JP2007021334A - Exhaust emission control device - Google Patents

Exhaust emission control device Download PDF

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JP2007021334A
JP2007021334A JP2005205559A JP2005205559A JP2007021334A JP 2007021334 A JP2007021334 A JP 2007021334A JP 2005205559 A JP2005205559 A JP 2005205559A JP 2005205559 A JP2005205559 A JP 2005205559A JP 2007021334 A JP2007021334 A JP 2007021334A
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catalyst material
material particles
fine particle
fine
porous substrate
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JP4844029B2 (en
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Kazuhiro Ito
和浩 伊藤
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Toyota Motor Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To ensure good exhaust cleaning by controlling decrease of the specific surface area of particles of the catalyst material while employing a catalyst material having small particle sizes. <P>SOLUTION: A fine particle portion supporting layer 2 is formed on the surface of the particulate filter 1 or the inside wall surface of the pore of the filter 1. When particles of a catalyst material composed of the fine particle portion PF of particle sizes smaller than the threshold value and the coarse particle portion PC of particle sizes larger than the threshold value in the form of slurry are applied to a porous substrate, the fine particle portion PF of the catalyst material is held selectively within the fine particle portion supporting layer 2. The coarse particle portion PC of the catalyst material is carried on the fine particle portion supporting layer 2 to form a catalyst material layer 3. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は排気浄化装置に関する。   The present invention relates to an exhaust emission control device.

従来より、パティキュレートフィルターのような多孔質基材上に触媒材料粒子が担持されることにより構成される排気浄化装置が知られている。この場合、多孔質基材の表面上だけでなく細孔内壁面上にも触媒材料を担持させることができれば、比表面積を増大させることができる。ところが、触媒材料粒子の粒径が大きいと、触媒材料粒子により多孔質基材の細孔が閉塞されてしまう。   2. Description of the Related Art Conventionally, exhaust gas purification apparatuses configured by supporting catalyst material particles on a porous substrate such as a particulate filter are known. In this case, if the catalyst material can be supported not only on the surface of the porous substrate but also on the inner wall surface of the pore, the specific surface area can be increased. However, when the particle diameter of the catalyst material particles is large, the pores of the porous substrate are blocked by the catalyst material particles.

そこで、触媒材料粒子をミリングし、平均粒径が小さい触媒材料粒子を多孔質基材上に担持するようにした排気浄化装置が公知である（特許文献１参照）。   Therefore, an exhaust emission control device is known in which catalyst material particles are milled to support catalyst material particles having a small average particle diameter on a porous substrate (see Patent Document 1).

なお、多孔質基材上に担持される触媒材料粒子は図８に示されるように、三次粒子Ｐ３として構成されたものであり、即ち複数の二次粒子Ｐ２が集まって形成されたものである。また、各二次粒子Ｐ２は複数の一次粒子Ｐ１が集まって形成されたものである。この場合、二次粒子Ｐ２同士の間に細孔ないし間隙ＭＰが形成されており、この細孔ＭＰ内壁面にも触媒金属が担持される。従って、排気ガスが細孔ＭＰ内に捕捉されることにより浄化される。   As shown in FIG. 8, the catalyst material particles supported on the porous substrate are configured as tertiary particles P3, that is, formed by a plurality of secondary particles P2. . Each secondary particle P2 is formed by a plurality of primary particles P1 gathering. In this case, pores or gaps MP are formed between the secondary particles P2, and the catalyst metal is also supported on the inner wall surfaces of the pores MP. Therefore, the exhaust gas is purified by being trapped in the pores MP.

特開２００４−５８０１３号公報JP 2004-58013 A 特開２００３−１７００５５号公報JP 2003-170055 A

特許文献１のようにミリングを行うと、触媒材料粒子の平均粒径を小さくすることができる。しかしながら、ミリングが行われた後の触媒材料粒子には、粒径がかなり小さい触媒材料粒子即ち微小径粒子も含まれることになる。ところが、この微小径粒子が上述した細孔ＭＰ内に入り込むと比表面積が減少し、かくして排気ガスを十分に浄化できなくなるおそれがある。   When milling is performed as in Patent Document 1, the average particle diameter of the catalyst material particles can be reduced. However, the catalyst material particles after milling also include catalyst material particles having a considerably small particle size, that is, fine particle. However, when the fine particles enter the above-described pores MP, the specific surface area decreases, and thus there is a possibility that the exhaust gas cannot be sufficiently purified.

また、微小径粒子と大径粒子とを含む触媒材料粒子が多孔質基材に適用されたときに、図９に示されるように微小径粒子ＰＳが大径粒子ＰＬと多孔質基材Ｓとの間に介在していると、大径粒子ＰＬがコロ又はボールベアリングの要領で移動しやすくなり、シンタリングが生じやすくなるおそれもある。シンタリングが生じた場合も比表面積が減少する。   Further, when the catalyst material particles including the fine particles and the large particles are applied to the porous substrate, the fine particles PS are converted into the large particles PL and the porous substrate S as shown in FIG. If they are interposed, the large-diameter particles PL are likely to move in the manner of a roller or a ball bearing, and sintering may occur easily. The specific surface area also decreases when sintering occurs.

即ち、このような微小径粒子が比表面積に対して悪影響を及ぼすことが判明したのである。   That is, it has been found that such fine particles have an adverse effect on the specific surface area.

そこで本発明は、粒径の小さい触媒材料粒子を使用しつつ比表面積の減少を抑制し、それにより良好な排気浄化を確保することができる排気浄化装置を提供することを目的とする。   Accordingly, an object of the present invention is to provide an exhaust purification device that can suppress a decrease in specific surface area while using catalyst material particles having a small particle size, and thereby ensure good exhaust purification.

前記課題を解決するために１番目の発明によれば、多孔質基材の表面又は細孔内壁面上に触媒材料粒子が担持されることにより構成される排気浄化装置において、触媒材料粒子が、粒径が境界値よりも小さい微粒部と、粒径が該境界値よりも大きい粗粒部とから構成されており、多孔質基材の表面又は細孔内壁面上に、触媒材料粒子の微粒部を選択的に保持するための微粒部保持層を形成し、製造時に触媒材料粒子がスラリーの形で多孔質基材に適用されると、触媒材料粒子の微粒部が該微粒部保持層内に保持され、触媒材料粒子の粗粒部が該微粒部保持層上に担持されるようにしている。   In order to solve the above problems, according to a first aspect of the present invention, in the exhaust gas purification apparatus configured by supporting the catalyst material particles on the surface of the porous substrate or the inner wall surface of the pores, It is composed of a fine particle part having a particle size smaller than the boundary value and a coarse particle part having a particle size larger than the boundary value. When the catalyst material particles are applied to the porous substrate in the form of a slurry at the time of production, a fine particle part of the catalyst material particles is formed in the fine particle part holding layer. The coarse portion of the catalyst material particles is supported on the fine portion holding layer.

また、２番目の発明によれば前記課題を解決するために、多孔質基材の表面又は細孔内壁面上に触媒材料粒子が担持されることにより構成される排気浄化装置において、触媒材料粒子が、粒径が境界値よりも小さい微粒部と、粒径が該境界値よりも大きい粗粒部とから構成されており、該微粒部が除去されるように触媒材料粒子を分級し、該分級された触媒材料粒子をスラリーの形で多孔質基材に適用することにより、該触媒材料粒子が多孔質基材上に担持されるようにしている。   According to a second aspect of the present invention, in order to solve the above-described problem, in the exhaust gas purification apparatus configured by supporting the catalyst material particles on the surface of the porous substrate or the inner wall surface of the pores, the catalyst material particles Is composed of a fine particle part having a particle size smaller than the boundary value and a coarse particle part having a particle size larger than the boundary value, and classifying the catalyst material particles so that the fine particle part is removed, The classified catalyst material particles are applied to the porous substrate in the form of a slurry so that the catalyst material particles are supported on the porous substrate.

また、３番目の発明によれば１又は２番目の発明において、前記境界値が、触媒材料粒子の平均粒径から標準偏差の３倍を差し引いて得られる値から、触媒材料粒子の平均粒径までの間にある。   According to a third aspect, in the first or second aspect, the boundary value is obtained by subtracting three times the standard deviation from the average particle diameter of the catalyst material particles, and then the average particle diameter of the catalyst material particles. Between.

また、４番目の発明によれば１又は２番目の発明において、触媒材料原料をミリングすることにより前記触媒材料粒子が形成されている。   According to the fourth invention, in the first or second invention, the catalyst material particles are formed by milling the catalyst material raw material.

粒径の小さい触媒材料粒子を使用しつつ比表面積の減少を抑制し、それにより良好な排気浄化を確保することができる。   While using catalyst material particles having a small particle size, the reduction in specific surface area can be suppressed, thereby ensuring good exhaust purification.

以下では、多孔質基材として排気ガス中の微粒子を捕集するためのパティキュレートフィルターを用い、このパティキュレートフィルターに触媒を担持する場合について説明する。   Hereinafter, a case where a particulate filter for collecting fine particles in exhaust gas is used as the porous substrate and a catalyst is supported on the particulate filter will be described.

図１にはパティキュレートフィルター１の構造が示されている。図１に示されるパティキュレートフィルター１はセラミック製ハニカム構造をなしており、互いに平行をなして延びる複数個の排気流通路１０，１１を具備する。これら排気流通路は下流端が栓１２により閉塞された排気ガス流入通路１０と、上流端が栓１３により閉塞された排気ガス流出通路１１とにより構成される。従って、排気ガス流入通路１０及び排気ガス流出通路１１は薄肉の隔壁１４を介して交互に配置される。云い換えると排気ガス流入通路１０及び排気ガス流出通路１１は各排気ガス流入通路１０が４つの排気ガス流出通路１１によって包囲され、各排気ガス流出通路１１が４つの排気ガス流入通路１０によって包囲されるように配置される。隔壁１４は多孔性を有し、従って排気ガス流入通路１０内に流入した排気ガスは図１に矢印で示されるように、周囲の隔壁１４内を通って隣接する排気ガス流出通路１１内に流出する。   FIG. 1 shows the structure of the particulate filter 1. The particulate filter 1 shown in FIG. 1 has a ceramic honeycomb structure and includes a plurality of exhaust flow passages 10 and 11 extending in parallel with each other. These exhaust flow passages are constituted by an exhaust gas inflow passage 10 whose downstream end is closed by a plug 12 and an exhaust gas outflow passage 11 whose upstream end is closed by a plug 13. Therefore, the exhaust gas inflow passages 10 and the exhaust gas outflow passages 11 are alternately arranged via the thin partition walls 14. In other words, the exhaust gas inflow passage 10 and the exhaust gas outflow passage 11 are each surrounded by four exhaust gas outflow passages 11, and each exhaust gas outflow passage 11 is surrounded by four exhaust gas inflow passages 10. Arranged so that. The partition wall 14 is porous, so that the exhaust gas flowing into the exhaust gas inflow passage 10 flows out into the adjacent exhaust gas outflow passage 11 through the surrounding partition wall 14 as indicated by arrows in FIG. To do.

パティキュレートフィルター１を形成する多孔質材料としてさまざまなものを用いることができ、例えば炭化珪素、コージェライト、フェリエライト、ゼオライト、炭化窒素などを用いることができる。   Various materials can be used as the porous material for forming the particulate filter 1, and for example, silicon carbide, cordierite, ferrierite, zeolite, nitrogen carbide and the like can be used.

なお、排気流通路の上流端及び下流端が閉塞されていないモノリス基材を多孔質基材として用いることもできる。   A monolith substrate in which the upstream end and the downstream end of the exhaust flow passage are not blocked can also be used as the porous substrate.

図２はパティキュレートフィルター１の部分拡大断面図であり、図３は図２のＡ部の拡大図である。図２及び図３からわかるように、パティキュレートフィルター１の表面及び細孔内壁面上には微粒部保持層２が形成され、この微粒部保持層２上に触媒材料層３が形成されている。詳しくは後述するが、微粒部保持層２には触媒材料粒子の微粒部ＰＦが保持されており、触媒材料層３は触媒材料粒子の粗粒部ＰＣから構成されている。   FIG. 2 is a partially enlarged sectional view of the particulate filter 1, and FIG. 3 is an enlarged view of a portion A in FIG. As can be seen from FIGS. 2 and 3, the fine particle holding layer 2 is formed on the surface of the particulate filter 1 and the inner wall surface of the pores, and the catalyst material layer 3 is formed on the fine particle holding layer 2. . As will be described in detail later, the fine particle portion holding layer 2 holds fine particle portions PF of catalyst material particles, and the catalyst material layer 3 is composed of coarse particle portions PC of catalyst material particles.

図４を参照して本発明による実施例の触媒担持方法を説明する。まず、上述したパティキュレートフィルターが用意される。次いで、このパティキュレートフィルターの表面及び細孔内壁面上に微粒部保持層２が形成される。この微粒部保持層２は多孔性を有するのが好ましく、例えばアルミナなどのウィスカーや微細粉末から構成される。このような微粒部保持層２の材料をパティキュレートフィルターに例えばガスでもって供給し、次いで焼成することによりパティキュレートフィルター１上に微粒部保持層２を形成することができる。   With reference to FIG. 4, the catalyst supporting method of the Example by this invention is demonstrated. First, the particulate filter described above is prepared. Next, the fine particle holding layer 2 is formed on the surface of the particulate filter and the inner wall surface of the pores. The fine particle holding layer 2 is preferably porous, and is made of whiskers such as alumina or fine powder. The material for the fine particle part holding layer 2 is supplied to the particulate filter with gas, for example, and then fired, whereby the fine particle part holding layer 2 can be formed on the particulate filter 1.

一方、触媒材料粒子を溶媒に分散させることによりスラリーが作成される。具体的には、触媒材料原料が水及びバインダーと共に混合され、かくしてスラリーが作成される。触媒材料として、アルミナ、ジルコニア、チタニア、シリカ、シリカ・アルミナなどの多孔質酸化物、又は出発原料の１次粒子の粒径の小さいものを用いることができる。なお、白金のような触媒種を多孔質酸化物に予め担持させておいてスラリーを作成することもできるし、後述の焼成後に多孔質酸化物に担持させることもできる。   On the other hand, a slurry is prepared by dispersing the catalyst material particles in a solvent. Specifically, the catalyst material raw material is mixed with water and a binder, thus creating a slurry. As the catalyst material, a porous oxide such as alumina, zirconia, titania, silica, silica / alumina, or a material having a small primary particle diameter of the starting material can be used. Note that a slurry can be prepared by previously supporting a catalyst species such as platinum on a porous oxide, or can be supported on a porous oxide after firing as described later.

次いで、上述のパティキュレートフィルターがこのスラリーに浸漬され、次いで例えばパティキュレートフィルターにエアーを吹き付け又は吸引することにより、余分なスラリーが除去される。次いで、パティキュレートフィルターが乾燥され、焼成され、かくして微粒部保持層２上に触媒材料層３が形成される。   Next, the above-mentioned particulate filter is immersed in this slurry, and then excess slurry is removed, for example, by blowing or sucking air to the particulate filter. Next, the particulate filter is dried and baked, and thus the catalyst material layer 3 is formed on the fine particle holding layer 2.

スラリーの作成の際に触媒材料粒子をミリングすると冒頭で述べたように、微小径粒子も生成され、この微小径粒子により比表面積が低減されるおそれがある。   When the catalyst material particles are milled during the preparation of the slurry, as described at the beginning, fine particles are also generated, and the specific surface area may be reduced by the fine particles.

ここで、ミリング後の触媒材料粒子は図５に示されるように、粒径が境界値ｄＢよりも小さい微粒部ＰＦと、粒径が境界値ｄＢよりも大きい粗粒部ＰＣとから構成されていると考えることができる。その上で、この微粒部ＰＦを除去すれば、比表面積が低減するおそれがなくなる。これが本発明の基本的な考え方である。   Here, as shown in FIG. 5, the milled catalyst material particles are composed of a fine particle portion PF having a particle size smaller than the boundary value dB and a coarse particle portion PC having a particle size larger than the boundary value dB. Can be considered. Then, if this fine particle portion PF is removed, there is no possibility that the specific surface area is reduced. This is the basic idea of the present invention.

そこで、本発明による実施例では図３に示されるように微粒部保持層２を形成し、この微粒部保持層２内に微粒部ＰＦを粗粒部ＰＣから分離保持するようにしている。即ち、微粒部保持層２が形成されたパティキュレートフィルター１にスラリーが適用されると、このスラリーに含まれる微粒部ＰＦが微粒部保持層２内に選択的に保持され、粗粒部３が微粒部保持層２上に担持されて触媒材料層３が形成される。この場合、微粒部ＰＦが触媒材料層３を形成するのに寄与しないという見方もできる。   Therefore, in the embodiment according to the present invention, the fine particle holding layer 2 is formed as shown in FIG. 3, and the fine particle portion PF is separated and held in the fine particle holding layer 2 from the coarse particle portion PC. That is, when the slurry is applied to the particulate filter 1 on which the fine particle holding layer 2 is formed, the fine particle portion PF contained in the slurry is selectively held in the fine particle holding layer 2 and the coarse particle portion 3 is formed. The catalyst material layer 3 is formed by being supported on the fine particle holding layer 2. In this case, the view that the fine particle part PF does not contribute to the formation of the catalyst material layer 3 can be considered.

このようにすると、微粒部ＰＦが粗粒部ＰＣ内の間隙（図８参照）内に入り込むのを抑制することができ、粗粒部ＰＣのシンタリングを抑制することもできる。従って、比表面積の減少を抑制することができる。   If it does in this way, it can control that fine particle part PF enters in the crevice (refer to Drawing 8) in coarse particle part PC, and can also suppress sintering of coarse particle part PC. Therefore, a decrease in specific surface area can be suppressed.

特に、パティキュレートフィルターは排気ガス中の微粒子を捕集するという目的から通常のモノリス基材に比べて細孔径が小さく、従って細孔内壁面に触媒材料層を薄く一様に形成するのが比較的困難である。しかしながら、本発明による実施例では、平均粒径の小さい触媒材料粒子を用いることができるので、パティキュレートフィルターの細孔内壁面にも触媒材料層を薄く一様に形成することが可能となる。   In particular, the particulate filter has a smaller pore size than ordinary monolithic substrates for the purpose of collecting particulates in the exhaust gas, and therefore the catalyst material layer is formed thinly and uniformly on the inner wall surface of the pore. Difficult. However, in the embodiment according to the present invention, since the catalyst material particles having a small average particle diameter can be used, the catalyst material layer can be formed thinly and uniformly on the inner wall surface of the pore of the particulate filter.

微粒部ＰＦが微粒部保持層２内に確実に保持されるようにするために、スラリーが水溶媒から作成される場合には微粒部保持層２を吸水性又は親水性の高い材料から構成するのが好ましい。また、排気ガスの浄化のために、微粒部保持層２は耐熱性を備えていることが好ましい。   In order to ensure that the fine particle part PF is held in the fine particle part holding layer 2, when the slurry is made from an aqueous solvent, the fine particle part holding layer 2 is made of a material having high water absorption or hydrophilicity. Is preferred. In order to purify the exhaust gas, the fine particle holding layer 2 preferably has heat resistance.

ここで、微粒部ＰＦと粗粒部ＰＣとの境界値ｄＢ（図５参照）は好ましくは、ミリング後の触媒材料粒子の平均粒径ｄｍから標準偏差σの３倍を差し引いて得られる値（ｄｍ−３σ）から、触媒材料粒子の平均粒径ｄｍまでの間にある。境界値ｄＢが（ｄｍ−３σ）よりも小さいと微小径粒子の影響を十分に排除することができず、平均粒径ｄｍよりも大きいと微粒部保持層２の保持容量を大きくしなければならないからである。   Here, the boundary value dB (see FIG. 5) between the fine particle part PF and the coarse particle part PC is preferably a value obtained by subtracting three times the standard deviation σ from the average particle diameter dm of the milled catalyst material particles ( dm−3σ) to the average particle diameter dm of the catalyst material particles. If the boundary value dB is smaller than (dm−3σ), the influence of the fine particles cannot be sufficiently eliminated, and if the boundary value dB is larger than the average particle size dm, the retention capacity of the fine particle retaining layer 2 must be increased. Because.

次に、本発明による別の実施例を説明する。   Next, another embodiment according to the present invention will be described.

図６は本発明による別の実施例の触媒担持方法を示している。図６を参照すると、まず、図４に示される実施例と同様に、パティキュレートフィルターが用意される。   FIG. 6 shows another embodiment of the catalyst loading method according to the present invention. Referring to FIG. 6, first, a particulate filter is prepared similarly to the embodiment shown in FIG.

次いで、触媒材料原料がミリングされ、その後、上述した微粒部ＰＦ（図５参照）が除去されるようにミリング後の触媒材料粒子が分級される。この場合の分級方法には、遠心分離、カットオフ、超音波、脈動、電磁振動等を用いて行うことができる。   Next, the catalyst material raw material is milled, and then the milled catalyst material particles are classified so that the above-described fine particle portion PF (see FIG. 5) is removed. As a classification method in this case, centrifugation, cutoff, ultrasonic waves, pulsation, electromagnetic vibration, and the like can be used.

次いで、分級された触媒材料粒子、即ち粗粒部ＰＣからなる触媒材料粒子が水溶媒及びバインダーと共に混合され、かくしてスラリーが作成される。次いで、パティキュレートフィルターがこのスラリーに浸漬され、次いで例えばパティキュレートフィルターにエアーを吹き付けることにより、余分なスラリーが除去される。次いで、パティキュレートフィルターが乾燥され、焼成され、かくしてパティキュレートフィルター１上に触媒材料層３が形成される。   Next, the classified catalyst material particles, that is, the catalyst material particles composed of the coarse portion PC are mixed together with the water solvent and the binder, and thus a slurry is formed. The particulate filter is then immersed in this slurry and then excess slurry is removed, for example by blowing air to the particulate filter. Next, the particulate filter is dried and fired, and thus the catalyst material layer 3 is formed on the particulate filter 1.

このようにすると、パティキュレートフィルター１に適用されるスラリー中には微粒部ＰＦが実質的に含まれていない。その結果、図７に示されるようにパティキュレートフィルター１の表面及び細孔内壁面上には、粗粒部ＰＣからなる触媒材料層３が直接的に形成されることになる。従って、この例でも、微粒部ＰＦが粗粒部ＰＣ内の間隙（図８参照）内に入り込むのを抑制することができ、粗粒部ＰＣのシンタリングを抑制することもできる。   If it does in this way, the fine particle part PF is not contained substantially in the slurry applied to the particulate filter 1. As a result, as shown in FIG. 7, on the surface of the particulate filter 1 and the inner wall surfaces of the pores, the catalyst material layer 3 composed of the coarse particle portion PC is directly formed. Accordingly, also in this example, the fine particle portion PF can be prevented from entering the gap (see FIG. 8) in the coarse particle portion PC, and sintering of the coarse particle portion PC can also be suppressed.

パティキュレートフィルターの断面図である。It is sectional drawing of a particulate filter. パティキュレートフィルターの部分拡大断面図である。It is a partial expanded sectional view of a particulate filter. 図２のＡ部の拡大図である。It is an enlarged view of the A section of FIG. 本発明による実施例の触媒担持方法を説明するための図である。It is a figure for demonstrating the catalyst supporting method of the Example by this invention. 微粒部及び粗粒部を説明するための図である。It is a figure for demonstrating a fine grain part and a coarse grain part. 本発明による別の実施例の触媒担持方法を説明するための図である。It is a figure for demonstrating the catalyst carrying | support method of another Example by this invention. 本発明による別の実施例のパティキュレートフィルターの部分拡大断面図である。It is a partial expanded sectional view of the particulate filter of another example by the present invention. 触媒材料粒子の拡大図である。It is an enlarged view of catalyst material particles. 従来技術を説明するための図である。It is a figure for demonstrating a prior art.

符号の説明Explanation of symbols

１ パティキュレートフィルター
２ 微粒子保持層
３ 触媒材料層
ＰＦ 微粒部
ＰＣ 粗粒部 1 Particulate Filter 2 Fine Particle Retaining Layer 3 Catalyst Material Layer PF Fine Particle Part PC Coarse Grain Part

Claims (4)

多孔質基材の表面又は細孔内壁面上に触媒材料粒子が担持されることにより構成される排気浄化装置において、触媒材料粒子が、粒径が境界値よりも小さい微粒部と、粒径が該境界値よりも大きい粗粒部とから構成されており、多孔質基材の表面又は細孔内壁面上に、触媒材料粒子の微粒部を選択的に保持するための微粒部保持層を形成し、製造時に触媒材料粒子がスラリーの形で多孔質基材に適用されると、触媒材料粒子の微粒部が該微粒部保持層内に保持され、触媒材料粒子の粗粒部が該微粒部保持層上に担持されるようにした排気浄化装置。   In an exhaust emission control device configured by supporting catalyst material particles on the surface of the porous substrate or on the inner wall surface of the pores, the catalyst material particles include a fine particle portion having a particle size smaller than the boundary value, and a particle size of It is composed of a coarse part larger than the boundary value, and a fine part holding layer for selectively holding the fine part of the catalyst material particles is formed on the surface of the porous substrate or the inner wall surface of the pore. When the catalyst material particles are applied to the porous substrate in the form of a slurry at the time of production, the fine particle portions of the catalyst material particles are held in the fine particle portion holding layer, and the coarse particle portions of the catalyst material particles are the fine particle portions. An exhaust emission control device supported on a holding layer. 多孔質基材の表面又は細孔内壁面上に触媒材料粒子が担持されることにより構成される排気浄化装置において、触媒材料粒子が、粒径が境界値よりも小さい微粒部と、粒径が該境界値よりも大きい粗粒部とから構成されており、該微粒部が除去されるように触媒材料粒子を分級し、該分級された触媒材料粒子をスラリーの形で多孔質基材に適用することにより、該触媒材料粒子が多孔質基材上に担持されるようにした排気浄化装置。   In an exhaust emission control device configured by supporting catalyst material particles on the surface of the porous substrate or on the inner wall surface of the pores, the catalyst material particles include a fine particle portion having a particle size smaller than the boundary value, and a particle size of The catalyst material particles are classified so that the fine particle portions are removed, and the classified catalyst material particles are applied to the porous substrate in the form of a slurry. By doing so, the exhaust gas purifying device in which the catalyst material particles are supported on the porous substrate. 前記境界値が、触媒材料粒子の平均粒径から標準偏差の３倍を差し引いて得られる値から、触媒材料粒子の平均粒径までの間にある請求項１又は２に記載の排気浄化装置。   The exhaust emission control device according to claim 1 or 2, wherein the boundary value is between a value obtained by subtracting three times the standard deviation from an average particle diameter of the catalyst material particles and an average particle diameter of the catalyst material particles. 触媒材料原料をミリングすることにより前記触媒材料粒子が形成されている請求項１又は２に記載の排気浄化装置。   The exhaust emission control device according to claim 1 or 2, wherein the catalyst material particles are formed by milling a catalyst material raw material.
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