JP4525909B2 - Water gas shift reaction catalyst, method for producing the same, and method for producing water gas - Google Patents
Water gas shift reaction catalyst, method for producing the same, and method for producing water gas Download PDFInfo
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Description
本発明は、高い酸素貯蔵放出能を有する触媒であって、水性ガスシフト反応及び排ガス浄化に好適に用いることができる触媒に関するものである。 The present invention relates to a catalyst having a high oxygen storage / release capability and can be suitably used for water gas shift reaction and exhaust gas purification.
水性ガスシフト反応（ＣＯ＋Ｈ２Ｏ→ＣＯ２＋Ｈ２）は、従来より、コークス、天然ガスなどの炭化水素及び水蒸気から得られる水性ガスに含まれるＣＯとＨ２Ｏの比率を変える、あるいはＨ２の製造等のため、化学工業プロセスにおいて利用されている大変重要な反応である。 The water gas shift reaction (CO + H 2 O → CO 2 + H 2 ) has conventionally changed the ratio of CO and H 2 O contained in water gas obtained from hydrocarbons such as coke and natural gas and water vapor, or H 2 It is a very important reaction that is used in chemical industry processes for manufacturing and the like.
また、近年注目を浴びている燃料電池の燃料となる水素を、都市ガス等を改質して得る場合、副生したＣＯが燃料電池電極を被毒して発電効率が低下するため、この副生したＣＯを低減させる反応として注目を集めている。こうした水性ガスシフト反応の触媒は、一般に、低温においては銅−亜鉛系や白金／アルミナ系が、高温においては、鉄−クロム系が使用される。 In addition, when hydrogen, which is the fuel of fuel cells that has been attracting attention in recent years, is obtained by reforming city gas or the like, the by-produced CO poisons the fuel cell electrode, reducing power generation efficiency. It is attracting attention as a reaction to reduce the generated CO. As a catalyst for such a water gas shift reaction, a copper-zinc system or a platinum / alumina system is generally used at a low temperature, and an iron-chromium system is used at a high temperature.
しかし、銅−亜鉛系触媒は、耐熱性に乏しく、高温では使用できない上に短時間で失活してしまう問題点がある。白金／アルミナ系触媒は耐熱性は高いが高い活性を発現させるためには白金の担持量を多くする必要があるため触媒自体が高価になってしまう問題点がある。鉄−クロム系触媒は耐熱性は高いが活性が低いという問題点がある。 However, the copper-zinc catalyst has a problem that it has poor heat resistance and cannot be used at high temperatures and deactivates in a short time. A platinum / alumina-based catalyst has high heat resistance, but in order to develop high activity, it is necessary to increase the amount of platinum supported, so that the catalyst itself becomes expensive. The iron-chromium catalyst has a problem of high heat resistance but low activity.
また、環境意識の向上から排ガス浄化触媒においても更なる特性の改善が求められている。自動車用エンジン等の内燃機関からの排気ガスは、白金、ロジウム、パラジウム等の触媒成分が担持された三元触媒等によって浄化されている。 In addition, further improvement of characteristics is demanded in exhaust gas purification catalysts due to the improvement of environmental awareness. Exhaust gas from an internal combustion engine such as an automobile engine is purified by a three-way catalyst or the like on which a catalyst component such as platinum, rhodium or palladium is supported.
適度な酸素貯蔵放出能（Ｏｘｙｇｅｎ Ｓｔｒａｇｅ Ｃａｐａｃｉｔｙ：以下、「ＯＳＣ」という。）を有する酸化物混合体が強く要求されている。 There is a strong demand for an oxide mixture having an appropriate oxygen storage capacity (Oxygen Storage Capacity: hereinafter referred to as “OSC”).
触媒としてさらに高活性のものが得られれば、一定条件下の化学工業プロセスのみならず、変動条件下における種々の利用が期待され、燃料電池に使用される燃料の改質、即ち、電極触媒の触媒毒となるＣＯを燃料電池に有用な燃料の水素に転化させる利用が期待される。 If a catalyst with higher activity can be obtained, it is expected to be used not only in chemical industrial processes under certain conditions but also under variable conditions. It is expected that CO, which is a catalyst poison, is converted to hydrogen, a fuel useful for fuel cells.
一方、排気ガス浄化用触媒は、活性は高いがコストが高いため、より安価で高い排気ガス浄化性能を有する触媒が要請されている。 On the other hand, since the exhaust gas purification catalyst has high activity but high cost, a catalyst that is cheaper and has high exhaust gas purification performance is required.
本発明の酸素貯蔵放出が可能な少なくともアルカリ土類金属及びアルミニウムからなる酸化物混合体は、アルカリ土類金属アルミネートを主成分として含んでおり、本発明の水性ガスシフト及び排ガス浄化用触媒としては、Ｃａ１２Ａｌ１４Ｏ３３（以下、「Ｃ１２Ａ７」とする。）およびＳｒ１２Ａｌ１４Ｏ３３主成分とするものが知られており、酸素ラジカルを持ち強い酸化力を有することが記載されている（特許文献１〜２、非特許文献１）。 The oxide mixture comprising at least an alkaline earth metal and aluminum capable of storing and releasing oxygen according to the present invention contains an alkaline earth metal aluminate as a main component, and the water gas shift and exhaust gas purification catalyst of the present invention , Ca 12 Al 14 O 33 (hereinafter referred to as “C12A7”) and Sr 12 Al 14 O 33 as main components are known and described as having oxygen radicals and strong oxidizing power. (Patent Literatures 1 and 2, Non-Patent Literature 1).
また、酸素ラジカルによって排ガス中に含まれる炭素微粒子が効率よく除去できることが記載されている（特許文献３）。 Further, it is described that carbon fine particles contained in exhaust gas can be efficiently removed by oxygen radicals (Patent Document 3).
前記特許文献１〜３及び非特許文献１記載の技術は、高温で焼成することによって触媒を得ているために比表面積が小さく、活性点が少ないことが推察される。 The techniques described in Patent Documents 1 to 3 and Non-Patent Document 1 are presumed to have a small specific surface area and few active points because the catalyst is obtained by firing at a high temperature.
そこで、本発明は、酸素貯蔵放出能が高い触媒を得ることを技術的課題とする。 Accordingly, the present invention has a technical problem to obtain a catalyst having a high oxygen storage / release capability.
前記技術的課題は、次の通りの本発明によって達成できる。 The technical problem can be achieved by the present invention as follows.
本発明者らは、鋭意検討を重ねたところ、特定の酸化物を使用することにより前記課題を解消できるとの知見を得て本発明を完成するに至った。 As a result of intensive studies, the present inventors have obtained the knowledge that the above problem can be solved by using a specific oxide, and have completed the present invention.
即ち、本発明は、カルシウム及びアルミニウムを主成分とし、前記アルミニウムに対して０．００１〜１０ｍｏｌ％の鉄を含有する複合酸化物からなる触媒であって、該触媒の５００℃での酸素貯蔵放出能が２０〜２００μｍｏｌ／ｇであり、ＢＥＴ比表面積値が２０ｍ２／ｇ以上であることを特徴とする触媒である（本発明１）。 That is, the present invention is a catalyst comprising a complex oxide containing calcium and aluminum as main components and 0.001 to 10 mol% of iron with respect to the aluminum, and the oxygen storage and release of the catalyst at 500 ° C. It is a catalyst characterized by having a performance of 20 to 200 μmol / g and a BET specific surface area value of 20 m 2 / g or more (Invention 1).
また、本発明は、カルシウム及びアルミニウムを主成分とする複合酸化物からなる触媒であり、該触媒にＡｕ，Ａｇ，Ｃｕ，Ｐｔ，Ｐｄ，Ｎｉ，Ｉｒ，Ｒｈ，Ｃｏ，Ｏｓ，Ｒｕの中から選ばれた１種または２種以上の金属元素を前記触媒に対して重量比で０．００１〜１０ｗｔ％担持しており、該触媒の５００℃での酸素貯蔵放出能が２０〜２００μｍｏｌ／ｇであり、ＢＥＴ比表面積値が２０ｍ２／ｇ以上であることを特徴とする触媒である（本発明２）。 Further, the present invention is a catalyst composed of a composite oxide mainly composed of calcium and aluminum, and the catalyst is selected from Au, Ag, Cu, Pt, Pd, Ni, Ir, Rh, Co, Os, and Ru. One or two or more selected metal elements are supported in a weight ratio of 0.001 to 10 wt% with respect to the catalyst, and the oxygen storage / release capacity at 500 ° C. of the catalyst is 20 to 200 μmol / g. And a BET specific surface area value of 20 m 2 / g or more (Invention 2).
また、本発明は、カルシウム及びアルミニウムを主成分とし、前記アルミニウムに対して０．００１〜１０ｍｏｌ％の鉄を含有する複合酸化物からなる触媒であって該触媒にＡｕ，Ａｇ，Ｃｕ，Ｐｔ，Ｐｄ，Ｎｉ，Ｉｒ，Ｒｈ，Ｃｏ，Ｏｓ，Ｒｕの中から選ばれた１種または２種以上の金属元素を前記触媒に対して重量比で０．００１〜１０ｗｔ％担持しており、該触媒の５００℃での酸素貯蔵放出能が２０〜２００μｍｏｌ／ｇであり、ＢＥＴ比表面積値が２０ｍ２／ｇ以上であることを特徴とする触媒である（本発明３）。 Further, the present invention is a catalyst comprising a composite oxide containing calcium and aluminum as main components and containing 0.001 to 10 mol% of iron with respect to the aluminum, and the catalyst includes Au, Ag, Cu, Pt, One or two or more metal elements selected from Pd, Ni, Ir, Rh, Co, Os, and Ru are supported at a weight ratio of 0.001 to 10 wt% with respect to the catalyst, and the catalyst Is a catalyst characterized by having an oxygen storage / release capacity at 500 ° C. of 20 to 200 μmol / g and a BET specific surface area value of 20 m 2 / g or more (Invention 3).
また、本発明は、本発明１乃至３のいずれかの触媒を構成するカルシウムとアルミニウムとの割合がモル比で０．１〜０．９の範囲であることを特徴とする触媒である（本発明４）。 Further, the present invention is a catalyst characterized in that the ratio of calcium and aluminum constituting the catalyst of any one of the present inventions 1 to 3 is in the range of 0.1 to 0.9 in terms of molar ratio (this book Invention 4).
また、本発明は、アルカリ性水溶液と、カルシウム塩原料、アルミニウム塩原料及び鉄塩原料とを混合し、ｐＨ値が７．０〜１４．０の範囲にて３００℃以下の温度範囲で熟成して層状複水酸化物粒子を得て、濾別、水洗した後、４００〜１０００℃の温度範囲で焼成することを特徴とする本発明１又は４の触媒の製造法である（本発明５）。 In the present invention, an alkaline aqueous solution, a calcium salt raw material, an aluminum salt raw material, and an iron salt raw material are mixed and aged in a temperature range of 300 ° C. or lower within a pH value range of 7.0 to 14.0. After obtaining layered double hydroxide particles, filtering and washing with water, firing in a temperature range of 400 to 1000 ° C. is a method for producing a catalyst of the present invention 1 or 4 (present invention 5).
また、本発明は、アルカリ性水溶液と、カルシウム塩原料及びアルミニウム塩原料とを混合し、ｐＨ値が７．０〜１４．０の範囲にて３００℃以下の温度範囲で熟成して層状複水酸化物粒子を得て、濾別、水洗した後、４００〜１０００℃の温度範囲で焼成し、次いで、Ａｕ，Ａｇ，Ｃｕ，Ｐｔ，Ｐｄ，Ｎｉ，Ｉｒ，Ｒｈ，Ｃｏ，Ｏｓ，Ｒｕから選ばれる少なくとも一種の元素を担持し、次いで、加熱することを特徴とする本発明２又は４の触媒の製造法である（本発明６）。 In the present invention, an alkaline aqueous solution is mixed with a calcium salt raw material and an aluminum salt raw material, and ripened in a temperature range of 300 ° C. or less within a pH value range of 7.0 to 14.0 to form a layered double hydroxide. After obtaining product particles, filtering, washing with water, firing in a temperature range of 400 to 1000 ° C., and then selected from Au, Ag, Cu, Pt, Pd, Ni, Ir, Rh, Co, Os, Ru This is a method for producing a catalyst of the present invention 2 or 4, wherein at least one element is supported and then heated (present invention 6).
また、本発明は、アルカリ性水溶液と、カルシウム塩原料、アルミニウム塩原料及びＡｕ，Ａｇ，Ｃｕ，Ｐｔ，Ｐｄ，Ｎｉ，Ｉｒ，Ｒｈ，Ｃｏ，Ｏｓ，Ｒｕから選ばれる少なくとも一種の元素の原料塩とを混合し、ｐＨ値が７．０〜１４．０の範囲にて３００℃以下の温度範囲で熟成して層状複水酸化物粒子を得て、濾別、水洗した後、４００〜１０００℃の温度範囲で焼成し、次いで、加熱することを特徴とする本発明２又は４の触媒の製造法である（本発明７）。 The present invention also provides an alkaline aqueous solution, a calcium salt raw material, an aluminum salt raw material, and a raw material salt of at least one element selected from Au, Ag, Cu, Pt, Pd, Ni, Ir, Rh, Co, Os, and Ru. The mixture was aged in a temperature range of 300 ° C. or lower within a pH value range of 7.0 to 14.0 to obtain layered double hydroxide particles, filtered and washed with water, and then 400 to 1000 ° C. It is a manufacturing method of the catalyst of the present invention 2 or 4 characterized by calcining in a temperature range and then heating (present invention 7).
また、本発明は、本発明１乃至４のいずれかの触媒からなる水性ガスシフト反応用触媒である（本発明８）。 Further, the present invention is a water gas shift reaction catalyst comprising the catalyst according to any one of the present inventions 1 to 4 (present invention 8).
また、本発明は、本発明８の水性ガスシフト反応用触媒、水及び一酸化炭素を、５０〜８００℃の温度範囲で反応させることによって、水素と二酸化炭素とを製造することを特徴とする水性ガスの製造方法である（本発明９）。 Moreover, this invention manufactures hydrogen and a carbon dioxide by making the catalyst for water gas shift reactions of this invention 8, water, and carbon monoxide react in the temperature range of 50-800 degreeC, It is characterized by the above-mentioned. This is a gas production method (Invention 9).
また、本発明は、本発明１乃至４のいずれかの触媒からなる排ガス浄化用触媒である（本発明１０）。 Further, the present invention is an exhaust gas purifying catalyst comprising the catalyst according to any one of the present inventions 1 to 4 (present invention 10).
また、本発明は、本発明１０の排ガス浄化用触媒と排ガスを、１５０℃〜１０００℃の温度範囲で接触させ、排ガスを浄化する方法である（本発明１１）。 The present invention is also a method for purifying exhaust gas by contacting the exhaust gas purifying catalyst of the present invention 10 and exhaust gas in a temperature range of 150 ° C. to 1000 ° C. (Invention 11).
本発明に係る触媒は、酸素貯蔵放出能が高いので、水性ガスシフト反応及び排ガス浄化をより効率よく行えるという優れた効果を奏する。 Since the catalyst according to the present invention has a high oxygen storage / release capacity, the water gas shift reaction and the exhaust gas purification can be performed more efficiently.
本発明の構成をより詳しく説明すれば次の通りである。 The configuration of the present invention will be described in more detail as follows.
本発明に係る触媒の５００℃の酸素貯蔵放出能（ＯＳＣ）は２０〜２００μｍｏｌ／ｇである。酸素貯蔵放出能が２０μｍｏｌ／ｇ未満の場合には、酸素貯蔵放出能が低いため触媒として機能が十分ではない。好ましくは４０〜２００μｍｏｌ／ｇである。 The oxygen storage / release capacity (OSC) at 500 ° C. of the catalyst according to the present invention is 20 to 200 μmol / g. When the oxygen storage / release capacity is less than 20 μmol / g, the oxygen storage / release capacity is low, so that the function as a catalyst is not sufficient. Preferably it is 40-200 micromol / g.
本発明に係る触媒のＢＥＴ比表面積値は２０ｍ２／ｇ以上である。比表面積が増大すると活性点の数が増加し、より高い活性が得られる。好ましくは２５ｍ２／ｇ以上であり、より好ましくは３０ｍ２／ｇ以上である。上限は１５０ｍ２／ｇ程度である。さらに貴金属を担持した場合には、比表面積が増大すると担持した金属が高分散しやすくなり、より高い触媒活性が得られる。 The catalyst according to the present invention has a BET specific surface area value of 20 m 2 / g or more. As the specific surface area increases, the number of active sites increases and higher activity is obtained. Preferably it is 25 m < 2 > / g or more, More preferably, it is 30 m < 2 > / g or more. The upper limit is about 150 m 2 / g. Furthermore, when a noble metal is supported, the supported metal becomes highly dispersed easily when the specific surface area is increased, and higher catalytic activity can be obtained.
本発明に係る触媒は、カルシウム及びアルミニウムからなる複合酸化物からなる。カルシウムとアルミニウムとのモル比（Ｃａ／Ａｌ）は０．１〜０．９の範囲であることが好ましく、より好ましくは０．３〜０．９の範囲である。カルシウムとアルミニウムの比率が小さくなるほど焼成時に細孔を持ちやすいアルミニウムの比率が増加し、比表面積は高くなる傾向にあるが、カルシウムとアルミニウムの比率が前記範囲を超えると、カルシウムの効果が減少してしまう。 The catalyst according to the present invention is composed of a complex oxide composed of calcium and aluminum. The molar ratio of calcium to aluminum (Ca / Al) is preferably in the range of 0.1 to 0.9, and more preferably in the range of 0.3 to 0.9. As the ratio between calcium and aluminum decreases, the ratio of aluminum that tends to have pores increases during firing and the specific surface area tends to increase.However, if the ratio between calcium and aluminum exceeds the above range, the effect of calcium decreases. End up.
本発明に係る触媒の構成相は、カルシウムアルミネートを主成分とすることが好ましく、水性ガスシフト用触媒及び排ガス浄化用触媒として用いる場合は、Ｃ１２Ａ７を主成分とするものが好ましい。 The constituent phase of the catalyst according to the present invention is preferably composed mainly of calcium aluminate, and when used as a water gas shift catalyst and an exhaust gas purification catalyst, those composed mainly of C12A7 are preferred.
また、本発明に係る触媒は、構成元素のアルミニウムを鉄で置換してもよく、単に、鉄を担持した触媒よりも鉄が高分散しやすいため、より高い活性が得られる。鉄の置換量はアルミニウムに対して０．００１〜１０ｍｏｌ％が好ましく、より好ましくは０．１〜５ｍｏｌ％である。 In addition, the catalyst according to the present invention may be obtained by replacing the constituent element aluminum with iron. Since the iron is more easily dispersed than the catalyst supporting iron, higher activity is obtained. The substitution amount of iron is preferably 0.001 to 10 mol%, more preferably 0.1 to 5 mol% with respect to aluminum.
さらに、本発明に係る触媒は、Ａｕ，Ａｇ，Ｃｕ，Ｐｔ，Ｐｄ，Ｎｉ，Ｉｒ，Ｒｈ，Ｃｏ，Ｏｓ，Ｒｕの中から選ばれた１種または２種以上の金属元素を触媒に対する重量比で０．００１〜１０ｗｔ％担持することが好ましい。また、金属成分の存在形態は、特に限定されるものではない。 Furthermore, the catalyst according to the present invention is a weight ratio of one or more metal elements selected from Au, Ag, Cu, Pt, Pd, Ni, Ir, Rh, Co, Os, and Ru to the catalyst. It is preferable to support 0.001 to 10 wt%. Moreover, the presence form of a metal component is not specifically limited.
次に、本発明に係る触媒の製造法について述べる。 Next, a method for producing the catalyst according to the present invention will be described.
本発明においては、アルカリ性水溶液と、カルシウム塩及びアルミニウム塩原料とを混合し、ｐＨ値が７．０〜１４．０の範囲、３００℃以下の温度範囲で熟成して層状複水酸化物粒子（ハイドロタルサイト粒子）を得て、濾別、水洗した後、４００〜１０００℃の温度範囲で焼成する。 In the present invention, an alkaline aqueous solution and calcium salt and aluminum salt raw materials are mixed and aged in the temperature range of pH 7.0 to 14.0 and 300 ° C. or lower to form layered double hydroxide particles ( Hydrotalcite particles) are obtained, filtered, washed with water, and then fired in a temperature range of 400 to 1000 ° C.
本発明におけるアルカリ性水溶液としては、水酸化ナトリウム水溶液、炭酸ナトリウム水溶液及び水酸化カリウム水溶液等が好ましい。 As alkaline aqueous solution in this invention, sodium hydroxide aqueous solution, sodium carbonate aqueous solution, potassium hydroxide aqueous solution, etc. are preferable.
本発明におけるカルシウム塩としては、硫酸塩、塩化物、硝酸塩などの各種金属塩を用いることができる。 As the calcium salt in the present invention, various metal salts such as sulfate, chloride and nitrate can be used.
本発明におけるアルミニウム塩原料としては水酸化アルミニウム、硫酸アルミニウム塩原料、塩化アルミニウム塩原料及び硝酸アルミニウム塩原料などであり、前記アルミニウム塩原料を溶解した水溶液を使用することができる。 Examples of the aluminum salt raw material in the present invention include aluminum hydroxide, aluminum sulfate salt raw material, aluminum chloride salt raw material, and aluminum nitrate salt raw material, and an aqueous solution in which the aluminum salt raw material is dissolved can be used.
カルシウム塩とアルミニウム塩原料との混合割合は、カルシウムとアルミニウムとのモル比が０．１〜０．９の範囲になる割合であり、より好ましくは０．３〜０．９である。 The mixing ratio of the calcium salt and the aluminum salt raw material is such that the molar ratio of calcium to aluminum is in the range of 0.1 to 0.9, more preferably 0.3 to 0.9.
本発明における熟成反応中のｐＨ値は７．０〜１４であり、好ましくは１０〜１３である。ｐＨ値が７．０未満の場合、板面径が大きく、適度な厚みを有した層状複水酸化物粒子が得られない。 The pH value during the ripening reaction in the present invention is 7.0 to 14, preferably 10 to 13. When the pH value is less than 7.0, layered double hydroxide particles having a large plate surface diameter and an appropriate thickness cannot be obtained.
本発明における熟成反応中の温度は３００℃以下であり、好ましくは２０〜１０５℃である。３００℃を越える場合は、超高圧に耐え得る装置が必要となるため好ましくない。 The temperature during the ripening reaction in the present invention is 300 ° C. or less, preferably 20 to 105 ° C. When the temperature exceeds 300 ° C., an apparatus capable of withstanding ultrahigh pressure is required, which is not preferable.
本発明における層状複水酸化物粒子の組成は、カルシウムとアルミニウムとのモル比が０．１〜０．９の範囲である。 The composition of the layered double hydroxide particles in the present invention is such that the molar ratio of calcium to aluminum is in the range of 0.1 to 0.9.
なお、本発明においては、所定のカルシウムとアルミニウムとのモル比を有する触媒を得るために、前記製造法において、過剰量のアルミニウムを用いることによって、所定の組成の層状複水酸化物粒子とアルミニウム化合物（アルミナ、ベーマイトなど）を混合させた後、加熱焼成する方法、又は、層状複水酸化物粒子を製造した後、アルミニウム化合物（アルミナ、ベーマイトなど）を添加、混合し、加熱処理する方法などを用いてもよい。 In the present invention, in order to obtain a catalyst having a predetermined molar ratio of calcium to aluminum, an excess amount of aluminum is used in the above production method, whereby layered double hydroxide particles having a predetermined composition and aluminum are used. A method in which a compound (alumina, boehmite, etc.) is mixed and then heated and fired, or a layered double hydroxide particle is produced, and then an aluminum compound (alumina, boehmite, etc.) is added, mixed, and heat treated. May be used.
また、得られた層状複水酸化物粒子を水洗することによって物質中のカルシウムを溶かし、カルシウムとアルミニウムの組成を変化させてもよく、より均一にカルシウムとアルミニウムが混合した状態になる。 Moreover, the calcium in a substance may be dissolved by washing the obtained layered double hydroxide particles with water, and the composition of calcium and aluminum may be changed, resulting in a more uniform mixture of calcium and aluminum.
本発明における焼成温度が４００℃未満の場合には、高い酸素貯蔵放出能を有する触媒が合成できず、１０００℃より高い温度では、比表面積が小さくなり、触媒性能が低下するので好ましくない。好ましくは６００〜８００℃の範囲である。 When the calcination temperature in the present invention is less than 400 ° C., a catalyst having a high oxygen storage / release capability cannot be synthesized, and a temperature higher than 1000 ° C. is not preferable because the specific surface area becomes small and the catalyst performance decreases. Preferably it is the range of 600-800 degreeC.
本発明における焼成のときの雰囲気は、大気中が好ましい。 The atmosphere during firing in the present invention is preferably in the air.
なお、本発明においては、前記焼成の後、５０〜８００℃の温度範囲で還元処理を行ってもよい。 In the present invention, after the firing, reduction treatment may be performed in a temperature range of 50 to 800 ° C.
本発明に係る鉄を含有する触媒は、前記製造法において、カルシウム塩及びアルミニウム塩原料とともに鉄塩原料を添加・混合すればよい。 The iron-containing catalyst according to the present invention may be prepared by adding and mixing an iron salt raw material together with a calcium salt and an aluminum salt raw material in the production method.
鉄塩原料としては、硫酸第一鉄、硫酸第二鉄塩原料化第一鉄塩原料化第二鉄などである。鉄塩原料の添加割合は、アルミニウムに対して０．００１〜１０ｍｏｌ％である。 Examples of the iron salt raw material include ferrous sulfate, ferric sulfate raw material ferrous salt raw material ferric iron and the like. The addition ratio of the iron salt raw material is 0.001 to 10 mol% with respect to aluminum.
本発明に係るＡｕ，Ａｇ，Ｃｕ，Ｐｔ，Ｐｄ，Ｎｉ，Ｉｒ，Ｒｈ，Ｃｏ，Ｏｓ，Ｒｕを担持した触媒は、前記製造法において加熱処理後の触媒に対して通常の方法で担持させればよく、例えば、硝酸ニッケル水溶液に該触媒を浸し、乾燥させてもよい。また、この後、加熱還元処理を行っても良い。 The catalyst supporting Au, Ag, Cu, Pt, Pd, Ni, Ir, Rh, Co, Os, Ru according to the present invention is supported on the catalyst after the heat treatment in the above production method by a usual method. For example, the catalyst may be immersed in an aqueous nickel nitrate solution and dried. Thereafter, a heat reduction treatment may be performed.
また、本発明においては、カルシウム塩及びアルミニウム塩原料、必要により鉄塩原料と、Ａｕ，Ａｇ，Ｃｕ，Ｐｔ，Ｐｄ，Ｎｉ，Ｉｒ，Ｒｈ，Ｃｏ，Ｏｓ，Ｒｕから選ばれる少なくとも一種の元素の塩原料とを、アルカリ性水溶液と混合することによって、Ａｕ，Ａｇ，Ｃｕ，Ｐｔ，Ｐｄ，Ｎｉ，Ｉｒ，Ｒｈ，Ｃｏ，Ｏｓ，Ｒｕから選ばれる少なくとも一種の元素を含有させてもよく、Ａｇ，Ｃｕ，Ｐｔ，Ｐｄ，Ｎｉ，Ｉｒ，Ｒｈ，Ｃｏ，Ｏｓ，Ｒｕから選ばれる少なくとも一種の元素をより高分散の状態で担持することができる。 Further, in the present invention, calcium salt and aluminum salt raw materials, and optionally iron salt raw materials, and at least one element selected from Au, Ag, Cu, Pt, Pd, Ni, Ir, Rh, Co, Os, Ru The salt raw material may be mixed with an alkaline aqueous solution to contain at least one element selected from Au, Ag, Cu, Pt, Pd, Ni, Ir, Rh, Co, Os, and Ru. At least one element selected from Cu, Pt, Pd, Ni, Ir, Rh, Co, Os, and Ru can be supported in a highly dispersed state.
次に、本発明に係る触媒を用いた水性ガスの製造法について述べる。 Next, a method for producing water gas using the catalyst according to the present invention will be described.
本発明に係る触媒の存在下で、水及び一酸化炭素を５０℃〜８００℃の温度範囲で反応させることで、水素と二酸化炭素が得られる。触媒の存在割合は水と一酸化炭素を合わせたガス空間速度で１００／ｈ以上が好ましい。 Hydrogen and carbon dioxide are obtained by reacting water and carbon monoxide in the temperature range of 50 ° C. to 800 ° C. in the presence of the catalyst according to the present invention. The presence ratio of the catalyst is preferably 100 / h or more in terms of gas space velocity in which water and carbon monoxide are combined.
次に、本発明に係る触媒を用いた排ガスの浄化方法について述べる。 Next, the exhaust gas purification method using the catalyst according to the present invention will be described.
本発明に係る触媒を、１５０℃〜１０００℃の温度範囲でＨＣ、ＣＯ等を含む排ガスと接触させて排ガスを浄化することができる。触媒の存在割合は全ガス空間速度で１００／ｈ以上が好ましい。 The catalyst according to the present invention can be purified by bringing it into contact with exhaust gas containing HC, CO, etc. in the temperature range of 150 ° C. to 1000 ° C. The catalyst content is preferably 100 / h or more in terms of the total gas space velocity.
＜作用＞
本発明において、最も重要な点は、カルシウム及びアルミニウムの複合酸化物を主成分とする触媒は、高い酸素貯蔵放出能を有する点である。
<Action>
In the present invention, the most important point is that a catalyst mainly composed of a complex oxide of calcium and aluminum has a high oxygen storage / release capability.
本発明においては、あらかじめ、カルシウムとアルミニウムとからなる層状複水酸化物を製造した後、加熱焼成してカルシウム及びアルミニウムからなる複合酸化物を主成分とする触媒としているので、構成元素がより均一に分散しており、焼成温度を低くしても、高い酸素貯蔵放出能を有するカルシウム及びアルミニウムからなる複合酸化物を得ることができ、且つ、層状複水酸化物に由来して高い比表面積を有する触媒を得ることができ、結果、活性点をより多くすることができる。従って、より高い活性を持つ触媒が得られる。 In the present invention, a layered double hydroxide composed of calcium and aluminum is produced in advance and then heated and fired to form a catalyst mainly composed of a composite oxide composed of calcium and aluminum, so that the constituent elements are more uniform. Even if the calcination temperature is lowered, a composite oxide composed of calcium and aluminum having a high oxygen storage and release ability can be obtained, and a high specific surface area is derived from the layered double hydroxide. The resulting catalyst can be obtained, and as a result, more active sites can be obtained. Therefore, a catalyst having higher activity can be obtained.
また、本発明に係る鉄を含有する触媒は、鉄もまたカルシウムやアルミニウムと同じように高分散しているため、より高い活性が得られる。 Moreover, since the iron-containing catalyst according to the present invention is highly dispersed in the same manner as calcium and aluminum, higher activity can be obtained.
また、本発明に係るＡｕ，Ａｇ，Ｃｕ，Ｐｔ，Ｐｄ，Ｎｉ，Ｉｒ，Ｒｈ，Ｃｏ，Ｏｓ，Ｒｕを担持した触媒は、より高い活性を有するものである。これら元素を担持する場合、特に低温域での触媒活性を高めるのに有用である。本発明に係る触媒が高い酸素貯蔵放出能を有するとともに、高い比表面積を有するので、前記Ａｕ等の金属が高分散しやすく、十分な反応が進行するためと推定している。 Further, the catalyst supporting Au, Ag, Cu, Pt, Pd, Ni, Ir, Rh, Co, Os, Ru according to the present invention has higher activity. When these elements are supported, it is useful for enhancing catalytic activity particularly in a low temperature range. Since the catalyst according to the present invention has a high oxygen storage / release capacity and a high specific surface area, it is presumed that the metal such as Au tends to be highly dispersed and a sufficient reaction proceeds.
また、本発明に係る触媒は、前述した通り高い活性を有するので、ＨＣやＣＯ等の酸化反応や排ガス浄化に対しても高い活性を示す。 In addition, since the catalyst according to the present invention has high activity as described above, it also exhibits high activity for oxidation reactions such as HC and CO and exhaust gas purification.
本発明の代表的な実施の形態は次の通りである。 A typical embodiment of the present invention is as follows.
触媒の酸素貯蔵放出能は、パルス式反応装置により、５００℃にてパルス一回当たり０．５ｃｃの２％ＣＯ／Ａｒガスを用いて、パルス法によって測定し、還元によって消失した酸素量を測定し、引き続き、５００℃にて２０％Ｏ２／Ｎ２ガスを用いて、パルス法によって測定し、酸化によって増加した酸素量を測定した。前記測定を連続して２回行い、消失した酸素量及び増加した酸素量の各酸素量について測定値を平均して、酸化還元時に移動した酸素量としてＯＳＣを算出した。 The oxygen storage / release capacity of the catalyst is measured by the pulse method using a pulse reactor at 500 ° C. with 0.5 cc of 2% CO / Ar gas per pulse, and the amount of oxygen lost by reduction is measured. Subsequently, measurement was performed by a pulse method using 20% O 2 / N 2 gas at 500 ° C., and the amount of oxygen increased by oxidation was measured. The measurement was performed twice in succession, the measured values were averaged for each of the lost oxygen amount and the increased oxygen amount, and the OSC was calculated as the amount of oxygen transferred during oxidation-reduction.
触媒を構成するカルシウム、アルミニウム、鉄、Ａｕ，Ａｇ，Ｃｕ，Ｐｔ，Ｐｄ，Ｎｉ，Ｉｒ，Ｒｈ，Ｃｏ，Ｏｓ，Ｒｕの含有量は、該触媒を酸で溶解し、「プラズマ発光分光分析装置 ＳＰＳ４０００（セイコー電子工業（株））」で測定して求めた。 The content of calcium, aluminum, iron, Au, Ag, Cu, Pt, Pd, Ni, Ir, Rh, Co, Os, and Ru constituting the catalyst is determined by dissolving the catalyst with an acid. SPS4000 (Seiko Electronics Co., Ltd.) "
ＢＥＴ比表面積値は、窒素によるＢＥＴ法により測定した。 The BET specific surface area value was measured by the BET method using nitrogen.
相の同定は、Ｘ線回折測定で行った。Ｘ線回折装置は「Ｘ線回折装置ＲＩＮＴ−２５００（理学電機（株）製）」（管球：Ｃｕ、管電圧：４０ｋＶ、管電流：３００ｍＡ、ゴニオメーター：広角ゴニオメーター、サンプリング幅：０．０２０°、走査速度：２°／ｍｉｎ、発散スリット：１°、散乱スリット：１°、受光スリット：０．５０ｍｍ）を使用した。 The phase was identified by X-ray diffraction measurement. The X-ray diffractometer is “X-ray diffractometer RINT-2500 (manufactured by Rigaku Corporation)” (tube: Cu, tube voltage: 40 kV, tube current: 300 mA, goniometer: wide angle goniometer, sampling width: 0. 020 °, scanning speed: 2 ° / min, divergence slit: 1 °, scattering slit: 1 °, light receiving slit: 0.50 mm).
＜実施例１＞
苛性ソーダ水溶液（濃度１８．５５ｍｏｌ／ｌ）５００ｍｌを４０℃に加熱して撹拌しておき、塩化アルミニウム六水和物 ６５．０１ｇ及び塩化カルシウム二水和物３３．９２ｇを水５００ｍｌに溶解した水溶液を添加し、４０℃に保持したまま４時間熟成した。得られた沈殿物を濾過、洗浄して、結晶構造を同定したところ、Ｃａ−Ａｌ系のハイドロタルサイトであった。次いで、７００℃で焼成した。
得られた粉末をジニトロジアンミン白金硝酸水溶液に浸漬して、Ｐｔを担持し、６００℃で２時間焼成した後、６００℃で水素還元を行った。白金の担持量は触媒全体に対し０．５ｗｔ％であった。構成相はＣ１２Ａ７であった。
<Example 1>
A 500 ml aqueous solution of caustic soda (concentration 18.55 mol / l) was heated to 40 ° C. and stirred, and an aqueous solution prepared by dissolving 65.01 g of aluminum chloride hexahydrate and 33.92 g of calcium chloride dihydrate in 500 ml of water. The mixture was added and aged for 4 hours while maintaining at 40 ° C. When the obtained precipitate was filtered and washed to identify the crystal structure, it was Ca-Al hydrotalcite. Subsequently, it baked at 700 degreeC.
The obtained powder was immersed in a dinitrodiammine platinum nitric acid aqueous solution to carry Pt, calcined at 600 ° C. for 2 hours, and then subjected to hydrogen reduction at 600 ° C. The amount of platinum supported was 0.5 wt% with respect to the entire catalyst. The constituent phase was C12A7.
＜実施例２＞
カルシウムとアルミニウムの比率を０．４９に変化させた以外は、実施例１と同様にして製造した。
<Example 2>
This was manufactured in the same manner as in Example 1 except that the ratio of calcium to aluminum was changed to 0.49.
＜実施例３＞
塩化カルシウム二水和物、塩化アルミニウム六水和物とともに第二塩化鉄を用いて実施例１と同様に合成した。鉄／（アルミニウム＋鉄）比は０．０２であり、白金の担持量は触媒全体に対し０．５ｗｔ％であった。構成相はＣ１２Ａ７であった。
<Example 3>
It was synthesized in the same manner as in Example 1 using ferric chloride together with calcium chloride dihydrate and aluminum chloride hexahydrate. The iron / (aluminum + iron) ratio was 0.02, and the amount of platinum supported was 0.5 wt% with respect to the total catalyst. The constituent phase was C12A7.
＜実施例４＞
塩化カルシウム二水和物、塩化アルミニウム六水和物とともに第二塩化鉄を用いて実施例１と同様に合成した。鉄／（アルミニウム＋鉄）比は０．０４であり、白金の担持量は触媒全体に対し０．５ｗｔ％であった。構成相はＣ１２Ａ７であった。
<Example 4>
It was synthesized in the same manner as in Example 1 using ferric chloride together with calcium chloride dihydrate and aluminum chloride hexahydrate. The iron / (aluminum + iron) ratio was 0.04, and the amount of platinum supported was 0.5 wt% with respect to the total catalyst. The constituent phase was C12A7.
＜実施例５＞
Ｐｔの担持量を３ｗｔ％とした以外は、実施例１と同様にして製造した。
<Example 5>
It was manufactured in the same manner as in Example 1 except that the amount of Pt supported was 3 wt%.
＜実施例６＞
Ｐｔの担持量を５ｗｔ％とした以外は、実施例１と同様にして製造した。
<Example 6>
It was manufactured in the same manner as in Example 1 except that the amount of Pt supported was 5 wt%.
＜実施例７＞
Ｐｔの変わりにＰｄを用いた以外は、実施例１と同様にして製造した。
<Example 7>
Manufactured in the same manner as in Example 1 except that Pd was used instead of Pt.
＜実施例８＞
Ｐｔの変わりにＲｕを用いた以外は、実施例１と同様にして製造した。
<Example 8>
Manufactured in the same manner as in Example 1 except that Ru was used instead of Pt.
＜実施例９＞
Ｐｔの変わりにＲｈを用いた以外は、実施例１と同様にして製造した。
<Example 9>
It was manufactured in the same manner as in Example 1 except that Rh was used instead of Pt.
＜実施例１０＞
Ｐｔの変わりにＣｕを用いた以外は、実施例１と同様にして製造した。
<Example 10>
Manufactured in the same manner as in Example 1 except that Cu was used instead of Pt.
＜実施例１１＞
Ｐｔの変わりにＡｕを用いた以外は、実施例１と同様にして製造した。
<Example 11>
Manufactured in the same manner as in Example 1 except that Au was used instead of Pt.
＜実施例１２＞
Ｐｔの変わりにＮｉを用いた以外は、実施例１と同様にして製造した。
<Example 12>
Manufactured in the same manner as in Example 1 except that Ni was used instead of Pt.
＜実施例１３＞
塩化カルシウム二水和物、塩化アルミニウム六水和物とともに第二塩化鉄を用いて実施例１と同様に合成した。鉄／（アルミニウム＋鉄）比は０．０２であり、白金の担持量は触媒全体に対し０ｗｔ％であった。構成相はＣ１２Ａ７であった。
<Example 13>
It was synthesized in the same manner as in Example 1 using ferric chloride together with calcium chloride dihydrate and aluminum chloride hexahydrate. The iron / (aluminum + iron) ratio was 0.02, and the supported amount of platinum was 0 wt% with respect to the total catalyst. The constituent phase was C12A7.
＜実施例１４＞
鉄／（アルミニウム＋鉄）比を０．０４とした以外は、前記実施例１３と同様にして製造した。
<Example 14>
It was manufactured in the same manner as in Example 13 except that the iron / (aluminum + iron) ratio was 0.04.
＜比較例１＞
水酸化アルミニウム ４２．１２ｇ及び炭酸カルシウム４８．００ｇに純水を５０ｍｌ加えてボールミルで粉砕し、乾燥させ、１３５０℃で焼成した。これにジニトロジアンミン白金硝酸水溶液を用いて、含浸法によりＰｔを担持し、６００℃で２時間焼成した後、６００℃で水素還元を行った。白金の担持量は０．５ｗｔ％とした。
<Comparative Example 1>
50 ml of pure water was added to 42.12 g of aluminum hydroxide and 48.00 g of calcium carbonate, pulverized with a ball mill, dried, and fired at 1350 ° C. A dinitrodiammine platinum nitric acid aqueous solution was used for this, Pt was supported by an impregnation method, calcined at 600 ° C. for 2 hours, and then subjected to hydrogen reduction at 600 ° C. The supported amount of platinum was 0.5 wt%.
＜比較例２＞
比較例１と同様に合成し、Ｐｔの担持量を３ｗｔ％とした。
<Comparative example 2>
Synthesis was performed in the same manner as in Comparative Example 1, and the amount of Pt supported was 3 wt%.
＜比較例３＞
γ−Ａｌ２Ｏ３にジニトロジアンミン白金硝酸水溶液を用いて、含浸法によりＰｔを担持し、６００℃で焼成した後、６００℃で水素還元を行った。白金の担持量は０．５ｗｔ％とした。
<Comparative Example 3>
Pt was supported by γ-Al 2 O 3 using a dinitrodiammine platinum nitrate aqueous solution by an impregnation method, calcined at 600 ° C., and then hydrogen reduced at 600 ° C. The supported amount of platinum was 0.5 wt%.
＜比較例４＞
実施例１と同様に合成し、カルシウムとアルミニウムの比率を０．０５とした。
<Comparative example 4>
Synthesis was performed in the same manner as in Example 1, and the ratio of calcium to aluminum was set to 0.05.
＜比較例５＞
実施例１と同様に合成し、カルシウムとアルミニウムの比率を２．００とした。
<Comparative Example 5>
Synthesis was performed in the same manner as in Example 1, and the ratio of calcium to aluminum was 2.00.
＜比較例６＞
比較例１と同様に合成し、カルシウムとアルミニウムの比率を０．６９とした。
<Comparative Example 6>
Synthesis was performed in the same manner as in Comparative Example 1, and the ratio of calcium to aluminum was 0.69.
＜比較例７＞
実施例１と同様に合成し、Ｐｔの担持量を１２ｗｔ％とした。
<Comparative Example 7>
Synthesis was performed in the same manner as in Example 1, and the supported amount of Pt was 12 wt%.
＜比較例８＞
実施例１４と同様に合成し、カルシウムとアルミニウムの比率を１．０７とし、鉄／（アルミニウム＋鉄）比は０．２とした。
<Comparative Example 8>
In the same manner as in Example 14, the ratio of calcium and aluminum was 1.07, and the iron / (aluminum + iron) ratio was 0.2.
＜比較例９＞
γ−Ａｌ２Ｏ３を７００℃で焼成した後、６００℃で水素還元を行った。
<Comparative Example 9>
After baking γ-Al 2 O 3 at 700 ° C., hydrogen reduction was performed at 600 ° C.
＜比較例１０＞
実施例１３と同様に合成し、カルシウムとアルミニウムの比率を０．９１とした。７００℃で焼成し、鉄を含浸法により鉄を担持し、６００℃で水素還元を行った。鉄の担持量を、鉄／（アルミニウム＋鉄）比で０．０５とした。
<Comparative Example 10>
Synthesis was performed in the same manner as in Example 13, and the ratio of calcium to aluminum was set to 0.91. It baked at 700 degreeC, iron was carry | supported by the impregnation method, and hydrogen reduction was performed at 600 degreeC. The iron loading was 0.05 in terms of iron / (aluminum + iron) ratio.
＜ＣＯ転化率の測定＞
実施例１〜１２、比較例１〜７
得られた各触媒を、０．５から１ｍｍに整粒した。
触媒の成形体を電気炉で加熱し、５００℃でＣＯが３３体積％、水蒸気が６７体積％のガスを空間速度（ＧＨＳＶ）が１０００００ｈ−１で流通させた。このときの出口ガス組成をガスクロマトグラフで測定した。
各触媒の諸特性及びＣＯ転化率を表１に示す。
<Measurement of CO conversion>
Examples 1-12, Comparative Examples 1-7
Each of the obtained catalysts was sized to 0.5 to 1 mm.
The catalyst compact was heated in an electric furnace, and a gas containing 33% by volume of CO and 67% by volume of water vapor was passed at 500 ° C. at a space velocity (GHSV) of 100,000 h −1 . The outlet gas composition at this time was measured with a gas chromatograph.
Table 1 shows the characteristics and CO conversion of each catalyst.
実施例１３〜１４、比較例８〜１０
触媒の成形体を電気炉で加熱し、５００℃でＣＯが３３体積％、水蒸気が６７体積％のガスを空間速度（ＧＨＳＶ）が２００００ｈ−１で流通させた。このときの出口ガス組成をガスクロマトグラフで測定した。
各触媒の諸特性及びＣＯ転化率を表２に示す。
Examples 13-14, Comparative Examples 8-10
The catalyst compact was heated in an electric furnace, and a gas having a volume of CO of 33% by volume and water vapor of 67% by volume was circulated at a space velocity (GHSV) of 20000 h −1 at 500 ° C. The outlet gas composition at this time was measured with a gas chromatograph.
Table 2 shows the characteristics and CO conversion of each catalyst.
なお、ＣＯ転化率が１００％にならないのは、反応平衡に依存するからである。 The reason why the CO conversion rate does not reach 100% is that it depends on the reaction equilibrium.
表１より、本発明に係る触媒は、高い比表面積を有するともに、酸素貯蔵放出能も高く、高い活性を示すものである。 From Table 1, the catalyst according to the present invention has high specific surface area, high oxygen storage / release capacity, and high activity.
また、本発明に係る触媒は、ＨＣやＣＯ等の酸化反応や排ガス浄化に対しても高い活性を示す。 In addition, the catalyst according to the present invention exhibits high activity for oxidation reactions such as HC and CO and exhaust gas purification.
本発明のカルシウム及びアルミニウム等からなる触媒は酸素貯蔵放出能が高いので、従来のものと比べ水性ガスシフト反応及び排ガス浄化をより効率よく行えるという優れた効果を奏する。
Since the catalyst made of calcium and aluminum according to the present invention has a high oxygen storage and release ability, it has an excellent effect that water gas shift reaction and exhaust gas purification can be performed more efficiently than conventional catalysts.
Claims (8)
Hydrogen and carbon dioxide are produced by reacting the water gas shift reaction catalyst according to any one of claims 1 to 4 , water and carbon monoxide in a temperature range of 50 to 800 ° C. A method for producing water gas.
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| JP4992773B2 (en) | 2007-03-20 | 2012-08-08 | 株式会社デンソー | Catalyst material |
| JP2009028694A (en) * | 2007-07-30 | 2009-02-12 | Mitsubishi Heavy Ind Ltd | Co shift catalyst, its manufacturing method, fuel reforming apparatus and fuel cell system |
| TW201026242A (en) * | 2008-11-06 | 2010-07-16 | Japan Tobacco Inc | Smoking article and manufacturing method for the same, and method for manufacturing carbon monoxide reducer |
| WO2011118043A1 (en) * | 2010-03-26 | 2011-09-29 | 日本たばこ産業株式会社 | Fuel element of non-combustion smoking article and method for producing same |
| JP6941454B2 (en) * | 2017-03-03 | 2021-09-29 | 太平洋マテリアル株式会社 | Method for producing catalyst carrier |
| JP7269562B2 (en) * | 2019-03-07 | 2023-05-09 | 太平洋マテリアル株式会社 | Catalyst carrier and catalyst manufacturing method |
| JP7442935B2 (en) | 2020-03-31 | 2024-03-05 | 太平洋マテリアル株式会社 | Catalyst manufacturing method |
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| JP2003128415A (en) * | 2001-10-18 | 2003-05-08 | Japan Science & Technology Corp | 12CaO-7Al2O3 COMPOUND AND METHOD FOR PREPARING THE SAME |
| JP2003190787A (en) * | 2001-12-28 | 2003-07-08 | Japan Science & Technology Corp | Catalyst for purifying engine exhaust gas |
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| JP2003128415A (en) * | 2001-10-18 | 2003-05-08 | Japan Science & Technology Corp | 12CaO-7Al2O3 COMPOUND AND METHOD FOR PREPARING THE SAME |
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| WO2015071716A1 (en) | 2013-11-14 | 2015-05-21 | Toyota Jidosha Kabushiki Kaisha | Exhaust gas control catalyst |
| US9937487B2 (en) | 2013-11-14 | 2018-04-10 | Toyota Jidosha Kabushiki Kaisha | Exhaust gas control catalyst |
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