JP2008296111A - Manufacturing method of exhaust gas purifying catalyst and exhaust gas purifying catalyst - Google Patents
Manufacturing method of exhaust gas purifying catalyst and exhaust gas purifying catalyst Download PDFInfo
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- 230000003197 catalytic effect Effects 0.000 claims abstract description 13
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 28
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
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- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
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- IXSUHTFXKKBBJP-UHFFFAOYSA-L azanide;platinum(2+);dinitrite Chemical compound [NH2-].[NH2-].[Pt+2].[O-]N=O.[O-]N=O IXSUHTFXKKBBJP-UHFFFAOYSA-L 0.000 description 1
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- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
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- VRQWWCJWSIOWHG-UHFFFAOYSA-J octadecanoate;zirconium(4+) Chemical compound [Zr+4].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O VRQWWCJWSIOWHG-UHFFFAOYSA-J 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
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- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
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- Catalysts (AREA)
Abstract
Description
この発明は、新規な排ガス浄化触媒の製造法および排ガス浄化触媒に関し、さらに詳しくは浄化能が改良された新規な排ガス浄化触媒の製造法および排ガス浄化触媒に関する。 The present invention relates to a novel method for producing an exhaust gas purification catalyst and an exhaust gas purification catalyst, and more particularly to a novel method for producing an exhaust gas purification catalyst and an exhaust gas purification catalyst with improved purification performance.
従来、自動車のガソリンエンジンジンなどの内燃機関から排出される排ガスに含まれる一酸化炭素（ＣＯ）、窒素酸化物（ＮＯＸ）、未燃焼の炭化水素（ＨＣ）を二酸化炭素、窒素、水に変換することにより排ガスを浄化するための三元触媒として、貴金属系触媒を酸化物担体に担持させた種々の担持触媒が知られている。
これらの担持触媒の触媒金属としては白金（Ｐｔ）、ロジウム(Ｒｈ)が、担体としてはＳｉＯ２、アルミナ（Ａｌ２Ｏ３）およびジルコニア（ＺｒＯ２）などが知られている。
Conventionally, carbon monoxide (CO), nitrogen oxides (NO x ), and unburned hydrocarbons (HC) contained in exhaust gas discharged from an internal combustion engine such as an automobile gasoline engine gin are converted into carbon dioxide, nitrogen, and water. Various supported catalysts in which a noble metal catalyst is supported on an oxide carrier are known as three-way catalysts for purifying exhaust gas by conversion.
Platinum (Pt) and rhodium (Rh) are known as catalyst metals of these supported catalysts, and SiO 2 , alumina (Al 2 O 3 ), zirconia (ZrO 2 ) and the like are known as supports.
そして、これらの担持触媒は、従来は含浸法や共沈法によって調製されており、Ｒｈは酸化物状態（Ｒｈ２Ｏ３）であるため、メタル状態に比べて活性が低い。
また、これらの排ガス浄化担持触媒は高温の排ガスにより触媒金属のシンタリングが避けられずこのためトータルの触媒活性が低くなり、稀少な貴金属触媒の資源問題もあり浄化能の改善が求められている。
このため、触媒活性、担持触媒の耐熱性および触媒のシンタリングの改良を目的として異種の触媒を組み合わせたりあるいは担体に他の金属酸化物を添加する試みが提案されている（特許文献１〜３）。
These supported catalysts have been conventionally prepared by an impregnation method or a coprecipitation method. Since Rh is in an oxide state (Rh 2 O 3 ), its activity is lower than that in a metal state.
In addition, these exhaust gas purifying supported catalysts cannot avoid sintering of the catalyst metal due to the high temperature exhaust gas. Therefore, the total catalytic activity is lowered, and there is a problem of rare noble metal catalyst resources, and improvement of purification performance is required. .
For this reason, attempts have been made to combine different kinds of catalysts or to add other metal oxides to the support in order to improve the catalytic activity, the heat resistance of the supported catalyst and the sintering of the catalyst (
上記の特開平１０−２１６５１４号公報には、アルミナとジルコニアとを含む担体にＲｈを担持した第１触媒粉末と、前記担体にＰｔを担持した第２触媒粉末とを混合することによって得られる排ガス浄化用触媒は触媒活性および耐久性に優れていることが記載されている。しかし、具体的に開示されている担体は酸性担体であるＡｌ２Ｏ３を主成分とするものでありシンタリング抑制効果には限界がある。また、Ａｌ２Ｏ３とＺｒＯ２との相互作用については記載がない。 JP-A-10-216514 discloses an exhaust gas obtained by mixing a first catalyst powder supporting Rh on a support containing alumina and zirconia and a second catalyst powder supporting Pt on the support. It is described that the purification catalyst is excellent in catalytic activity and durability. However, the specifically disclosed carrier is mainly composed of Al 2 O 3 which is an acidic carrier, and there is a limit to the sintering suppression effect. Further, there is no description about the interaction of Al 2 O 3 and ZrO 2.
上記の特開２００２−２８２６９２公報には、Ａｌ２Ｏ３粉末とＣｅＯ２およびＺｒＯ２の複合酸化物とアルミナゾルとから得られる酸化物担体にＰｔを担持させた下触媒層にＬａ２Ｏ３などのランタノイド元素を含む添加物を添加したＺｒＯ２担体にＲｈを担持させた上触媒層を形成した２層の担持触媒からなる排ガス浄化用触媒は耐熱性および高い活性を示すことが記載されている。しかし、均一な担持触媒を製造するためには触媒の製造工程が複雑である。また、Ａｌ２Ｏ３とＺｒＯ２との相互作用については記載がない。 In the above-mentioned Japanese Patent Application Laid-Open No. 2002-282692, La 2 O 3 or the like is formed on a lower catalyst layer in which Pt is supported on an oxide carrier obtained from Al 2 O 3 powder, a composite oxide of CeO 2 and ZrO 2 and alumina sol. It is described that an exhaust gas purifying catalyst comprising a two-layer supported catalyst in which an upper catalyst layer is formed by supporting Rh on a ZrO 2 carrier to which an additive containing a lanthanoid element is added exhibits heat resistance and high activity. . However, the production process of the catalyst is complicated in order to produce a uniform supported catalyst. Further, there is no description about the interaction of Al 2 O 3 and ZrO 2.
上記の特開２００６−２６５５６号公報には、ＳｉＯ２からなる担体上にＲｈとＡｌ、Ｃｅ、Ｌａやアルカリ土類金属を担持した触媒と、更にＺｒＯ２にＲｈを担持した触媒とを混合した排ガス浄化用触媒はシンタリングが抑制されることが記載されている。しかし、担体の主成分は酸性担体であるＳｉＯ２でありシンタリング抑制効果には限界がある。また、ＳｉＯ２とＺｒＯ２との相互作用については記載がない。 In the above Japanese Patent Application Laid-Open No. 2006-26556, Rh and a catalyst supporting Al, Ce, La or an alkaline earth metal on a support made of SiO 2 and a catalyst supporting Rh on ZrO 2 are mixed. It is described that the exhaust gas purifying catalyst suppresses sintering. However, the main component of the carrier is limited to a SiO 2 sintering inhibiting effect is acidic carrier. Moreover, there is no description about the interaction between SiO 2 and ZrO 2 .
この発明者らは、排ガス浄化用担持触媒の活性を改良することを目的として研究した結果、担体の酸点および塩基点が触媒のシンタリングおよび触媒活性に関係していることを見出しさらに研究を続けた結果、この発明を完成した。
従って、この発明の目的は、触媒活性が良好で浄化能が改良された排ガス浄化用触媒の製造法および排ガス浄化用触媒を提供することである。
As a result of research aimed at improving the activity of a supported catalyst for exhaust gas purification, the present inventors have found that the acid point and base point of the support are related to the sintering and catalyst activity of the catalyst. As a result of continuing, this invention was completed.
Accordingly, an object of the present invention is to provide a method for producing an exhaust gas purifying catalyst having good catalytic activity and improved purifying ability, and an exhaust gas purifying catalyst.
この発明は、塩基性担体原料の水酸化物と酸性担体原料の塩又は酸性担体とを混合し、焼成して担体を作製することを特徴とする排ガス浄化触媒の製造法に関する。
また、この発明は、前記の製造法によって得られる排ガス浄化触媒に関する。
さらに、この発明は、Ｘ線回折分析で２θ（ｄｅｇ）が６０．２°にピークを有し、少なくともアルミナ、ジルコニアからなる金属複合酸化物を含む担体に触媒金属が担持されてなる排ガス浄化触媒に関する。
さらに、この発明は、Ａｌ０．１６Ｚｒ０．８４Ｏ１．９６を含む担体に触媒金属が担持されてなる排ガス浄化触媒に関する。
The present invention relates to a method for producing an exhaust gas purification catalyst characterized in that a hydroxide of a basic carrier material and a salt of an acidic carrier material or an acidic carrier are mixed and calcined to produce a carrier.
The present invention also relates to an exhaust gas purification catalyst obtained by the above production method.
Furthermore, the present invention relates to an exhaust gas purification catalyst in which a catalyst metal is supported on a support having a metal complex oxide composed of at least alumina and zirconia, with 2θ (deg) having a peak at 60.2 ° by X-ray diffraction analysis. About.
Furthermore, the present invention relates to an exhaust gas purification catalyst in which a catalyst metal is supported on a support containing Al 0.16 Zr 0.84 O 1.96 .
この発明において塩基性担体とは、Ａ．Ｌ．ＡｌｌｒｅｄとＥ．Ｇ．Ｒｏｃｈｏｗの近似（Ｊ．Ｉｎｏｒｇ．Ｎｕｃｌ．Ｃｈｅｍ．，１９５８，５２６４）を用いた電気陰性度（コットンウィルキンソンガウス基礎無機化学原書第２版ｐ５９）が、１．２３より小さく、１．０１より大きい元素の酸化物担体をいう。 In this invention, the basic carrier means A. L. Allred and E.M. G. Elements having an electronegativity (Cotton Wilkinson Gauss Fundamental Inorganic Chemistry Book 2nd edition p59) using the Rochow approximation (J. Inorg. Nucl. Chem., 1958, 5264) of less than 1.23 and greater than 1.01 An oxide support of
また、この発明において酸性担体とは、Ａ．Ｌ．ＡｌｌｒｅｄとＥ．Ｇ．Ｒｏｃｈｏｗの近似（Ｊ．Ｉｎｏｒｇ．Ｎｕｃｌ．Ｃｈｅｍ．，１９５８，５２６４）を用いた電気陰性度（コットンウィルキンソンガウス基礎無機化学原書第２版ｐ５９）が、１．２３以上の元素の酸化物担体をいう。複合酸化物の場合、Ｘ線光電子分光法（ＸＰＳ）によって測定される複合酸化物の表面組成から算出した電気陰性度の平均値で示す。 In this invention, the acidic carrier means A. L. Allred and E.M. G. Electronegativity (Cotton Wilkinson Gauss Fundamental Inorganic Chemistry, Second Edition, p59) using the Rochow approximation (J. Inorg. Nucl. Chem., 1958, 5264) refers to an oxide support of an element having 1.23 or more. . In the case of the complex oxide, the average value of the electronegativity calculated from the surface composition of the complex oxide measured by X-ray photoelectron spectroscopy (XPS) is shown.
さらに、この発明においてＸ線回折分析で２θ（ｄｅｇ）が６０．２°にピークを有し、少なくともアルミナ、ジルコニアからなる金属複合酸化物を含むとは、アルミナとジルコニアとの組成が変化してもＸ線回折分析で２θ（ｄｅｇ）が６０．２°の一定の位置に明確なピークを有する金属複合酸化物を含むことを意味する。 Furthermore, in the present invention, 2θ (deg) has a peak at 60.2 ° by X-ray diffraction analysis, and that it contains a metal composite oxide composed of at least alumina and zirconia, the composition of alumina and zirconia changes. Means that a metal complex oxide having a clear peak at a constant position where 2θ (deg) is 60.2 ° in X-ray diffraction analysis is included.
この発明によれば、触媒のシンタリングが抑制されて良好な触媒活性を示し浄化能が改良された排ガス浄化触媒を簡単な方法で製造することができる。
また、この発明によれば、触媒のシンタリングが抑制されて良好な触媒活性を示し浄化能が改良された排ガス浄化触媒を得ることができる。
According to the present invention, it is possible to manufacture an exhaust gas purifying catalyst that suppresses sintering of the catalyst, exhibits good catalytic activity, and has improved purifying ability, by a simple method.
In addition, according to the present invention, it is possible to obtain an exhaust gas purifying catalyst that suppresses sintering of the catalyst, exhibits good catalytic activity, and has improved purifying ability.
この発明における好適な態様を次に示す。
１）前記担体にＲｈを担持する前記の製造法。
２）塩基性担体成分がＺｒＯ２であり、酸性担体成分がＡｌ２Ｏ３であり、排ガス浄化触媒全体に対するＡｌ２Ｏ３の質量割合が１０〜３０％である前記の製造法。
A preferred embodiment of the present invention will be described below.
1) The said manufacturing method which carries | supports Rh on the said support | carrier.
2) a basic carrier component is ZrO 2, acidic support component is Al 2 O 3, wherein the process is 10-30% by weight ratio of Al 2 O 3 is for the entire exhaust gas purifying catalyst.
この発明においては、塩基性担体原料の水酸化物と酸性担体原料の塩又は酸性担体とを混合し、焼成して担体を作製することが必要である。
前記の塩基性担体原料の水酸化物を単独で使用しても塩基性担体をそのまま使用する場合に比べて効果はあるが十分ではなく、また酸性担体原料の塩又は酸性担体を単独で使用したのでは触媒活性が低く好ましくない。
In the present invention, it is necessary to prepare a carrier by mixing a hydroxide of a basic carrier material and a salt of an acidic carrier material or an acidic carrier and baking them.
Even if the hydroxide of the basic carrier raw material is used alone, there is an effect as compared with the case where the basic carrier is used as it is, but the salt of the acidic carrier raw material or the acidic carrier is used alone. In this case, the catalytic activity is low, which is not preferable.
前記の塩基性担体原料の水酸化物としては、排ガス浄化触媒用の塩基性担体を与える水酸化物であれば特に制限はなく、好適には水酸化ジルコニウムを挙げることができる。
また、塩基性担体原料としては、排ガス浄化触媒用の塩基性担体を与えかつ水酸化物となりえるものであれば特に制限はなく、オキシ硝酸ジルコニウム、酸塩化ジルコニウム、酸水酸化ジルコニウム、硫酸ジルコニウム、酢酸ジルコニウム、炭酸ジルコニウムアンモニウム、ステアリン酸ジルコニウム、オクチル酸ジルコニウムなどを挙げることができる。
The hydroxide of the basic carrier raw material is not particularly limited as long as it is a hydroxide that provides a basic carrier for an exhaust gas purification catalyst, and zirconium hydroxide can be preferably used.
The basic carrier material is not particularly limited as long as it provides a basic carrier for an exhaust gas purification catalyst and can be a hydroxide. Zirconium oxynitrate, zirconium oxychloride, zirconium oxyhydroxide, zirconium sulfate, Examples thereof include zirconium acetate, ammonium zirconium carbonate, zirconium stearate, and zirconium octylate.
前記の酸性担体原料の塩又は酸性担体としては、Ａｌ（ＮＯ３）３、Ａｌ２（ＳＯ４）３、Ａｌ（ＳＣＮ）３、Ａｌ（Ｃ２Ｈ３Ｏ２）３、Ａｌ２Ｏ３、ＳｉＯ２など、好適にはＡｌ（ＮＯ２）３、Ａｌ２（ＳＯ４）３、Ａｌ（ＳＣＮ）３、Ａｌ（Ｃ２Ｈ３Ｏ２）３、Ａｌ２Ｏ３などを挙げることができる。 Examples of the salt of the acidic carrier raw material or the acidic carrier include Al (NO 3 ) 3 , Al 2 (SO 4 ) 3 , Al (SCN) 3 , Al (C 2 H 3 O 2 ) 3 , Al 2 O 3 , Examples thereof include SiO 2 , preferably Al (NO 2 ) 3 , Al 2 (SO 4 ) 3 , Al (SCN) 3 , Al (C 2 H 3 O 2 ) 3 , and Al 2 O 3 .
前記の酸性担体原料の塩又は酸性担体は単独で用いることが好ましいが、Ｃｅ、Ｌａおよびアルカリ土類金属（Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｒａ、Ｂｅなど）を加えてもよい。
これらのＣｅ、Ｌａおよびアルカリ土類金属はその硝酸塩などの金属塩を含浸法、イオン交換法、吸着法、還元析出法等によって添加することができる。
The above-mentioned salt or acidic carrier of the acidic carrier raw material is preferably used alone, but Ce, La and alkaline earth metals (Mg, Ca, Sr, Ba, Ra, Be, etc.) may be added.
These Ce, La and alkaline earth metals can be added by impregnation method, ion exchange method, adsorption method, reduction precipitation method and the like with a metal salt such as nitrate.
この発明においては、先ず前記の塩基性担体原料の水酸化物と酸性担体原料の塩又は酸性担体とを混合する。
前記の塩基性担体成分と酸性担体との割合は、塩基性担体が主成分となる割合、つまり触媒全体に対する酸性担体成分の質量％表示の割合［（酸性担体成分／触媒全体）ｘ１００％］が、１００質量％未満、特に５０質量％以下５質量％以上、その中でも１０〜３０質量％であることが好ましい。
特に、塩基性担体成分がＺｒＯ２であり酸性担体成分がＡｌ２Ｏ３であり、触媒全体に対するＡｌ２Ｏ３の割合が１０〜３０質量％であることが好ましい。
In the present invention, first, the hydroxide of the basic carrier raw material and the salt of the acidic carrier raw material or the acidic carrier are mixed.
The ratio of the basic carrier component to the acidic carrier is the ratio of the basic carrier as the main component, that is, the ratio of the mass percentage of the acidic carrier component to the whole catalyst [(acidic carrier component / whole catalyst) × 100%]. , Less than 100% by mass, particularly 50% by mass or less, 5% by mass or more, and preferably 10 to 30% by mass.
In particular, it is preferable that the basic carrier component is ZrO 2 , the acidic carrier component is Al 2 O 3 , and the ratio of Al 2 O 3 to the entire catalyst is 10 to 30% by mass.
前記の塩基性担体原料の水酸化物は、前記の塩基性担体の出発原料とアンモニアとを均一混合した後、好適には濾過あるいは遠心分離などによって固形混合物を取得し、１００℃以上、好適には１００〜２００℃で数時間〜１昼夜程度の時間加熱乾燥した後、必要であれば解砕することによって得ることができる。 The hydroxide of the basic carrier raw material is obtained by uniformly mixing the starting raw material of the basic carrier and ammonia, and then obtaining a solid mixture, preferably by filtration or centrifugal separation. Can be obtained by heating and drying at 100 to 200 ° C. for several hours to about 1 day and then pulverizing if necessary.
この発明においては、前記の塩基性担体原料の水酸化物を必要であれば溶媒、例えば水に入れ、酸性担体原料の塩又は酸性担体と混合し、必要であれば任意の形状、例えばペレット状又はハニカム形状に成形して、好適には１００℃以上、特に１００〜２００℃程度の温度で数時間〜１昼夜程度の時間加熱乾燥した後、好適には２００℃以上、特に２００〜３００℃程度の温度で１０分〜１晩程度の時間焼成し、好適には４００℃以上、特に４００〜１０００℃で１０分間〜１０時間程度の時間焼成して担体を得ることができる。 In the present invention, the hydroxide of the basic carrier raw material is put in a solvent, for example, water if necessary, and mixed with the salt of the acidic carrier raw material or the acidic carrier, and if necessary, any shape, for example, a pellet shape Alternatively, it is formed into a honeycomb shape, and is preferably heated and dried at a temperature of about 100 ° C. or more, particularly about 100 to 200 ° C. for several hours to about 1 day and night, and then preferably 200 ° C. or more, particularly about 200 to 300 ° C. The carrier can be obtained by firing at a temperature of 10 minutes to 1 night, preferably at 400 ° C. or higher, particularly at 400 to 1000 ° C. for 10 minutes to 10 hours.
この発明における担持触媒は、任意の形状、好適にはペレット状、ハニカム形状の成形体の前記担体に触媒金属を担持させることによって、あるいは担体に触媒金属を担持して得られた担持触媒を任意の形状の成形体に成形することによって、製造することができる。
例えば、酸化ロジウムＲｈ２Ｏ３、硝酸ロジウムＲｈ（ＮＯ３）３、塩化ロジウムＲｈＣｌ３・４Ｈ２Ｏ等のロジウム化合物、ジニトロジアンミン白金Ｐｔ（ＮＨ３）２（ＮＯ２）２、ジクロロテトラアンミン白金Ｐｔ（ＮＨ３）４Ｃｌ２・ｎＨ２Ｏ（ｎ＝１）、ヘキサクロロ白金酸六水和物Ｈ２［ＰｔＣｌ６］・６Ｈ２０、酸化白金ＰｔＯ２、有機白金などの白金化合物を触媒成分として用い、蒸発凝固法、含浸法、イオン交換法、吸着法、還元析出法等の触媒担持法、好適には含浸法によってＲｈやＰｔなどの触媒金属を担持させることができる。
前記の触媒金属の担持量は、担体に対して０．０２５〜１質量％程度、特に０．０２５〜０．５質量％程度であることが好ましい。
The supported catalyst in the present invention may be any supported catalyst obtained by supporting a catalyst metal on the carrier in an arbitrary shape, preferably a pellet-shaped or honeycomb-shaped molded body, or by supporting the catalyst metal on a carrier. It can manufacture by shape | molding to the molded object of the shape of.
For example, rhodium compounds such as rhodium oxide Rh 2 O 3 , rhodium nitrate Rh (NO 3 ) 3 , rhodium chloride RhCl 3 .4H 2 O, dinitrodiammine platinum Pt (NH 3 ) 2 (NO 2 ) 2 , dichlorotetraammine platinum Pt (NH 3 ) 4 Cl 2 .nH 2 O (n = 1), hexachloroplatinic acid hexahydrate H 2 [PtCl 6 ] .
The amount of the catalyst metal supported is preferably about 0.025 to 1% by mass, particularly about 0.025 to 0.5% by mass, based on the carrier.
この発明の排ガス浄化触媒は、例えば、前記の塩基性担体原料の水酸化物と酸性担体原料の塩又は酸性担体を、必要であれば溶媒、例えば水と混合し、任意の形状、好適にはペレット状、ハニカム形状に成形した担体に触媒金属を担持させることによって形成してもよく、あるいは前記担体に触媒金属を担持した後に解砕して担持触媒とした後、任意の形状、好適にはハニカム形状に成形することによって製造することができる。 The exhaust gas purifying catalyst of the present invention comprises, for example, the basic carrier raw material hydroxide and the salt of the acidic carrier raw material or the acidic carrier mixed with a solvent, for example, water, if necessary, in any shape, preferably It may be formed by supporting the catalyst metal on a pellet-shaped or honeycomb-shaped support, or after supporting the catalyst metal on the support and crushing it to form a supported catalyst, It can be manufactured by forming into a honeycomb shape.
また、この発明の排ガス浄化触媒は、例えばコージェライト（２ＭｇＯ・２Ａｌ２Ｏ３・５ＳｉＯ２）などのＭｇＯ・Ａｌ２Ｏ３・ＳｉＯ２複合酸化物から形成されるハニカム形状の支持基材に前記の担体からなるコート層を任意の方法、例えば含浸、塗布などによって形成し、次いで担体からなるコート層に触媒金属を任意の方法によって担持する方法によって、あるいは前記のハニカム形状の支持基材に予め調製した前記の担体と前記の触媒金属とからなる担持触媒を任意の方法によって積層することによっても製造することができる。 Further, the exhaust gas purifying catalyst of the present invention, for example, cordierite (2MgO · 2Al 2 O 3 · 5SiO 2) The support substrate of a honeycomb shape formed from MgO · Al 2 O 3 · SiO 2 composite oxide such as The coating layer made of the above support is formed by any method, for example, impregnation, coating, etc., and then the catalyst metal is supported on the coating layer made of the support by any method, or on the honeycomb-shaped support substrate in advance. It can also be produced by laminating the prepared supported catalyst composed of the carrier and the catalyst metal by any method.
前記の触媒金属成分を担体に担持する方法としては、好適には、前記の成形された担体に触媒金属成分のスラリーを塗布、噴霧する、好適には触媒金属成分のスラリーをゾーンコートするか、又は成形された担体を触媒金属成分のスラリーに含浸するか、あるいは担体と触媒金属成分のスラリーとを混合し、水を蒸発させながら混練して触媒金属ペーストとし、これを押出し成形機などで押し出して、担体に触媒金属成分を含浸させる方法などが挙げられる。 As a method for supporting the catalyst metal component on a support, preferably, a slurry of the catalyst metal component is preferably applied and sprayed on the molded support, and preferably, the slurry of the catalyst metal component is preferably zone coated. Or impregnate the molded carrier into the catalyst metal component slurry, or mix the carrier and the catalyst metal component slurry, knead while evaporating water to form a catalyst metal paste, and extrude it with an extrusion molding machine etc. And a method of impregnating the support with a catalytic metal component.
この発明において、好適には、１００℃以上、特に１００〜２００℃程度の温度で数時間〜１昼夜程度の時間加熱乾燥した後、４００℃以上、特に４００〜８００℃で３０分間〜５時間程度の時間焼成し必要であれば触媒金属成分を還元することによって、この発明の排ガス浄化触媒を製造することができる。 In the present invention, preferably, after drying by heating at a temperature of about 100 ° C. or more, particularly about 100 to 200 ° C. for several hours to about 1 day or night, at 400 ° C. or more, particularly 400 to 800 ° C. for about 30 minutes to about 5 hours. The exhaust gas purification catalyst of the present invention can be produced by calcining for a period of time and reducing the catalyst metal component if necessary.
以下、この発明の好適な態様である、前述の記載に従って水酸化ジルコニウムとアルミニウム塩とを混合し、焼成して担体を作製し、得られた担体に触媒金属成分を含浸させた排ガス浄化触媒の具体例のＸ線回折図（ＸＲＤ）である図４〜６を用いて説明する。
これらの図において、図４はＡｌ２Ｏ３／触媒全体が１０質量％、図５はＡｌ２Ｏ３／触媒全体が２０質量％、図６はＡｌ２Ｏ３／触媒全体が３０質量％の場合の担持触媒を示す。
Hereinafter, according to the above description, which is a preferred embodiment of the present invention, zirconium hydroxide and an aluminum salt are mixed and calcined to prepare a carrier, and the resulting carrier is impregnated with a catalytic metal component. A specific example will be described with reference to FIGS. 4 to 6 which are X-ray diffraction diagrams (XRD).
In these figures, 4 is Al 2 O 3 /
これら図４〜図６において、Ｘ線回折分析で強度は異なるが２θ（ｄｅｇ）が一定の６０．２°にピークを有している。
従って、これらの担体はＡｌ、ＺｒおよびＯからなる同一の金属複合酸化物を含むと考えられる。
そして、この複合酸化物は、組成式としてはＡｌ０．１６Ｚｒ０．８４Ｏ１．９６で示される。
4 to 6, the X-ray diffraction analysis has a peak at 60.2 ° where 2θ (deg) is constant although the intensity is different.
Therefore, these supports are considered to contain the same metal complex oxide composed of Al, Zr and O.
This composite oxide is represented by Al 0.16 Zr 0.84 O 1.96 as a composition formula.
この発明の触媒は、必要であれば圧縮・解砕し、所望の形状の触媒、例えば直径１〜２ｍｍのペレット状又はハニカム形状の触媒として、良好な浄化能を有する排ガス浄化触媒として使用することができる。 The catalyst of the present invention is compressed and crushed if necessary, and used as a catalyst having a desired shape, for example, a pellet-shaped or honeycomb-shaped catalyst having a diameter of 1 to 2 mm, as an exhaust gas purification catalyst having a good purification ability. Can do.
この発明における担体中にはＡｌ０．１６Ｚｒ０．８４Ｏ１．９６が含まれるが、このＡｌ０．１６Ｚｒ０．８４Ｏ１．９６のＡｌ含有率は３．８７質量％、Ｚｒ含有率は６８．６２質量％、Ｏ含有率は２７．５１質量％である。
Ａｌ２Ｏ３＝１０質量％、ＺｒＯ２＝８９．７５質量％のＡｌ含有率は５．２９質量％、Ｚｒ含有率は６６．４４質量である。
Ｚｒが全てＡｌ０．１６Ｚｒ０．８４Ｏ１．９６になっているとすると、余分なＡｌ含有率は１．５５質量％である。
Ａｌ２Ｏ３＝２０質量％、ＺｒＯ２＝７９．７５質量％のＡｌ含有率は１０．５８質量％、Ｚｒ含有率は５９．０４質量％である。
Ｚｒが全てＡｌ０．１６Ｚｒ０．８４Ｏ１．９６になっているとすると、余分なＡｌ含有率は７．２６質量％である。
Ａｌ２Ｏ３＝３０質量％、ＺｒＯ２＝６９．７５質量％のＡｌ含有率は１５．８８質量％、Ｚｒ含有率は５１．６４質量％である。
Ｚｒが全てＡｌ０．１６Ｚｒ０．８４Ｏ１．９６になっているとすると、余分なＡｌ含有率は１２．９７質量％である。
Although the carrier in the present invention include Al 0.16 Zr 0.84 O 1.96, the Al 0.16 Zr 0.84 O Al content of 1.96 3.87 wt%, Zr content The rate is 68.62% by mass, and the O content is 27.51% by mass.
The Al content of Al 2 O 3 = 10 mass% and ZrO 2 = 89.75 mass% is 5.29 mass%, and the Zr content is 66.44 mass.
Assuming that all Zr is Al 0.16 Zr 0.84 O 1.96 , the excess Al content is 1.55% by mass.
The Al content of Al 2 O 3 = 20 mass% and ZrO 2 = 79.75 mass% is 10.58 mass%, and the Zr content is 59.04 mass%.
Assuming that all Zr is Al 0.16 Zr 0.84 O 1.96 , the excess Al content is 7.26% by mass.
The Al content of Al 2 O 3 = 30% by mass and ZrO 2 = 69.75% by mass is 15.88% by mass, and the Zr content is 51.64% by mass.
Assuming that all Zr is Al 0.16 Zr 0.84 O 1.96 , the excess Al content is 12.97% by mass.
以下、この発明の実施例を示す。
以下の各例において、排ガス浄化触媒の性能は以下に記載の測定法によって行い、評価した。
１．担持触媒の酸量測定
アンモニア昇温脱離法ＴＰＤ（Temperature Programmed desorption）によって、吸着ガスとしてアンモニアを用いてＮＨ３脱離量から酸量を測定し、試料の酸点の強度分布を評価した。装置はＴＰＤ−ＭＡＳＳを使用した。ＮＨ３脱離量について単位を省略して表示する場合があるが、この場合の単位はＡｌ２Ｏ３が１０質量％のときの値を２００７．９７としたときの相対値を意味する。
Examples of the present invention will be described below.
In each of the following examples, the performance of the exhaust gas purification catalyst was evaluated by the measurement method described below.
1. Measurement of acid amount of supported catalyst By ammonia temperature programmed desorption (TPD), the acid amount was measured from NH 3 desorption amount using ammonia as an adsorption gas, and the intensity distribution of acid points of the sample was evaluated. The device used was TPD-MASS. The NH 3 desorption amount may be displayed by omitting the unit. In this case, the unit means a relative value when the value when Al 2 O 3 is 10 mass% is 2007.97.
２．担持触媒の還元温度測定
昇温還元型ＴＰＲ（Temperature Programmed Reduction/Reaction）によって、還元性ガスとしてＨ２を用いて触媒（Ｒｈ２Ｏ３）の還元温度を測定した。還元温度が低い程貴金属触媒は還元されやすく、活性が高い。装置はＴＰＤ−ＭＡＳＳを使用した。
３．浄化特性試験
得られた触媒（形状：ペレット）を排ガス浄化性能装置にセットし、下記表１に示すガス組成で、空間速度４０００００ｈ−１の条件におけるＣ３Ｈ６、ＮＯｘ、ＣＯの各５０％浄化温度をそれぞれ測定し、触媒活性を評価した。尚、リッチガスのλ（空気過剰率＝空燃比／理論空燃比）＝０．４６、リーンガスのλ＝２．３２であった。５０％浄化温度が低いほど触媒活性が高い。
2. Measurement of reduction temperature of supported catalyst The reduction temperature of the catalyst (Rh 2 O 3 ) was measured by using temperature-reduction TPR (Temperature Programmed Reduction / Reaction) using H 2 as the reducing gas. The lower the reduction temperature, the easier the noble metal catalyst is reduced and the higher the activity. The device used was TPD-MASS.
3. Purification characteristic test The obtained catalyst (shape: pellet) was set in an exhaust gas purification performance apparatus, and each of C 3 H 6 , NO x , and CO under the conditions of a space velocity of 400000 h −1 with the gas composition shown in Table 1 below. % Purification temperature was measured and the catalytic activity was evaluated. The rich gas λ (excess air ratio = air / fuel ratio / theoretical air / fuel ratio) = 0.46, and the lean gas λ = 2.32. The lower the 50% purification temperature, the higher the catalytic activity.
４．ＣＯ吸着量測定
常法により定容型吸着量測定装置を用いて、金属表面へのＣＯ吸着量を測定し、下記の換算式より触媒Ｒｈの粒子径を求めた。装置はＣＯパルスを使用した。
換算式：１８６０．４６５１１６×Ｃ／（Ｖ×ａ２×ｄ／吸着比）（Å）＝３．８８７１２３７４６／Ｖ（Å）
Ｃ：Ｒｈの担持濃度＝０．２５（％）
Ｖ：触媒１グラム当たりのＣＯ吸着量
ａ：Ｒｈの格子定数（Å）＝３．８０３０
吸着比：Ｒｈ１モルに吸着するＣＯのモル比＝１．５
ｄ：Ｒｈの比重（ｇ／ｃｃ）＝１２．４１
５．担持触媒の塩基量測定
二酸化炭素昇温脱離法ＴＰＤ（Temperature Programmed reduction）によって、吸着ガスとしてＣＯ２を用いて試料の脱離ＣＯ２量から塩基量を測定し、塩基点の強度分布を評価した。装置はＴＰＤ−ＭＡＳＳを使用した。ＣＯ２脱離量について単位を省略して表示する場合には、単位は共沈法で調製したＲｈ／ＺｒＯ２の値を５×１０−９としたときの相対値を意味する。
６．Ｘ線回折（ＸＲＤ）測定
ＸＲＤの測定条件
装置：ＲＩＮＴ２５００製
測定方法…連続
開始角…３度
終了角…８５度
サンプリング幅…０．０２度
スキャンスピード…５．０度／ｍｉｎ
電圧…５０ｋＶ
電流…３００ｍＡ
4). Measurement of CO adsorption amount Using a constant volume type adsorption amount measurement device, the amount of CO adsorption on the metal surface was measured by a conventional method, and the particle size of the catalyst Rh was determined from the following conversion formula. The apparatus used a CO pulse.
Conversion formula: 1860.465116 × C / (V × a 2 × d / adsorption ratio) (Å) = 3.887123746 / V (Å)
C: Rh loading concentration = 0.25 (%)
V: CO adsorption amount per gram of catalyst a: Lh lattice constant (Å) = 3.8030
Adsorption ratio: molar ratio of CO adsorbed on Rh1 mole = 1.5
d: Rh specific gravity (g / cc) = 12.41
5. Measurement of the base amount of the supported catalyst Using the temperature programmed desorption method TPD (Temperature Programmed reduction), the base amount is measured from the desorbed CO 2 amount of the sample using CO 2 as the adsorption gas, and the intensity distribution of the base points is evaluated. did. The device used was TPD-MASS. When the unit is omitted and displayed for the CO 2 desorption amount, the unit means a relative value when the value of Rh / ZrO 2 prepared by the coprecipitation method is 5 × 10 −9 .
6). X-ray diffraction (XRD) measurement XRD measurement conditions Apparatus: manufactured by RINT2500 Measurement method: Continuous Start angle: 3 degrees End angle: 85 degrees Sampling width: 0.02 degrees Scanning speed: 5.0 degrees / min
Voltage ... 50kV
Current: 300mA
実施例１
オキシ硝酸ジルコニウムにアンモニアを入れ、一晩攪拌した後、遠心分離機で分離、洗浄して固形分を取得し、固形分を１２０℃で解砕した。解砕後、出来上がった水酸化ジルコニウムを水、さらに硝酸アルミニウムをＡｌ２Ｏ３／触媒全体が１０質量％となる割合で入れて、混合した後、１２０℃で一晩乾燥させた。次いで、２５０℃で１時間焼成し、解砕して、８００℃で３時間焼成して、担体を得た。
この担体に、硝酸ロジウムを含浸させた後、１２０℃で一晩乾燥させ、５００℃で２時間焼成して、担持量０．２５質量％（Ｒｈ／担体）の担持触媒を得た。
この担持触媒である排ガス浄化触媒について評価した。結果をまとめて表２、図１、図２および図３に示す。
Example 1
Ammonia was added to zirconium oxynitrate and stirred overnight, then separated and washed with a centrifuge to obtain a solid content, and the solid content was crushed at 120 ° C. After the pulverization, the finished zirconium hydroxide was mixed with water and aluminum nitrate at a ratio of Al 2 O 3 / total catalyst of 10% by mass, mixed and then dried at 120 ° C. overnight. Next, it was calcined at 250 ° C. for 1 hour, crushed, and calcined at 800 ° C. for 3 hours to obtain a carrier.
This support was impregnated with rhodium nitrate, dried at 120 ° C. overnight, and calcined at 500 ° C. for 2 hours to obtain a supported catalyst having a supported amount of 0.25% by mass (Rh / support).
The exhaust gas purification catalyst which is this supported catalyst was evaluated. The results are summarized in Table 2, FIG. 1, FIG. 2 and FIG.
実施例２
硝酸アルミニウムをＡｌ２Ｏ３／触媒全体が２０質量％となる割合で入れた他は実施例１と同様に実施して、担持触媒を得た。
この担持触媒である排ガス浄化触媒について評価した。結果をまとめて表２、および表３、図１、図２および図３に示す。
Example 2
A supported catalyst was obtained in the same manner as in Example 1 except that aluminum nitrate was added at a ratio of 20% by mass of Al 2 O 3 / total catalyst.
The exhaust gas purification catalyst which is this supported catalyst was evaluated. The results are collectively shown in Table 2 and Table 3, FIG. 1, FIG. 2 and FIG.
実施例３
硝酸アルミニウムをＡｌ２Ｏ３／触媒全体が３０質量％となる割合で入れた他は実施例１と同様に実施して、担持触媒を得た。
この担持触媒である排ガス浄化触媒について評価した。結果をまとめて表２、図１、図２および図３に示す。
Example 3
A supported catalyst was obtained in the same manner as in Example 1 except that aluminum nitrate was added at a ratio of Al 2 O 3 / total catalyst of 30% by mass.
The exhaust gas purification catalyst which is this supported catalyst was evaluated. The results are summarized in Table 2, FIG. 1, FIG. 2 and FIG.
比較例１
硝酸アルミニウムを全く加えなかった他は実施例１と同様に実施して、担持触媒を得た。
この担持触媒について評価した。結果をまとめて表２、表３、図１、図２および図３に示す。
Comparative Example 1
A supported catalyst was obtained in the same manner as in Example 1 except that no aluminum nitrate was added.
This supported catalyst was evaluated. The results are summarized in Table 2, Table 3, FIG. 1, FIG. 2 and FIG.
比較例２〜４
公知の共沈法である下記の方法によって、硝酸アルミニウムをアルミナとして１０、２０、又は３０質量％の割合となるように加えて、担持量０．２５質量％（Ｒｈ／担体）の担持触媒を得た。
共沈法の手順：オキシ硝酸ジルコニウムに硝酸アルミニウムを入れてｐＨが約８になるようにアンモニアを滴下した後、一晩攪拌して、１２０℃で１日乾燥、５００℃で２時間焼成。
これらの担持触媒について評価した。結果をまとめて表２および表３、図１、図２および図３に示す。
Comparative Examples 2-4
According to the following method, which is a known coprecipitation method, aluminum nitrate is added as alumina in a proportion of 10, 20, or 30% by mass, and a supported catalyst with a supported amount of 0.25% by mass (Rh / carrier) is added. Obtained.
Procedure of coprecipitation method: Ammonia was dropped into zirconium oxynitrate so that the pH was about 8, and the mixture was stirred overnight, dried at 120 ° C. for one day, and calcined at 500 ° C. for 2 hours.
These supported catalysts were evaluated. The results are collectively shown in Table 2 and Table 3, FIG. 1, FIG. 2 and FIG.
また、実施例１〜３、比較例１で得られた担持触媒について脱離ＣＯ２量から塩基量を測定したところ、実施例１〜３では２０ｘ１０−９〜３５ｘ１０−９、比較例１では１２ｘ１０−９であった。 Moreover, when the amount of bases was measured from the amount of desorbed CO 2 for the supported catalysts obtained in Examples 1 to 3 and Comparative Example 1, 20 × 10 −9 to 35 × 10 −9 in Examples 1 to 3 and 12 × 10 in Comparative Example 1. -9 .
以上より、実施例１〜３と比較例１〜４とを比較すると、この発明による担持触媒である排ガス浄化触媒は、酸点および塩基点のいずれの量もＡｌ２Ｏ３、ＺｒＯ２単独の場合よりも増えており、これによって貴金属（Ｒｈ）が易還元性となりメタル化されて高活性となり、また塩基点よって貴金属（Ｒｈ）のシンタリングが抑制され、このため高活性と低シンタリングを兼ね備えた浄化能の高い排ガス浄化触媒が得られた。 From the above, when Examples 1 to 3 and Comparative Examples 1 to 4 are compared, the exhaust gas purifying catalyst which is a supported catalyst according to the present invention has both the acid point and base point amount of Al 2 O 3 and ZrO 2 alone. As a result, noble metal (Rh) becomes easily reducible and becomes metallized and becomes highly active, and the base point suppresses sintering of the noble metal (Rh), so that high activity and low sintering are achieved. An exhaust gas purifying catalyst having a high purifying ability and having a combination was obtained.
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