JP5864443B2 - Exhaust gas purification catalyst - Google Patents

Exhaust gas purification catalyst Download PDF

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JP5864443B2
JP5864443B2 JP2012551832A JP2012551832A JP5864443B2 JP 5864443 B2 JP5864443 B2 JP 5864443B2 JP 2012551832 A JP2012551832 A JP 2012551832A JP 2012551832 A JP2012551832 A JP 2012551832A JP 5864443 B2 JP5864443 B2 JP 5864443B2
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exhaust gas
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catalyst
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JPWO2012093599A1 (en
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啓太 石崎
啓太 石崎
直樹 大矢
直樹 大矢
貴弘 中
貴弘 中
直樹 光田
直樹 光田
弘志 大野
弘志 大野
高橋　進
進 高橋
彦睦 渡邉
彦睦 渡邉
啓充 高木
啓充 高木
晶子 杉岡
晶子 杉岡
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Honda Motor Co Ltd
Mitsui Mining and Smelting Co Ltd
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Mitsui Mining and Smelting Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/104—Silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/204—Alkaline earth metals
    • B01D2255/2045—Calcium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B01D2255/2061—Yttrium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/2073—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/908—O2-storage component incorporated in the catalyst

Description

本発明は自動車等の内燃機関から排出される排気ガスを浄化するために使用される排気ガス浄化用触媒に関する。   The present invention relates to an exhaust gas purifying catalyst used for purifying exhaust gas discharged from an internal combustion engine such as an automobile.

自動車等の内燃機関から排出される排ガス中には、炭化水素、一酸化炭素、窒素酸化物等の有害成分が含まれている。それで、従来から、これら有害成分を浄化して無害化する三元触媒が用いられている。   The exhaust gas discharged from an internal combustion engine such as an automobile contains harmful components such as hydrocarbons, carbon monoxide, and nitrogen oxides. Therefore, conventionally, a three-way catalyst for purifying and detoxifying these harmful components has been used.

このような三元触媒として、Ｐｔ、Ｐｄ、Ｒｈ等の貴金属とアルミナ、セリア、ジルコニア又はこれらの複酸化物とを任意に組み合わせて、セラミックス又は金属等のハニカム担体上に担持させたものがある。更に、酸素吸蔵性助触媒を併用したものも提案されている。   As such a three-way catalyst, there is a catalyst in which a noble metal such as Pt, Pd, or Rh and an alumina, ceria, zirconia, or a double oxide thereof are arbitrarily combined and supported on a honeycomb carrier such as ceramic or metal. . Furthermore, a combination of oxygen storage promoters has been proposed.

また、ディーゼルエンジンから排出される排気ガスはパティキュレート（粒子状物質）を含んでおり、これらの物質がそのまま大気中に放出されると大気汚染の原因になる。パティキュレートを取り除くための有効な手段として、ススを捕集するためのディーゼル・パティキュレート・フィルター（ＤＰＦ）を用いたディーゼル排ガストラップシステムがある。しかし、このＤＰＦでは捕集したパティキュレートを連続的に酸化除去してＤＰＦを再生する必要がある。   Further, the exhaust gas discharged from the diesel engine contains particulates (particulate matter), and if these materials are released into the atmosphere as they are, they cause air pollution. As an effective means for removing particulates, there is a diesel exhaust gas trap system using a diesel particulate filter (DPF) for collecting soot. However, in this DPF, it is necessary to regenerate the DPF by continuously oxidizing and removing the collected particulates.

これまでに提案された連続再生システムとしては、担体、例えば、酸化ジルコニウム、酸化バナジウム、酸化セリウム等の無機酸化物からなる担体にＰｔなどの高価な貴金属を担持させた触媒（例えば、特許文献１、２及び３参照）を用いるシステムがある。更に、酸素吸蔵性能を有する材料を助触媒として添加することも提案されている。   As a continuous regeneration system proposed so far, a catalyst (for example, Patent Document 1) in which an expensive noble metal such as Pt is supported on a support, for example, a support made of an inorganic oxide such as zirconium oxide, vanadium oxide, or cerium oxide. 2 and 3). Furthermore, it has also been proposed to add a material having oxygen storage performance as a promoter.

特開平１０−０４７０３５号公報Japanese Patent Laid-Open No. 10-047035 特開２００３−３３４４４３号公報JP 2003-334443 A 特開２００４−０５８０１３号公報JP 2004-058013 A

本発明は自動車等の内燃機関から排出される排気ガスを浄化するために使用される酸素吸蔵性に優れた排気ガス浄化用触媒を提供することを目的としている。   An object of the present invention is to provide an exhaust gas purifying catalyst that is excellent in oxygen storage and used for purifying exhaust gas discharged from an internal combustion engine such as an automobile.

本発明者らは上記の目的を達成するために種々の物質を用いて種々の実験を行った結果、化学式Ｙ１−ＸＡＸＭｎ２−ＺＢＺＯ５で表わされる複酸化物が酸素吸蔵性に優れていることを見出し、本発明を完成した。The present inventors have results of various experiments with various materials to achieve the above object, double oxide represented by the chemical formula Y 1-X A X Mn 2 -Z B Z O 5 is oxygen The present invention was completed by finding that it has excellent occlusion.

即ち、本発明の排気ガス浄化用触媒は、セラミックス又は金属材料からなる触媒支持体と、該触媒支持体上に担持されている複酸化物Ｙ１−ＸＡＸＭｎ２−ＺＢＺＯ５（式中、ＡはＬａ、Ｓｒ、Ｃｅ、Ｂａ、Ｃａ、Ｓｃ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ又はＢｉであり、ＢはＣｏ、Ｆｅ、Ｎｉ、Ｃｒ、Ｍｇ、Ｔｉ、Ｎｂ、Ｔａ、Ｃｕ又はＲｕであり、０．５≧Ｘ≧０であり、１≧Ｚ≧０である）と、該複酸化物Ｙ１−ＸＡＸＭｎ２−ＺＢＺＯ５に担持されているＡｇ、Ｐｔ、Ａｕ、Ｐｄ、Ｒｈ、Ｃｕ及びＭｎからなる群から選択される少なくとも一種の原子とを有することを特徴とする。That is, the exhaust gas purifying catalyst of the present invention includes a catalyst support made of ceramics or a metal material, and a double oxide Y 1-X A X Mn 2-Z B Z O 5 supported on the catalyst support. (In the formula, A is La, Sr, Ce, Ba, Ca, Sc, Ho, Er, Tm, Yb, Lu or Bi, and B is Co, Fe, Ni, Cr, Mg, Ti, Nb, Ta, Cu or Ru, 0.5 ≧ X ≧ 0, and 1 ≧ Z ≧ 0), and Ag supported on the double oxide Y 1-X A X Mn 2-Z B Z O 5 And at least one atom selected from the group consisting of Pt, Au, Pd, Rh, Cu and Mn.

また、本発明の排気ガス浄化用触媒は、（１）セラミックス又は金属材料からなる触媒支持体と、（２）該触媒支持体上に担持されている複酸化物の合計質量を基準にして５０質量％以上の複酸化物ＹＭｎ２Ｏ５と、該触媒支持体上に担持されている複酸化物の合計質量を基準にして５０質量％未満の複酸化物ＹＭｎＯ３及び複酸化物Ｙ２Ｍｎ２Ｏ７の少なくとも１種とからなる混合複酸化物と、（３）該混合複酸化物に担持されているＡｇ、Ｐｔ、Ａｕ、Ｐｄ、Ｒｈ、Ｃｕ及びＭｎからなる群から選択される少なくとも一種の原子とを有することを特徴とする。In addition, the exhaust gas purifying catalyst of the present invention comprises (1) a catalyst support made of ceramics or a metal material, and (2) 50 based on the total mass of the double oxide supported on the catalyst support. More than 50% by mass of double oxide YMn 2 O 5 and less than 50% by mass of double oxide YMnO 3 and double oxide Y 2 Mn based on the total mass of the double oxide supported on the catalyst support a mixed mixed oxide consisting of at least one and the 2 O 7, (3) Ag carried on the mixed double oxide, at least selected Pt, Au, Pd, Rh, from the group consisting of Cu and Mn It has a kind of atom.

更に、本発明の排気ガス浄化用触媒は、セラミックス又は金属材料からなる触媒支持体と、該触媒支持体上に担持されている複酸化物Ｙ１−ＸＡＸＭｎ２−ＺＢＺＯ５（式中、ＡはＬａ、Ｓｒ、Ｃｅ、Ｂａ、Ｃａ、Ｓｃ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ又はＢｉであり、ＢはＣｏ、Ｆｅ、Ｎｉ、Ｃｒ、Ｍｇ、Ｔｉ、Ｎｂ、Ｔａ、Ｃｕ又はＲｕであり、０．５≧Ｘ≧０であり、１≧Ｚ≧０である）とを有することを特徴とする。Furthermore, the exhaust gas purifying catalyst of the present invention includes a catalyst support made of ceramics or a metal material, and a double oxide Y 1-X A X Mn 2-Z B Z O 5 supported on the catalyst support. (In the formula, A is La, Sr, Ce, Ba, Ca, Sc, Ho, Er, Tm, Yb, Lu or Bi, and B is Co, Fe, Ni, Cr, Mg, Ti, Nb, Ta, Cu or Ru, 0.5 ≧ X ≧ 0, and 1 ≧ Z ≧ 0).

また、本発明の排気ガス浄化用触媒は、（１）セラミックス又は金属材料からなる触媒支持体と、（２）該触媒支持体上に担持されている複酸化物の合計質量を基準にして５０質量％以上の複酸化物ＹＭｎ２Ｏ５と、該触媒支持体上に担持されている複酸化物の合計質量を基準にして５０質量％未満の複酸化物ＹＭｎＯ３及び複酸化物Ｙ２Ｍｎ２Ｏ７の少なくとも１種とからなる混合複酸化物とを有することを特徴とする。In addition, the exhaust gas purifying catalyst of the present invention comprises (1) a catalyst support made of ceramics or a metal material, and (2) 50 based on the total mass of the double oxide supported on the catalyst support. More than 50% by mass of double oxide YMn 2 O 5 and less than 50% by mass of double oxide YMnO 3 and double oxide Y 2 Mn based on the total mass of the double oxide supported on the catalyst support and having a mixing mixed oxide consisting of at least one and the 2 O 7.

更にまた、本発明の排気ガス浄化用触媒は、上記の本発明の酸素吸蔵性に優れた排気ガス浄化用触媒において、触媒支持体がハニカム形状であるか、又はＤＰＦであることを特徴とする。   Furthermore, the exhaust gas purifying catalyst of the present invention is the above exhaust gas purifying catalyst having an excellent oxygen storage property according to the present invention, wherein the catalyst support has a honeycomb shape or a DPF. .

本発明の排気ガス浄化用触媒は酸素吸蔵性（酸素貯蔵・放出性）に優れているので、自動車等の内燃機関から排出される排気ガスを浄化するのに有効である。   Since the exhaust gas purifying catalyst of the present invention is excellent in oxygen storage (oxygen storage / release), it is effective for purifying exhaust gas discharged from an internal combustion engine such as an automobile.

実施例１、実施例２及び比較例１で得られた各々のパティキュレートフィルター形状の排ガス浄化用触媒のＣＯ浄化性能を示すグラフである。4 is a graph showing the CO purification performance of each particulate filter-shaped exhaust gas purification catalyst obtained in Example 1, Example 2 and Comparative Example 1. FIG. 実施例１、実施例２及び比較例１で得られた各々のパティキュレートフィルター形状の排ガス浄化用触媒のＨＣ浄化性能を示すグラフである。4 is a graph showing the HC purification performance of each particulate filter-shaped exhaust gas purification catalyst obtained in Example 1, Example 2 and Comparative Example 1. 実施例３、実施例４及び実施例５で得られた各々のハニカム形状の排ガス浄化用触媒のＣＯ浄化性能を示すグラフである。4 is a graph showing the CO purification performance of each honeycomb-shaped exhaust gas purification catalyst obtained in Example 3, Example 4 and Example 5. FIG. 実施例３、実施例４及び実施例５で得られた各々のハニカム形状の排ガス浄化用触媒のＨＣ浄化性能を示すグラフである。6 is a graph showing the HC purification performance of each honeycomb-shaped exhaust gas purification catalyst obtained in Example 3, Example 4 and Example 5. FIG. 代表的なＹ１−ＸＡＸＭｎ２−ＺＢＺＯ５のＸＲＤを示すチャートである。It is a chart showing the XRD of a representative Y 1-X A X Mn 2 -Z B Z O 5.

以下に、本発明の排気ガス浄化用触媒について説明する。   The exhaust gas purifying catalyst of the present invention will be described below.

本発明の排気ガス浄化用触媒で用いる複酸化物Ｙ１−ＸＡＸＭｎ２−ＺＢＺＯ５（式中、ＡはＬａ、Ｓｒ、Ｃｅ、Ｂａ、Ｃａ、Ｓｃ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ又はＢｉであり、ＢはＣｏ、Ｆｅ、Ｎｉ、Ｃｒ、Ｍｇ、Ｔｉ、Ｎｂ、Ｔａ、Ｃｕ又はＲｕであり、０．５≧Ｘ≧０であり、１≧Ｚ≧０である）の基本型は化学式ＹＭｎ２Ｏ５で表わされる複酸化物であり、この複酸化物ＹＭｎ２Ｏ５は例えば下記の方法で製造することができる。Mixed oxide Y 1-X A X Mn 2 -Z B Z O 5 ( where used in the exhaust gas purifying catalyst of the present invention, A is La, Sr, Ce, Ba, Ca, Sc, Ho, Er, Tm Yb, Lu or Bi, B is Co, Fe, Ni, Cr, Mg, Ti, Nb, Ta, Cu or Ru, 0.5 ≧ X ≧ 0, and 1 ≧ Z ≧ 0 ) Is a double oxide represented by the chemical formula YMn 2 O 5 , and this double oxide YMn 2 O 5 can be produced, for example, by the following method.

製造方法の一例を以下に示す。   An example of the manufacturing method is shown below.

原料としてＹ２Ｏ３及びＭｎＯ２をＹ／Ｍｎの原子比が１／２となるように秤取し、例えば、ボールミルを用いて３時間以上粉砕・混合する。その後、大気雰囲気下、８００〜１１００℃、好ましくは８５０〜９５０℃で１〜２４時間、好ましくは４〜１０時間焼成することにより複酸化物ＹＭｎ２Ｏ５が得られる。As raw materials, Y 2 O 3 and MnO 2 are weighed so that the Y / Mn atomic ratio becomes 1/2, and, for example, pulverized and mixed for 3 hours or more using a ball mill. Thereafter, the atmosphere, 800 to 1100 ° C., preferably 1 to 24 hours at 850 to 950 ° C., preferably the mixed oxide YMn 2 O 5 obtained by calcining 4-10 hours.

上記のＹＭｎ２Ｏ５の製造においては、複酸化物ＹＭｎ２Ｏ５、複酸化物ＹＭｎＯ３及び複酸化物Ｙ２Ｍｎ２Ｏ７からなる混合物が生じることもある。これらの混合物も、複酸化物ＹＭｎ２Ｏ５５０質量％以上と、複酸化物ＹＭｎＯ３及び複酸化物Ｙ２Ｍｎ２Ｏ７の少なくとも１種５０質量％未満とからなる混合物であれば複酸化物ＹＭｎ２Ｏ５の良好な排ガス浄化性能を十分に発揮することができる。ＹＭｎ２Ｏ５の混合比率は８０質量％以上であることがより好ましい。無論、製造で生じた混合物であっても、それらの３種の複酸化物を混合して得た混合物であっても同様である。In the production of YMn 2 O 5 described above, a mixture composed of double oxide YMn 2 O 5 , double oxide YMnO 3 and double oxide Y 2 Mn 2 O 7 may be formed. If these mixtures are also a mixture consisting of 50% by mass or more of double oxide YMn 2 O 5 and at least one kind of double oxide YMnO 3 and double oxide Y 2 Mn 2 O 7 , double oxidation Good exhaust gas purification performance of the product YMn 2 O 5 can be sufficiently exhibited. The mixing ratio of YMn 2 O 5 is more preferably 80% by mass or more. Of course, even if it is the mixture produced by manufacture and the mixture obtained by mixing those 3 types of double oxides, it is the same.

製造方法の他の例としては、ＹとＭｎとを含む溶液に沈殿剤を添加して、ＹとＭｎとがおよそ１／２の原子比で含有される前駆体の沈殿物を得て、これを乾燥、焼成することにより、前駆体を結晶化させて複酸化物ＹＭｎ２Ｏ５を得る方法を挙げることができる。As another example of the production method, a precipitant is added to a solution containing Y and Mn to obtain a precursor precipitate containing Y and Mn in an atomic ratio of approximately 1/2. A method of crystallizing the precursor to obtain a double oxide YMn 2 O 5 by drying and firing the can be mentioned.

上記それぞれの製造方法で用いたＹ化合物を、Ｌａ化合物、Ｓｒ化合物、Ｃｅ化合物、Ｂａ化合物、Ｃａ化合物、Ｓｃ化合物、Ｈｏ化合物、Ｅｒ化合物、Ｔｍ化合物、Ｙｂ化合物、Ｌｕ化合物及びＢｉ化合物からなる群から選ばれた化合物の１種以上で、Ｙ化合物のＹ原子の半量以下の原子の量となるように置き換えて上記の製造方法を実施することにより複酸化物Ｙ１−ＸＡＸＭｎ２Ｏ５（式中、ＡはＬａ、Ｓｒ、Ｃｅ、Ｂａ、Ｃａ、Ｓｃ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ又はＢｉであり、０．５≧Ｘ＞０である）を製造することができる。Y compound used in each of the above production methods is a group consisting of La compound, Sr compound, Ce compound, Ba compound, Ca compound, Sc compound, Ho compound, Er compound, Tm compound, Yb compound, Lu compound and Bi compound. The compound O 1 -X A X Mn 2 O is obtained by substituting one or more of the compounds selected from the above so that the amount of atoms is less than half the amount of Y atoms of the Y compound and carrying out the above production method. 5 (wherein A is La, Sr, Ce, Ba, Ca, Sc, Ho, Er, Tm, Yb, Lu, or Bi, and 0.5 ≧ X> 0).

上記それぞれの製造方法で用いたＭｎ化合物を、Ｃｏ化合物、Ｆｅ化合物、Ｎｉ化合物、Ｃｒ化合物、Ｍｇ化合物、Ｔｉ化合物、Ｎｂ化合物、Ｔａ化合物、Ｒｕ化合物及びＣｕ化合物からなる群から選ばれた化合物の１種以上で、Ｍｎ化合物のＭｎ原子の半量以下の原子の量となるように置き換えて上記の製造方法を実施することにより複酸化物ＹＭｎ２−ＺＢＺＯ５（式中、ＢはＣｏ、Ｆｅ、Ｎｉ、Ｃｒ、Ｍｇ、Ｔｉ、Ｎｂ、Ｔａ、Ｒｕ又はＣｕであり、１≧Ｚ＞０である）を製造することができる。The Mn compound used in each of the above production methods is a compound selected from the group consisting of Co compound, Fe compound, Ni compound, Cr compound, Mg compound, Ti compound, Nb compound, Ta compound, Ru compound and Cu compound. The compound oxide YMn 2 -Z B Z O 5 (wherein B represents Co is obtained by carrying out the above production method by replacing one or more kinds so that the amount of atoms is less than half of the Mn atoms of the Mn compound. , Fe, Ni, Cr, Mg, Ti, Nb, Ta, Ru or Cu, and 1 ≧ Z> 0.

更に、上記の製造方法で用いたＹ化合物を、Ｌａ化合物、Ｓｒ化合物、Ｃｅ化合物、Ｂａ化合物、Ｃａ化合物、Ｓｃ化合物、Ｈｏ化合物、Ｅｒ化合物、Ｔｍ化合物、Ｙｂ化合物、Ｌｕ化合物及びＢｉ化合物からなる群から選ばれた化合物の１種以上で、Ｙ化合物のＹ原子の半量以下の原子の量となるように置き換え、Ｍｎ化合物を、Ｃｏ化合物、Ｆｅ化合物、Ｎｉ化合物、Ｃｒ化合物、Ｍｇ化合物、Ｔｉ化合物、Ｎｂ化合物、Ｔａ化合物、Ｒｕ化合物及びＣｕ化合物からなる群から選ばれた化合物の１種以上で、Ｍｎ化合物のＭｎ原子の半量以下の原子の量となるように置き換えて上記の製造方法を実施することにより複酸化物Ｙ１−ＸＡＸＭｎ２−ＺＢＺＯ５（式中、ＡはＬａ、Ｓｒ、Ｃｅ、Ｂａ、Ｃａ、Ｓｃ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ又はＢｉであり、ＢはＣｏ、Ｆｅ、Ｎｉ、Ｃｒ、Ｍｇ、Ｔｉ、Ｎｂ、Ｔａ、Ｃｕ又はＲｕであり、０．５≧Ｘ＞０であり、１≧Ｚ＞０である）を製造することができる。Further, the Y compound used in the above production method is composed of La compound, Sr compound, Ce compound, Ba compound, Ca compound, Sc compound, Ho compound, Er compound, Tm compound, Yb compound, Lu compound and Bi compound. The Mn compound is replaced with a Co compound, Fe compound, Ni compound, Cr compound, Mg compound, Ti, or the like, with one or more compounds selected from the group replaced with an amount of atoms equal to or less than half of the Y atoms of the Y compound. The above production method is replaced with one or more compounds selected from the group consisting of compounds, Nb compounds, Ta compounds, Ru compounds and Cu compounds so that the amount of atoms is less than half the amount of Mn atoms of the Mn compound. By carrying out the double oxide Y 1-X A X Mn 2-Z B Z O 5 (wherein A is La, Sr, Ce, Ba, Ca, Sc, Ho, Er, Tm, Yb, Lu, or Bi, B is Co, Fe, Ni, Cr, Mg, Ti, Nb, Ta, Cu, or Ru, and 0.5 ≧ X> 0 and 1 ≧ Z> 0) Can be manufactured.

ここで、ＡサイトのＹを置き換える原子として列挙したＬａ、Ｓｒ、Ｃｅ、Ｂａ、Ｃａ、Ｓｃ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ又はＢｉは、Ｙを置き換え得るイオン半径を有したものであるが、この中でも特に、Ｙのイオン半径に対して±１０％以内のイオン半径を有する、Ｌａ、Ｃｅ、Ｃａ、Ｓｃ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ又はＢｉが安定的に置換できることから好ましい。   Here, La, Sr, Ce, Ba, Ca, Sc, Ho, Er, Tm, Yb, Lu, or Bi listed as atoms replacing Y at the A site have an ionic radius that can replace Y. However, among these, La, Ce, Ca, Sc, Ho, Er, Tm, Yb, Lu, or Bi having an ionic radius within ± 10% with respect to the ionic radius of Y can be stably substituted. .

また、ＢサイトのＭｎを置き換える原子として列挙したＣｏ、Ｆｅ、Ｎｉ、Ｃｒ、Ｍｇ、Ｔｉ、Ｎｂ、Ｔａ、Ｃｕ又はＲｕは、Ｍｎを置き換え得るイオン半径を有しているものであるが、この中でも特に、Ｍｎのイオン半径に対して±１０％以内のイオン半径を有する、Ｃｏ、Ｆｅ、Ｎｉ、Ｃｒ、Ｍｇ、Ｔｉ又はＣｕが安定的に置換できることから好ましい。   Further, Co, Fe, Ni, Cr, Mg, Ti, Nb, Ta, Cu or Ru listed as atoms replacing Mn at the B site have an ionic radius that can replace Mn. Among these, Co, Fe, Ni, Cr, Mg, Ti or Cu having an ionic radius within ± 10% with respect to the ionic radius of Mn is particularly preferable because it can be stably replaced.

一般式Ｙ１−ＸＡＸＭｎ２−ＺＢＺＯ５（式中、ＡはＬａ、Ｓｒ、Ｃｅ、Ｂａ、Ｃａ、Ｓｃ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ又はＢｉであり、ＢはＣｏ、Ｆｅ、Ｎｉ、Ｃｒ、Ｍｇ、Ｔｉ、Ｎｂ、Ｔａ、Ｒｕ又はＣｕであり、０．５≧Ｘ≧０であり、１≧Ｚ≧０である）で示される複酸化物は上記の全ての複酸化物を包含する。In the general formula Y 1-X A X Mn 2 -Z B Z O 5 ( wherein, A is La, Sr, Ce, Ba, Ca, Sc, Ho, Er, Tm, Yb, Lu , or Bi, B is Co, Fe, Ni, Cr, Mg, Ti, Nb, Ta, Ru or Cu, and 0.5 ≧ X ≧ 0 and 1 ≧ Z ≧ 0) Of the double oxide.

ここで、一般式Ｙ１−ＸＡＸＭｎ２−ＺＢＺＯ５は、ＸＲＤパターンから、空間群Ｐｂａｍに含まれる、マンガン酸ジスプロシウム構造（ＤｙＭｎ２Ｏ５構造、ICSD(Inorganic crystal structure database)参照）をとる結晶であると同定された。そして、一般式Ｙ１−ＸＡＸＭｎ２−ＺＢＺＯ５は化学量論比で示されるものであるが、組成比が化学量論比から多少ずれて、一部の元素が過剰になったり欠損したりしたものであっても、マンガン酸ジスプロシウム構造（ＤｙＭｎ２Ｏ５構造）をとる結晶であれば、本発明の効果を奏するものであり、本発明の排気ガス浄化用触媒に包含されるものである。Here, the general formula Y 1-X A X Mn 2 -Z B Z O 5 , from the XRD pattern, included in the space group Pbam, manganese, dysprosium structure (DyMn 2 O 5 structure, ICSD (Inorganic crystal structure database) Crystal). Then, although the general formula Y 1-X A X Mn 2 -Z B Z O 5 is represented by the stoichiometric ratio, slightly deviated from the composition ratio a stoichiometric ratio, part of the elements is excessively Even if the crystal has a dysprosium manganate structure (DyMn 2 O 5 structure), the effect of the present invention can be obtained even if it is lost or lost, and is included in the exhaust gas purifying catalyst of the present invention. It is what is done.

すなわち、マンガン酸ジスプロシウム構造（ＤｙＭｎ２Ｏ５構造）をとる複酸化物であって、ＡサイトにＹを５０％以上含み、ＢサイトにＭｎを５０％以上含むものであれば、本発明の排気ガス浄化用触媒に包含され、同様な効果を奏するものである。That is, as long as it is a double oxide having a dysprosium manganate structure (DyMn 2 O 5 structure) and containing 50% or more of Y at the A site and 50% or more of Mn at the B site, the exhaust of the present invention It is included in the gas purification catalyst and has the same effect.

図５に代表的なＹ１−ＸＡＸＭｎ２−ＺＢＺＯ５（下記実施例６に相当）のＸＲＤを示す。波線を付与したピークがマンガン酸ジスプロシウム構造（ＤｙＭｎ２Ｏ５構造）、すなわち、この場合にはＹＭｎ２Ｏ５に起因するピークである。FIG. 5 shows an XRD of a representative Y 1-X A X Mn 2-Z B Z O 5 (corresponding to Example 6 below). The peak given the wavy line is the dysprosium manganate structure (DyMn 2 O 5 structure), that is, the peak due to YMn 2 O 5 in this case.

上記の全ての複酸化物は酸素吸蔵性（酸素貯蔵・放出性）に優れている。さらに、Ａｇ、Ｐｔ、Ａｕ、Ｐｄ、Ｒｈ、Ｃｕ及びＭｎからなる群から選択される少なくとも一種の原子を担持することにより、酸素吸蔵性がより向上する。また、担持された金属の量が金属＋担体の合計質量基準で１〜１０質量％とすることにより、排気ガス浄化性能が向上する。   All the double oxides described above are excellent in oxygen storage (oxygen storage / release). Furthermore, by supporting at least one atom selected from the group consisting of Ag, Pt, Au, Pd, Rh, Cu and Mn, the oxygen storage property is further improved. Moreover, exhaust gas purification performance improves because the quantity of the carried | supported metal shall be 1-10 mass% on the total mass reference | standard of a metal + support | carrier.

本発明の排気ガス浄化用触媒においては、セラミックス又は金属材料からなる触媒支持体の形状は、特に限定されるものではないが、一般的にはハニカム形状、板、ペレット、ＤＰＦ等の形状であり、好ましくはハニカム形状又はＤＰＦである。また、このような触媒支持体の材質としては、例えば、アルミナ（Ａｌ２Ｏ３）、ムライト（３Ａｌ２Ｏ３−２ＳｉＯ２）、コージェライト（２ＭｇＯ−２Ａｌ２Ｏ３−５ＳｉＯ２）、炭化ケイ素（ＳｉＣ）等のセラミックスや、ステンレス等の金属材料を挙げることができる。In the exhaust gas purifying catalyst of the present invention, the shape of the catalyst support made of a ceramic or metal material is not particularly limited, but is generally a honeycomb shape, a plate, a pellet, a DPF, or the like. Preferably, it is a honeycomb shape or DPF. The material of such a catalyst support, e.g., alumina (Al 2 O 3), mullite (3Al 2 O 3 -2SiO 2) , cordierite (2MgO-2Al 2 O 3 -5SiO 2), silicon carbide Examples thereof include ceramics such as (SiC) and metal materials such as stainless steel.

これらの触媒支持体の表面に上記の複酸化物Ｙ１−ＸＡＸＭｎ２−ＺＢＺＯ５を含む層を設ける。Ｙ１−ＸＡＸＭｎ２−ＺＢＺＯ５を含む層は貴金属が存在していない状態でも酸素吸蔵性に優れているので、セラミックス又は金属材料からなる触媒支持体と、該触媒支持体上に担持されている複酸化物Ｙ１−ＸＡＸＭｎ２−ＺＢＺＯ５とを有する構成のものも酸素吸蔵性に優れた排気ガス浄化用触媒となる。The above double oxide on the surface of these catalyst supports Y 1-X A X Mn 2 -Z B providing a layer containing a Z O 5. Since the layer comprising Y 1-X A X Mn 2 -Z B Z O 5 is excellent in the oxygen storage property even in a state that does not exist a noble metal, a catalyst support made of a ceramic or metallic material, said catalyst support the composite oxide Y 1-X a X Mn 2 -Z B Z O 5 and excellent exhaust gas purifying catalyst to be oxygen-storing those configurations having carried on the top.

また、Ａｇ、Ｐｔ、Ａｕ、Ｐｄ、Ｒｈ、Ｃｕ及びＭｎからなる群から選択される少なくとも一種の原子を担持したＹ１−ＸＡＸＭｎ２−ＺＢＺＯ５を含む層を上記の触媒支持体の表面に設けることもできる。即ち、セラミックス又は金属材料からなる触媒支持体と、該触媒支持体上に担持されている複酸化物Ｙ１−ＸＡＸＭｎ２−ＺＢＺＯ５と、該Ｙ１−ＸＡＸＭｎ２−ＺＢＺＯ５に担持されているＡｇ、Ｐｔ、Ａｕ、Ｐｄ、Ｒｈ、Ｃｕ及びＭｎからなる群から選択される少なくとも一種の原子とを有する構成の酸素吸蔵性に優れた排気ガス浄化用触媒とすることもできる。この貴金属等を担持した排気ガス浄化用触媒は酸素吸蔵性の点では貴金属等を担持していない上記の排気ガス浄化用触媒とあまり変わらないが、排気ガス浄化用触媒として用いた場合には燃焼開始温度及びピークトップ温度が改善される。Further, Ag, Pt, Au, Pd , Rh, at least one of the atoms Y carrying 1-X A X Mn 2- Z B Z O 5 layer of the above catalyst containing selected from the group consisting of Cu and Mn It can also be provided on the surface of the support. That is, a catalyst support made of ceramics or a metal material, a double oxide Y 1-X A X Mn 2-Z B Z O 5 supported on the catalyst support, and the Y 1-X A X Mn 2-Z B Z O 5 is supported on Ag, Pt, Au, Pd, Rh, at least one arrangement oxygen storage with excellent exhaust gas purification having an atom selected from the group consisting of Cu and Mn It can also be used as a catalyst. This exhaust gas purifying catalyst carrying noble metal etc. is not much different from the above exhaust gas purifying catalyst not carrying noble metal etc. in terms of oxygen storage, but when used as an exhaust gas purifying catalyst, it burns Start temperature and peak top temperature are improved.

以下に、実施例及び比較例に基づいて本発明を具体的に説明する。   Hereinafter, the present invention will be described in detail based on examples and comparative examples.

実施例１
硝酸銀０．１２４ｇに水３７．５ｇを加え、攪拌して硝酸銀水溶液とし、この水溶液にＹＭｎ２Ｏ５からなる担体粉末１．５ｇを投入し、３０分間攪拌した。得られたスラリーを直径２５．４ｍｍ×長さ７６．２ｍｍのコージェライト製パティキュレートフィルター上にコートさせた。これを１２０℃で３時間乾燥した後、空気中６００℃で１時間焼成した。得られたパティキュレートフィルター形状の排ガス浄化用触媒のＡｇ担持量は金属Ａｇ＋担体の合計質量基準で５質量％であった。Example 1
37.5 g of water was added to 0.124 g of silver nitrate and stirred to obtain an aqueous silver nitrate solution. To this aqueous solution, 1.5 g of carrier powder composed of YMn 2 O 5 was added and stirred for 30 minutes. The obtained slurry was coated on a cordierite particulate filter having a diameter of 25.4 mm and a length of 76.2 mm. This was dried at 120 ° C. for 3 hours and then calcined in air at 600 ° C. for 1 hour. The amount of Ag supported on the obtained particulate filter-shaped exhaust gas purification catalyst was 5% by mass based on the total mass of metal Ag + carrier.

実施例２
水３０ｇにＹＭｎ２Ｏ５からなる粉末１．５ｇを投入し、３０分間攪拌した。得られたスラリーを用いて直径２５．４ｍｍ×長さ７６．２ｍｍのコージェライト製パティキュレートフィルター上にＹＭｎ２Ｏ５をコートさせた。これを１２０℃で３時間乾燥した後、空気中６００℃で１時間焼成してパティキュレートフィルター形状の排ガス浄化用触媒を得た。Example 2
To 30 g of water, 1.5 g of a powder composed of YMn 2 O 5 was added and stirred for 30 minutes. YMn 2 O 5 was coated on a cordierite particulate filter having a diameter of 25.4 mm and a length of 76.2 mm using the obtained slurry. This was dried at 120 ° C. for 3 hours and then calcined in air at 600 ° C. for 1 hour to obtain an exhaust gas purifying catalyst in the form of a particulate filter.

実施例３
硝酸マンガン（II）六水和物を５倍質量の水に溶解させた溶液にＹＭｎ２Ｏ５を分散させ、撹拌しながら２００℃で加熱、乾燥させた。その後、大気中、６００℃で２時間焼成し、Ｍｎ担持ＹＭｎ２Ｏ５粉末を得た。この場合にＭｎの担持量が金属Ｍｎ＋担体の合計質量基準で５．５７質量％となるようにした。このＭｎ担持ＹＭｎ２Ｏ５粉末６．０８ｇに水３０ｇを加え、３０分間撹拌してスラリーとした。得られたスラリーを直径２５．４ｍｍ×長さ６０ｍｍのコージェライト製ハニカムにコートした。これを１２０℃で３時間乾燥した後、空気中、５００℃で１時間焼成した。コージェライト製ハニカムに担持されたＭｎ担持ＹＭｎ２Ｏ５の量は、ハニカム容積１Ｌあたり２００ｇであった。Example 3
YMn 2 O 5 was dispersed in a solution in which manganese (II) nitrate hexahydrate was dissolved in 5 times mass of water, and heated and dried at 200 ° C. with stirring. Thereafter, in the air, and calcined for 2 hours at 600 ° C., to obtain a Mn-carrying YMn 2 O 5 powder. In this case, the amount of Mn supported was 5.57% by mass based on the total mass of the metal Mn + carrier. 30 g of water was added to 6.08 g of this Mn-supported YMn 2 O 5 powder and stirred for 30 minutes to form a slurry. The obtained slurry was coated on a cordierite honeycomb having a diameter of 25.4 mm and a length of 60 mm. This was dried at 120 ° C. for 3 hours and then calcined in air at 500 ° C. for 1 hour. The amount of Mn-supported YMn 2 O 5 supported on the cordierite honeycomb was 200 g per 1 L of honeycomb volume.

実施例４
ＹＭｎ２Ｏ５粉末６．０８ｇに水３０ｇを加え、３０分間撹拌してスラリーとした。得られたスラリーを直径２５．４ｍｍ×長さ６０ｍｍのコージェライト製ハニカムにコートした。これを１２０℃で３時間乾燥した後、空気中、５００℃で１時間焼成した。コージェライト製ハニカムに担持されたＹＭｎ２Ｏ５の量は、ハニカム容積１Ｌあたり２００ｇであった。Example 4
30 g of water was added to 6.08 g of YMn 2 O 5 powder and stirred for 30 minutes to form a slurry. The obtained slurry was coated on a cordierite honeycomb having a diameter of 25.4 mm and a length of 60 mm. This was dried at 120 ° C. for 3 hours and then calcined in air at 500 ° C. for 1 hour. The amount of YMn 2 O 5 supported on the cordierite honeycomb was 200 g per 1 L of honeycomb volume.

実施例５
硝酸銀を水３０ｇに溶解させた溶液にＹＭｎ２Ｏ５を分散させ、撹拌しながら２００℃で加熱、乾燥させた。その後、大気中、６００℃で２時間焼成し、Ａｇ担持ＹＭｎ２Ｏ５粉末を得た。この場合にＡｇの担持量が金属Ａｇ＋担体の合計質量基準で５．５７質量％となるようにした。このＡｇ担持ＹＭｎ２Ｏ５粉末６．０８ｇに水３０ｇを加え、３０分間撹拌してスラリーとした。得られたスラリーを直径２５．４ｍｍ×長さ６０ｍｍのコージェライト製ハニカムにコートした。これを１２０℃で３時間乾燥した後、空気中、５００℃で１時間焼成した。コージェライト製ハニカムに担持されたＡｇ担持ＹＭｎ２Ｏ５の量は、ハニカム容積１Ｌあたり２００ｇであった。Example 5
YMn 2 O 5 was dispersed in a solution in which silver nitrate was dissolved in 30 g of water, and heated and dried at 200 ° C. with stirring. Thereafter, in the air, and calcined for 2 hours at 600 ° C., to obtain a Ag supported YMn 2 O 5 powder. In this case, the supported amount of Ag was 5.57% by mass based on the total mass of the metal Ag + carrier. 30 g of water was added to 6.08 g of this Ag-supported YMn 2 O 5 powder and stirred for 30 minutes to form a slurry. The obtained slurry was coated on a cordierite honeycomb having a diameter of 25.4 mm and a length of 60 mm. This was dried at 120 ° C. for 3 hours and then calcined in air at 500 ° C. for 1 hour. The amount of Ag-supported YMn 2 O 5 supported on the cordierite honeycomb was 200 g per 1 L of honeycomb volume.

比較例１
実施例２に記載の製造方法においてＹＭｎ２Ｏ５の代わりにＣｅＯ２（３０質量％）−ＺｒＯ２（７０質量％）を用いた以外は実施例２と同様に処理してパティキュレートフィルター形状の排ガス浄化用触媒を得た。Comparative Example 1
CeO 2 (30 wt%) instead of YMn 2 O 5 in the manufacturing method described in Example 2 - except for the use of ZrO 2 (70 mass%) was treated in the same manner as in Example 2 of the particulate filter shape An exhaust gas purification catalyst was obtained.

比較例２
実施例２に記載の方法においてＹＭｎ２Ｏ５の代わりにＡｌ２Ｏ３を用いた以外は実施例２と同様に処理してパティキュレートフィルター形状の排ガス浄化用触媒を得た。Comparative Example 2
A particulate filter-shaped exhaust gas purification catalyst was obtained in the same manner as in Example 2 except that Al 2 O 3 was used instead of YMn 2 O 5 in the method described in Example 2.

＜酸素吸蔵性の評価＞
実施例１〜２及び比較例１〜２において得られた各々の試料粉末２５ｍｇを反応器に充填し、６００℃にて酸素雰囲気下で１０分間処理して清浄表面とした。その後、５０％Ｏ２／Ｈｅガス及びＨ２ガスを用いて２００〜６００℃の温度範囲で酸素吸蔵能（ＯＳＣ）を測定した。ＯＳＣは、試料粉末１ｇ当たりのＯ２吸蔵量（μｍｏｌ／ｇ）として評価した。試料粉末１ｇ当たりのＯ２吸蔵量（μｍｏｌ／ｇ）と温度との相関関係は第１表に示す通りであった。<Evaluation of oxygen storage>
25 mg of each sample powder obtained in Examples 1 and 2 and Comparative Examples 1 and 2 was charged into a reactor and treated at 600 ° C. in an oxygen atmosphere for 10 minutes to obtain a clean surface. Thereafter, oxygen storage capacity (OSC) was measured in a temperature range of 200 to 600 ° C. using 50% O 2 / He gas and H 2 gas. OSC was evaluated as O 2 occlusion amount (μmol / g) per 1 g of sample powder. The correlation between the O 2 occlusion amount per 1 g of the sample powder (μmol / g) and the temperature was as shown in Table 1.

Figure 0005864443
Figure 0005864443

第１表に示すデータから明らかなように、本発明の実施例１〜２に係る試料粉末は、比較例１〜２に係る試料粉末と比較して酸素吸蔵性に優れたものであった。   As is clear from the data shown in Table 1, the sample powders according to Examples 1 and 2 of the present invention were excellent in oxygen storage compared with the sample powders according to Comparative Examples 1 and 2.

＜昇温反応法（ＴＰＲ）による評価＞
実施例１〜２及び比較例１〜２において得られた各々の試料粉末２００ｍｇとカーボン２０ｍｇ（デグサ社製、Ｐｒｉｎｔｅｘ−Ｖ、トナーカーボン）とをメノウ乳鉢で１０分間混合し、この混合物から２０ｍｇを分取し、石英反応管の中央部に石英ウールを使って固定した。下記組成の流通ガスを下記の流量で流しながら電気炉によってその石英反応管の温度を下記の昇温速度で昇温させながら出口側でのＣＯ及びＣＯ２の濃度を赤外線分析計で測定した。このＣＯの濃度とＣＯ２の濃度との和が３０ｐｐｍになった時の触媒入り口側の温度（電気炉制御温度）をＴｉｇ（燃焼開始温度）とした。
ガス組成：Ｏ２：１０％、Ｎ２：残余
流量：４００ｃｃ／ｍｉｎ
昇温速度：１０℃／ｍｉｎ<Evaluation by temperature rising reaction method (TPR)>
200 mg of each sample powder obtained in Examples 1-2 and Comparative Examples 1-2 and 20 mg of carbon (Degussa, Printex-V, toner carbon) were mixed for 10 minutes in an agate mortar, and 20 mg of this mixture was mixed. The sample was collected and fixed to the center of the quartz reaction tube using quartz wool. The concentration of CO and CO 2 at the outlet side was measured with an infrared analyzer while the temperature of the quartz reaction tube was raised at the following rate of temperature rise by an electric furnace while flowing the following gas at the following flow rate. The temperature at the catalyst inlet side (electric furnace control temperature) when the sum of the CO concentration and the CO 2 concentration was 30 ppm was defined as Tig (combustion start temperature).
Gas composition: O 2 : 10%, N 2 : residual flow rate: 400 cc / min
Temperature increase rate: 10 ° C / min

実施例１〜２及び比較例１〜２に係る試料粉末のＴＰＲの評価結果は第２表に示す通りであった。   The TPR evaluation results of the sample powders according to Examples 1 and 2 and Comparative Examples 1 and 2 were as shown in Table 2.

Figure 0005864443
Figure 0005864443

第２表に示すデータから明らかなように、Ａｇを担持している本発明の実施例１に係る試料粉末は、Ａｇを担持していない本発明の実施例２に係る試料粉末と比較してＴＰＲの評価において優れたものであった。   As is clear from the data shown in Table 2, the sample powder according to Example 1 of the present invention supporting Ag is compared with the sample powder according to Example 2 of the present invention not supporting Ag. It was excellent in evaluation of TPR.

＜排ガス浄化性能試験＞
実施例１、実施例２、実施例３、実施例４、実施例５及び比較例１で得られた各々の排ガス浄化用触媒について大気中、７００℃で３０時間の耐久処理を行った。その後、それらの排ガス浄化用触媒を別々にモデルガス測定装置（堀場製作所製ＭＥＸＡ−７５００Ｄ）に装填し、下記の第３表に示す組成の排気モデルガスを空間速度２９０００／ｈで流通させながら、６００℃から１７℃／分の降温速度で降温させ、ＣＯ、ＨＣ浄化率を連続的に測定した。ＣＯの浄化率は図１及び図３に示す通りであり、ＨＣの浄化率は図２及び図４に示す通りであった。<Exhaust gas purification performance test>
Each exhaust gas purifying catalyst obtained in Example 1, Example 2, Example 3, Example 4, Example 5 and Comparative Example 1 was subjected to an endurance treatment at 700 ° C. for 30 hours in the atmosphere. Then, these exhaust gas purification catalysts were separately loaded into a model gas measuring device (MEXA-7500D manufactured by Horiba, Ltd.), and the exhaust model gas having the composition shown in Table 3 below was circulated at a space velocity of 29000 / h. The temperature was lowered from 600 ° C. at a rate of 17 ° C./min, and the CO and HC purification rates were measured continuously. The CO purification rate was as shown in FIGS. 1 and 3, and the HC purification rate was as shown in FIGS.

Figure 0005864443
Figure 0005864443

図１及び図２に示すグラフから明らかなように、ＣｅＯ２−ＺｒＯ２を用いた場合よりもＹＭｎ２Ｏ５を用いた場合に浄化性能が優れており、ＹＭｎ２Ｏ５を用いた場合よりもＡｇ／ＹＭｎ２Ｏ５を用いた場合に浄化性能が優れている。また、図３及び図４に示すグラフから明らかなように、ＹＭｎ２Ｏ５を用いた場合よりもＡｇやＭｎをＹＭｎ２Ｏ５に担持させることによって浄化性能を高めることができる。As apparent from the graph shown in FIG. 1 and FIG. 2, in the case of using CeO 2 -ZrO 2 and purification performance superior when using YMn 2 O 5 than, than with YMn 2 O 5 Also, when Ag / YMn 2 O 5 is used, the purification performance is excellent. Further, as is apparent from the graphs shown in FIGS. 3 and 4, the purification performance can be improved by supporting Ag or Mn on YMn 2 O 5 than when YMn 2 O 5 is used.

実施例６〜１０
Ｙ２Ｏ３及びＬｕ２Ｏ３を下記第４表の割合で溶解した硝酸溶液と、下記第４表の硝酸マンガン溶液とを混合し、５００ｍＬとした溶液に、２．５％ＮＨ３水溶液３５９．２ｍＬと、３０％過酸化水素水１７ｍＬとを加え、沈殿を生成した。続いて、沈殿物をろ過し、洗浄した後、１２０℃で一晩乾燥させた。その後、大気中、６００℃で５時間焼成し、さらに、８００℃で５時間焼成し、ＬｕドープＹＭｎ２Ｏ５粉末（実施例６についてはＬｕ未ドープ）を得た。Examples 6-10
A nitric acid solution in which Y 2 O 3 and Lu 2 O 3 are dissolved in the ratio shown in Table 4 below and a manganese nitrate solution in Table 4 below are mixed to make 500 mL, and a 2.5% NH 3 aqueous solution 359 is added. 2 mL and 17 mL of 30% aqueous hydrogen peroxide were added to form a precipitate. Subsequently, the precipitate was filtered, washed, and dried overnight at 120 ° C. Thereafter, in the air, and calcined for 5 hours at 600 ° C., further calcined 5 hours at 800 ° C., Lu doped YMn 2 O 5 powder (for Example 6 Lu undoped) was obtained.

硝酸銀０．１２４ｇに水３７．５ｇを加え、攪拌して硝酸銀水溶液とし、この水溶液に、各ＬｕドープＹＭｎ２Ｏ５粉末を１．５ｇを投入し、加熱して水分を揮発させた。得られた粉末を、１２０℃で２時間乾燥した後、空気中６００℃で１時間焼成し、実施例６〜１０の排ガス浄化用触媒を得た。得られた排ガス浄化用触媒のＡｇ担持量は金属Ａｇ＋担体の合計質量基準で５．５７質量％であった。37.5 g of water was added to 0.124 g of silver nitrate and stirred to form an aqueous silver nitrate solution. To this aqueous solution, 1.5 g of each Lu-doped YMn 2 O 5 powder was added and heated to volatilize water. The obtained powder was dried at 120 ° C. for 2 hours and then calcined in air at 600 ° C. for 1 hour to obtain exhaust gas purifying catalysts of Examples 6 to 10. The amount of Ag supported on the obtained exhaust gas purifying catalyst was 5.57% by mass based on the total mass of metal Ag + carrier.

＜固定床模擬ガス浄化性能評価試験１＞
実施例６〜１０の排ガス浄化用触媒について大気中、７００℃で３０時間の耐久処理を行った。その後、実施例６〜１０で得られた各々の排気ガス浄化用触媒の触媒活性を以下のようにして評価した。<Fixed bed simulation gas purification performance evaluation test 1>
The exhaust gas purifying catalysts of Examples 6 to 10 were subjected to an endurance treatment at 700 ° C. for 30 hours in the air. Thereafter, the catalytic activity of each exhaust gas purifying catalyst obtained in Examples 6 to 10 was evaluated as follows.

まず、固定床流通型反応装置を用い、反応管に触媒粉を０．１ｇセットし、上記第３表の組成から成る模擬排気ガスを１Ｌ／ｍｉｎで流通させ、５００℃まで昇温後１０分間保持し、前処理を行った。その後、一旦冷却後、１００℃〜５００℃まで１０℃／ｍｉｎで昇温し、１００〜５００℃における出口ガス成分をＣＯ／ＨＣ／ＮＯ分析計を用いて測定した。得られたライトオフ性能評価結果より、ＣＯ及びＨＣの５０％浄化率に到達する温度（Ｔ５０）を求めた。その結果は第４表に示す通りであった。   First, using a fixed bed flow type reactor, 0.1 g of catalyst powder was set in a reaction tube, and simulated exhaust gas having the composition shown in Table 3 was circulated at 1 L / min. Retained and pretreated. Then, after cooling, the temperature was raised from 100 ° C. to 500 ° C. at 10 ° C./min, and the outlet gas component at 100 to 500 ° C. was measured using a CO / HC / NO analyzer. From the obtained light-off performance evaluation results, the temperature (T50) at which 50% purification rate of CO and HC was reached was determined. The results were as shown in Table 4.

第４表には、耐久処理後の比表面積（ＢＥＴ法で測定）をあわせて示す。   Table 4 also shows the specific surface area (measured by the BET method) after the durability treatment.

この結果、実施例７〜１０に係るＹの一部をＬｕで置換した排ガス浄化用触媒については、Ｌｕドープ量が多くなるほどＴ５０が低下していき、ドープ量が０．２（Ｙ：Ｌｕ＝８：２）の実施例９で最も良好な結果を示すことがわかった。   As a result, for the exhaust gas purifying catalyst in which part of Y according to Examples 7 to 10 is replaced with Lu, T50 decreases as the Lu doping amount increases, and the doping amount becomes 0.2 (Y: Lu = It was found that Example 9 of 8: 2) showed the best results.

Figure 0005864443
Figure 0005864443

実施例１１〜１６
Ｙ２Ｏ３を下記第５表の割合で溶解した硝酸溶液と、第５表に示した濃度の水酸化カルシウム硝酸溶液と、下記第５表の硝酸マンガン溶液とを混合し、５００ｍＬとした溶液に、２．５％ＮＨ３水溶液３５０．４ｍＬと、３０％過酸化水素水１７ｍＬとを加え、沈殿を生成した。続いて、沈殿物をろ過し、洗浄した後、１２０℃で一晩乾燥させた。その後、大気中、６００℃で５時間焼成し、さらに、８００℃で５時間焼成し、ＣａドープＹＭｎ２Ｏ５粉末（実施例１１はＣａ未ドープ）を得た。Examples 11-16
A solution in which Y 2 O 3 is dissolved in a proportion shown in Table 5 below, a calcium hydroxide nitric acid solution having a concentration shown in Table 5 and a manganese nitrate solution shown in Table 5 below are mixed to make 500 mL. In addition, 350.4 mL of 2.5% NH 3 aqueous solution and 17 mL of 30% aqueous hydrogen peroxide were added to form a precipitate. Subsequently, the precipitate was filtered, washed, and dried overnight at 120 ° C. Thereafter, in the air, and calcined for 5 hours at 600 ° C., further calcined 5 hours at 800 ° C., Ca-doped YMn 2 O 5 powder (Example 11 Ca undoped) was obtained.

硝酸銀０．１２４ｇに水３７．５ｇを加え、攪拌して硝酸銀水溶液とし、この水溶液に、各ＹＭｎ２Ｏ５粉末を１．５ｇを投入し、加熱して水分を揮発させた。得られた粉末を、１２０℃で３時間乾燥した後、空気中６００℃で１時間焼成し、実施例１１〜１６の排ガス浄化用触媒を得た。得られた排ガス浄化用触媒のＡｇ担持量は金属Ａｇ＋担体の合計質量基準で５．５７質量％であった。37.5 g of water was added to 0.124 g of silver nitrate and stirred to obtain an aqueous silver nitrate solution. To this aqueous solution, 1.5 g of each YMn 2 O 5 powder was added and heated to volatilize water. The obtained powder was dried at 120 ° C. for 3 hours and then calcined in air at 600 ° C. for 1 hour to obtain exhaust gas purifying catalysts of Examples 11 to 16. The amount of Ag supported on the obtained exhaust gas purifying catalyst was 5.57% by mass based on the total mass of metal Ag + carrier.

＜固定床模擬ガス浄化性能評価試験２＞
実施例１１〜１６の排ガス浄化用触媒について、固定床模擬ガス浄化性能評価試験１と同様に試験し各々の排気ガス浄化用触媒の触媒活性を以下のようにして評価した。得られたライトオフ性能評価結果より、ＣＯ及びＨＣの５０％浄化率に到達する温度（Ｔ５０）を求めた。その結果は第５表に示す通りであった。<Fixed bed simulation gas purification performance evaluation test 2>
The exhaust gas purification catalysts of Examples 11 to 16 were tested in the same manner as the fixed bed simulated gas purification performance evaluation test 1, and the catalytic activity of each exhaust gas purification catalyst was evaluated as follows. From the obtained light-off performance evaluation results, the temperature (T50) at which 50% purification rate of CO and HC was reached was determined. The results were as shown in Table 5.

第５表には、耐久処理後の比表面積（ＢＥＴ法で測定）をあわせて示す。   Table 5 also shows the specific surface area (measured by the BET method) after the durability treatment.

この結果、実施例１１〜１６に係るＹの一部をＣａで置換した排ガス浄化用触媒についてもＣａドープ量が多くなるほどＴ５０が低下していき、ドープ量が０．１（Ｙ：Ｃａ＝９：１）の実施例１５で最も良好な結果を示すことがわかった。   As a result, for the exhaust gas purifying catalyst in which a part of Y according to Examples 11 to 16 is replaced with Ca, T50 decreases as the Ca doping amount increases, and the doping amount becomes 0.1 (Y: Ca = 9 1) was found to give the best results in Example 15.

Figure 0005864443
Figure 0005864443

実施例１７〜２０
Ｙ（１−ｘ）ＢｉｘＭｎ２Ｏ５のｘ＝０、０．１、０．２及び０．３となるように、所定量の硝酸イットリウム、硝酸ビスマス及び硝酸マンガンをそれぞれ秤量後、１６モル倍のイオン交換水に投入し、溶解した。各溶液に、６モル倍のクエン酸を入れ、攪拌し、温度を８０℃まで昇温してクエン酸を完全に溶解させる。次に、各溶液を１５０℃の炉で蒸発乾固し、続いて、３５０℃で２時間一次焼成を行い、さらに、８００℃で２時間二次焼成を行い、実施例１７〜２０の排ガス浄化用触媒を得た。なお、実施例１８〜２０の排ガス浄化用触媒は、ＢｉドープＹＭｎ２Ｏ５である。Examples 17-20
After weighing a predetermined amount of yttrium nitrate, bismuth nitrate and manganese nitrate so that x = 0, 0.1, 0.2 and 0.3 of Y (1-x) BixMn 2 O 5 is 16 mol times, In ion-exchanged water and dissolved. 6 mol times citric acid is added to each solution, stirred, and the temperature is raised to 80 ° C. to completely dissolve the citric acid. Next, each solution was evaporated to dryness in a furnace at 150 ° C., followed by primary baking at 350 ° C. for 2 hours, and further secondary baking at 800 ° C. for 2 hours. A catalyst was obtained. Incidentally, the exhaust gas purifying catalyst of Examples 18 to 20 is a Bi-doped YMn 2 O 5.

＜昇温脱離法による評価＞
実施例１７〜２０の排ガス浄化用触媒をそれぞれ１００ｍｇ秤量し、前処理として、１００ｍＬ／ｍｉｎで大気を導入した雰囲気下で、室温から１０℃／ｍｉｎで７００℃まで昇温し、その後、同じ雰囲気で５０℃まで放冷した。<Evaluation by temperature programmed desorption method>
100 mg of each of the exhaust gas purifying catalysts of Examples 17 to 20 was weighed, and as a pretreatment, the temperature was raised from room temperature to 700 ° C. at 10 ° C./min in an atmosphere introduced with air at 100 mL / min, and then the same atmosphere And allowed to cool to 50 ° C.

各サンプルについて、昇温脱離法（ＴＰＤ）により、酸素放出ピーク温度を測定した。測定条件は、２％Ｈ２含有Ｈｅを５０ｍＬ／ｍｉｎ導入した雰囲気下で、５０℃から７００℃まで１０℃／ｍｉｎで昇温し、放出されたガスの質量を測定し、酸素放出のピーク温度（℃）を求めた。結果は下記第６表に示す。For each sample, the oxygen release peak temperature was measured by a temperature programmed desorption method (TPD). Measurement conditions were as follows: 2% H 2 containing He was introduced at 50 mL / min, the temperature was raised from 50 ° C. to 700 ° C. at 10 ° C./min, the mass of the released gas was measured, and the peak temperature of oxygen release (° C.) was determined. The results are shown in Table 6 below.

この結果、Ｙの一部をＢｉで置換した実施例１８〜２０のＢｉドープＹＭｎ２Ｏ５からなる排ガス浄化触媒は、Ｂｉがドープされない実施例１７と比較してより低温で酸素を放出できることがわかった。As a result, the exhaust gas purification catalyst composed of Bi-doped YMn 2 O 5 of Examples 18 to 20 in which a part of Y is substituted with Bi can release oxygen at a lower temperature than Example 17 in which Bi is not doped. all right.

Figure 0005864443
Figure 0005864443

実施例２１
硝酸銅を所定量秤量し、適量のイオン交換水に入れて攪拌し、溶解させた。硝酸銅が完全に溶解した後、所定量のＹＭｎ２Ｏ５粉末を投入し、攪拌して分散させる。次いで、６０℃で真空脱気を行い、蒸発乾固させ、６００℃で２時間焼成を行い、５質量％Ｃｕ担持ＹＭｎ２Ｏ５粉末を得た。Example 21
A predetermined amount of copper nitrate was weighed, placed in an appropriate amount of ion-exchanged water, stirred and dissolved. After the copper nitrate is completely dissolved, a predetermined amount of YMn 2 O 5 powder is added and stirred to disperse. Subsequently, vacuum deaeration was performed at 60 ° C., evaporation to dryness, and baking was performed at 600 ° C. for 2 hours to obtain 5 mass% Cu-supported YMn 2 O 5 powder.

＜固定床模擬ガス浄化性能評価試験３＞
実施例２１の排ガス浄化用触媒について、固定床模擬ガス浄化性能評価試験１と同様に試験し各々の排気ガス浄化用触媒の触媒活性を以下のようにして評価した。得られたライトオフ性能評価結果より、ＣＯ及びＨＣの５０％浄化率に到達する温度（Ｔ５０）を求めた。その結果は第７表に示す通りであった。<Fixed bed simulation gas purification performance evaluation test 3>
The exhaust gas purification catalyst of Example 21 was tested in the same manner as the fixed bed simulated gas purification performance evaluation test 1, and the catalytic activity of each exhaust gas purification catalyst was evaluated as follows. From the obtained light-off performance evaluation results, the temperature (T50) at which 50% purification rate of CO and HC was reached was determined. The results were as shown in Table 7.

この結果、実施例２１に係るＣｕ担持ＹＭｎ２Ｏ５も浄化性能を発揮することがわかった。なお、実施例２１は測定条件が異なるため、他の実施例と単純な比較はできない。As a result, it was found that the Cu-supported YMn 2 O 5 according to Example 21 also exhibited purification performance. Since Example 21 has different measurement conditions, a simple comparison with other examples is not possible.

Figure 0005864443
Figure 0005864443

実施例２２〜２４
実施例６の合成方法で得られたＹＭｎ２Ｏ５と、これと同様な方法でＹ／Ｍｎが１／１になる様にして合成して得られたＹＭｎＯ３とを、第８表に示す比率で混合し、マンガン酸イットリウム担体の混合物（実施例２２はＹＭｎＯ３未混合）を得た。Examples 22-24
Table 8 shows YMn 2 O 5 obtained by the synthesis method of Example 6 and YMnO 3 obtained by synthesizing Y / Mn to be 1/1 by the same method. The mixture was mixed at a ratio to obtain a mixture of yttrium manganate support (Example 22 was not mixed with YMnO 3 ).

次に、硝酸Ａｇ０．１２４ｇに水３７．５ｇを加え、攪拌して硝酸Ａｇ水溶液とし、この水溶液に上記のＹＭｎ２Ｏ５とＹＭｎＯ３との混合物１．５ｇを投入し、加熱攪拌して水分を揮発させた。得られた粉末を１２０℃で３時間乾燥した後、空気中６００℃で２時間焼成し、排ガス浄化用触媒を得た。得られた排ガス浄化用触媒のＡｇ担持量は金属Ａｇ＋担体の合計質量基準で５．５７質量％であった。Next, 37.5 g of water is added to 0.124 g of nitric acid Ag and stirred to obtain an aqueous solution of Ag nitric acid. To this aqueous solution, 1.5 g of the above-mentioned mixture of YMn 2 O 5 and YMnO 3 is added, and heated and stirred to obtain moisture. Was volatilized. The obtained powder was dried at 120 ° C. for 3 hours and then calcined in air at 600 ° C. for 2 hours to obtain an exhaust gas purifying catalyst. The amount of Ag supported on the obtained exhaust gas purifying catalyst was 5.57% by mass based on the total mass of metal Ag + carrier.

＜固定床模擬ガス浄化性能評価試験４＞
実施例２２から２４の排ガス浄化用触媒について、固定床模擬ガス浄化性能評価試験１と同様に試験し各々の排気ガス浄化用触媒の触媒活性を以下のようにして評価した。得られたライトオフ性能評価結果より、ＣＯ及びＨＣの５０％浄化率に到達する温度(Ｔ５０)を求めた。その結果は第８表に示す通りであった。<Fixed bed simulation gas purification performance evaluation test 4>
The exhaust gas purification catalysts of Examples 22 to 24 were tested in the same manner as the fixed bed simulated gas purification performance evaluation test 1, and the catalytic activity of each exhaust gas purification catalyst was evaluated as follows. From the obtained light-off performance evaluation results, the temperature (T50) at which 50% CO and HC purification rates were achieved was determined. The results were as shown in Table 8.

第８表には、耐久処理後の比表面積（ＢＥＴ法で測定）をあわせて示す。   Table 8 also shows the specific surface area (measured by the BET method) after the durability treatment.

この結果、ＹＭｎＯ３未混合のＹＭｎ２Ｏ５である実施例２２が最も良好な排ガス浄化性能を示したが、ＹＭｎＯ３を混合した実施例２３、２４も、概ね同様の排ガス浄化性能を示すことがわかった。これは、ＹＭｎ２Ｏ５固有の優れた排ガス浄化性能による効果は勿論、ＹＭｎ２Ｏ５が比較的に高い比表面積を得られやすいことにも起因するものと思われる。なお、実施例２２〜２４の測定条件は他と異なるため、他の実施例と単純な比較はできない。As a result, Example 22 which is YMn 2 O 5 not mixed with YMnO 3 showed the best exhaust gas purification performance, but Examples 23 and 24 mixed with YMnO 3 also showed almost the same exhaust gas purification performance. I understood. This effect YMn 2 O 5 unique excellent exhaust gas purification performance, of course, are believed to be due to the YMn 2 O 5 is obtained a relatively high specific surface area tends to. In addition, since the measurement conditions of Examples 22-24 are different from others, a simple comparison with other Examples cannot be performed.

Figure 0005864443
Figure 0005864443

Claims (5)

セラミックス又は金属材料からなる触媒支持体と、該触媒支持体上に担持されている複酸化物Ｙ１−ＸＡＸＭｎ２Ｏ５（式中、ＡはＣａ、Ｌｕ又はＢｉであり、０．５≧Ｘ≧０である）と、該複酸化物Ｙ１−ＸＡＸＭｎ２Ｏ５に担持されているＡｇ、Ｃｕ及びＭｎからなる群から選択される少なくとも一種の原子からなる金属とを有し、担持された金属の量が金属＋担体の合計質量基準で５〜１０質量％であることを特徴とする排気ガス浄化用触媒。 Catalyst support made of ceramic or metal material, and double oxide Y 1-X A X Mn 2 O 5 supported on the catalyst support (wherein A is Ca, Lu or Bi; 5 ≧ X ≧ 0) and a metal comprising at least one atom selected from the group consisting of Ag, Cu and Mn supported on the double oxide Y 1-X A X Mn 2 O 5 An exhaust gas purifying catalyst characterized in that the amount of the supported and supported metal is 5 to 10% by mass based on the total mass of the metal + support . 複酸化物Ｙ１−ＸＡＸＭｎ２Ｏ５がＹＭｎ２Ｏ５である請求項１記載の排気ガス浄化用触媒。 2. The exhaust gas purifying catalyst according to claim 1, wherein the double oxide Y 1-X A X Mn 2 O 5 is YMn 2 O 5 . 前記複酸化物Ｙ１−ＸＡＸＭｎ２Ｏ５に担持されている原子がＡｇである請求項１記載の排気ガス浄化用触媒。 The mixed oxide Y 1-X A X Mn 2 O 5 is supported on the atom is Ag claim 1 exhaust gas purifying catalyst according. 触媒支持体がハニカム形状であることを特徴とする請求項１〜３の何れか１項に記載の排気ガス浄化用触媒。 The exhaust gas purifying catalyst according to any one of claims 1 to 3, wherein the catalyst support has a honeycomb shape. 触媒支持体がＤＰＦであることを特徴とする請求項１〜３の何れか１項に記載の排気ガス浄化用触媒。 The exhaust gas purifying catalyst according to any one of claims 1 to 3, wherein the catalyst support is a DPF.
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