JP2009262102A - Oxidation catalyst device for purification of exhaust gas - Google Patents
Oxidation catalyst device for purification of exhaust gas Download PDFInfo
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- Processes For Solid Components From Exhaust (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
- Exhaust Gas After Treatment (AREA)
Abstract
Description
本発明は、内燃機関の排ガスに含まれるパティキュレートを、複合金属酸化物からなる触媒を用いて酸化して浄化する排ガス浄化用酸化触媒装置に関するものである。 The present invention relates to an oxidation catalyst device for purifying exhaust gas that oxidizes and purifies particulates contained in exhaust gas of an internal combustion engine by using a catalyst made of a composite metal oxide.
従来、内燃機関の排ガスに含まれるパティキュレートや炭化水素を酸化して浄化するために、ペロブスカイト型複合金属酸化物からなる触媒を用いた排ガス浄化用酸化触媒装置が知られている。 Conventionally, an oxidation catalyst device for exhaust gas purification using a catalyst made of a perovskite-type composite metal oxide for oxidizing and purifying particulates and hydrocarbons contained in exhaust gas of an internal combustion engine is known.
前記排ガス浄化用酸化触媒装置としては、多孔質フィルタ基材の表面に第１の触媒層を備えるとともに、該多孔質フィルタ基材の気孔を形成する壁面表面に第２の触媒層を備えものが提案されている（例えば特許文献１参照）。前記第１の触媒層及び前記第２の触媒層としては、一般式ＡＢＭＯ３で表されるペロブスカイト型複合金属酸化物からなり、ＡはＬａ，Ｙ，Ｄｙ，Ｎｄのうち１種以上であり、ＢはＳｒ，Ｂａ，Ｍｇのうち１種以上であり、ＭはＭｎ，Ｆｅ，Ｃｏのうち１種以上のものが挙げられる。前記第１の触媒層及び前記第２の触媒層を備える前記排ガス浄化用酸化触媒装置によれば、前記パティキュレートの燃焼温度を低下させることができるとされている。 The exhaust gas purification oxidation catalyst device includes a first catalyst layer on the surface of a porous filter base material and a second catalyst layer on a wall surface forming pores of the porous filter base material. It has been proposed (see, for example, Patent Document 1). The first catalyst layer and the second catalyst layer are made of a perovskite-type composite metal oxide represented by the general formula ABMO 3 and A is one or more of La, Y, Dy, and Nd, B is at least one of Sr, Ba, and Mg, and M is at least one of Mn, Fe, and Co. According to the exhaust gas purifying oxidation catalyst device including the first catalyst layer and the second catalyst layer, the combustion temperature of the particulates can be lowered.
しかしながら、排ガス浄化用酸化触媒装置においては、前記パティキュレートの燃焼温度をさらに低下させることが望まれる。
本発明は、かかる不都合を解消して、内燃機関の排ガス中のパティキュレートをより低温で酸化し浄化することができる排ガス浄化用酸化触媒装置を提供することを目的とする。 An object of the present invention is to provide an oxidation catalyst device for exhaust gas purification that can eliminate such inconvenience and oxidize and purify particulates in exhaust gas of an internal combustion engine at a lower temperature.
かかる目的を達成するために、本発明は、内燃機関の排ガス中のパティキュレートを、複合金属酸化物からなる触媒を用いて酸化して浄化する排ガス浄化用酸化触媒装置であって、軸方向に貫通して形成された複数の貫通孔のうち、排ガス流入部が開放されるとともに排ガス流出部が閉塞された複数の流入セルと、該複数の貫通孔の排ガス流入部が閉塞されるとともに排ガス流出部が開放された複数の流出セルとを備え、該流入セル及び該流出セルを交互に配設して各セルの境界部をセル隔壁とするウォールフロー構造を有する多孔質フィルタ基材と、該セル隔壁の少なくとも該流入セル側の表面に担持された該複合金属酸化物からなる第１の触媒層と、該多孔質フィルタ基材の気孔を形成する壁面表面に担持された該複合金属酸化物からなる第２の触媒層とを備え、各触媒層が多孔質体からなることを特徴とする。 In order to achieve such an object, the present invention provides an oxidation catalyst device for purifying exhaust gas that oxidizes and purifies particulates in exhaust gas of an internal combustion engine using a catalyst made of a composite metal oxide, in an axial direction. Among a plurality of through holes formed through, a plurality of inflow cells in which an exhaust gas inflow portion is opened and an exhaust gas outflow portion is blocked, and an exhaust gas inflow portion of the plurality of through holes is closed and an exhaust gas outflow A porous filter base material having a wall flow structure including a plurality of outflow cells opened at a portion, alternately arranging the inflow cells and the outflow cells, and using cell boundaries as cell partition walls, A first catalyst layer comprising the composite metal oxide supported on at least a surface of the cell partition wall on the inflow cell side; and the composite metal oxide supported on a wall surface forming pores of the porous filter substrate. Kara And a second catalyst layer, the catalyst layer is characterized by comprising a porous body.
本発明によれば、前記内燃機関の排ガスは、前記流入セルの前記排ガス流入部から該流入セル内へ導入される。前記流入セルは前記排ガス流出部が閉塞されているので、該流入セル内へ導入された前記排ガスは、前記セル隔壁を構成する前記多孔質フィルタ基材の気孔を通過して前記流出セル内へ移動する。このとき、前記排ガスは、前記セル隔壁の表面に担持された前記第１の触媒層と、前記気孔を形成する壁面表面に担持された第２の触媒層とに接触し、各触媒層の触媒の作用により燃焼除去される。 According to the present invention, the exhaust gas of the internal combustion engine is introduced into the inflow cell from the exhaust gas inflow portion of the inflow cell. Since the exhaust gas outflow portion of the inflow cell is blocked, the exhaust gas introduced into the inflow cell passes through the pores of the porous filter base material constituting the cell partition wall and enters the outflow cell. Moving. At this time, the exhaust gas comes into contact with the first catalyst layer supported on the surface of the cell partition wall and the second catalyst layer supported on the wall surface forming the pores, and the catalyst of each catalyst layer It is burned out by the action of.
本発明によれば、前記第１の触媒層及び前記第２の触媒層が多孔質体からなるので、前記排ガスが、該多孔質体の細孔を形成する壁面の表面を介して該触媒層に接触することにより、該排ガスと該触媒層との接触確率が高まることとなる。したがって、本発明によれば、従来技術の排ガス浄化用酸化触媒装置と比較して、内燃機関の排ガス中のパティキュレートをより低温で酸化し浄化することができる。 According to the present invention, since the first catalyst layer and the second catalyst layer are made of a porous body, the exhaust gas passes through the surface of the wall surface forming the pores of the porous body. Contact probability increases the contact probability between the exhaust gas and the catalyst layer. Therefore, according to the present invention, it is possible to oxidize and purify particulates in the exhaust gas of the internal combustion engine at a lower temperature as compared with the oxidation catalyst device for exhaust gas purification of the prior art.
また、本発明においては、前記各触媒層は、直径が０．０１〜３．５μｍの範囲である細孔を備える多孔質体からなり、前記多孔質フィルタ基材及び該各触媒層全体の気孔率が、４５〜５０体積％の範囲であることが好ましい。前記多孔質フィルタ基材の気孔の内部に前記第２の触媒層が担持されていることにより、該多孔質フィルタ基材及び該各触媒層全体の気孔率が前記範囲に構成されている。本発明によれば、前記構成により、前記パティキュレートを前記各触媒層に十分に接触させることができ、この結果、パティキュレートの燃焼温度を確実に低くすることができる。 Further, in the present invention, each catalyst layer is composed of a porous body having pores having a diameter in the range of 0.01 to 3.5 μm, and the pores of the porous filter substrate and the entire catalyst layers The rate is preferably in the range of 45-50% by volume. By supporting the second catalyst layer inside the pores of the porous filter base material, the porosity of the porous filter base material and each of the catalyst layers as a whole is configured in the above range. According to the present invention, according to the configuration, the particulates can be sufficiently brought into contact with the catalyst layers, and as a result, the combustion temperature of the particulates can be reliably lowered.
このとき、前記各触媒層の前記細孔の直径が０．０１μｍ未満である場合には、圧力損失が増大することがある。一方、前記各触媒層の前記細孔の直径が３．５μｍを超える場合には、前記排ガス中の前記パティキュレートが該細孔の表面に十分に接触することができなくなり、該パティキュレートの燃焼温度を低下させる効果が得られないことがある。 At this time, when the diameter of the pores of each catalyst layer is less than 0.01 μm, the pressure loss may increase. On the other hand, when the diameter of the pores of each catalyst layer exceeds 3.5 μm, the particulates in the exhaust gas cannot sufficiently contact the surface of the pores, and the particulates burn. The effect of lowering the temperature may not be obtained.
また、前記多孔質フィルタ基材及び前記各触媒層全体の気孔率が４５％未満である場合には、前記排ガスが前記気孔を通過する際に圧力損失が増大することがある。一方、前記多孔質フィルタ基材及び前記各触媒層全体の気孔率が５０％を超える場合には、前記排ガスと該触媒層との接触確率が低下し、該パティキュレートの燃焼温度を低下させる十分な効果が得られないことがある。 Further, when the porosity of the porous filter base material and each of the catalyst layers is less than 45%, pressure loss may increase when the exhaust gas passes through the pores. On the other hand, when the porosity of the porous filter base material and each of the catalyst layers exceeds 50%, the contact probability between the exhaust gas and the catalyst layer is lowered, and the combustion temperature of the particulates is sufficiently reduced. Effects may not be obtained.
本発明において、前記各触媒層は、例えば、一般式Ｙ１−ｘＡｇｘＭｎ１−ｙＲｕｙＯ３で表され、０．０１≦ｘ≦０．１５かつ０．００５≦ｙ≦０．２である複合金属酸化物からなるものとすることができる。 In the present invention, each of the catalyst layer, for example, is represented by the general formula Y 1-x Ag x Mn 1 -y Ru y O 3, 0.01 ≦ x ≦ 0.15 and 0.005 ≦ y ≦ 0. 2 or a composite metal oxide.
次に、添付の図面を参照しながら本発明の実施の形態についてさらに詳しく説明する。図１は本実施形態の排ガス浄化用酸化触媒装置の説明図であり、図１（ａ）は説明的断面図であり、図１（ｂ）は図１（ａ）のＡ部の模式的拡大図である。図２，７，１０，１３，１６，１９，２２は、実施例１〜７及び比較例の排ガス浄化用酸化触媒装置による排出ガスのＣＯ２濃度を示すグラフである。図３は、実施例１〜７及び比較例の排ガス浄化用酸化触媒装置によるパティキュレート燃焼量を示すグラフである。図４，８，１１，１４，１７，２０，２３，２５は、実施例１〜７及び比較例の排ガス浄化用酸化触媒装置の断面画像である。図４，８，１１，１４，１７，２０，２３，２５の各図において、（ａ）は倍率１００倍の断面画像であり、（ｂ）は倍率１００００倍の断面画像であって（ａ）のＡ部の拡大図である。図５，９，１２，１５，１８，２１，２４は、実施例１〜７及び比較例の排ガス浄化用酸化触媒装置に係る多孔質フィルタ基材の気孔の直径及び各触媒層の細孔の直径を示すグラフである。図６は、実施例１〜７及び比較例の排ガス浄化用酸化触媒装置に係る多孔質フィルタ基材及び各触媒層全体の気孔率を示すグラフである。 Next, embodiments of the present invention will be described in more detail with reference to the accompanying drawings. FIG. 1 is an explanatory view of an oxidation catalyst device for exhaust gas purification according to the present embodiment, FIG. 1 (a) is an explanatory sectional view, and FIG. 1 (b) is a schematic enlargement of a portion A in FIG. 1 (a). FIG. 2, 7, 10, 13, 16, 19, and 22 are graphs showing the CO 2 concentration of exhaust gas by the oxidation catalyst devices for exhaust gas purification of Examples 1 to 7 and Comparative Example. FIG. 3 is a graph showing particulate combustion amounts by the exhaust gas purifying oxidation catalyst devices of Examples 1 to 7 and Comparative Example. 4, 8, 11, 14, 17, 20, 23, and 25 are cross-sectional images of the oxidation catalyst devices for exhaust gas purification of Examples 1 to 7 and Comparative Example. 4, 8, 11, 14, 17, 20, 23, and 25, (a) is a cross-sectional image at a magnification of 100 times, and (b) is a cross-sectional image at a magnification of 10000 times (a). It is an enlarged view of the A section. 5, 9, 12, 15, 18, 21, and 24 are the diameters of the pores of the porous filter substrate and the pores of each catalyst layer according to the oxidation catalyst devices for exhaust gas purification of Examples 1 to 7 and Comparative Example. It is a graph which shows a diameter. FIG. 6 is a graph showing the porosity of the porous filter substrate and the entire catalyst layers according to the exhaust gas purification oxidation catalyst devices of Examples 1 to 7 and the comparative example.
本実施形態の排ガス浄化用酸化触媒装置１について説明する。図１（ａ）に示す排ガス浄化用酸化触媒装置１は、ウォールフロー構造を有する多孔質フィルタ基材２と、多孔質フィルタ基材２に担持された触媒層３とを備え、内燃機関の排ガスを流通させることにより、該排ガスに含まれるパティキュレートを酸化して浄化するものである。 The exhaust gas purifying oxidation catalyst device 1 of the present embodiment will be described. An exhaust gas purification oxidation catalyst device 1 shown in FIG. 1 (a) includes a porous filter base material 2 having a wall flow structure and a catalyst layer 3 supported on the porous filter base material 2, and is an exhaust gas of an internal combustion engine. By circulating the gas, the particulates contained in the exhaust gas are oxidized and purified.
多孔質フィルタ基材２は、軸方向に貫通する複数の貫通孔が断面格子状に配設された略直方体のＳｉＣ多孔質体からなり、該貫通孔からなる複数の流入セル４と複数の流出セル５とを備えている。多孔質フィルタ基材２は、直径が１〜１００μｍの範囲である複数の気孔７を備えていて、それ自体の気孔率が５０〜６０体積％の範囲となっている。流入セル４は、排ガス流入部４ａが開放されるとともに排ガス流出部４ｂが閉塞されている。一方、流出セル５は、排ガス流入部５ａが閉塞されるとともに排ガス流出部５ｂが開放されている。流入セル４及び流出セル５は、断面市松格子状となるように交互に配設されていて、各セル４，５の境界部をセル隔壁６とするウォールフロー構造を構成している。 The porous filter substrate 2 is composed of a substantially rectangular parallelepiped SiC porous body in which a plurality of through-holes penetrating in the axial direction are arranged in a cross-sectional lattice shape, and a plurality of inflow cells 4 and a plurality of outflows comprising the through-holes Cell 5. The porous filter substrate 2 includes a plurality of pores 7 having a diameter in the range of 1 to 100 μm, and its own porosity is in the range of 50 to 60% by volume. In the inflow cell 4, the exhaust gas inflow portion 4a is opened and the exhaust gas outflow portion 4b is closed. On the other hand, in the outflow cell 5, the exhaust gas inflow portion 5a is closed and the exhaust gas outflow portion 5b is opened. The inflow cells 4 and the outflow cells 5 are alternately arranged so as to have a checkered cross section, and constitute a wall flow structure in which the boundary portions of the cells 4 and 5 are the cell partition walls 6.
図１（ａ）に示すように、セル隔壁６の流入セル４側の表面には、触媒層３としての第１の触媒層３ａが担持されている。また、図１（ｂ）に示すように、セル隔壁６の気孔７すなわち多孔質フィルタ基材２の気孔７を形成する壁面の表面には、触媒層３としての第２の触媒層３ｂが担持されている。各触媒層３ａ，３ｂは、直径が０．０１〜３．５μｍの範囲である細孔（図示せず）を備える多孔質体であって、複合金属酸化物Ｙ１−ｘＡｇｘＭｎ１−ｙＲｕｙＯ３（ただし、０．０１≦ｘ≦０．１５かつ０．００５≦ｙ≦０．２）からなる。また、多孔質フィルタ基材２及び各触媒層３ａ，３ｂは、両者を合わせた全体の気孔率が４５〜５０体積％の範囲となっている。また、図示しないが、最外層のセル隔壁６の外周部には、排ガスの流出を規制する金属からなる規制部材が設けられている。 As shown in FIG. 1A, the first catalyst layer 3 a as the catalyst layer 3 is supported on the surface of the cell partition wall 6 on the inflow cell 4 side. Further, as shown in FIG. 1B, the second catalyst layer 3b as the catalyst layer 3 is supported on the surface of the wall surface forming the pores 7 of the cell partition walls 6, that is, the pores 7 of the porous filter substrate 2. Has been. Each catalyst layer 3a, 3b is a porous body having pores (not shown) having a diameter in the range of 0.01 to 3.5 μm, and is a composite metal oxide Y 1-x Ag x Mn 1− y Ru y O 3 (where 0.01 ≦ x ≦ 0.15 and 0.005 ≦ y ≦ 0.2). The porous filter base material 2 and each of the catalyst layers 3a and 3b have a total porosity in the range of 45 to 50% by volume. Although not shown, a regulating member made of a metal that regulates the outflow of exhaust gas is provided on the outer peripheral portion of the outermost cell partition wall 6.
排ガス浄化用酸化触媒装置１においては、第１の触媒層３ａは、セル隔壁６の流入セル４側の表面のみに担持されているが、流入セル４側の表面と流出セル５側の表面との両方に担持されていてもよい。また、多孔質フィルタ基材２として、ＳｉＣ多孔質体からなるものを用いているが、Ｓｉ−ＳｉＣ多孔質体からなるものを用いてもよい。 In the oxidation catalyst device 1 for exhaust gas purification, the first catalyst layer 3a is supported only on the surface on the inflow cell 4 side of the cell partition wall 6, but the surface on the inflow cell 4 side and the surface on the outflow cell 5 side It may be carried on both. Moreover, although what consists of a SiC porous body is used as the porous filter base material 2, you may use what consists of a Si-SiC porous body.
以上の構成を備えた排ガス浄化用酸化触媒装置１は、次のようにして製造することができる。まず、硝酸イットリウムと、硝酸銀と、硝酸マンガンと、硝酸ルテニウムと、クエン酸と、水とからなる混合物を、２００〜４００℃の範囲の温度で１〜１０時間の範囲で一次焼成し、触媒前駆体を形成する。次に、得られた触媒前駆体と、水と、バインダーとを混合し粉砕して、スラリーを調製する。前記スラリーは、例えば、０．５〜１０μｍの範囲の粒子径分布を有する触媒前駆体を含有するとともに、２．０ｍＰａ・ｓ以下、好ましくは１．３〜２．０ｍＰａ・ｓの範囲の粘度を有するように調製される。 The exhaust gas purifying oxidation catalyst device 1 having the above-described configuration can be manufactured as follows. First, a catalyst precursor is obtained by first firing a mixture of yttrium nitrate, silver nitrate, manganese nitrate, ruthenium nitrate, citric acid, and water at a temperature in the range of 200 to 400 ° C. for 1 to 10 hours. Form the body. Next, the obtained catalyst precursor, water, and a binder are mixed and pulverized to prepare a slurry. The slurry contains, for example, a catalyst precursor having a particle size distribution in the range of 0.5 to 10 μm and a viscosity of 2.0 mPa · s or less, preferably 1.3 to 2.0 mPa · s. It is prepared to have.
次に、軸方向に貫通する複数の貫通孔が断面格子状に配設された多孔質フィルタ基材２（日本碍子株式会社製ＳｉＣ多孔質体、商品名ＭＳＣ１４、仕様を表１に示す）を用意する。 Next, a porous filter substrate 2 (SiC porous body manufactured by Nippon Choshi Co., Ltd., trade name MSC14, specifications are shown in Table 1) in which a plurality of through-holes penetrating in the axial direction are arranged in a cross-sectional lattice shape. prepare.
次に、多孔質フィルタ基材２の前記貫通孔の一端部を一つ置きに（すなわち、断面市松格子状となるように）、シリカを主成分とするセラミックス接着剤にて閉塞することにより、流出セル５を形成する。次に、多孔質フィルタ基材２に、前記端部が閉塞されている側から前記スラリーを流し込むことにより、端部が閉塞されていない前記複数の貫通孔（すなわち、流出セル５以外のセル）内に該スラリーを流通させる。このとき、スラリーが前記範囲の粘度を有するように調整されているので、該スラリーを吸引することなく、多孔質フィルタ基材２に流通させるだけで、該スラリーが多孔質フィルタ基材２の気孔の開口部を塞ぐことなく、該スラリーを気孔の内部に侵入させ付着させることができる。続いて、多孔質フィルタ基材２から過剰な前記スラリーを除去する。 Next, every other end of the through hole of the porous filter base material 2 (that is, so as to have a cross-sectional checkered cross section), and clogged with a ceramic adhesive mainly composed of silica, An outflow cell 5 is formed. Next, by pouring the slurry into the porous filter substrate 2 from the side where the end is closed, the plurality of through holes whose ends are not closed (that is, cells other than the outflow cell 5). The slurry is circulated inside. At this time, since the slurry is adjusted so as to have the viscosity in the above range, the slurry can be passed through the porous filter base material 2 without sucking the slurry, and the slurry can be pores of the porous filter base material 2. The slurry can enter and adhere to the inside of the pores without blocking the opening. Subsequently, the excess slurry is removed from the porous filter substrate 2.
次に、前記スラリーが付着された多孔質フィルタ基材２を、８００〜１０００℃の範囲の温度で１〜１０時間の範囲の時間で二次焼成する。これにより、流出セル５以外のセルのセル隔壁６の表面に、複合金属酸化物Ｙ１−ｘＡｇｘＭｎ１−ｙＲｕｙＯ３（ただし、０．０１≦ｘ≦０．１５かつ０．００５≦ｙ≦０．２）からなる第１の触媒層３ａが形成されるとともに、セル隔壁６の気孔７を形成する壁面の表面に、該複合酸化物からなる第２の触媒層３ｂが形成される。触媒層３ａ，３ｂは、前記範囲の温度及び時間で二次焼成された結果、直径が０．０１〜３．５μｍの範囲である細孔（図示せず）を備える多孔質体として形成される。次に、流出セル５以外のセルの前記端部が閉塞された側とは反対側の端部を、シリカを主成分とするセラミックス接着剤にて閉塞することにより、流入セル４を形成する。以上により製造される排ガス浄化用酸化触媒装置１は、多孔質フィルタ基材２及び触媒層３ａ，３ｂを合わせた全体の４５〜５０体積％の範囲の気孔率を備えている。 Next, the porous filter substrate 2 to which the slurry is attached is secondarily fired at a temperature in the range of 800 to 1000 ° C. for a time in the range of 1 to 10 hours. Thus, the composite metal oxide Y 1-x Ag x Mn 1-y Ru y O 3 (however, 0.01 ≦ x ≦ 0.15 and 0.001) is formed on the surface of the cell partition wall 6 of the cells other than the outflow cell 5. 005 ≦ y ≦ 0.2) is formed, and the second catalyst layer 3b made of the composite oxide is formed on the surface of the wall surface forming the pores 7 of the cell partition wall 6. Is done. The catalyst layers 3a and 3b are formed as a porous body having pores (not shown) having a diameter in the range of 0.01 to 3.5 μm as a result of secondary firing at the temperature and time in the above range. . Next, the inflow cell 4 is formed by closing the end of the cell other than the outflow cell 5 on the side opposite to the side where the end is closed with a ceramic adhesive mainly composed of silica. The exhaust gas purification oxidation catalyst device 1 manufactured as described above has a porosity in the range of 45 to 50% by volume of the total of the porous filter substrate 2 and the catalyst layers 3a and 3b.
次に、図１を参照して本実施形態の排ガス浄化用酸化触媒装置１の作動について説明する。まず、排ガス浄化用酸化触媒装置１を、流入セル４及び流出セル５の排ガス流入部４ａ，５ａが内燃機関の排ガスの流路に対して上流側となるように設置する。前記排ガスは、図１（ｂ）に矢示するように、流入セル４の排ガス流入部４ａから流入セル４内へ導入される。 Next, the operation of the exhaust gas purifying oxidation catalyst device 1 of the present embodiment will be described with reference to FIG. First, the exhaust gas purifying oxidation catalyst device 1 is installed such that the exhaust gas inflow portions 4a and 5a of the inflow cell 4 and the outflow cell 5 are upstream of the exhaust gas flow path of the internal combustion engine. The exhaust gas is introduced into the inflow cell 4 from the exhaust gas inflow portion 4a of the inflow cell 4 as shown by an arrow in FIG.
このとき、流出セル５は排ガス流入部５ａが閉塞されているので、流出セル５内へ前記排ガスが導入されることはない。また、流入セル４は排ガス流出部４ｂが閉塞されている。 At this time, since the exhaust gas inflow portion 5a of the outflow cell 5 is blocked, the exhaust gas is not introduced into the outflow cell 5. The inflow cell 4 is closed at the exhaust gas outflow portion 4b.
そこで、流入セル４内へ導入された前記排ガスは、セル隔壁６の気孔７を通過して流出セル５内へ移動する。このとき、前記排ガスは、セル隔壁６の表面に担持された第１の触媒層３ａと、気孔７を形成する壁面表面に担持された第２の触媒層３ｂとに接触し、各触媒層３ａ，３ｂの触媒の作用により燃焼除去される。 Therefore, the exhaust gas introduced into the inflow cell 4 passes through the pores 7 of the cell partition wall 6 and moves into the outflow cell 5. At this time, the exhaust gas comes into contact with the first catalyst layer 3a supported on the surface of the cell partition wall 6 and the second catalyst layer 3b supported on the wall surface forming the pores 7, and each catalyst layer 3a. , 3b is burned and removed by the action of the catalyst.
この結果、前記パティキュレートが燃焼除去された前記排ガスが、流出セル５内に移動し、排ガス流出部５ｂから排出される。以上により、排ガス浄化用酸化触媒装置１は、内燃機関の排ガス中のパティキュレートを酸化し浄化することができる。 As a result, the exhaust gas from which the particulates have been burned and removed moves into the outflow cell 5 and is discharged from the exhaust gas outflow portion 5b. As described above, the exhaust gas purification oxidation catalyst device 1 can oxidize and purify the particulates in the exhaust gas of the internal combustion engine.
本実施形態の排ガス浄化用酸化触媒装置１によれば、第１の触媒層３ａ及び第２の触媒層３ｂが多孔質体からなるので、前記排ガスが、該多孔質体の細孔を形成する壁面の表面を介して触媒層３ａ，３ｂに接触することにより、該排ガスと該触媒層３ａ，３ｂとの接触確率が高まることとなる。したがって、本発明によれば、従来技術の排ガス浄化用酸化触媒装置と比較して、内燃機関の排ガス中のパティキュレートをより低温で酸化し浄化することができる。 According to the exhaust gas purification oxidation catalyst device 1 of the present embodiment, since the first catalyst layer 3a and the second catalyst layer 3b are made of a porous body, the exhaust gas forms pores of the porous body. By contacting the catalyst layers 3a and 3b through the surface of the wall surface, the contact probability between the exhaust gas and the catalyst layers 3a and 3b is increased. Therefore, according to the present invention, it is possible to oxidize and purify particulates in the exhaust gas of the internal combustion engine at a lower temperature as compared with the oxidation catalyst device for exhaust gas purification of the prior art.
また、本実施形態の排ガス浄化用酸化触媒装置１は、各触媒層３ａ，３ｂが、直径が０．０１〜３．５μｍの範囲である前記細孔を備え、多孔質フィルタ基材２及び各触媒層３ａ，３ｂを合わせた全体が４５〜５０体積％の範囲の気孔率を備えている。多孔質フィルタ基材２の気孔７の内部に第２の触媒層３ｂが担持されていることにより、多孔質フィルタ基材２及び各触媒層３ａ，３ｂ全体の気孔率が前記範囲に構成されている。本実施形態の排ガス浄化用酸化触媒装置１によれば、前記構成により、前記パティキュレートを各触媒層３ａ，３ｂに十分に接触させることができ、この結果、パティキュレートの燃焼温度を確実に低くすることができる。 Further, in the oxidation catalyst device 1 for exhaust gas purification of the present embodiment, each of the catalyst layers 3a and 3b includes the pores having a diameter in the range of 0.01 to 3.5 μm, and the porous filter substrate 2 and each The total of the catalyst layers 3a and 3b has a porosity in the range of 45 to 50% by volume. Since the second catalyst layer 3b is supported inside the pores 7 of the porous filter base material 2, the porosity of the porous filter base material 2 and each of the catalyst layers 3a and 3b is configured in the above range. Yes. According to the exhaust gas purifying oxidation catalyst device 1 of the present embodiment, with the above-described configuration, the particulates can be sufficiently brought into contact with the catalyst layers 3a and 3b, and as a result, the combustion temperature of the particulates can be reliably lowered. can do.
また、本実施形態の排ガス浄化用酸化触媒装置１においては、各触媒層３ａ，３ｂは、一般式Ｙ１−ｘＡｇｘＭｎ１−ｙＲｕｙＯ３で表され、０．０１≦ｘ≦０．１５かつ０．００５≦ｙ≦０．２である複合金属酸化物からなる。前記複合金属酸化物は、一般式ＹＭｎＯ３で表される複合金属酸化物において、第１の金属であるＹの一部を第３の金属であるＡｇで置換するとともに、第２の金属であるＭｎの一部を第４の金属であるＲｕで置換したものである。したがって、排ガス浄化用酸化触媒装置１によれば、各触媒層３ａ，３ｂの触媒の作用により、前記排ガス中のパティキュレートを十分に燃焼除去することができる。 In the oxidation catalyst apparatus for purifying an exhaust gas 1 of the present embodiment, each catalyst layer 3a, 3b is represented by the general formula Y 1-x Ag x Mn 1 -y Ru y O 3, 0.01 ≦ x ≦ It consists of a composite metal oxide satisfying 0.15 and 0.005 ≦ y ≦ 0.2. In the composite metal oxide represented by the general formula YMnO 3 , the composite metal oxide is a second metal while substituting a part of Y as the first metal with Ag as the third metal. A part of Mn is substituted with Ru as the fourth metal. Therefore, according to the oxidation catalyst device 1 for exhaust gas purification, the particulates in the exhaust gas can be sufficiently burned and removed by the action of the catalysts of the catalyst layers 3a and 3b.
次に本発明の実施例と比較例とを示す。 Next, examples of the present invention and comparative examples will be shown.
本実施例では、まず、硝酸イットリウムと、硝酸銀と、硝酸マンガンと、硝酸ルテニウムと、クエン酸と、水とを、０．９５：０．０５：０．９５：０．０５：６：４０のモル比となるように混合した。前記混合は、乳鉢を用いて２５℃の温度で１５分間行った。得られた混合物を、４００℃の温度に１時間維持して一次焼成を行い、触媒前駆体を形成した。次に、得られた触媒前駆体と、水と、バインダーとしての市販の水分散ジルコニアゾルとを１０：１００：５の重量比となるように秤量し、回転式ボールミルにて１００回転／分で５時間混合して粉砕し、触媒前駆体スラリーを調製した。 In this example, first, yttrium nitrate, silver nitrate, manganese nitrate, ruthenium nitrate, citric acid, and water were mixed at 0.95: 0.05: 0.95: 0.05: 6: 40. It mixed so that it might become a molar ratio. The mixing was performed using a mortar at a temperature of 25 ° C. for 15 minutes. The obtained mixture was maintained at a temperature of 400 ° C. for 1 hour to perform primary firing to form a catalyst precursor. Next, the obtained catalyst precursor, water, and a commercially available water-dispersed zirconia sol as a binder are weighed so as to have a weight ratio of 10: 100: 5, and are rotated at 100 rpm with a rotary ball mill. The mixture was pulverized by mixing for 5 hours to prepare a catalyst precursor slurry.
次に、軸方向に貫通する複数の貫通孔が断面格子状に配設された、多孔質フィルタ基材２（日本碍子株式会社製ＳｉＣ多孔質体、商品名ＭＳＣ１４、寸法３６ｍｍ×３６ｍｍ×５０ｍｍ）を用意し、多孔質フィルタ基材２の該貫通孔の一端部を一つ置きに（すなわち、断面市松格子状となるように）、シリカを主成分とするセラミックス接着剤にて閉塞し、流出セル５を形成した。次に、多孔質フィルタ基材２に、前記端部が閉塞された側から前記触媒前駆体スラリーを流し込むことにより、端部が閉塞されていない前記複数の貫通孔（すなわち、流出セル５以外のセル）内に該スラリーを流通させた。続いて、多孔質フィルタ基材２から過剰な前記スラリーを除去した。 Next, a porous filter substrate 2 (SiC porous body manufactured by Nippon Choshi Co., Ltd., trade name MSC14, dimensions 36 mm × 36 mm × 50 mm) in which a plurality of through holes penetrating in the axial direction are arranged in a cross-sectional lattice shape The other end of the through-hole of the porous filter base material 2 is closed (that is, so as to have a checkered cross section), and is clogged with a ceramic adhesive mainly composed of silica. Cell 5 was formed. Next, by pouring the catalyst precursor slurry into the porous filter substrate 2 from the side where the end is closed, the plurality of through-holes whose ends are not closed (that is, other than the outflow cell 5) The slurry was circulated in the cell. Subsequently, the excess slurry was removed from the porous filter substrate 2.
次に、前記スラリーが付着された多孔質フィルタ基材２を８００℃の温度に１時間維持して二次焼成を行い、前記端部が閉塞されていない前記貫通孔の表面に、見かけ体積１Ｌ当たりの担持量が１００ｇとなるように、複合金属酸化物Ｙ０．９５Ａｇ０．０５Ｍｎ０．９５Ｒｕ０．０５Ｏ３からなる第１の触媒層３ａを形成するとともに、セル隔壁６の気孔７を形成する壁面の表面に、該複合金属酸化物からなる第２の触媒層３ｂを形成した。次に、流出セル５以外のセルの前記端部が閉塞された側とは反対側の端部を、シリカを主成分とするセラミックス接着剤にて閉塞することにより、流入セル４を形成し、排ガス浄化用酸化触媒装置１を完成させた。 Next, the porous filter base material 2 to which the slurry is adhered is maintained at a temperature of 800 ° C. for 1 hour to perform secondary firing, and an apparent volume of 1 L is formed on the surface of the through hole where the end is not blocked. The first catalyst layer 3a made of the composite metal oxide Y 0.95 Ag 0.05 Mn 0.95 Ru 0.05 O 3 is formed so that the amount of support per unit is 100 g. A second catalyst layer 3b made of the composite metal oxide was formed on the surface of the wall surface forming the pores 7. Next, the inflow cell 4 is formed by closing the end of the cell other than the outflow cell 5 opposite to the side where the end is closed with a ceramic adhesive mainly composed of silica, The oxidation catalyst device 1 for exhaust gas purification was completed.
次に、本実施例の排ガス浄化用酸化触媒装置１に対して、次のようにして触媒評価性能試験を行った。まず、排ガス浄化用酸化触媒装置１を、排気量が２．４Ｌであるディーゼルエンジンを搭載したエンジンベンチの排気系に搭載した。次に、パティキュレートを含む雰囲気ガス下において、該雰囲気ガスの排ガス浄化用酸化触媒装置１に対する流入温度１８０℃、エンジン回転数１５００回転／分、トルク７０Ｎ／ｍの条件で、前記ディーゼルエンジンを２０分間運転した。以上により、排ガス浄化用酸化触媒装置１に、その見かけ体積１Ｌあたりパティキュレートを３ｇ捕集させた。 Next, a catalyst evaluation performance test was performed on the oxidation catalyst device 1 for exhaust gas purification of this example as follows. First, the exhaust gas purification oxidation catalyst device 1 was mounted on an exhaust system of an engine bench equipped with a diesel engine having a displacement of 2.4 L. Next, in an atmosphere gas containing particulates, the diesel engine is operated under the conditions of an inflow temperature of the atmosphere gas to the exhaust gas purification oxidation catalyst device 1 of 180 ° C., an engine speed of 1500 rpm, and a torque of 70 N / m. Drove for a minute. As described above, 3 g of the particulate per 1 L of the apparent volume was collected by the oxidation catalyst device 1 for exhaust gas purification.
次に、パティキュレートが捕集された排ガス浄化用酸化触媒装置１を前記排気系から取り出し、流通型昇温度装置内の石英管内に固定した。次に、石英管の一端部（供給口）から、酸素と窒素との体積比が１０：９０である雰囲気ガスを空間速度２００００／時間で供給し、石英管の他端部（排出口）から排出させながら、排ガス浄化用酸化触媒装置１を室温から７００℃の温度まで３℃／分で加熱した。前記加熱には、流通型昇温度装置内の管状マッフル炉を用いた。このとき、石英管からの排出ガスのＣＯ２濃度を質量分析計を用いて測定した。結果を図２に示す。図２において、ＣＯ２濃度のピークがパティキュレートの燃焼温度に相当する。次に、図２から、３００℃以下の温度範囲において、排ガス浄化用酸化触媒装置１により燃焼されたパティキュレートの質量を算出した。結果を図３に示す。図３に示すように、排ガス浄化用酸化触媒装置１の見かけ体積１Ｌあたりに捕集されたパティキュレート３ｇのうち、燃焼された量は２．３ｇであった。 Next, the exhaust gas-purifying oxidation catalyst device 1 in which the particulates were collected was taken out from the exhaust system and fixed in a quartz tube in a flow-type temperature rising device. Next, an atmospheric gas having a volume ratio of oxygen to nitrogen of 10:90 is supplied from one end (supply port) of the quartz tube at a space velocity of 20000 / hour, and from the other end (discharge port) of the quartz tube. While discharging, the oxidation catalyst device 1 for exhaust gas purification was heated from room temperature to a temperature of 700 ° C. at 3 ° C./min. For the heating, a tubular muffle furnace in a flow type temperature rising device was used. At this time, the CO 2 concentration of the exhaust gas from the quartz tube was measured using a mass spectrometer. The results are shown in FIG. In FIG. 2, the peak of CO 2 concentration corresponds to the combustion temperature of the particulates. Next, from FIG. 2, the mass of the particulates burned by the exhaust gas purification oxidation catalyst device 1 in the temperature range of 300 ° C. or less was calculated. The results are shown in FIG. As shown in FIG. 3, the amount burned out of 3 g of particulates collected per 1 L of apparent volume of the oxidation catalyst device 1 for exhaust gas purification was 2.3 g.
次に、本実施例の排ガス浄化用酸化触媒装置１をダイヤモンドカッターにて切削することにより、５ｍｍ角の立方体を２個製作した。 Next, two 5 mm square cubes were manufactured by cutting the oxidation catalyst device 1 for exhaust gas purification of this example with a diamond cutter.
次に、１個目の立方体の排ガス浄化用酸化触媒装置１に対して、透過型電子顕微鏡を用いて断面画像を撮影した。図４（ａ），（ｂ）に排ガス浄化用酸化触媒装置１の断面画像を示す。図４（ｂ）に示すように、セル隔壁６の気孔７を形成する壁面の表面に第２の触媒層３ｂが形成されていることが明らかである。 Next, a cross-sectional image of the first cubic exhaust gas purification oxidation catalyst device 1 was taken using a transmission electron microscope. 4A and 4B show cross-sectional images of the oxidation catalyst device 1 for exhaust gas purification. As shown in FIG. 4B, it is clear that the second catalyst layer 3b is formed on the surface of the wall surface forming the pores 7 of the cell partition wall 6.
次に、２個目の立方体の排ガス浄化用酸化触媒装置１に対して、自動水銀ポロシメータを用いて、多孔質フィルタ基材２の気孔の直径及び触媒層３ａ，３ｂの細孔の直径と、多孔質フィルタ基材２及び触媒層３ａ，３ｂを合わせた全体の気孔率とを測定した。結果を図５及び図６に示す。図５に示すように、触媒層３ａ，３ｂの細孔の直径は０．０１〜２．０μｍの範囲であった。また、図６に示すように、多孔質フィルタ基材２及び触媒層３ａ，３ｂを合わせた全体の気孔率は４９．０体積％であった。 Next, for the second cubic oxidation catalyst device 1 for exhaust gas purification, using an automatic mercury porosimeter, the pore diameter of the porous filter substrate 2 and the pore diameters of the catalyst layers 3a, 3b, The total porosity of the porous filter substrate 2 and the catalyst layers 3a and 3b was measured. The results are shown in FIGS. As shown in FIG. 5, the diameters of the pores of the catalyst layers 3a and 3b were in the range of 0.01 to 2.0 μm. Further, as shown in FIG. 6, the total porosity of the porous filter substrate 2 and the catalyst layers 3a and 3b was 49.0% by volume.
本実施例では、見かけ体積１Ｌ当たりの担持量が３０ｇとなるように触媒層３ａ，３ｂを形成した点を除いて実施例１と全く同一にして、排ガス浄化用酸化触媒装置１を形成した。 In this example, the exhaust gas purification oxidation catalyst device 1 was formed in exactly the same way as in Example 1 except that the catalyst layers 3a and 3b were formed so that the loading amount per 1 L of apparent volume was 30 g.
次に、本実施例の排ガス浄化用酸化触媒装置１について、実施例１と全く同一にして、触媒評価性能試験を行い排出ガスのＣＯ２濃度を測定した。結果を図７に示す。次に、図７から、３００℃以下の温度範囲において、排ガス浄化用酸化触媒装置１により燃焼されたパティキュレートの質量を算出した。結果を図３に示す。図３に示すように、排ガス浄化用酸化触媒装置１の見かけ体積１Ｌあたりに捕集されたパティキュレート３ｇのうち、燃焼された量は１．２ｇであった。 Next, the exhaust gas purification oxidation catalyst device 1 of this example was subjected to a catalyst evaluation performance test in exactly the same manner as in Example 1 to measure the CO 2 concentration of the exhaust gas. The results are shown in FIG. Next, from FIG. 7, the mass of the particulates burned by the exhaust gas purification oxidation catalyst device 1 in the temperature range of 300 ° C. or less was calculated. The results are shown in FIG. As shown in FIG. 3, the amount burned out of 3 g of particulates collected per 1 L of apparent volume of the oxidation catalyst device 1 for exhaust gas purification was 1.2 g.
次に、本実施例の排ガス浄化用酸化触媒装置１について、実施例１と全く同一にして、断面画像を撮影した。図８（ａ），（ｂ）に排ガス浄化用酸化触媒装置１の断面画像を示す。図８（ｂ）に示すように、セル隔壁６の気孔７を形成する壁面の表面に第２の触媒層３ｂが形成されていることが明らかである。 Next, a cross-sectional image of the oxidation catalyst device 1 for exhaust gas purification of this example was taken in exactly the same way as in Example 1. 8A and 8B show cross-sectional images of the oxidation catalyst device 1 for exhaust gas purification. As shown in FIG. 8 (b), it is clear that the second catalyst layer 3 b is formed on the surface of the wall surface that forms the pores 7 of the cell partition wall 6.
次に、本実施例の排ガス浄化用酸化触媒装置１について、実施例１と全く同一にして、多孔質フィルタ基材２の気孔の直径及び触媒層３ａ，３ｂの細孔の直径と、多孔質フィルタ基材２及び触媒層３ａ，３ｂを合わせた全体の気孔率とを測定した。結果を図９及び図６に示す。図９に示すように、触媒層３ａ，３ｂの細孔の直径は０．０５〜０．２μｍの範囲であった。また、図６に示すように、多孔質フィルタ基材２及び触媒層３ａ，３ｂを合わせた全体の気孔率は４８．６体積％であった。 Next, regarding the oxidation catalyst device 1 for exhaust gas purification of this example, exactly the same as in Example 1, the pore diameter of the porous filter substrate 2, the pore diameters of the catalyst layers 3a and 3b, and the porous The total porosity of the filter substrate 2 and the catalyst layers 3a and 3b was measured. The results are shown in FIGS. As shown in FIG. 9, the pore diameters of the catalyst layers 3a and 3b were in the range of 0.05 to 0.2 μm. Further, as shown in FIG. 6, the total porosity of the porous filter substrate 2 and the catalyst layers 3a and 3b was 48.6% by volume.
本実施例では、見かけ体積１Ｌ当たりの担持量が５０ｇとなるように触媒層３ａ，３ｂを形成した点を除いて実施例１と全く同一にして、排ガス浄化用酸化触媒装置１を形成した。 In this example, the exhaust gas purification oxidation catalyst device 1 was formed in exactly the same way as in Example 1 except that the catalyst layers 3a and 3b were formed so that the loading amount per 1 L of apparent volume was 50 g.
次に、本実施例の排ガス浄化用酸化触媒装置１について、実施例１と全く同一にして、触媒評価性能試験を行い排出ガスのＣＯ２濃度を測定した。結果を図１０に示す。次に、図１０から、３００℃以下の温度範囲において、排ガス浄化用酸化触媒装置１により燃焼されたパティキュレートの質量を算出した。結果を図３に示す。図３に示すように、排ガス浄化用酸化触媒装置１の見かけ体積１Ｌあたりに捕集されたパティキュレート３ｇのうち、燃焼された量は２．１ｇであった。 Next, the exhaust gas purification oxidation catalyst device 1 of this example was subjected to a catalyst evaluation performance test in exactly the same manner as in Example 1 to measure the CO 2 concentration of the exhaust gas. The results are shown in FIG. Next, from FIG. 10, the mass of the particulates burned by the exhaust gas purification oxidation catalyst device 1 in the temperature range of 300 ° C. or less was calculated. The results are shown in FIG. As shown in FIG. 3, the amount burned out of 3 g of particulates collected per apparent volume of 1 L of the exhaust gas purifying oxidation catalyst device 1 was 2.1 g.
次に、本実施例の排ガス浄化用酸化触媒装置１について、実施例１と全く同一にして、断面画像を撮影した。図１１（ａ），（ｂ）に排ガス浄化用酸化触媒装置１の断面画像を示す。図１１（ｂ）に示すように、セル隔壁６の気孔７を形成する壁面の表面に第２の触媒層３ｂが形成されていることが明らかである。 Next, a cross-sectional image of the oxidation catalyst device 1 for exhaust gas purification of this example was taken in exactly the same way as in Example 1. 11A and 11B show cross-sectional images of the exhaust gas purification oxidation catalyst device 1. FIG. As shown in FIG. 11 (b), it is clear that the second catalyst layer 3 b is formed on the surface of the wall surface forming the pores 7 of the cell partition 6.
次に、本実施例の排ガス浄化用酸化触媒装置１について、実施例１と全く同一にして、多孔質フィルタ基材２の気孔の直径及び触媒層３ａ，３ｂの細孔の直径と、多孔質フィルタ基材２及び触媒層３ａ，３ｂを合わせた全体の気孔率とを測定した。結果を図１２及び図６に示す。図１２に示すように、触媒層３ａ，３ｂの細孔の直径は０．０１〜２．０μｍの範囲であった。また、図６に示すように多孔質フィルタ基材２及び触媒層３ａ，３ｂを合わせた全体の気孔率は４８．３体積％であった。 Next, regarding the oxidation catalyst device 1 for exhaust gas purification of this example, exactly the same as in Example 1, the pore diameter of the porous filter substrate 2, the pore diameters of the catalyst layers 3a and 3b, and the porous The total porosity of the filter substrate 2 and the catalyst layers 3a and 3b was measured. The results are shown in FIGS. As shown in FIG. 12, the diameters of the pores of the catalyst layers 3a and 3b were in the range of 0.01 to 2.0 μm. Further, as shown in FIG. 6, the total porosity of the porous filter substrate 2 and the catalyst layers 3a and 3b was 48.3% by volume.
本実施例では、見かけ体積１Ｌ当たりの担持量が８０ｇとなるように触媒層３ａ，３ｂを形成した点を除いて実施例１と全く同一にして、排ガス浄化用酸化触媒装置１を形成した。 In this example, the oxidation catalyst device 1 for exhaust gas purification was formed in exactly the same way as in Example 1 except that the catalyst layers 3a and 3b were formed so that the carrying amount per 1 L of apparent volume was 80 g.
次に、本実施例の排ガス浄化用酸化触媒装置１について、実施例１と全く同一にして、触媒評価性能試験を行い排出ガスのＣＯ２濃度を測定した。結果を図１３に示す。次に、図１３から、３００℃以下の温度範囲において、排ガス浄化用酸化触媒装置１により燃焼されたパティキュレートの質量を算出した。結果を図３に示す。図３により、排ガス浄化用酸化触媒装置１の見かけ体積１Ｌあたりに捕集されたパティキュレート３ｇのうち、燃焼された量は２．４ｇであった。 Next, the exhaust gas purification oxidation catalyst device 1 of this example was subjected to a catalyst evaluation performance test in exactly the same manner as in Example 1 to measure the CO 2 concentration of the exhaust gas. The results are shown in FIG. Next, from FIG. 13, the mass of the particulates burned by the exhaust gas purification oxidation catalyst device 1 in the temperature range of 300 ° C. or less was calculated. The results are shown in FIG. According to FIG. 3, the amount burned out of 3 g of particulates collected per 1 L of apparent volume of the oxidation catalyst device 1 for exhaust gas purification was 2.4 g.
次に、本実施例の排ガス浄化用酸化触媒装置１について、実施例１と全く同一にして、断面画像を撮影した。図１４（ａ），（ｂ）に排ガス浄化用酸化触媒装置１の断面画像を示す。図１４（ｂ）に示すように、セル隔壁６の気孔７を形成する壁面の表面に第２の触媒層３ｂが形成されていることが明らかである。 Next, a cross-sectional image of the oxidation catalyst device 1 for exhaust gas purification of this example was taken in exactly the same way as in Example 1. 14A and 14B show cross-sectional images of the exhaust gas purification oxidation catalyst device 1. FIG. As shown in FIG. 14 (b), it is clear that the second catalyst layer 3 b is formed on the surface of the wall surface forming the pores 7 of the cell partition 6.
次に、本実施例の排ガス浄化用酸化触媒装置１について、実施例１と全く同一にして、多孔質フィルタ基材２の気孔の直径及び触媒層３ａ，３ｂの細孔の直径と、多孔質フィルタ基材２及び触媒層３ａ，３ｂを合わせた全体の気孔率とを測定した。結果を図１５及び図６に示す。図１５に示すように、触媒層３ａ，３ｂの細孔の直径は０．０１〜２．０μｍの範囲であった。また、図６に示すように多孔質フィルタ基材２及び触媒層３ａ，３ｂを合わせた全体の気孔率は４８．６体積％であった。 Next, regarding the oxidation catalyst device 1 for exhaust gas purification of this example, exactly the same as in Example 1, the pore diameter of the porous filter substrate 2, the pore diameters of the catalyst layers 3a and 3b, and the porous The total porosity of the filter substrate 2 and the catalyst layers 3a and 3b was measured. The results are shown in FIG. 15 and FIG. As shown in FIG. 15, the diameters of the pores of the catalyst layers 3a and 3b were in the range of 0.01 to 2.0 μm. Further, as shown in FIG. 6, the total porosity of the porous filter substrate 2 and the catalyst layers 3a and 3b was 48.6% by volume.
本実施例では、まず、硝酸イットリウムと、硝酸銀と、硝酸マンガンと、硝酸ルテニウムを、０．９５：０．０５：０．９５：０．０５のモル比となるように混合した。前記混合は、乳鉢を用いて２５℃の温度で１５分間行った。得られた混合物を水に溶解させ、イットリウム濃度が０．１ｍｏｌ／Ｌである触媒原料溶液を調製した。 In this example, first, yttrium nitrate, silver nitrate, manganese nitrate, and ruthenium nitrate were mixed at a molar ratio of 0.95: 0.05: 0.95: 0.05. The mixing was performed using a mortar at a temperature of 25 ° C. for 15 minutes. The obtained mixture was dissolved in water to prepare a catalyst raw material solution having an yttrium concentration of 0.1 mol / L.
次に、前記触媒原料溶液を用いる点を除いて実施例１と全く同一にして、多孔質フィルタ基材２の端部が閉塞されていない前記複数の貫通孔内に該触媒原料溶液を流通させ、続いて、多孔質フィルタ基材２から過剰な該触媒原料溶液を除去した。 Next, except that the catalyst raw material solution is used, the catalyst raw material solution is circulated in the plurality of through holes in which the end portion of the porous filter base material 2 is not blocked, exactly the same as in Example 1. Subsequently, the excess catalyst raw material solution was removed from the porous filter substrate 2.
次に、多孔質フィルタ基材２を８００℃の温度に１時間維持して二次焼成を行い、前記端部が閉塞されていない前記貫通孔の表面に、見かけ体積１Ｌ当たりの担持量が１０ｇとなるように、セル隔壁６の流入セル４側の表面に、複合金属酸化物Ｙ０．９５Ａｇ０．０５Ｍｎ０．９５Ｒｕ０．０５Ｏ３からなる第１の触媒層３ａを形成するとともに、セル隔壁６の気孔７を形成する壁面の表面に、該複合金属酸化物からなる第２の触媒層３ｂを形成した。 Next, the porous filter base material 2 is maintained at a temperature of 800 ° C. for 1 hour to perform secondary firing, and the loading amount per 1 L of apparent volume is 10 g on the surface of the through hole where the end is not blocked. The first catalyst layer 3a made of the composite metal oxide Y 0.95 Ag 0.05 Mn 0.95 Ru 0.05 O 3 is formed on the surface of the cell partition wall 6 on the inflow cell 4 side. At the same time, the second catalyst layer 3b made of the composite metal oxide was formed on the surface of the wall surface forming the pores 7 of the cell partition wall 6.
次に、硝酸イットリウムと、硝酸銀と、硝酸マンガンと、硝酸ルテニウムと、クエン酸と、水とを、０．９５：０．０５：０．９５：０．０５：６：４０のモル比となるように混合した。前記混合は、乳鉢を用いて２５℃の温度で１５分間行った。得られた混合物を、４００℃の温度に１時間維持して一次焼成を行い、触媒前駆体を形成した。次に、得られた触媒前駆体と、水と、バインダーとしての市販の水分散ジルコニアゾルとを１０：１００：５の重量比となるように秤量し、回転式ボールミルにて１００回転／分で５時間混合して粉砕し、触媒前駆体スラリーを調製した。 Next, the molar ratio of yttrium nitrate, silver nitrate, manganese nitrate, ruthenium nitrate, citric acid, and water is 0.95: 0.05: 0.95: 0.05: 6: 40. Mixed. The mixing was performed using a mortar at a temperature of 25 ° C. for 15 minutes. The obtained mixture was maintained at a temperature of 400 ° C. for 1 hour to perform primary firing to form a catalyst precursor. Next, the obtained catalyst precursor, water, and a commercially available water-dispersed zirconia sol as a binder are weighed so as to have a weight ratio of 10: 100: 5, and are rotated at 100 rpm with a rotary ball mill. The mixture was pulverized by mixing for 5 hours to prepare a catalyst precursor slurry.
次に、見かけ体積１Ｌ当たりの担持量が１０ｇである触媒層３ａ，３ｂが形成された多孔質フィルタ基材２を用いる点を除いて実施例１と全く同一にして、多孔質フィルタ基材２の端部が閉塞されていない前記複数の貫通孔内に前記触媒前駆体スラリーを流通させ、続いて、多孔質フィルタ基材２から過剰な該触媒前駆体スラリーを除去した。 Next, the porous filter base material 2 is exactly the same as that of Example 1 except that the porous filter base material 2 on which the catalyst layers 3a and 3b having an apparent loading amount of 1 g are formed is used. The catalyst precursor slurry was circulated through the plurality of through holes whose end portions were not closed, and then the excess catalyst precursor slurry was removed from the porous filter substrate 2.
次に、多孔質フィルタ基材２を８００℃の温度に１時間維持して三次焼成を行い、前記端部が閉塞されていない前記貫通孔の表面に、見かけ体積１Ｌ当たりの担持量が５０ｇとなるように、セル隔壁６の流入セル４側の表面に、複合金属酸化物Ｙ０．９５Ａｇ０．０５Ｍｎ０．９５Ｒｕ０．０５Ｏ３からなる第１の触媒層３ａを形成するとともに、セル隔壁６の気孔７を形成する壁面の表面に、該複合金属酸化物からなる第２の触媒層３ｂを形成した。ここで、前記担持量５０ｇは、前記二次焼成による担持量１０ｇを含めた値である。次に、流出セル５以外のセルの前記端部が閉塞された側とは反対側の端部を、シリカを主成分とするセラミックス接着剤にて閉塞することにより、流入セル４を形成し、排ガス浄化用酸化触媒装置１を完成させた。 Next, the porous filter base material 2 is maintained at a temperature of 800 ° C. for 1 hour to perform the third firing, and the loading amount per apparent volume of 1 L is 50 g on the surface of the through hole where the end is not blocked. The first catalyst layer 3 a made of the composite metal oxide Y 0.95 Ag 0.05 Mn 0.95 Ru 0.05 O 3 is formed on the surface of the cell partition wall 6 on the inflow cell 4 side. The second catalyst layer 3b made of the composite metal oxide was formed on the surface of the wall surface forming the pores 7 of the cell partition wall 6. Here, the carrying amount 50 g is a value including the carrying amount 10 g by the secondary firing. Next, the inflow cell 4 is formed by closing the end of the cell other than the outflow cell 5 opposite to the side where the end is closed with a ceramic adhesive mainly composed of silica, The oxidation catalyst device 1 for exhaust gas purification was completed.
次に、本実施例の排ガス浄化用酸化触媒装置１について、実施例１と全く同一にして、触媒評価性能試験を行い排出ガスのＣＯ２濃度を測定した。結果を図１６に示す。次に、図１６から、３００℃以下の温度範囲において、排ガス浄化用酸化触媒装置１により燃焼されたパティキュレートの質量を算出した。結果を図３に示す。図３に示すように、排ガス浄化用酸化触媒装置１の見かけ体積１Ｌあたりに捕集されたパティキュレート３ｇのうち、燃焼された量は２．５ｇであった。 Next, the exhaust gas purification oxidation catalyst device 1 of this example was subjected to a catalyst evaluation performance test in exactly the same manner as in Example 1 to measure the CO 2 concentration of the exhaust gas. The results are shown in FIG. Next, from FIG. 16, in the temperature range of 300 ° C. or less, the mass of the particulates burned by the exhaust gas purification oxidation catalyst device 1 was calculated. The results are shown in FIG. As shown in FIG. 3, the burned amount of 2.5 g of the particulates collected per 1 L of the apparent volume of the oxidation catalyst device 1 for exhaust gas purification was 2.5 g.
次に、本実施例の排ガス浄化用酸化触媒装置１について、実施例１と全く同一にして、断面画像を撮影した。図１７（ａ），（ｂ）に排ガス浄化用酸化触媒装置１の断面画像を示す。図１７（ｂ）に示すように、セル隔壁６の気孔７を形成する壁面の表面に第２の触媒層３ｂが形成されていることが明らかである。 Next, a cross-sectional image of the oxidation catalyst device 1 for exhaust gas purification of this example was taken in exactly the same way as in Example 1. FIGS. 17A and 17B show cross-sectional images of the oxidation catalyst device 1 for exhaust gas purification. As shown in FIG. 17 (b), it is clear that the second catalyst layer 3 b is formed on the surface of the wall surface that forms the pores 7 of the cell partition 6.
次に、本実施例の排ガス浄化用酸化触媒装置１について、実施例１と全く同一にして、多孔質フィルタ基材２の気孔の直径及び触媒層３ａ，３ｂの細孔の直径と、多孔質フィルタ基材２及び触媒層３ａ，３ｂを合わせた全体の気孔率とを測定した。結果を図１８及び図６に示す。図１８に示すように、触媒層３ａ，３ｂの細孔の直径は０．０３〜２．５μｍの範囲であった。また、図６に示すように多孔質フィルタ基材２及び触媒層３ａ，３ｂを合わせた全体の気孔率は４９．０体積％であった。 Next, regarding the oxidation catalyst device 1 for exhaust gas purification of this example, exactly the same as in Example 1, the pore diameter of the porous filter substrate 2, the pore diameters of the catalyst layers 3a and 3b, and the porous The total porosity of the filter substrate 2 and the catalyst layers 3a and 3b was measured. The results are shown in FIGS. As shown in FIG. 18, the diameters of the pores of the catalyst layers 3a and 3b were in the range of 0.03 to 2.5 μm. Further, as shown in FIG. 6, the total porosity of the porous filter substrate 2 and the catalyst layers 3a and 3b was 49.0% by volume.
本実施例では、３次焼成により見かけ体積１Ｌ当たりの担持量が８０ｇとなるように触媒層３ａ，３ｂを形成した点を除いて実施例５と全く同一にして、排ガス浄化用酸化触媒装置１を形成した。 In this embodiment, the oxidation catalyst device 1 for exhaust gas purification is exactly the same as the embodiment 5 except that the catalyst layers 3a and 3b are formed so that the carrying amount per 1 L apparent volume is 80 g by the third firing. Formed.
次に、本実施例の排ガス浄化用酸化触媒装置１について、実施例１と全く同一にして、触媒評価性能試験を行い排出ガスのＣＯ２濃度を測定した。結果を図１９に示す。次に、図２９から、３００℃以下の温度範囲において、排ガス浄化用酸化触媒装置１により燃焼されたパティキュレートの質量を算出した。結果を図３に示す。図３に示すように、排ガス浄化用酸化触媒装置１の見かけ体積１Ｌあたりに捕集されたパティキュレート３ｇのうち、燃焼された量は２．２ｇであった。 Next, the exhaust gas purification oxidation catalyst device 1 of this example was subjected to a catalyst evaluation performance test in exactly the same manner as in Example 1 to measure the CO 2 concentration of the exhaust gas. The results are shown in FIG. Next, from FIG. 29, the mass of the particulates burned by the exhaust gas purifying oxidation catalyst device 1 in the temperature range of 300 ° C. or less was calculated. The results are shown in FIG. As shown in FIG. 3, the amount burned out of 3 g of particulates collected per 1 L of apparent volume of the oxidation catalyst device 1 for exhaust gas purification was 2.2 g.
次に、本実施例の排ガス浄化用酸化触媒装置１について、実施例１と全く同一にして、断面画像を撮影した。図２０（ａ），（ｂ）に排ガス浄化用酸化触媒装置１の断面画像を示す。図２０（ｂ）に示すように、セル隔壁６の気孔７を形成する壁面の表面に第２の触媒層３ｂが形成されていることが明らかである。 Next, a cross-sectional image of the oxidation catalyst device 1 for exhaust gas purification of this example was taken in exactly the same way as in Example 1. FIGS. 20A and 20B show cross-sectional images of the oxidation catalyst device 1 for exhaust gas purification. As shown in FIG. 20 (b), it is clear that the second catalyst layer 3 b is formed on the surface of the wall surface forming the pores 7 of the cell partition 6.
次に、本実施例の排ガス浄化用酸化触媒装置１について、実施例１と全く同一にして、多孔質フィルタ基材２の気孔７の直径及び触媒層３ａ，３ｂの細孔の直径と、多孔質フィルタ基材２及び触媒層３ａ，３ｂを合わせた全体の気孔率とを測定した。結果を図２１及び図６に示す。図２１に示すように、触媒層３ａ，３ｂの細孔の直径は０．０２〜３．５μｍの範囲であった。また、図６に示すように多孔質フィルタ基材２及び触媒層３ａ，３ｂを合わせた全体の気孔率は４７．３体積％であった。 Next, regarding the oxidation catalyst device 1 for exhaust gas purification of this example, exactly the same as in Example 1, the diameter of the pores 7 of the porous filter substrate 2, the diameters of the pores of the catalyst layers 3a, 3b, and the porous The total porosity of the quality filter substrate 2 and the catalyst layers 3a and 3b was measured. The results are shown in FIG. 21 and FIG. As shown in FIG. 21, the diameters of the pores of the catalyst layers 3a and 3b were in the range of 0.02 to 3.5 μm. Further, as shown in FIG. 6, the total porosity of the porous filter substrate 2 and the catalyst layers 3a and 3b was 47.3% by volume.
本実施例では、得られた前記触媒前駆体と、水と、バインダーとしての市販の水分散ジルコニアゾルとを１０：７０：５の重量比となるように秤量した点を除いて実施例１と全く同一にして、排ガス浄化用酸化触媒装置１を形成した。 In this example, Example 1 except that the obtained catalyst precursor, water, and a commercially available water-dispersed zirconia sol as a binder were weighed to a weight ratio of 10: 70: 5. Exhaust gas purification oxidation catalyst device 1 was formed exactly the same.
次に、本実施例の排ガス浄化用酸化触媒装置１について、実施例１と全く同一にして、触媒評価性能試験を行い排出ガスのＣＯ２濃度を測定した。結果を図２２に示す。次に、図２２から、３００℃以下の温度範囲において、排ガス浄化用酸化触媒装置１により燃焼されたパティキュレートの質量を算出した。結果を図３に示す。図３に示すように、排ガス浄化用酸化触媒装置１の見かけ体積１Ｌあたりに捕集されたパティキュレート３ｇのうち、燃焼された量は１．５２ｇであった。 Next, the exhaust gas purification oxidation catalyst device 1 of this example was subjected to a catalyst evaluation performance test in exactly the same manner as in Example 1 to measure the CO 2 concentration of the exhaust gas. The results are shown in FIG. Next, from FIG. 22, in the temperature range of 300 ° C. or less, the mass of the particulate burned by the exhaust gas purification oxidation catalyst device 1 was calculated. The results are shown in FIG. As shown in FIG. 3, the amount burned out of 3 g of particulates collected per 1 L of apparent volume of the oxidation catalyst device 1 for exhaust gas purification was 1.52 g.
次に、本実施例の排ガス浄化用酸化触媒装置１について、実施例１と全く同一にして、断面画像を撮影した。図２３（ａ），（ｂ）に排ガス浄化用酸化触媒装置１の断面画像を示す。図２３（ｂ）に示すように、セル隔壁６の気孔７を形成する壁面の表面に第２の触媒層３ｂが形成されていることが明らかである。 Next, a cross-sectional image of the oxidation catalyst device 1 for exhaust gas purification of this example was taken in exactly the same way as in Example 1. FIGS. 23A and 23B show cross-sectional images of the oxidation catalyst device 1 for exhaust gas purification. As shown in FIG. 23 (b), it is clear that the second catalyst layer 3 b is formed on the surface of the wall surface that forms the pores 7 of the cell partition wall 6.
次に、本実施例の排ガス浄化用酸化触媒装置１について、実施例１と全く同一にして、多孔質フィルタ基材２の気孔の直径及び触媒層３ａ，３ｂの細孔の直径と、多孔質フィルタ基材２及び触媒層３ａ，３ｂを合わせた全体の気孔率とを測定した。結果を図２４及び図６に示す。図２４に示すように、触媒層３ａ，３ｂの細孔の直径は０．０５〜２．０μｍの範囲であった。また、図６に示すように多孔質フィルタ基材２及び触媒層３ａ，３ｂを合わせた全体の気孔率は４９．３体積％であった。
〔比較例〕
本比較例では、まず、硝酸イットリウムと、硝酸銀と、硝酸マンガンと、硝酸ルテニウムと、リンゴ酸と、水とを、０．９５：０．０５：０．９５：０．０５：６：４０のモル比となるように混合した。前記混合は、乳鉢を用いて２５℃の温度で１５分間行った。得られた混合物を、３５０℃の温度に１時間維持して一次焼成を行い、触媒前駆体を形成した。次に、得られた触媒前駆体と、水と、バインダーとしての市販の水分散ジルコニアゾルとを１０：１００：１０の重量比となるように秤量し、回転式ボールミルにて１００回転／分で５時間混合して粉砕し、触媒前駆体スラリーを調製した。
Next, regarding the oxidation catalyst device 1 for exhaust gas purification of this example, exactly the same as in Example 1, the pore diameter of the porous filter substrate 2, the pore diameters of the catalyst layers 3a and 3b, and the porous The total porosity of the filter substrate 2 and the catalyst layers 3a and 3b was measured. The results are shown in FIGS. As shown in FIG. 24, the diameters of the pores of the catalyst layers 3a and 3b were in the range of 0.05 to 2.0 μm. Further, as shown in FIG. 6, the total porosity of the porous filter substrate 2 and the catalyst layers 3a and 3b was 49.3% by volume.
[Comparative example]
In this comparative example, first, yttrium nitrate, silver nitrate, manganese nitrate, ruthenium nitrate, malic acid, and water were mixed at 0.95: 0.05: 0.95: 0.05: 6: 40. It mixed so that it might become a molar ratio. The mixing was performed using a mortar at a temperature of 25 ° C. for 15 minutes. The obtained mixture was maintained at a temperature of 350 ° C. for 1 hour to perform primary firing to form a catalyst precursor. Next, the obtained catalyst precursor, water, and a commercially available water-dispersed zirconia sol as a binder are weighed so as to have a weight ratio of 10: 100: 10, and are rotated at 100 rpm with a rotary ball mill. The mixture was pulverized by mixing for 5 hours to prepare a catalyst precursor slurry.
次に、前記スラリーが付着された前記多孔質フィルタ基材を８００℃の温度に１時間維持して二次焼成を行い、前記端部が閉塞されていない前記貫通孔の表面に、見かけ体積１Ｌ当たりの担持量が１００ｇとなるように、セル隔壁の流入セル側の表面に、複合金属酸化物Ｙ０．９５Ａｇ０．０５Ｍｎ０．９５Ｒｕ０．０５Ｏ３からなる第１の触媒層を形成した。このとき、セル隔壁の気孔を形成する壁面の表面には、第２の触媒層が形成されなかった。次に、実施例１と全く同一にして、流出セル以外のセルの前記端部が閉塞された側とは反対側の端部を、シリカを主成分とするセラミックス接着剤にて閉塞することにより、流入セルを形成し、排ガス浄化用酸化触媒装置を完成させた。 Next, the porous filter substrate to which the slurry is attached is maintained at a temperature of 800 ° C. for 1 hour to perform secondary firing, and an apparent volume of 1 L is formed on the surface of the through hole where the end is not blocked. The first catalyst layer made of the composite metal oxide Y 0.95 Ag 0.05 Mn 0.95 Ru 0.05 O 3 on the surface of the cell partition wall on the inflow cell side so that the supported amount per unit cell is 100 g Formed. At this time, the second catalyst layer was not formed on the surface of the wall surface forming the pores of the cell partition wall. Next, exactly the same as in Example 1, by closing the end of the cell other than the outflow cell opposite to the side where the end was closed with a ceramic adhesive mainly composed of silica. The inflow cell was formed, and the exhaust gas purification oxidation catalyst device was completed.
次に、本比較例の排ガス浄化用酸化触媒装置について、実施例１と全く同一にして、触媒評価性能試験を行い排出ガスのＣＯ２濃度を測定した。結果を図２に示す。次に、図２から、３００℃以下の温度範囲において、本比較例の排ガス浄化用酸化触媒装置により燃焼されたパティキュレートの質量を算出した。結果を図３に示す。図３に示すように、排ガス浄化用酸化触媒装置１の見かけ体積１Ｌあたりに捕集されたパティキュレート３ｇのうち、燃焼された量は０．４ｇであった。 Next, the exhaust gas purification oxidation catalyst device of this comparative example was subjected to a catalyst evaluation performance test in exactly the same manner as in Example 1, and the CO 2 concentration of the exhaust gas was measured. The results are shown in FIG. Next, from FIG. 2, in the temperature range of 300 ° C. or less, the mass of the particulates burned by the exhaust gas purification oxidation catalyst device of this comparative example was calculated. The results are shown in FIG. As shown in FIG. 3, the amount burned out of 3 g of the particulates collected per 1 L of the apparent volume of the oxidation catalyst device 1 for exhaust gas purification was 0.4 g.
次に、本比較例の排ガス浄化用酸化触媒装置について、実施例１と全く同一にして、断面画像を撮影した。図２５（ａ），（ｂ）に本比較例の排ガス浄化用酸化触媒装置の断面画像を示す。図２５（ｂ）に示すように、セル隔壁の気孔を形成する壁面の表面に第２の触媒層を備えていないことが明らかである。 Next, regarding the oxidation catalyst device for exhaust gas purification of this comparative example, a cross-sectional image was taken in exactly the same manner as in Example 1. 25 (a) and 25 (b) show cross-sectional images of the oxidation catalyst device for exhaust gas purification of this comparative example. As shown in FIG. 25 (b), it is clear that the second catalyst layer is not provided on the surface of the wall surface forming the pores of the cell partition wall.
次に、本比較例の排ガス浄化用酸化触媒装置について、実施例１と全く同一にして、多孔質フィルタ基材の気孔の直径及び第１の触媒層の細孔の直径と、多孔質フィルタ基材及び第１の触媒層の触媒層を合わせた全体の気孔率とを測定した。結果を図５及び図６に示す。図５に示すように、第１の触媒層の細孔の直径は０．０２〜１０μｍの範囲であった。また、図６に示すように多孔質フィルタ基材及び第１の触媒層を合わせた全体の気孔率は５２．５体積％であった。 Next, regarding the oxidation catalyst device for exhaust gas purification of this comparative example, exactly the same as in Example 1, the pore diameter of the porous filter substrate and the pore diameter of the first catalyst layer, and the porous filter base The total porosity of the material and the catalyst layer of the first catalyst layer was measured. The results are shown in FIGS. As shown in FIG. 5, the diameter of the pores of the first catalyst layer was in the range of 0.02 to 10 μm. Moreover, as shown in FIG. 6, the total porosity of the porous filter substrate and the first catalyst layer was 52.5% by volume.
図２，７，１０，１３，１６，１９，２２から、実施例１〜７の排ガス浄化用酸化触媒装置１によれば、比較例の排ガス浄化用酸化触媒装置と比較して、パティキュレートをより低温で酸化（燃焼）できることが明らかである。 2, 7, 10, 13, 16, 19, 22, according to the oxidation catalyst device 1 for exhaust gas purification of Examples 1 to 7, the particulates are compared with the oxidation catalyst device for exhaust gas purification of the comparative example. It is clear that it can be oxidized (combusted) at lower temperatures.
これは、図４，８，１１，１４，１７，２０，２３，２５から明らかであるように、比較例の排ガス浄化用酸化触媒装置は、セル隔壁の表面に第１の触媒層が形成されているだけであるが、実施例１〜７の排ガス浄化用酸化触媒装置１は、第１の触媒層３ａに加えて、セル隔壁６の気孔７を形成する壁面表面に第２の触媒層３ｂが形成されていることにより、前記排ガス中の前記パティキュレートの触媒層３ａ，３ｂへの接触確率が高まるためであると考えられる。 As is apparent from FIGS. 4, 8, 11, 14, 17, 20, 23, and 25, the oxidation catalyst device for exhaust gas purification of the comparative example has the first catalyst layer formed on the surface of the cell partition wall. However, in addition to the first catalyst layer 3a, the oxidation catalyst device 1 for exhaust gas purification of Examples 1 to 7 has the second catalyst layer 3b on the wall surface forming the pores 7 of the cell partition wall 6. This is considered to be because the probability of contact of the particulates in the exhaust gas with the catalyst layers 3a and 3b is increased.
１…排ガス浄化用酸化触媒装置、 ２…多孔質フィルタ基材、 ３ａ…第１の触媒層、 ３ｂ…第２の触媒層、 ４…流入セル、 ４ａ…排ガス流入部、 ４ｂ…排ガス流出部、 ５…流出セル、 ５ａ…排ガス流出部、 ５ｂ…排ガス流入部、 ６…セル隔壁、 ７…気孔。 DESCRIPTION OF SYMBOLS 1 ... Oxidation catalyst apparatus for exhaust gas purification, 2 ... Porous filter base material, 3a ... 1st catalyst layer, 3b ... 2nd catalyst layer, 4 ... Inflow cell, 4a ... Exhaust gas inflow part, 4b ... Exhaust gas outflow part, 5 ... Outflow cell, 5a ... Exhaust gas outflow part, 5b ... Exhaust gas inflow part, 6 ... Cell partition, 7 ... Pore.
Claims (3)
軸方向に貫通して形成された複数の貫通孔のうち、排ガス流入部が開放されるとともに排ガス流出部が閉塞された複数の流入セルと、該複数の貫通孔の排ガス流入部が閉塞されるとともに排ガス流出部が開放された複数の流出セルとを備え、該流入セル及び該流出セルを交互に配設して各セルの境界部をセル隔壁とするウォールフロー構造を有する多孔質フィルタ基材と、
該セル隔壁の少なくとも該流入セル側の表面に担持された該複合金属酸化物からなる第１の触媒層と、
該多孔質フィルタ基材の気孔を形成する壁面表面に担持された該複合金属酸化物からなる第２の触媒層とを備え、
各触媒層が多孔質体からなることを特徴とする排ガス浄化用酸化触媒装置。 An oxidation catalyst device for exhaust gas purification that purifies particulates in exhaust gas of an internal combustion engine by oxidizing using a catalyst made of a composite metal oxide,
Among a plurality of through holes formed so as to penetrate in the axial direction, a plurality of inflow cells in which an exhaust gas inflow portion is opened and an exhaust gas outflow portion is blocked, and an exhaust gas inflow portion of the plurality of through holes are closed. And a plurality of outflow cells whose exhaust gas outflow portions are opened, and a porous filter base material having a wall flow structure in which the inflow cells and the outflow cells are alternately arranged and a boundary between each cell is a cell partition wall When,
A first catalyst layer comprising the composite metal oxide supported on at least the surface of the cell partition wall on the inflow cell side;
A second catalyst layer made of the composite metal oxide supported on the wall surface forming pores of the porous filter substrate,
An oxidation catalyst device for exhaust gas purification, wherein each catalyst layer is made of a porous material.
前記多孔質フィルタ基材及び該各触媒層全体の気孔率が、４５〜５０体積％の範囲であることを特徴とする請求項１記載の排ガス浄化用酸化触媒装置。 Each catalyst layer is composed of a porous body having pores having a diameter in the range of 0.01 to 3.5 μm,
The oxidation catalyst device for exhaust gas purification according to claim 1, wherein the porosity of the porous filter substrate and each of the catalyst layers is in the range of 45 to 50% by volume.
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| JP2008117149A JP2009262102A (en) | 2008-04-28 | 2008-04-28 | Oxidation catalyst device for purification of exhaust gas |
| EP09156695.0A EP2113303B1 (en) | 2008-04-25 | 2009-03-30 | Production method of oxidation catalyst device for exhaust gas purification |
| EP10163127A EP2230013A1 (en) | 2008-04-25 | 2009-03-30 | Production method of oxidation catalyst device for exhaust gas purificatiion |
| US12/420,173 US8168559B2 (en) | 2008-04-25 | 2009-04-08 | Production method of oxidation catalyst device for exhaust gas purification |
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