JP5041367B2 - Manufacturing method of oxidation catalyst device for exhaust gas purification - Google Patents
Manufacturing method of oxidation catalyst device for exhaust gas purification Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims description 48
- 239000011148 porous material Substances 0.000 claims description 65
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- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 12
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- 238000005192 partition Methods 0.000 description 9
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- 230000000694 effects Effects 0.000 description 5
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- 229910052748 manganese Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Processes For Solid Components From Exhaust (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Description
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浄化する排ガス浄化用酸化触媒装置の製造方法に関するものである。 The present invention relates to a method for manufacturing an oxidation catalyst device for exhaust gas purification that oxidizes and purifies particulates in exhaust gas of an internal combustion engine 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、軸方向に貫通して形成された貫通孔からなる複数のセルを有し、各セルの境界部をセル隔壁とする多孔質フィルタ基材に、ペロブスカイト型複合金属酸化物からなる触媒が担持された排ガス浄化用酸化触媒装置が知られている。 Conventionally, in order to oxidize and purify particulates and hydrocarbons contained in the exhaust gas of an internal combustion engine, it has a plurality of cells composed of through holes formed through in the axial direction, and the boundary between each cell is a cell. There is known an oxidation catalyst device for purifying exhaust gas in which a catalyst made of a perovskite complex metal oxide is supported on a porous filter base material used as a partition wall.
前記触媒として用いられるペロブスカイト型複合金属酸化物として、例えば、一般式ＡＭＯ３で表され、ＡはＬａ、Ｙ、Ｄｙ、Ｎｄからなる群から選択される少なくとも１種の金属とＳｒ、Ｂａ、Ｍｇからなる群から選択される少なくとも１種の金属とであり、ＭはＭｎ、Ｆｅ、Ｃｏからなる群から選択される少なくとも１種の金属である複合金属酸化物が知られている（例えば特許文献１参照）。 As the perovskite-type composite metal oxide used as the catalyst, for example, represented by the general formula AMO 3 , A is at least one metal selected from the group consisting of La, Y, Dy, and Nd, and Sr, Ba, Mg There is known a composite metal oxide in which at least one metal selected from the group consisting of M and M is at least one metal selected from the group consisting of Mn, Fe, and Co (for example, Patent Documents) 1).
前記排ガス浄化用酸化触媒装置は、例えば次のようにして製造される。まず、前記ペロブスカイト型複合金属酸化物を合成するための前駆体を調製する。前記前駆体は、前記複合金属酸化物を構成する金属の塩（前記一般式ＡＭＯ３の前記Ａ成分の塩及び前記Ｍ成分の塩）を含む原料塩水溶液を調製し、該原料塩水溶液と中和剤とを混合して各金属の水酸化物を共沈させた後、得られた共沈物を乾燥することにより調製される。各金属の塩としては、硫酸塩、硝酸塩、リン酸塩、塩化物等の無機塩や、酢酸塩、シュウ酸塩等の有機酸塩等を使用することができる。また、中和剤としては、アンモニア、苛性ソーダ、苛性カリ等の無機塩基や、トリエチルアミン、ピリジン等の有機塩基等を使用することができる。次に、前記前駆体のスラリーを調製し、該スラリーを前記多孔質フィルタ基材の前記貫通孔の開口部から該貫通孔内に導入することにより、前記前駆体を該多孔質フィルタ基材の気孔内に付着させる。次に、前記多孔質フィルタ基材を焼成することにより、該多孔質フィルタ基材に前記前駆体の酸化物としてのペロブスカイト型複合金属酸化物からなる多孔質触媒層を形成する。以上により、前記ペロブスカイト型複合金属酸化物からなる触媒が担持された前記排ガス浄化用酸化触媒装置を得ることができる。 The exhaust gas purification oxidation catalyst device is manufactured as follows, for example. First, a precursor for synthesizing the perovskite complex metal oxide is prepared. The precursor is prepared as a raw salt aqueous solution containing a metal salt constituting the composite metal oxide (the salt of the A component and the salt of the M component of the general formula AMO 3 ). It is prepared by drying the obtained coprecipitate after coprecipitation of a hydroxide of each metal by mixing with a hydrating agent. As each metal salt, inorganic salts such as sulfates, nitrates, phosphates and chlorides, and organic acid salts such as acetates and oxalates can be used. Moreover, as a neutralizing agent, inorganic bases, such as ammonia, caustic soda, and caustic potash, organic bases, such as a triethylamine and a pyridine, etc. can be used. Next, a slurry of the precursor is prepared, and the slurry is introduced into the through-hole from the opening of the through-hole of the porous filter substrate, whereby the precursor is removed from the porous filter substrate. Adhere in the pores. Next, the porous filter substrate is fired to form a porous catalyst layer made of a perovskite-type composite metal oxide as an oxide of the precursor on the porous filter substrate. As described above, the oxidation catalyst device for purifying exhaust gas carrying the catalyst made of the perovskite complex metal oxide can be obtained.
しかしながら、前記複合金属酸化物を構成する金属の水酸化物の共沈物を乾燥させて調製された前駆体を含むスラリーを用いた従来の製造方法では、前記パティキュレートを酸化する温度を低くすることができる多孔質触媒層を得ることが困難であるという不都合がある。
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の製造方法を提供することを目的とする。 An object of the present invention is to provide a method for manufacturing an oxidation catalyst device for purifying exhaust gas that can eliminate such inconvenience and oxidize and purify particulates in the exhaust gas of an internal combustion engine at a lower temperature.
本発明者らは、複数の金属の化合物とリンゴ酸と水とを一次焼成して一次焼成物を得て、該一次焼成物を二次焼成することにより得られた複合金属酸化物からなる多孔質触媒層は、従来の製造方法で得られた多孔質触媒層と比較して、排ガス中のパティキュレートの燃焼温度を低くすることができることを知見した。リンゴ酸を用いて製造された前記多孔質触媒層は、細孔の直径が０．０５〜１０μｍの範囲であった。しかし、排ガス浄化用酸化触媒装置としては、さらに該燃焼温度を低くすることできる多孔質触媒層が望まれる。 The inventors of the present invention provide a porous metal oxide comprising a composite metal oxide obtained by first firing a plurality of metal compounds, malic acid and water to obtain a first fired product, and second firing the first fired product. It has been found that the porous catalyst layer can lower the combustion temperature of the particulates in the exhaust gas as compared with the porous catalyst layer obtained by the conventional production method. The porous catalyst layer produced using malic acid had a pore diameter in the range of 0.05 to 10 μm. However, as an oxidation catalyst device for exhaust gas purification, a porous catalyst layer that can further reduce the combustion temperature is desired.
そこで、かかる目的を達成するために、本発明の排ガス浄化用酸化触媒装置の製造方法は、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浄化する排ガス浄化用酸化触媒装置の製造方法であって、該複合金属酸化物を構成する複数の金属の化合物とクエン酸と水とを焼成して焼成物を得る工程と、得られた該焼成物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工程と、該スラリーを多孔質フィルタ基材に塗布する工程と、該スラリーが塗布された該多孔質フィルタ基材を焼成して、該多孔質フィルタ基材に担持された該複合金属酸化物からなる多孔質触媒層を形成する工程とを備え、該複数の金属の化合物は、イットリウム化合物と、マンガン化合物と、銀化合物と、ルテニウム化合物とからなることを特徴とする。 Therefore, in order to achieve this object, the method for producing an oxidation catalyst device for exhaust gas purification according to the present invention oxidizes and purifies particulates in the exhaust gas of an internal combustion engine using a catalyst made of a composite metal oxide. A method for producing an oxidation catalyst device for use in the present invention includes a step of calcining a compound of a plurality of metals, citric acid and water constituting the composite metal oxide to obtain a calcined product, and the obtained calcined product and water. A step of preparing a slurry by mixing and pulverizing a binder, a step of applying the slurry to a porous filter substrate, and firing the porous filter substrate coated with the slurry, thereby the porous filter and forming a porous catalyst layer consisting of the composite metal oxide supported on a substrate, the compounds of the plurality of metals, and yttrium compound, a manganese compound, a silver compound, a ruthenium compound Tona and said Rukoto.
本発明の製造方法により製造された排ガス浄化用酸化触媒装置において、前記多孔質フィルタ基材へ導入された前記内燃機関の排ガスは、前記多孔質触媒層の細孔を通過して該多孔質触媒層に接触する。ここで、本発明の製造方法により製造された排ガス浄化用酸化触媒装置は、前記複数の金属の化合物とクエン酸と水とを焼成して前記焼成物を得ることにより、リンゴ酸を用いて製造された排ガス浄化用酸化触媒装置と比較して、前記多孔質触媒層の細孔の直径の分布が小さい側へ移動していて、直径の小さい細孔が増加している。このため、前記多孔質触媒層は、前記排ガス中の前記パティキュレートを該多孔質触媒層に接触させるのに好適な直径を有する前記細孔を多数備えることとなるので、該パティキュレートの該多孔質触媒層への接触確率が高まることとなる。したがって、本発明の製造方法により製造された排ガス浄化用酸化触媒装置によれば、リンゴ酸を用いて製造された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。
前記排ガス浄化用酸化触媒装置において、前記複数の金属の化合物は、イットリウム化合物と、マンガン化合物と、銀化合物と、ルテニウム化合物とからなる。前記複数の金属の化合物から得られる前記複合金属酸化物は、一般式ＹＭｎＯ ３ 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。前記複合金属酸化物は、その結晶構造が六方晶とペロブスカイト構造との混晶となり、高い触媒活性を有することとなる。したがって、本発明によれば、前記排ガスが前記多孔質触媒層の前記細孔を通過する際に、該多孔質触媒層の触媒の作用により該排ガス中の前記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 device for purifying exhaust gas produced by the production method of the present invention, the exhaust gas of the internal combustion engine introduced into the porous filter base material passes through the pores of the porous catalyst layer and passes through the porous catalyst layer. Contact layer. Here, the oxidation catalyst device for exhaust gas purification manufactured by the manufacturing method of the present invention is manufactured using malic acid by firing the plurality of metal compounds, citric acid and water to obtain the fired product. Compared with the oxidation catalyst device for exhaust gas purification, the pore diameter distribution of the porous catalyst layer has moved to the smaller side, and the pores with smaller diameters have increased. Therefore, the porous catalyst layer has a large number of pores having a diameter suitable for bringing the particulates in the exhaust gas into contact with the porous catalyst layer. The probability of contact with the quality catalyst layer is increased. Therefore, according to the oxidation catalyst device for exhaust gas purification manufactured by the manufacturing method of the present invention, the particulate matter in the exhaust gas of the internal combustion engine is more improved compared to the oxidation catalyst device for exhaust gas purification manufactured using malic acid. It can be oxidized and purified at low temperatures .
In the exhaust gas purifying oxidation catalyst device, the plurality of metal compounds include an yttrium compound, a manganese compound, a silver compound, and a ruthenium compound. In the composite metal oxide obtained from the compound of the plurality of metals, in the composite metal oxide represented by the general formula YMnO 3 , a part of Y that is the first metal is replaced with Ag that is the third metal. In addition, a part of Mn as the second metal is substituted with Ru as the fourth metal. The composite metal oxide has a mixed crystal of a hexagonal crystal and a perovskite structure, and has a high catalytic activity. Therefore, according to the present invention, when the exhaust gas passes through the pores of the porous catalyst layer, the particulates in the exhaust gas are sufficiently burned and removed by the action of the catalyst of the porous catalyst layer. Can do.
また、本発明において、前記多孔質触媒層は、直径が０．０２〜５μｍの範囲である細孔を備え、該多孔質フィルタ基材及び前記多孔質触媒層全体の気孔率が、５０〜６０体積％の範囲であることが好ましい。前記構成によれば、前記細孔を介して前記排ガス中の前記パティキュレートを前記多孔質触媒層に接触させることにより、燃焼温度を確実に低下させることができるとともに、該排ガスが該細孔を通過する際に圧力損失が大きくなることを防ぐことができる。 In the present invention, the porous catalyst layer has pores having a diameter in the range of 0.02 to 5 μm, and the porosity of the porous filter substrate and the entire porous catalyst layer is 50 to 60. It is preferably in the range of volume%. According to the above configuration, the particulate matter in the exhaust gas is brought into contact with the porous catalyst layer through the pores, so that the combustion temperature can be reliably lowered, and the exhaust gas causes the pores to pass through the pores. It is possible to prevent an increase in pressure loss when passing.
このとき、前記多孔質触媒層の前記細孔の直径が０．０２μｍ未満である場合には、前記排ガスが前記細孔を通過する際に圧力損失が大きくなることがある。一方、前記多孔質触媒層の前記細孔の直径が５μｍを超える場合には、前記排ガスが前記細孔を通過する際に、該排ガス中の前記パティキュレートが前記多孔質触媒層の表面に十分に接触することができなくなり、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 pore diameter of the porous catalyst layer is less than 0.02 μm, pressure loss may increase when the exhaust gas passes through the pores. On the other hand, when the diameter of the pores of the porous catalyst layer exceeds 5 μm, the particulates in the exhaust gas are sufficiently on the surface of the porous catalyst layer when the exhaust gas passes through the pores. May not be able to come into contact with the fuel, and the effect of lowering the combustion temperature may not be obtained.
また、前記多孔質フィルタ基材及び前記多孔質触媒層全体の気孔率が５０体積％未満である場合には、前記排ガスが前記細孔を通過する際に圧力損失が大きくなることがある。一方、前記多孔質フィルタ基材及び前記多孔質触媒層全体の気孔率が６０体積％を超える場合には、前記排ガスが前記細孔を通過する際に、該排ガス中の前記パティキュレートが前記多孔質触媒層の表面に十分に接触することができなくなり、燃焼温度を低下させる効果が得られないことがある。 Further, when the porosity of the porous filter substrate and the entire porous catalyst layer is less than 50% by volume, pressure loss may increase when the exhaust gas passes through the pores. On the other hand, when the porosity of the porous filter substrate and the entire porous catalyst layer exceeds 60% by volume, the particulates in the exhaust gas pass through the pores when the exhaust gas passes through the pores. It may not be possible to sufficiently contact the surface of the porous catalyst layer, and the effect of lowering the combustion temperature may not be obtained.
また、本発明において、前記多孔質触媒層は１０〜１２０μｍの範囲である厚さを有することが好ましい。前記構成によれば、前記細孔を介して前記排ガス中の前記パティキュレートを前記多孔質触媒層に十分に接触させることにより、燃焼温度を確実に低下させることができるとともに、該排ガスが該細孔を通過する際に圧力損失が大きくなることを防ぐことができる。このとき、前記多孔質触媒層の厚さが１０μｍ未満の場合には、前記排ガスが前記細孔を通過する際に、該排ガス中の前記パティキュレートが前記多孔質触媒層の表面に十分に接触することができなくなり、燃焼温度を低下させる効果が得られないことがある。一方、前記多孔質触媒層の厚さが１２０μｍを超える場合には、前記排ガスが前記細孔を通過する際に圧力損失が大きくなることがある。 In the present invention, the porous catalyst layer preferably has a thickness in the range of 10 to 120 μm. According to the above configuration, the particulate matter in the exhaust gas can be sufficiently brought into contact with the porous catalyst layer through the pores, so that the combustion temperature can be reliably lowered and the exhaust gas can be reduced. It is possible to prevent an increase in pressure loss when passing through the hole. At this time, when the thickness of the porous catalyst layer is less than 10 μm, the particulates in the exhaust gas sufficiently contact the surface of the porous catalyst layer when the exhaust gas passes through the pores. Cannot be achieved, and the effect of lowering the combustion temperature may not be obtained. On the other hand, when the thickness of the porous catalyst layer exceeds 120 μm, pressure loss may increase when the exhaust gas passes through the pores.
前記バインダーは、ジルコニアからなるゾルであることが好ましい。 Before SL binder is preferably a sol comprising zirconia.
本発明において、前記多孔質触媒層は、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ことが好ましい。本発明によれば、前記排ガスが前記多孔質触媒層の前記細孔を通過する際に、該多孔質触媒層の触媒の作用により該排ガス中の前記パティキュレートを確実に燃焼除去することができる。 In the present invention, the porous catalyst layer is represented by 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 It is preferable that the composite metal oxide is. According to the present invention, when the exhaust gas passes through the pores of the porous catalyst layer, the particulates in the exhaust gas can be surely burned and removed by the action of the catalyst of the porous catalyst layer. .
このとき、ｘが０．０１未満である場合には、触媒活性を高める効果が不十分になることがある。一方、ｘが０．１５を超える場合には、混晶を維持することが困難になることがある。また、ｙが０．００５未満である場合には、触媒活性を高める効果が不十分になることがある。一方、ｙが０．２を超える場合には、混晶を維持することが困難になることがある。 At this time, when x is less than 0.01, the effect of increasing the catalytic activity may be insufficient. On the other hand, when x exceeds 0.15, it may be difficult to maintain a mixed crystal. Moreover, when y is less than 0.005, the effect of increasing the catalytic activity may be insufficient. On the other hand, when y exceeds 0.2, it may be difficult to maintain a mixed crystal.
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は本実施形態の製造方法により形成される排ガス浄化用酸化触媒装置の説明的断面図である。図２は、実施例、参考例、及び比較例の製造方法により形成された排ガス浄化用酸化触媒装置によるパティキュレートの燃焼温度を示すグラフである。図３は、実施例及び比較例の製造方法により形成された排ガス浄化用酸化触媒装置による圧力損失を示すグラフである。図４，７，９，１１，１３は、実施例及び比較例の製造方法により形成された排ガス浄化用酸化触媒装置の断面画像である。図４（ａ），７（ａ），９（ａ），１１（ａ），１３（ａ）は、実施例及び比較例の製造方法により形成された排ガス浄化用酸化触媒装置の正面断面画像であり、図４（ｂ），７（ｂ），９（ｂ），１１（ｂ），１３（ｂ）は、図４（ａ），７（ａ），９（ａ），１１（ａ），１３（ａ）におけるＢ部拡大断面画像である。図５，８，１０，１２は、実施例及び比較例の製造方法により形成された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多孔質触媒層の細孔の直径を示すグラフである。図６は、実施例及び比較例の製造方法により形成された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多孔質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 cross-sectional view of an oxidation catalyst device for exhaust gas purification formed by the manufacturing method of the present embodiment. FIG. 2 is a graph showing the combustion temperature of the particulates by the exhaust gas purifying oxidation catalyst device formed by the production methods of Examples, Reference Examples, and Comparative Examples. FIG. 3 is a graph showing the pressure loss due to the exhaust gas purification oxidation catalyst device formed by the production methods of the examples and comparative examples. 4, 7, 9, 11, and 13 are cross-sectional images of the oxidation catalyst device for exhaust gas purification formed by the manufacturing methods of Examples and Comparative Examples. 4 (a), 7 (a), 9 (a), 11 (a), and 13 (a) are front cross-sectional images of an oxidation catalyst device for exhaust gas purification formed by the manufacturing methods of Examples and Comparative Examples. 4 (b), 7 (b), 9 (b), 11 (b), 13 (b) are shown in FIGS. 4 (a), 7 (a), 9 (a), 11 (a), It is a B section enlarged cross-sectional image in 13 (a). 5, 8, 10, and 12 show the pore diameter of the porous filter substrate and the diameter of the pores of the porous catalyst layer according to the oxidation catalyst device for exhaust gas purification formed by the manufacturing methods of Examples and Comparative Examples. It is a graph to show. FIG. 6 is a graph showing the porosity of the porous filter substrate and the entire porous catalyst layer according to the exhaust gas purifying oxidation catalyst device formed by the production methods of Examples and Comparative Examples.
本実施形態の製造方法により形成される排ガス浄化用酸化触媒装置１について説明する。図１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に担持された多孔質触媒層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 formed by the manufacturing method of the present embodiment will be described. An exhaust gas purifying oxidation catalyst device 1 shown in FIG. 1 includes a porous filter base material 2 having a wall flow structure and a porous catalyst layer 3 supported on the porous filter base material 2, and exhaust gas from an internal combustion engine. By circulating, 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（図示せず）を備えていて、それ自体の気孔率が３０〜６０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 composed of the through-holes. Cell 5. The porous filter substrate 2 is provided with a plurality of pores (not shown) having a diameter in the range of 1 to 100 μm, and the porosity of the porous filter substrate 2 is in the range of 30 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.
セル隔壁６の流入セル４側の表面には、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多孔質触媒層３が担持されている。多孔質触媒層３は、直径が０．０２〜５μｍの範囲である細孔（図示せず）を備え、１０〜１２０μｍの範囲である厚さを備える。また、多孔質フィルタ基材２及び多孔質触媒層３は、両者を合わせた全体の気孔率が５０〜６０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。 The inflow cell 4 side of the surface of the cell partition wall 6 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 is supported on the porous catalyst layer 3 made of a composite metal oxide. The porous catalyst layer 3 includes pores (not shown) having a diameter in the range of 0.02 to 5 μm, and has a thickness in the range of 10 to 120 μm. The porous filter base material 2 and the porous catalyst layer 3 have a total porosity in the range of 50 to 60% by volume when both are combined. 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、多孔質触媒層３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 porous catalyst layer 3 is supported only on the surface of the cell partition wall 6 on the inflow cell 4 side, but the surface between 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する。次に、得られた結果物と、水と、バインダーとしてのジルコニアからなるゾルとを混合し粉砕して、スラリーを調製する。 The exhaust gas purifying oxidation catalyst device 1 having the above-described configuration can be manufactured as follows. First, a mixture of yttrium nitrate, silver nitrate, manganese nitrate, ruthenium nitrate, citric acid, and water is primarily fired at a temperature in the range of 200 to 400 ° C. for 1 to 10 hours. Next, the obtained product, water, and a sol made of zirconia as a binder are mixed and pulverized to prepare a 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ＳｉＣ多孔質体を用意する。ＳｉＣ多孔質体として、例えば表１に示す日本碍子株式会社製の商品名ＭＳＣ１４を用いることができる。次に、前記ＳｉＣ多孔質体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、前記ＳｉＣ多孔質体に、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。続いて、前記ＳｉＣ多孔質体から過剰な前記スラリーを除去する。 Next, a SiC porous body in which a plurality of through holes penetrating in the axial direction is arranged in a cross-sectional lattice shape is prepared. As the SiC porous body, for example, trade name MSC14 manufactured by Nippon Choshi Co., Ltd. shown in Table 1 can be used. Next, every other end of the through-hole of the SiC porous body (that is, in a cross-sectional checkered pattern) is closed with a ceramic adhesive containing silica as a main component, so that the outflow occurs. A cell 5 is formed. Next, by pouring the slurry into the SiC porous body from the side where the end is closed, the inside of the plurality of through-holes (that is, cells other than the outflow cell 5) where the end is not closed The slurry is circulated. Subsequently, the excess slurry is removed from the SiC porous body.
次に、前記ＳｉＣ多孔質体を、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とにより、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）からなる多孔質触媒層３を形成する。このとき、多孔質触媒層３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０．０２〜５μｍの範囲である細孔（図示せず）を備えるとともに、厚さが１０〜１２０μｍの範囲に形成される。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及び多孔質触媒層３を合わせた全体の５０〜６０体積％の範囲の気孔率を備えている。 Next, the SiC porous body is subjected to secondary firing at a temperature in the range of 800 to 1000 ° C. for a time in the range of 1 to 10 hours, thereby forming a composite on the surface of the cell partition walls 6 of the cells other than the outflow cell 5. The porous catalyst layer 3 made of the 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) is formed. . At this time, the porous catalyst layer 3 is provided with pores (not shown) having a diameter in the range of 0.02 to 5 μm and having a thickness of 10 as a result of the secondary firing at the temperature and time in the above range. It is formed in a range of ˜120 μm. 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 purifying oxidation catalyst device 1 manufactured as described above has a porosity in the range of 50 to 60% by volume of the total of the porous filter substrate 2 and the porous catalyst layer 3.
次に、図１を参照して本実施形態の製造方法により形成される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、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。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。 Next, the operation of the exhaust gas purifying oxidation catalyst device 1 formed by the manufacturing method 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 4 a of the inflow cell 4. 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.
続いて、流入セル４は排ガス流出部４ｂが閉塞されているので、流入セル４内へ導入された前記排ガスは、セル隔壁６の表面に担持された多孔質触媒層３の前記細孔と多孔質フィルタ基材２のセル隔壁６の気孔とを通過して、流出セル５内へ移動する。前記排ガスが多孔質触媒層３の前記細孔を流通する際、該排ガス中のパティキュレートは、該細孔を形成している触媒の表面に接触し、多孔質触媒層３の触媒の作用により燃焼除去される。 Subsequently, since the exhaust gas outflow portion 4 b of the inflow cell 4 is closed, the exhaust gas introduced into the inflow cell 4 is not porous and porous with respect to the porous catalyst layer 3 supported on the surface of the cell partition wall 6. It passes through the pores of the cell partition wall 6 of the quality filter substrate 2 and moves into the outflow cell 5. When the exhaust gas flows through the pores of the porous catalyst layer 3, the particulates in the exhaust gas come into contact with the surface of the catalyst forming the pores, and due to the action of the catalyst of the porous catalyst layer 3. Burned away.
そして、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が開放されているので、流出セル５内へ移動した前記排ガスは、排ガス流出部５ｂから排出されることとなる。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。 And since the exhaust gas inflow part 5a is obstruct | occluded and the exhaust gas outflow part 5b is open | released in the outflow cell 5, the said exhaust gas which moved into the outflow cell 5 will be discharged | emitted from the exhaust gas outflow part 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.
本実施形態の製造方法によれば、前記複数の金属の化合物とクエン酸と水とを一次焼成したことにより、リンゴ酸を用いて製造された排ガス浄化用酸化触媒装置と比較して、細孔の直径の分布が小さい側へ移動していて直径の小さい細孔が増加した前記多孔質触媒層を備える排ガス浄化用酸化触媒層１が製造される。排ガス浄化用酸化触媒装置１においては、多孔質触媒層３の前記細孔の直径が０．０２〜５μｍの範囲に形成され、前記排ガス中の前記パティキュレートを該多孔質触媒層に接触させるのに好適な直径となっているので、該排ガスが多孔質触媒層３の前記細孔を通過する際に、該パティキュレートの多孔質触媒層３への接触確率が高まることとなる。したがって、排ガス浄化用酸化触媒装置１によれば、リンゴ酸を用いて製造され、細孔の直径が０．０５〜１０μｍの範囲である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 manufacturing method of this embodiment, the pores are compared with the oxidation catalyst device for exhaust gas purification manufactured using malic acid by primary firing of the plurality of metal compounds, citric acid and water. The oxidation catalyst layer 1 for exhaust gas purification comprising the porous catalyst layer in which the distribution of the diameter of the catalyst is moved to the smaller side and the pores with the smaller diameter are increased is manufactured. In the oxidation catalyst device 1 for exhaust gas purification, the pore diameter of the porous catalyst layer 3 is formed in the range of 0.02 to 5 μm, and the particulates in the exhaust gas are brought into contact with the porous catalyst layer. Therefore, when the exhaust gas passes through the pores of the porous catalyst layer 3, the probability of contact of the particulates with the porous catalyst layer 3 is increased. Therefore, according to the oxidation catalyst device 1 for exhaust gas purification, compared with the oxidation catalyst device for exhaust gas purification manufactured using malic acid and having a pore diameter in the range of 0.05 to 10 μm, the exhaust gas of the internal combustion engine The particulates inside can be oxidized and purified at a lower temperature.
また、本実施形態の製造方法により形成される排ガス浄化用酸化触媒装置１は、多孔質触媒層３が１０〜１２０μｍの範囲である厚さを有するとともに、多孔質フィルタ基材２及び多孔質触媒層３を合わせた全体の５０〜６０体積％の範囲の気孔率を備えている。これにより、前記細孔を介して排ガス中のパティキュレートを多孔質触媒層３に十分に接触させることにより、燃焼温度を確実に低下させることができるとともに、該排ガスが該細孔を通過する際に圧力損失が大きくなることを防ぐことができる。 Further, the exhaust gas purification oxidation catalyst device 1 formed by the manufacturing method of the present embodiment has a thickness in which the porous catalyst layer 3 is in the range of 10 to 120 μm, and the porous filter substrate 2 and the porous catalyst. It has a porosity in the range of 50 to 60% by volume of the entire layer 3 combined. Thereby, the particulate matter in the exhaust gas is sufficiently brought into contact with the porous catalyst layer 3 through the pores, so that the combustion temperature can be reliably lowered and the exhaust gas passes through the pores. It is possible to prevent the pressure loss from increasing.
また、本実施形態の製造方法により形成される排ガス浄化用酸化触媒装置１においては、多孔質触媒層３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っている。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。この置換により、Ｙ１−ｘＡｇｘＭｎ１−ｙＲｕｙＯ３は、その結晶構造が六方晶とペロブスカイト構造との混晶となり、高い触媒活性を有することとなる。したがって、排ガス浄化用酸化触媒装置１によれば、前記排ガスが多孔質触媒層３の前記細孔を通過する際に、多孔質触媒層３の触媒の作用により該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 which is formed by the production method of the present embodiment, the porous catalyst layer 3 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. 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. This substitution, Y 1-x Ag x Mn 1-y Ru y O 3 , the crystal structure becomes a mixed crystal of hexagonal crystal and perovskite structures and has a high catalytic activity. Therefore, according to the oxidation catalyst device 1 for exhaust gas purification, when the exhaust gas passes through the pores of the porous catalyst layer 3, the particulates in the exhaust gas are sufficiently removed by the action of the catalyst of the porous catalyst layer 3. It can be burned off.
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、次のようにして排ガス浄化用酸化触媒装置１を製造した。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った。次に、前記一次焼成で得られた結果物と、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。 In this example, the exhaust gas purification oxidation catalyst device 1 was manufactured as follows. First, 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 for 15 minutes using a mortar. The obtained mixture was maintained at a temperature of 350 ° C. for 1 hour for primary firing. Next, the resulting product obtained by the primary firing, 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 rotated 100 times with a rotary ball mill. The mixture was pulverized by mixing for 5 hours at a minute 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、ＳｉＣ多孔質体（日本碍子株式会社製、商品名ＭＳＣ１４、寸法３６ｍｍ×３６ｍｍ×５０ｍｍ）を用意し、該ＳｉＣ多孔質体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、前記ＳｉＣ多孔質体に、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、前記ＳｉＣ多孔質体から過剰な前記スラリーを除去した。 Next, an 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 lattice shape is prepared. Every other one end of the through hole of the porous body (that is, so as to have a checkered cross section) was closed with a ceramic adhesive mainly composed of silica to form the outflow cell 5. Next, by pouring the catalyst precursor slurry into the SiC porous body 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 was circulated in the inside. Subsequently, the excess slurry was removed from the SiC porous body.
次に、前記ＳｉＣ多孔質体を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からなる多孔質触媒層３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 SiC porous body is maintained at a temperature of 800 ° C. for 1 hour to perform secondary firing, and the loading amount per apparent volume of 1 L is 100 g on the surface of the through hole where the end is not blocked. so that, to form a porous catalyst layer 3 comprising a composite metal oxide Y 0.95 Ag 0.05 Mn 0.95 Ru 0.05 O 3. 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、本実施例で得られた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２４００ｃｃ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に対する流入温度が１８０℃であり、エンジン回転数が１５００回転／分であり、トルクが７０Ｎ／ｍであるようにして、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の見かけ体積１Ｌあたりパティキュレートを２ｇ捕集させた。 Next, a catalyst evaluation performance test was performed on the oxidation catalyst device 1 for exhaust gas purification obtained in 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 2400 cc. Next, in an atmosphere gas containing particulates, the inflow temperature of the atmosphere gas to the exhaust gas purification oxidation catalyst device 1 is 180 ° C., the engine speed is 1500 rpm, and the torque is 70 N / m. Thus, the diesel engine was operated for 20 minutes. As described above, 2 g of particulates were collected per 1 L of apparent volume of 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が用いられた。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計測し、ＣＯ２濃度のピークからパティキュレートの燃焼温度を求めた。結果を図２に示す。また、石英管の供給口と排出口とにおける圧力差を計測することにより、排ガス浄化用酸化触媒装置１の圧力損失を求めた。結果を図３に示す。 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 raising device was used. At this time, the CO 2 concentration of the exhaust gas from the quartz tube was measured using a mass spectrometer, and the combustion temperature of the particulate was determined from the peak of the CO 2 concentration. The results are shown in FIG. Moreover, the pressure loss of the oxidation catalyst device 1 for exhaust gas purification was determined by measuring the pressure difference between the supply port and the discharge port of the quartz tube. The results are shown in FIG.
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、透過式電子顕微鏡を用いて断面画像を撮影し、多孔質触媒層３の厚さを計測した。図４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）から多孔質触媒層３の厚さは７０〜１００μｍであると計測された。 Next, a cross-sectional image was taken using a transmission electron microscope for the first cubic oxidation catalyst device 1 for exhaust gas purification, and the thickness of the porous catalyst layer 3 was measured. FIG. 4 shows a cross-sectional image of the oxidation catalyst device 1 for exhaust gas purification. From FIG.4 (b), the thickness of the porous catalyst layer 3 was measured to be 70-100 micrometers.
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３の気孔の直径及び多孔質触媒層２の細孔の直径と、多孔質フィルタ基材２及び多孔質触媒層３を合わせた全体の気孔率とを計測した。結果を図５及び図６に示す。図５から細孔の直径は０．０２〜５μｍの範囲であると計測された。図６に示すように多孔質フィルタ基材２及び多孔質触媒層３を合わせた全体の気孔率は５０．１体積％であると計測された。 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 3 and the pore diameter of the porous catalyst layer 2 are: The total porosity of the porous filter substrate 2 and the porous catalyst layer 3 was measured. The results are shown in FIGS. From FIG. 5, the diameter of the pore was measured to be in the range of 0.02 to 5 μm. As shown in FIG. 6, the total porosity of the porous filter substrate 2 and the porous catalyst layer 3 was measured to be 50.1% by volume.
次に、参考例として、前記ＳｉＣ多孔質体に多孔質触媒層を形成しない排ガス浄化用酸化触媒装置を用いた以外は、実施例１と全く同一にして、パティキュレートの燃焼温度を求めた。結果を図２に示す。 Next, as a reference example, the combustion temperature of the particulates was determined in exactly the same manner as in Example 1 except that an exhaust gas purification oxidation catalyst device in which no porous catalyst layer was formed on the SiC porous body was used. The results are shown in FIG.
本実施例では、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、０．９５：０．０５：０．９５：０．０５：３：４０のモル比となるように混合した点を除いて実施例１と全く同一にして、複合金属酸化物Ｙ０．９５Ａｇ０．０５Ｍｎ０．９５Ｒｕ０．０５Ｏ３からなる多孔質触媒層３を有する排ガス浄化用酸化触媒装置１を製造した。 In this example, yttrium nitrate, silver nitrate, manganese nitrate, ruthenium nitrate, citric acid, and water are in a molar ratio of 0.95: 0.05: 0.95: 0.05: 3: 40. The porous catalyst layer 3 is made of the composite metal oxide Y 0.95 Ag 0.05 Mn 0.95 Ru 0.05 O 3 in exactly the same manner as in Example 1 except that the mixing is performed. An oxidation catalyst device 1 for exhaust gas purification was produced.
次に、本実施例で得られた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、パティキュレートの燃焼温度と排ガス浄化用酸化触媒装置１の圧力損失とを求めた。結果を図２及び図３に示す。 Next, the exhaust gas purification oxidation catalyst device 1 obtained in this example was exactly the same as in Example 1, and the combustion temperature of the particulates and the pressure loss of the exhaust gas purification oxidation catalyst device 1 were determined. The results are shown in FIGS.
次に、本実施例で得られた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、多孔質触媒層３の厚さを計測した。図７に排ガス浄化用酸化触媒装置１の断面画像を示す。図７（ｂ）から多孔質触媒層３の厚さは８０〜１２０μｍであると計測された。 Next, regarding the oxidation catalyst device 1 for exhaust gas purification obtained in this example, a cross-sectional image was taken in exactly the same manner as in Example 1, and the thickness of the porous catalyst layer 3 was measured. FIG. 7 shows a cross-sectional image of the oxidation catalyst device 1 for exhaust gas purification. From FIG.7 (b), the thickness of the porous catalyst layer 3 was measured to be 80-120 micrometers.
次に、本実施例で得られた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３の気孔の直径及び多孔質触媒層２の細孔の直径と、多孔質フィルタ基材２及び多孔質触媒層３を合わせた全体の気孔率とを計測した。結果を図８及び図６に示す。図８から細孔の直径は０．０２〜５μｍの範囲であると計測された。図６に示すように多孔質フィルタ基材２及び多孔質触媒層３を合わせた全体の気孔率は５４．３体積％であると計測された。 Next, regarding the oxidation catalyst device 1 for exhaust gas purification obtained in this example, exactly the same as in Example 1, the pore diameter of the porous filter substrate 3 and the pore diameter of the porous catalyst layer 2 The total porosity of the porous filter substrate 2 and the porous catalyst layer 3 was measured. The results are shown in FIGS. From FIG. 8, the diameter of the pore was measured to be in the range of 0.02 to 5 μm. As shown in FIG. 6, the total porosity of the porous filter substrate 2 and the porous catalyst layer 3 was measured to be 54.3% by volume.
本実施例では、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、０．９５：０．０５：０．９５：０．０５：１２：４０のモル比となるように混合した点を除いて実施例１と全く同一にして、複合金属酸化物Ｙ０．９５Ａｇ０．０５Ｍｎ０．９５Ｒｕ０．０５Ｏ３からなる多孔質触媒層３を有する排ガス浄化用酸化触媒装置１を製造した。 In this example, yttrium nitrate, silver nitrate, manganese nitrate, ruthenium nitrate, citric acid, and water are in a molar ratio of 0.95: 0.05: 0.95: 0.05: 12: 40. The porous catalyst layer 3 is made of the composite metal oxide Y 0.95 Ag 0.05 Mn 0.95 Ru 0.05 O 3 in exactly the same manner as in Example 1 except that the mixing is performed. An oxidation catalyst device 1 for exhaust gas purification was produced.
次に、本実施例で得られた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、パティキュレートの燃焼温度と排ガス浄化用酸化触媒装置１の圧力損失とを求めた。結果を図２及び図３に示す。 Next, the exhaust gas purification oxidation catalyst device 1 obtained in this example was exactly the same as in Example 1, and the combustion temperature of the particulates and the pressure loss of the exhaust gas purification oxidation catalyst device 1 were determined. The results are shown in FIGS.
次に、本実施例で得られた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、多孔質触媒層３の厚さを計測した。図９に排ガス浄化用酸化触媒装置１の断面画像を示す。図９（ｂ）から多孔質触媒層３の厚さは１０〜３０μｍであると計測された。 Next, regarding the oxidation catalyst device 1 for exhaust gas purification obtained in this example, a cross-sectional image was taken in exactly the same manner as in Example 1, and the thickness of the porous catalyst layer 3 was measured. FIG. 9 shows a cross-sectional image of the oxidation catalyst device 1 for exhaust gas purification. From FIG. 9B, the thickness of the porous catalyst layer 3 was measured to be 10 to 30 μm.
次に、本実施例で得られた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３の気孔の直径及び多孔質触媒層２の細孔の直径と、多孔質フィルタ基材２及び多孔質触媒層３を合わせた全体の気孔率とを計測した。結果を図１０及び図６に示す。図１０から細孔の直径は０．０２〜５μｍの範囲であると計測された。図６に示すように多孔質フィルタ基材２及び多孔質触媒層３を合わせた全体の気孔率は５５．６体積％であると計測された。 Next, regarding the oxidation catalyst device 1 for exhaust gas purification obtained in this example, exactly the same as in Example 1, the pore diameter of the porous filter substrate 3 and the pore diameter of the porous catalyst layer 2 The total porosity of the porous filter substrate 2 and the porous catalyst layer 3 was measured. The results are shown in FIGS. From FIG. 10, the diameter of the pore was measured to be in the range of 0.02 to 5 μm. As shown in FIG. 6, the total porosity of the porous filter substrate 2 and the porous catalyst layer 3 was measured to be 55.6% by volume.
本実施例では、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、０．９５：０．０５：０．９５：０．０５：１８：４０のモル比となるように混合した点を除いて実施例１と全く同一にして、複合金属酸化物Ｙ０．９５Ａｇ０．０５Ｍｎ０．９５Ｒｕ０．０５Ｏ３からなる多孔質触媒層３を有する排ガス浄化用酸化触媒装置１を製造した。 In this example, yttrium nitrate, silver nitrate, manganese nitrate, ruthenium nitrate, citric acid, and water are in a molar ratio of 0.95: 0.05: 0.95: 0.05: 18: 40. The porous catalyst layer 3 is made of the composite metal oxide Y 0.95 Ag 0.05 Mn 0.95 Ru 0.05 O 3 in exactly the same manner as in Example 1 except that the mixing is performed. An oxidation catalyst device 1 for exhaust gas purification was produced.
次に、本実施例で得られた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、パティキュレートの燃焼温度と排ガス浄化用酸化触媒装置１の圧力損失とを求めた。結果を図２及び図３に示す。 Next, the exhaust gas purification oxidation catalyst device 1 obtained in this example was exactly the same as in Example 1, and the combustion temperature of the particulates and the pressure loss of the exhaust gas purification oxidation catalyst device 1 were determined. The results are shown in FIGS.
次に、本実施例で得られた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、多孔質触媒層３の厚さを計測した。図１１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）から多孔質触媒層３の厚さは１０〜３０μｍであると計測された。 Next, regarding the oxidation catalyst device 1 for exhaust gas purification obtained in this example, a cross-sectional image was taken in exactly the same manner as in Example 1, and the thickness of the porous catalyst layer 3 was measured. FIG. 11 shows a cross-sectional image of the oxidation catalyst device 1 for exhaust gas purification. The thickness of the porous catalyst layer 3 was measured to be 10 to 30 μm from FIG.
次に、本実施例で得られた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３の気孔の直径及び多孔質触媒層２の細孔の直径と、多孔質フィルタ基材２及び多孔質触媒層３を合わせた全体の気孔率とを計測した。結果を図１２及び図６に示す。図１２から細孔の直径は０．０２〜５μｍの範囲であると計測された。図６に示すように多孔質フィルタ基材２及び多孔質触媒層３を合わせた全体の気孔率は５０．８体積％であると計測された。
〔比較例１〕
本比較例では、クエン酸に代えてリンゴ酸を用いた点を除いて実施例１と全く同一にして、複合金属酸化物Ｙ０．９５Ａｇ０．０５Ｍｎ０．９５Ｒｕ０．０５Ｏ３からなる多孔質触媒層３を有する排ガス浄化用酸化触媒装置１を製造した。
Next, regarding the oxidation catalyst device 1 for exhaust gas purification obtained in this example, exactly the same as in Example 1, the pore diameter of the porous filter substrate 3 and the pore diameter of the porous catalyst layer 2 The total porosity of the porous filter substrate 2 and the porous catalyst layer 3 was measured. The results are shown in FIGS. From FIG. 12, the diameter of the pore was measured to be in the range of 0.02 to 5 μm. As shown in FIG. 6, the total porosity of the porous filter substrate 2 and the porous catalyst layer 3 was measured to be 50.8% by volume.
[Comparative Example 1]
In this comparative example, the composite metal oxide Y 0.95 Ag 0.05 Mn 0.95 Ru 0.05 O 3 was made exactly the same as Example 1 except that malic acid was used instead of citric acid. An exhaust gas purification oxidation catalyst device 1 having a porous catalyst layer 3 made of
次に、本比較例で得られた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、パティキュレートの燃焼温度と排ガス浄化用酸化触媒装置１の圧力損失とを求めた。結果を図２及び図３に示す。 Next, the exhaust gas purification oxidation catalyst device 1 obtained in this comparative example was exactly the same as in Example 1, and the combustion temperature of the particulates and the pressure loss of the exhaust gas purification oxidation catalyst device 1 were determined. The results are shown in FIGS.
次に、本比較例で得られた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、多孔質触媒層３の厚さを計測した。図１３に排ガス浄化用酸化触媒装置１の断面画像を示す。図１３（ｂ）から多孔質触媒層３の厚さは１μｍ未満であると計測された。 Next, regarding the oxidation catalyst device 1 for exhaust gas purification obtained in this comparative example, a cross-sectional image was taken in the same manner as in Example 1, and the thickness of the porous catalyst layer 3 was measured. FIG. 13 shows a cross-sectional image of the oxidation catalyst device 1 for exhaust gas purification. From FIG. 13B, the thickness of the porous catalyst layer 3 was measured to be less than 1 μm.
次に、本比較例で得られた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３の気孔の直径及び多孔質触媒層２の細孔の直径と、多孔質フィルタ基材２及び多孔質触媒層３を合わせた全体の気孔率とを計測した。結果を図５，８，１０，１２に示す。図５から細孔の直径は０．０５〜１０μｍの範囲であると計測された。図６に示すように多孔質フィルタ基材２及び多孔質触媒層３を合わせた全体の気孔率は４７．４体積％であると計測された。 Next, regarding the oxidation catalyst device 1 for exhaust gas purification obtained in the present comparative example, the pore diameter of the porous filter substrate 3 and the pore diameter of the porous catalyst layer 2 were exactly the same as in Example 1. The total porosity of the porous filter substrate 2 and the porous catalyst layer 3 was measured. The results are shown in FIGS. From FIG. 5, the diameter of the pore was measured to be in the range of 0.05 to 10 μm. As shown in FIG. 6, the total porosity of the porous filter substrate 2 and the porous catalyst layer 3 was measured to be 47.4% by volume.
図２から、比較例の製造方法によりリンゴ酸を用いて形成された排ガス浄化用酸化触媒装置は、多孔質触媒層が形成されていない排ガス浄化用酸化触媒装置（参考例）と比較して、パティキュレートを低温で酸化（燃焼）できることが明らかである。また、実施例１〜４の製造方法によりクエン酸を用いて形成された排ガス浄化用酸化触媒装置１によれば、比較例の製造方法によりリンゴ酸を用いて形成された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さらに低温で酸化（燃焼）できることが明らかである。 From FIG. 2, the oxidation catalyst device for exhaust gas purification formed using malic acid by the production method of the comparative example is compared with the oxidation catalyst device for exhaust gas purification (reference example) in which the porous catalyst layer is not formed. It is clear that the particulates can be oxidized (burned) at low temperatures. Moreover, according to the oxidation catalyst apparatus 1 for exhaust gas purification formed using citric acid by the manufacturing method of Examples 1-4, the oxidation catalyst apparatus for exhaust gas purification formed using malic acid by the manufacturing method of the comparative example It is clear that the particulates can be oxidized (burned) at a lower temperature as compared with.
これは、図５，８，１０，１２から明らかであるように、比較例の製造方法によりリンゴ酸を用いて形成された排ガス浄化用酸化触媒装置は多孔質触媒層の細孔の直径が０．０５〜１０μｍの範囲であるが、実施例１〜４の製造方法によりクエン酸を用いて形成された排ガス浄化用酸化触媒装置１は多孔質触媒層３の細孔の直径が０．０２〜５μｍの範囲であって、比較例の製造方法によりリンゴ酸を用いて形成された排ガス浄化用酸化触媒装置の前記細孔の直径よりも全体的に小さいためであると考えられる。 As is apparent from FIGS. 5, 8, 10, and 12, the oxidation catalyst device for exhaust gas purification formed using malic acid by the manufacturing method of the comparative example has a pore diameter of 0 in the porous catalyst layer. The oxidation catalyst device 1 for exhaust gas purification formed using citric acid by the production method of Examples 1 to 4 has a pore diameter of 0.02 to 0.02 in the range of 0.05 to 10 μm. This is considered to be because it is in the range of 5 μm and is generally smaller than the diameter of the pores of the oxidation catalyst device for purifying exhaust gas formed using malic acid by the production method of the comparative example.
また、図３から、実施例１〜４の製造方法によりクエン酸を用いて形成された排ガス浄化用酸化触媒装置１によれば、比較例の製造方法によりリンゴ酸を用いて形成された排ガス浄化用酸化触媒装置と比較して、０〜５００℃の範囲の温度において圧力損失がほぼ同等であり実用上問題ないことが明らかである。 Also, from FIG. 3, according to the oxidation catalyst device 1 for exhaust gas purification formed using citric acid by the production method of Examples 1 to 4, the exhaust gas purification formed using malic acid by the production method of the comparative example It is clear that the pressure loss is almost the same at a temperature in the range of 0 to 500 ° C. as compared with the oxidation catalyst device for use, and there is no practical problem.
１…排ガス浄化用酸化触媒装置、 ２…多孔質フィルタ基材、 ３…多孔質触媒層、 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。 DESCRIPTION OF SYMBOLS 1 ... Oxidation catalyst apparatus for exhaust gas purification, 2 ... Porous filter base material, 3 ... Porous 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.
Claims (5)
該複合金属酸化物を構成する複数の金属の化合物とクエン酸と水とを焼成して焼成物を得る工程と、
得られた該焼成物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工程と、
該スラリーを多孔質フィルタ基材に塗布する工程と、
該スラリーが塗布された該多孔質フィルタ基材を焼成して、該多孔質フィルタ基材に担持された該複合金属酸化物からなる多孔質触媒層を形成する工程とを備え、
該複数の金属の化合物は、イットリウム化合物と、マンガン化合物と、銀化合物と、ルテニウム化合物とからなることを特徴とする排ガス浄化用酸化触媒装置の製造方法。 A method for producing an oxidation catalyst device for exhaust gas purification that oxidizes and purifies particulates in exhaust gas of an internal combustion engine using a catalyst made of a composite metal oxide,
A step of firing a plurality of metal compounds constituting the composite metal oxide, citric acid and water to obtain a fired product;
A step of mixing the obtained fired product, water and a binder and crushing to prepare a slurry;
Applying the slurry to a porous filter substrate;
Firing the porous filter substrate coated with the slurry, and forming a porous catalyst layer made of the composite metal oxide supported on the porous filter substrate ,
The method for producing an oxidation catalyst device for exhaust gas purification, wherein the plurality of metal compounds comprise an yttrium compound, a manganese compound, a silver compound, and a ruthenium compound .
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