that can reversibly convert an oxidation state and a reduction state.

酸化還元可能な金属酸化物の好ましい例は、酸化セリウム、酸化ランタン、酸化サマリウムなどの希土類金属酸化物である。また、酸化還元可能な金属酸化物は、希土類金属と、マグネシウム、チタン、ジルコニウム、イットリウム、アルミニウム、ケイ素、コバルト、鉄およびガリウムからなる群から選ばれる少なくとも1種の金属との複合酸化物であってもよく、また、希土類金属と、マグネシウム、チタン、ジルコニウム、イットリウム、アルミニウム、ケイ素、コバルト、鉄およびガリウムからなる群から選ばれる少なくとも2種の金属との複合酸化物であってもよい。   Preferable examples of the metal oxide capable of redox are rare earth metal oxides such as cerium oxide, lanthanum oxide, and samarium oxide. The metal oxide capable of redox is a composite oxide of a rare earth metal and at least one metal selected from the group consisting of magnesium, titanium, zirconium, yttrium, aluminum, silicon, cobalt, iron and gallium. Alternatively, it may be a composite oxide of a rare earth metal and at least two metals selected from the group consisting of magnesium, titanium, zirconium, yttrium, aluminum, silicon, cobalt, iron and gallium.

担体に担持される触媒活性金属は、好ましくは、ルテニウム、白金、ロジウム、パラジウム、鉄、コバルト、ニッケルなどの第VIII族金属、スズ、銅、銀、マンガン、クロムおよびバナジウムからなる群から選ばれる少なくとも一種の金属である。   The catalytically active metal supported on the support is preferably selected from the group consisting of Group VIII metals such as ruthenium, platinum, rhodium, palladium, iron, cobalt, nickel, tin, copper, silver, manganese, chromium and vanadium. At least one kind of metal.

本発明によるアンモニア酸化・分解触媒は、水素気流中で200℃以上、好ましくは200〜700℃、特に好ましくは200〜600℃で加熱処理し、担体を構成する金属酸化物の一部または全部を還元した後、アンモニア酸化・分解反応に供される。アンモニア酸化・分解触媒の還元処理は、同触媒反応器に充填する前に行っても後に行っても良い。   The ammonia oxidation / decomposition catalyst according to the present invention is heat-treated at 200 ° C. or higher, preferably 200 to 700 ° C., particularly preferably 200 to 600 ° C. in a hydrogen stream, and a part or all of the metal oxide constituting the carrier is partially heated. After reduction, it is subjected to ammonia oxidation / decomposition reaction. The reduction treatment of the ammonia oxidation / decomposition catalyst may be performed before or after filling the catalyst reactor.

アンモニア酸化・分解触媒の担体は例えば下記の方法で調製することができる。   The ammonia oxidation / decomposition catalyst carrier can be prepared, for example, by the following method.

1.担体の前駆物質として金属塩、例えば硝酸塩を用い、これの水溶液をアンモニア水溶液で処理して金属水酸化物を析出させる。複合酸化物の場合は複数の金属塩の水溶液濃度が等モルずつになるように、金属塩濃度を調整する。   1. A metal salt such as nitrate is used as a support precursor, and an aqueous solution thereof is treated with an aqueous ammonia solution to precipitate a metal hydroxide. In the case of a complex oxide, the metal salt concentration is adjusted so that the aqueous solution concentrations of the plurality of metal salts are equimolar.

2.析出物を含む液を遠心分離に付す。   2. The liquid containing the precipitate is subjected to centrifugation.

3.析出物を回収し例えば120℃で乾燥させる。   3. The precipitate is collected and dried at 120 ° C., for example.

4.乾燥した析出物を空気中で例えば700℃で焼成し、担体を得る。   4). The dried precipitate is calcined in air at, for example, 700 ° C. to obtain a carrier.

こうして調製した担体に触媒活性金属を担持してアンモニア酸化・分解触媒を得る方法は、例えば下記の通りである。   A method for obtaining an ammonia oxidation / decomposition catalyst by supporting a catalytically active metal on the carrier thus prepared is as follows, for example.

1.貴金属系の金属の前駆物質として例えば金属塩化物、金属酸塩化物を用い、卑金属系の金属の前駆物質として例えば硝酸塩を用いる。   1. For example, a metal chloride or a metal acid chloride is used as a noble metal precursor, and a nitrate is used as a base metal precursor.

2.上記金属前駆物質を溶液に溶解させ、この溶液に、上記で得られた担体を、触媒活性金属の担持量が所望の値になるように分散させる。   2. The metal precursor is dissolved in a solution, and the support obtained above is dispersed in the solution so that the amount of the catalytically active metal supported becomes a desired value.

3.この分散液を加熱し、溶媒を緩やかに蒸発させる。   3. The dispersion is heated to slowly evaporate the solvent.

4.得られた粉末を例えば300℃の空気中で焼成し、アンモニア酸化・分解触媒を得る。   4). The obtained powder is calcined in, for example, 300 ° C. air to obtain an ammonia oxidation / decomposition catalyst.

上記のアンモニア酸化・分解触媒を反応器内に充填し、例えば600℃に加熱しながら水素気流中で担体の還元を行う。つぎに、常温でアンモニアと空気を接触させると、まず還元状態にある担体が酸素と反応することで酸化熱が発生し、瞬時に触媒層温度が上昇する。一旦、触媒層温度がアンモニアと酸素が反応する温度(200℃)まで上昇すると、その後は自立的に上述した式(II)に従ってアンモニア酸化反応が進行する。この発熱反応(II)で生じた熱が、上述した式(I)に従って触媒活性金属の存在下にアンモニアを分解する過程で使われ、水素が生成する。   The ammonia oxidation / decomposition catalyst is filled in the reactor, and the support is reduced in a hydrogen stream while being heated to 600 ° C., for example. Next, when ammonia and air are brought into contact with each other at room temperature, first, the carrier in the reduced state reacts with oxygen to generate heat of oxidation, and the catalyst layer temperature rises instantaneously. Once the catalyst layer temperature rises to the temperature at which ammonia and oxygen react (200 ° C.), the ammonia oxidation reaction proceeds autonomously according to the above-described formula (II) thereafter. The heat generated in the exothermic reaction (II) is used in the process of decomposing ammonia in the presence of the catalytically active metal in accordance with the above-described formula (I) to generate hydrogen.

上述したように、本発明による酸化還元可能な金属酸化物からなる担体に触媒活性金属が担持されてなるアンモニア酸化・分解触媒に、常温でアンモニアと空気を接触させることにより、まず還元状態にある担体が酸素と反応して酸化熱が発生し、瞬時に触媒層温度が上昇する。一旦、触媒層温度がアンモニアと酸素が反応する温度まで上昇すると、その後は自立的にアンモニア酸化反応が進行する。この発熱反応(II)で生じた熱が、上述した式(I)に従って触媒活性金属の存在下にアンモニアを分解する過程で使われ、水素が生成する。これにより、電気ヒータ等での予備加熱を不要とし、水素の製造コストを削減することができる。   As described above, the ammonia oxidation / decomposition catalyst in which a catalytically active metal is supported on a support made of a redox-capable metal oxide according to the present invention is first brought into a reduced state by contacting ammonia and air at room temperature. The carrier reacts with oxygen to generate oxidation heat, and the catalyst layer temperature instantaneously rises. Once the catalyst layer temperature rises to a temperature at which ammonia and oxygen react, the ammonia oxidation reaction proceeds autonomously thereafter. The heat generated in the exothermic reaction (II) is used in the process of decomposing ammonia in the presence of the catalytically active metal in accordance with the above-described formula (I) to generate hydrogen. This eliminates the need for preheating with an electric heater or the like, and reduces the hydrogen production cost.

つぎに、本発明を具体的に説明するために、本発明の実施例およびこれとの比較を示すための比較例をいくつか挙げる。   Next, in order to specifically explain the present invention, some examples of the present invention and comparative examples for showing comparison with the examples will be given.

実施例1〜22
a)担体の調製
1.表1に示す各担体の前駆物質として硝酸塩を用い、この硝酸塩水溶液(濃度0.4mol/L)に金属量論量の1.2倍に相当するアンモニア水溶液(濃度28wt%)を加えて金属水酸化物を析出させた。複合酸化物の場合は複数の金属塩の水溶液濃度が等モルずつになるように、金属塩濃度を調整した。
Examples 1-22
a) Preparation of carrier Using nitrate as a precursor for each carrier shown in Table 1, an aqueous ammonia solution (concentration 28 wt%) corresponding to 1.2 times the stoichiometric amount of metal was added to the aqueous nitrate solution (concentration 0.4 mol / L). Oxide was precipitated. In the case of the composite oxide, the metal salt concentration was adjusted so that the aqueous solution concentrations of the plurality of metal salts were equimolar.

2.析出物を含む液を遠心分離に付した。   2. The liquid containing the precipitate was subjected to centrifugation.

3.析出物を回収し120℃で乾燥させた。   3. The precipitate was collected and dried at 120 ° C.

4.乾燥した析出物を700℃の空気中で焼成し、それぞれ担体を得た。   4). The dried precipitates were fired in air at 700 ° C. to obtain carriers.

b)触媒活性金属の担持
1.表1に示す触媒活性金属の内、貴金属系の金属の前駆物質として、塩化ルテニウム、塩化白金酸、塩化ロジウム、硝酸パラジウムを用い、卑金属系の金属の前駆物質として硝酸塩を用いた。
b) Loading of catalytically active metal Of the catalytically active metals shown in Table 1, ruthenium chloride, chloroplatinic acid, rhodium chloride, and palladium nitrate were used as the noble metal precursor, and nitrate was used as the base metal precursor.

2.上記金属前駆物質を純水に溶解させ、この溶液に、上記で得られた担体を、触媒活性金属の担持量が2重量%(金属として)になるように分散させた。   2. The metal precursor was dissolved in pure water, and the carrier obtained above was dispersed in this solution so that the amount of the catalytically active metal supported was 2% by weight (as metal).

3.この分散液を加熱し、水を緩やかに蒸発させた。   3. This dispersion was heated to slowly evaporate the water.

4.得られた粉末を300℃の空気中で焼成し、触媒活性金属を2重量%含むアンモニア酸化・分解触媒を得た。   4). The obtained powder was calcined in air at 300 ° C. to obtain an ammonia oxidation / decomposition catalyst containing 2% by weight of a catalytically active metal.

比較例1〜2
1.塩化ルテニウムを水に溶解させ、この溶液に、酸化アルミニウム、酸化ケイ素を、触媒活性金属の担持量が2重量%(金属として)になるように分散させた。
Comparative Examples 1-2
1. Ruthenium chloride was dissolved in water, and aluminum oxide and silicon oxide were dispersed in this solution so that the amount of the catalytically active metal supported was 2% by weight (as metal).

2.この分散液を加熱し、水を緩やかに蒸発させた。   2. This dispersion was heated to slowly evaporate the water.

3.得られた粉末を300℃の空気中で焼成し、触媒活性金属を2重量%含むアンモニア酸化・分解触媒を得た。   3. The obtained powder was calcined in air at 300 ° C. to obtain an ammonia oxidation / decomposition catalyst containing 2% by weight of a catalytically active metal.

性能試験
実施例および比較例で得られたアンモニア酸化・分解触媒について、下記の方法で性能試験を行った。
Performance Test The ammonia oxidation / decomposition catalyst obtained in Examples and Comparative Examples was subjected to a performance test by the following method.

流通型反応器内に、表1に示す充填量でアンモニア酸化・分解触媒を充填した後、水素気流中600℃で2時間加熱することで、同触媒を還元処理した。常温まで冷却した後、この反応器にアンモニアガスと空気を供給した。アンモニア供給量は100NL/minと一定にし、空気供給量は空気/NH=1.0とした。アンモニア酸化・分解触媒の出口温度および水素発生量の計測を行った。水素発生量の計測は、質量分析計によりガス濃度を測定することにより行った。 After the ammonia oxidation / decomposition catalyst was filled in the flow reactor in the filling amount shown in Table 1, the catalyst was reduced by heating in a hydrogen stream at 600 ° C. for 2 hours. After cooling to room temperature, ammonia gas and air were supplied to the reactor. The ammonia supply amount was fixed at 100 NL / min, and the air supply amount was air / NH 3 = 1.0. The temperature at the outlet of the ammonia oxidation / decomposition catalyst and the amount of hydrogen generation were measured. The amount of hydrogen generation was measured by measuring the gas concentration with a mass spectrometer.

試験結果を表1に示す。   The test results are shown in Table 1.



Figure 2010269239
Figure 2010269239

表1から明らかなように、本発明によるアンモニア酸化・分解触媒を用いることにより、アンモニア酸化反応を常温で起動させることができ、電気ヒータ等での予備加熱を用いることなく、アンモニアを分解して高い収率で水素を得ることができ、水素の製造コストダウンを達成することができる。

As is apparent from Table 1, by using the ammonia oxidation / decomposition catalyst according to the present invention, the ammonia oxidation reaction can be started at room temperature, and ammonia can be decomposed without using preheating with an electric heater or the like. Hydrogen can be obtained with a high yield, and the production cost of hydrogen can be reduced.

Claims (8)

酸化還元可能な金属酸化物からなる担体に触媒活性金属が担持されてなるアンモニア酸化・分解触媒。 An ammonia oxidation / decomposition catalyst in which a catalytically active metal is supported on a support made of a metal oxide capable of redox. 金属酸化物が複合酸化物である請求項1記載のアンモニア酸化・分解触媒。 The ammonia oxidation / decomposition catalyst according to claim 1, wherein the metal oxide is a composite oxide. 金属酸化物が希土類金属酸化物である請求項1または2記載のアンモニア酸化・分解触媒。 The ammonia oxidation / decomposition catalyst according to claim 1 or 2, wherein the metal oxide is a rare earth metal oxide. 希土類金属酸化物が酸化セリウム、酸化ランタンまたは酸化サマリウムである請求項3に記載のアンモニア酸化・分解触媒。 The ammonia oxidation / decomposition catalyst according to claim 3, wherein the rare earth metal oxide is cerium oxide, lanthanum oxide or samarium oxide. 金属酸化物が希土類金属と、マグネシウム、チタン、ジルコニウム、イットリウム、アルミニウム、ケイ素、コバルト、鉄およびガリウムからなる群から選ばれる少なくとも1種の金属との複合酸化物である請求項2に記載のアンモニア酸化・分解触媒。 The ammonia according to claim 2, wherein the metal oxide is a composite oxide of a rare earth metal and at least one metal selected from the group consisting of magnesium, titanium, zirconium, yttrium, aluminum, silicon, cobalt, iron and gallium. Oxidation / decomposition catalyst. 金属酸化物が希土類金属と、マグネシウム、チタン、ジルコニウム、イットリウム、アルミニウム、ケイ素、コバルト、鉄およびガリウムからなる群から選ばれる少なくとも2種の金属との複合酸化物である請求項2に記載のアンモニア酸化・分解触媒。 The ammonia according to claim 2, wherein the metal oxide is a composite oxide of a rare earth metal and at least two metals selected from the group consisting of magnesium, titanium, zirconium, yttrium, aluminum, silicon, cobalt, iron and gallium. Oxidation / decomposition catalyst. 触媒活性金属が第VIII族金属、スズ、銅、銀、マンガン、クロムおよびバナジウムからなる群から選ばれる少なくとも一種の金属である請求項1〜6のいずれかに記載のアンモニア酸化・分解触媒。 The ammonia oxidation / decomposition catalyst according to any one of claims 1 to 6, wherein the catalytically active metal is at least one metal selected from the group consisting of Group VIII metals, tin, copper, silver, manganese, chromium and vanadium. 200℃以上で還元処理した請求項1〜7のいずれかに記載のアンモニア酸化・分解触媒。


The ammonia oxidation / decomposition catalyst according to any one of claims 1 to 7, which has been subjected to a reduction treatment at 200 ° C or higher.


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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012063846A1 (en) * 2010-11-09 2012-05-18 日立造船株式会社 Ammonia oxidation/decomposition catalyst
WO2012090739A1 (en) * 2010-12-30 2012-07-05 株式会社豊田中央研究所 Hydrogen generator and internal combustion engine provided with hydrogen generator
WO2014073576A1 (en) * 2012-11-06 2014-05-15 Jx日鉱日石エネルギー株式会社 Oxidative decomposition catalyst for ammonia, method for producing hydrogen, and apparatus for producing hydrogen
JP2014176792A (en) * 2013-03-14 2014-09-25 Tanaka Kikinzoku Kogyo Kk Ammonia reformation catalyst and method for manufacturing the same
WO2015177773A1 (en) * 2014-05-22 2015-11-26 Sabic Global Technologies B.V. Mixed metal oxide catalysts for ammonia decomposition
JP2018001095A (en) * 2016-07-01 2018-01-11 株式会社日本触媒 Catalyst for decomposing ammonia and method for producing hydrogen-containing gas using the same
US11891301B2 (en) 2018-08-21 2024-02-06 University Of South Carolina Ammonia decomposition catalyst systems

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11724245B2 (en) 2021-08-13 2023-08-15 Amogy Inc. Integrated heat exchanger reactors for renewable fuel delivery systems
US11994061B2 (en) 2021-05-14 2024-05-28 Amogy Inc. Methods for reforming ammonia
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US11539063B1 (en) 2021-08-17 2022-12-27 Amogy Inc. Systems and methods for processing hydrogen
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US11866328B1 (en) 2022-10-21 2024-01-09 Amogy Inc. Systems and methods for processing ammonia
US11795055B1 (en) 2022-10-21 2023-10-24 Amogy Inc. Systems and methods for processing ammonia

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02198639A (en) * 1989-01-27 1990-08-07 Nkk Corp Catalyst for decomposing ammonia
JPH02284618A (en) * 1989-03-29 1990-11-22 Boc Group Inc:The Method for reducing oxygen concentration
JPH0824651A (en) * 1994-07-22 1996-01-30 Nippon Shokubai Co Ltd Ammonia decomposition catalyst and method for decomposing ammonia using the same
JPH0889758A (en) * 1994-09-26 1996-04-09 Mitsubishi Heavy Ind Ltd Decomposing method of ammonia
JPH09271637A (en) * 1996-02-06 1997-10-21 Toyota Central Res & Dev Lab Inc Catalyst device for purifying ammonia
JP2005131469A (en) * 2003-10-28 2005-05-26 Research Institute Of Innovative Technology For The Earth Ethanol/steam reforming catalyst, its manufacturing method and hydrogen manufacturing method
JP2006289211A (en) * 2005-04-07 2006-10-26 Ne Chemcat Corp Ammonia oxidation catalyst
JP2009254981A (en) * 2008-04-17 2009-11-05 Nippon Shokubai Co Ltd Ammonia decomposing catalyst and method of decomposing ammonia
JP2010094668A (en) * 2008-09-17 2010-04-30 Nippon Shokubai Co Ltd Catalyst for ammonia decomposition, process for producing the same, and method for treating ammonia
JP2010207783A (en) * 2009-03-12 2010-09-24 Toyota Central R&D Labs Inc Ammonia decomposition catalyst, ammonia decomposition method using the same and ammonia decomposition reaction device
JP2010531227A (en) * 2007-06-25 2010-09-24 ジョンソン、マッセイ、パブリック、リミテッド、カンパニー Non-zeolite base metal SCR catalyst
JP2010241647A (en) * 2009-04-07 2010-10-28 Toyota Motor Corp Hydrogen generating apparatus and hydrogen generating method
JP2010240646A (en) * 2009-03-17 2010-10-28 Nippon Shokubai Co Ltd Catalyst for producing hydrogen, and method of producing hydrogen using the same
WO2012029122A1 (en) * 2010-08-31 2012-03-08 日立造船株式会社 Ammonia oxidation/decomposition catalyst
WO2012063846A1 (en) * 2010-11-09 2012-05-18 日立造船株式会社 Ammonia oxidation/decomposition catalyst

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02198639A (en) * 1989-01-27 1990-08-07 Nkk Corp Catalyst for decomposing ammonia
JPH02284618A (en) * 1989-03-29 1990-11-22 Boc Group Inc:The Method for reducing oxygen concentration
JPH0824651A (en) * 1994-07-22 1996-01-30 Nippon Shokubai Co Ltd Ammonia decomposition catalyst and method for decomposing ammonia using the same
JPH0889758A (en) * 1994-09-26 1996-04-09 Mitsubishi Heavy Ind Ltd Decomposing method of ammonia
JPH09271637A (en) * 1996-02-06 1997-10-21 Toyota Central Res & Dev Lab Inc Catalyst device for purifying ammonia
JP2005131469A (en) * 2003-10-28 2005-05-26 Research Institute Of Innovative Technology For The Earth Ethanol/steam reforming catalyst, its manufacturing method and hydrogen manufacturing method
JP2006289211A (en) * 2005-04-07 2006-10-26 Ne Chemcat Corp Ammonia oxidation catalyst
JP2010531227A (en) * 2007-06-25 2010-09-24 ジョンソン、マッセイ、パブリック、リミテッド、カンパニー Non-zeolite base metal SCR catalyst
JP2009254981A (en) * 2008-04-17 2009-11-05 Nippon Shokubai Co Ltd Ammonia decomposing catalyst and method of decomposing ammonia
JP2010094668A (en) * 2008-09-17 2010-04-30 Nippon Shokubai Co Ltd Catalyst for ammonia decomposition, process for producing the same, and method for treating ammonia
JP2010207783A (en) * 2009-03-12 2010-09-24 Toyota Central R&D Labs Inc Ammonia decomposition catalyst, ammonia decomposition method using the same and ammonia decomposition reaction device
JP2010240646A (en) * 2009-03-17 2010-10-28 Nippon Shokubai Co Ltd Catalyst for producing hydrogen, and method of producing hydrogen using the same
JP2010241647A (en) * 2009-04-07 2010-10-28 Toyota Motor Corp Hydrogen generating apparatus and hydrogen generating method
WO2012029122A1 (en) * 2010-08-31 2012-03-08 日立造船株式会社 Ammonia oxidation/decomposition catalyst
WO2012063846A1 (en) * 2010-11-09 2012-05-18 日立造船株式会社 Ammonia oxidation/decomposition catalyst

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012063846A1 (en) * 2010-11-09 2012-05-18 日立造船株式会社 Ammonia oxidation/decomposition catalyst
US9896332B2 (en) 2010-11-09 2018-02-20 Hitachi Zosen Corporation Ammonia oxidation/decomposition catalyst
WO2012090739A1 (en) * 2010-12-30 2012-07-05 株式会社豊田中央研究所 Hydrogen generator and internal combustion engine provided with hydrogen generator
US20120167840A1 (en) * 2010-12-30 2012-07-05 Toyota Jidosha Kabushiki Kaisha Hydrogen generator and internal combustion engine provided with hydrogen generator
CN103249668A (en) * 2010-12-30 2013-08-14 丰田自动车株式会社 Hydrogen generator and internal combustion engine provided with hydrogen generator
US8561578B2 (en) 2010-12-30 2013-10-22 Kabushiki Kaisha Toyota Chuo Kenkyusho Hydrogen generator and internal combustion engine provided with hydrogen generator
WO2014073576A1 (en) * 2012-11-06 2014-05-15 Jx日鉱日石エネルギー株式会社 Oxidative decomposition catalyst for ammonia, method for producing hydrogen, and apparatus for producing hydrogen
JP2014111517A (en) * 2012-11-06 2014-06-19 Jx Nippon Oil & Energy Corp Oxidative decomposition catalyst of ammonia, hydrogen production method, and hydrogen production apparatus
JP2014176792A (en) * 2013-03-14 2014-09-25 Tanaka Kikinzoku Kogyo Kk Ammonia reformation catalyst and method for manufacturing the same
WO2015177773A1 (en) * 2014-05-22 2015-11-26 Sabic Global Technologies B.V. Mixed metal oxide catalysts for ammonia decomposition
JP2018001095A (en) * 2016-07-01 2018-01-11 株式会社日本触媒 Catalyst for decomposing ammonia and method for producing hydrogen-containing gas using the same
US11891301B2 (en) 2018-08-21 2024-02-06 University Of South Carolina Ammonia decomposition catalyst systems

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