JP2002331241A - Exhaust gas cleaning catalyst and exhaust gas cleaning material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an exhaust gas cleaning catalyst having high catalytic activity in the combustion of particulates, capable of sufficiently developing respective catalytic characteristics, capable of sufficiently removing particulates at a temperature near to the temperature of exhaust gas by combustion and having high exhaust gas cleaning efficiency, and an exhaust gas cleaning material capable of burning and removing particulates with extremely high efficiency and extremely excellent in durability and economical efficiency. SOLUTION: The exhaust gas cleaning catalyst contains a first catalyst, which has an inorganic oxide having heat resistance and the transition metal oxide catalyst layer supported on the surface of the inorganic oxide, and a second catalyst having at least one kind of an alkali metal sulfate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an exhaust gas for purifying an exhaust gas by burning particulates (solid carbon fine particles, liquid or solid high molecular weight hydrocarbon fine particles) contained in exhaust gas discharged from a diesel engine. It relates to a purification catalyst and an exhaust gas purification material.

[0002]

2. Description of the Related Art In recent years, particulates discharged from diesel engines have a particle diameter of almost 1 micron or less, are easily suspended in the air, are easily taken into the human body by respiration, and include benzopyrene. It has become clear that carcinogens such as carcinogens are contained, and the effect on the human body has become a serious problem.
For this reason, the regulation of particulate emissions discharged from diesel engines has been increasingly tightened, and accordingly, there has been a long-awaited demand for exhaust gas purifying catalysts and exhaust gas purifying materials capable of efficiently removing particulates.

Conventionally, as one of the methods for removing particulates from exhaust gas, particulates in exhaust gas have been collected using an exhaust gas purifying material having a heat-resistant three-dimensional structure, and the back pressure has been increased. After that, there is a method in which the exhaust gas purifier is heated by a heating means such as a burner or an electric heater, and the deposited particulates are burned, converted into carbon dioxide gas and released to the outside.

However, the above method has a problem that the burning temperature of the particulates is high, and a large amount of energy is required to burn and remove the collected particulates and regenerate the filter. Was.
Further, there is a problem that the filter is melted or cracked due to the combustion in a high temperature range and the heat of reaction. Furthermore,
Since a special device is required, there has been a problem that the size and cost of the purification device are increased.

On the other hand, there is a method in which fine particles are catalyzed to cause a combustion reaction using a catalyst, and combustion regeneration is performed at a temperature of the exhaust gas in the exhaust gas without using a heating means such as a heater.

As an exhaust gas purifying material carrying a catalyst, there is a material in which an exhaust gas purifying catalyst made of a metal oxide or the like is carried on a heat-resistant three-dimensional structure, and the particulates collected here are exhaust gas purifying materials. By the catalytic action of the catalyst for use, it can be burned at a lower temperature.

[0007] If the particulates can be burned at the temperature of the exhaust gas using the exhaust gas purifying material carrying such an exhaust gas purifying catalyst, there is no need to arrange a heating means in the exhaust gas purifying apparatus. Can be simplified.

However, at present, it is difficult for exhaust gas purifying materials carrying exhaust gas purifying catalysts to sufficiently burn particulates at the exhaust gas temperature, and it is essential to use them together with heating means. Therefore, development of an exhaust gas purifying catalyst and an exhaust gas purifying material supporting an exhaust gas purifying catalyst having a high catalytic activity capable of burning particulates at lower temperatures is desired.

It has been known that a catalyst using a metal oxide such as copper or vanadium has a relatively high activity as an exhaust gas purifying catalyst.

For example, Japanese Patent Application Laid-Open No. 58-143840 (hereinafter referred to as “A”) discloses “at least one selected from copper and its compounds, and at least one selected from metals and compounds that can assume a plurality of oxidation states. A particulate purification catalyst comprising a combination of at least one of the methods described above.

Japanese Patent Application Laid-Open No. 58-174236 (hereinafter referred to as
B) discloses a "catalyst for purifying particulates in exhaust gas comprising at least one selected from vanadium and a vanadium compound."

Japanese Patent Publication No. 4-42063 (hereinafter referred to as "C") discloses a catalyst for purifying exhaust gas obtained by adding an alkali metal oxide and a noble metal to a metal oxide such as copper, manganese and molybdenum, and a method for producing the same. Is disclosed.

[0013]

However, the above-mentioned conventional exhaust gas purifying catalysts and exhaust gas purifying materials have the following problems. (1) In the exhaust gas purifying catalysts described in A and B, the catalytic activity of the exhaust gas purifying catalyst is not high enough to sufficiently burn the particulates at a low exhaust gas temperature, so that the exhaust gas purifying catalyst is trapped in the exhaust gas purifying material. The burned particulates cannot be burned at the temperature of the exhaust gas, and the combined use with heating means is indispensable. (2) The exhaust gas purifying catalyst described in the publication No. C uses an alkali metal oxide in the structure of the exhaust gas purifying catalyst, but the alkali metal oxide has poor heat resistance and is scattered by heat of the exhaust gas. There was a problem that a reaction with another catalyst component occurred. (3) The catalyst for purifying exhaust gas described in the publication No. C has a problem that it is poisoned by sulfur oxides contained in the exhaust gas and the catalytic activity is reduced.

The present invention solves the above-mentioned conventional problems, has a high catalytic activity in particulate combustion, can sufficiently exhibit the respective catalytic characteristics, and sufficiently enhances particulates at a temperature close to the exhaust gas temperature. It is an object of the present invention to provide an exhaust gas purifying catalyst capable of burning and removing and having a high exhaust gas purification rate, and to provide an exhaust gas purifying material which is capable of burning and removing particulates with extremely high efficiency and is extremely excellent in durability and economy. .

[0015]

In order to solve the above problems, an exhaust gas purifying catalyst of the present invention comprises an inorganic oxide having heat resistance and an oxide catalyst layer of a transition metal supported on the surface of the inorganic oxide. A first catalyst having a heat-resistant inorganic oxide, a third catalyst having a noble metal catalyst layer supported on the surface of the inorganic oxide, and a second catalyst having at least one alkali metal sulfate. And a catalyst.

[0016] Thus, by separately providing the catalysts having different functions, it is possible to sufficiently bring out the different catalyst characteristics, and it is possible to suppress the deterioration due to the reaction between the catalysts. Deterioration of the activity of the catalyst can be prevented, and a highly active exhaust gas purifying catalyst can be obtained.

Further, by forming a catalyst component on the surface of the heat-resistant inorganic oxide, the catalyst surface area is increased, and as a result, the contact points with the particulates in the diesel exhaust gas are increased. Can be obtained.

In order to solve the above problems, the exhaust gas purifying material of the present invention comprises a three-dimensional structure having heat resistance and a layer of the exhaust gas purifying catalyst according to claim 2 formed on the three-dimensional structure. And a configuration having:

Thus, by separately providing the catalysts having different functions, the reaction between the heat-resistant three-dimensional structure and the catalyst component can be suppressed, and a highly active exhaust gas purifying material can be obtained.

Further, the required amount of the noble metal can be reduced, the cost can be reduced, and an exhaust gas purifying material excellent in economy can be obtained.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The exhaust gas purifying catalyst according to claim 1 of the present invention comprises a first catalyst having an inorganic oxide having heat resistance and an oxide catalyst layer of a transition metal supported on the surface of the inorganic oxide. And a second catalyst having at least one alkali metal sulfate.

With this configuration, the following operation can be obtained. (1) By having different catalysts with different functions,
It is possible to sufficiently bring out different catalyst characteristics from each other, and it is possible to suppress the deterioration due to the reaction between the catalysts. As a result, it is possible to prevent the deterioration of the activity of the catalyst,
A highly active exhaust gas purifying catalyst can be obtained. (2) By forming the catalyst component on the surface of the inorganic oxide having heat resistance, the catalyst surface area is increased, and as a result, the contact points with the particulates in diesel exhaust gas are increased,
A highly active exhaust gas purifying catalyst can be obtained. (3) By forming a catalyst component on the surface of the inorganic oxide having heat resistance, the required amount of the catalyst can be reduced, and an exhaust gas purifying catalyst can be obtained at low cost, which is excellent in economy. (4) An inorganic oxide-supported transition metal oxide catalyst having heat resistance and an alkali metal sulfate catalyst are separately provided to increase the catalyst surface area, thereby increasing the contact points with particulates in diesel exhaust gas. To increase the catalytic activity. (5) By individually providing a transition metal oxide catalyst supporting an inorganic oxide having heat resistance and a catalyst of an alkali metal sulfate, the necessary and sufficient amounts of the transition metal oxide and the alkali metal sulfate can be reduced. It is possible to obtain an exhaust gas purifying catalyst at low cost, and it is economical. (6) By individually providing a transition metal oxide catalyst supporting an inorganic oxide having heat resistance and a catalyst of an alkali metal sulfate, a reaction between the catalysts due to heat as seen during particulate combustion or the like can be prevented. Thus, different catalyst characteristics can be sufficiently exhibited, and the catalyst activity can be prevented from deteriorating to enhance the durability.

Here, the inorganic oxide having heat resistance as a carrier is Ta ₂ O ₅ , Nb ₂ O ₅ , WO ₃ , SnO ₂ , Si.
O ₂ , TiO ₂ , Al ₂ O ₃ , ZrO _2, etc.
One or more of them may be used.

As transition metals, Cu, Mn, Co, V,
Mo and W may be mentioned, and any one or more of them may be used.

As the alkali metal, Li, Na, K, R
b and Cs, and any one or more of them may be used.

The method of supporting the transition metal oxide catalyst layer on the surface of the inorganic oxide having heat resistance is not particularly limited, and any method can be used. For example, an evaporation to dryness method is preferable. .

The exhaust gas purifying catalyst according to claim 2 of the present invention comprises a first catalyst having an inorganic oxide having heat resistance and an oxide catalyst layer of a transition metal supported on a surface of the inorganic oxide; A configuration including a heat-resistant inorganic oxide, a third catalyst having a noble metal catalyst layer supported on the surface of the inorganic oxide, and a second catalyst having at least one alkali metal sulfate. have.

With this configuration, the following operation can be obtained. (1) By adding noble metals, harmful components such as carbon monoxide, nitrogen oxides, and hydrocarbons can be reduced,
Air pollution can be prevented. (2) By having different catalysts with different functions,
The required and sufficient amount of the noble metal can be reduced, and an exhaust gas purifying catalyst can be obtained at low cost, which is economical. (3) The catalyst surface area can be increased by forming the catalyst component on the surface of the inorganic oxide having heat resistance.
As a result, the number of contact points with the particulates in the diesel exhaust gas increases, and a highly active exhaust gas purifying catalyst can be obtained. (4) By forming the catalyst component on the surface of the inorganic oxide having heat resistance, the required amount of the catalyst can be reduced, and a low-cost exhaust gas purification catalyst having excellent purification performance can be obtained. (5) By having different catalysts with different functions,
It is possible to sufficiently bring out different catalyst characteristics from each other, and it is possible to suppress the deterioration due to the reaction between the catalysts. As a result, it is possible to prevent the deterioration of the activity of the catalyst,
A highly active exhaust gas purifying catalyst can be obtained. (6) To individually provide a heat-resistant inorganic oxide-supported transition metal oxide catalyst, a heat-resistant inorganic oxide-supported noble metal catalyst layer, and an alkali metal sulfate catalyst to increase the catalyst surface area. Thereby, the contact point with the particulates in the diesel exhaust gas can be increased and the catalytic activity can be increased. (7) A transition metal oxide catalyst supporting an inorganic oxide having heat resistance, a noble metal catalyst layer supporting an inorganic oxide having heat resistance, and a catalyst of an alkali metal sulfate are separately provided, whereby a transition metal oxidation catalyst is provided. It is possible to reduce the necessary and sufficient amounts of the substance, the noble metal catalyst layer and the alkali metal sulfate, and it is possible to obtain an exhaust gas purifying catalyst at low cost and to be excellent in economic efficiency. (8) Particulate combustion by separately providing a heat-resistant inorganic oxide-supported transition metal oxide catalyst, a heat-resistant inorganic oxide-supported noble metal catalyst layer, and an alkali metal sulfate catalyst The reaction between the catalysts due to heat, which is sometimes observed, can be prevented, and different catalyst characteristics can be sufficiently exhibited, and the catalyst activity can be prevented from deteriorating and durability can be increased.

Here, the inorganic oxide having heat resistance as a carrier is Ta ₂ O ₅ , Nb ₂ O ₅ , WO ₃ , SnO ₂ , Si.
O ₂ , TiO ₂ , Al ₂ O ₃ , ZrO _2, etc.
One or more of them may be used.

As transition metals, Cu, Mn, Co, V,
Mo and W may be mentioned, and any one or more of them may be used.

Examples of the noble metal include Pt, Pd, Rh, and Ru, and one or more of them may be used.

As the alkali metal, Li, Na, K, R
b and Cs, and any one or more of them may be used.

The method of supporting the transition metal oxide catalyst layer on the surface of the inorganic oxide having heat resistance is not particularly limited, and any method may be used. For example, an evaporation to dryness method is preferable. .

[0034] The exhaust gas purifying catalyst according to claim 3 of the present invention has a structure according to claim 2, wherein the noble metal contains Pt.

With this configuration, in addition to the function of claim 2,
The following effects are obtained. (1) Since the noble metal contains Pt, the SOF component other than the carbon component in the particulate by the noble metal catalyst can be burned and purified most efficiently and stably,
Extremely excellent exhaust gas purification capacity.

According to a fourth aspect of the present invention, in the exhaust gas purifying catalyst according to any one of the first to third aspects, the oxide of the transition metal is selected from Cu, Mn, Co, V, Mo, and W. It has a configuration containing at least one type of metal oxide.

With this configuration, the following operation is obtained in addition to the operation of any one of the first to third aspects. (1) The transition metal oxide is Cu, Mn, Co, V, M
Since it contains at least one metal oxide selected from o and W, it is possible to obtain an exhaust gas purifying catalyst having high catalytic activity when burning particulates.

According to a fifth aspect of the present invention, there is provided the exhaust gas purifying catalyst according to any one of the first to fourth aspects.
The oxide of u has at least one selected from CuO, Cu ₂ O, and Cu ₂ O ₃ .

According to this configuration, the following operation is obtained in addition to the operation of any one of the first to fourth aspects. (1) Since the oxide of Cu is at least one selected from CuO, Cu ₂ O, and Cu ₂ O ₃ , an exhaust gas purifying catalyst having high catalytic activity when burning particulates can be obtained.

According to a sixth aspect of the present invention, there is provided the exhaust gas purifying catalyst according to any one of the first to fifth aspects, wherein the oxide of the transition metal contains a composite metal oxide composed of Cu and V. have.

With this configuration, the following operation is obtained in addition to the operation of any one of the first to fifth aspects. (1) Since the oxide of the transition metal contains a composite metal oxide composed of Cu and V, the particulates can be efficiently burned and removed, and the catalytic activity can be enhanced. (2) Particulates can be removed by an oxidation reaction at a predetermined exhaust gas temperature.

According to a seventh aspect of the present invention, in the exhaust gas purifying catalyst according to any one of the first to sixth aspects, the composite metal oxide is Cu ₅ V ₂ O ₁₀ , CuV ₂ O ₆ , Cu _3. V ₂ O
_It has a configuration that is at least one selected from _eight .

With this configuration, the following operation is obtained in addition to the operation of any one of the first to sixth aspects. (1) a composite metal oxide _{Cu 5 V 2 O 10, CuV} 2 O 6, C
at least one selected from u ₃ V ₂ O ₈
An exhaust gas purifying catalyst having higher catalytic activity during particulate combustion can be obtained.

The exhaust gas purifying catalyst according to claim 8 of the present invention, in any one of claims 1 to 7, has a structure in which the alkali metal sulfate contains cesium sulfate.

With this configuration, the following operation can be obtained in addition to the operation of any one of the first to seventh aspects. (1) Since the alkali metal sulfate contains cesium sulfate, the catalytic activity is enhanced and the particulates can be efficiently burned, and the exhaust gas purifying ability is extremely excellent.

A ninth aspect of the present invention provides the exhaust gas purifying catalyst according to any one of the first to eighth aspects, wherein the sulfate of the alkali metal contains a mixture of cesium sulfate and potassium sulfate. Have.

According to this configuration, the following operation is obtained in addition to the operation of any one of the first to eighth aspects. (1) Since the alkali metal sulfate contains a mixture of cesium sulfate and potassium sulfate, it is possible to obtain an exhaust gas purifying catalyst having extremely high catalytic activity in burning particulates.

According to a tenth aspect of the present invention, in the exhaust gas purifying catalyst according to any one of the first to ninth aspects, the heat-resistant inorganic oxide is Ta ₂ O ₅ , Nb ₂ O ₅ , or WO _3. , S
It has a configuration containing at least one inorganic oxide selected from nO ₂ , SiO ₂ , TiO ₂ , Al ₂ O ₃ , and ZrO ₂ .

According to this configuration, the following operation is obtained in addition to the operation of any one of the first to ninth aspects. (1) Ta ₂ as a carrier for supporting a transition metal oxide
O ₅ , Nb ₂ O ₅ , WO ₃ , SnO ₂ , SiO ₂ , TiO ₂ ,
Since it contains at least one inorganic oxide selected from Al ₂ O ₃ and ZrO ₂ , the surface area of the transition metal oxide catalyst is increased, and as a result, the number of contacts with the particulates is increased. Performance can be exhibited most efficiently and stably.

An exhaust gas purifying material according to an eleventh aspect of the present invention includes a three-dimensional structure having heat resistance, and a layer of the exhaust gas purifying catalyst according to the first aspect formed on the three-dimensional structure. , Is provided.

With this configuration, the following operations can be obtained. (1) By having different catalysts with different functions,
The reaction between the heat-resistant three-dimensional structure and the catalyst component is suppressed, and a highly active exhaust gas purifying material can be obtained. (2) By providing a heat-resistant inorganic oxide-supported transition metal oxide catalyst and an alkali metal sulfate catalyst individually, the reaction between the heat-resistant three-dimensional structure and the catalyst component is suppressed, The catalyst can be prevented from deteriorating and has excellent catalytic activity. (3) By having different catalysts with different functions,
A reaction between the three-dimensional structure having heat resistance and the catalyst component is suppressed, and a highly active exhaust gas purifying material can be obtained. (4) By having different catalysts with different functions,
It is possible to sufficiently bring out different catalyst characteristics from each other, and it is possible to suppress the deterioration due to the reaction between the catalysts. As a result, it is possible to prevent the deterioration of the activity of the catalyst,
A highly active exhaust gas purifying material can be obtained. (5) By forming the catalyst component on the surface of the inorganic oxide having heat resistance, the catalyst surface area is increased, and as a result, the contact points with the particulates in the diesel exhaust gas are increased,
A highly active exhaust gas purifying material can be obtained. (6) By forming the catalyst component on the surface of the inorganic oxide having heat resistance, the required amount of the catalyst can be reduced, the exhaust gas purifying material can be obtained at low cost, and the economy is excellent. (7) A transition metal oxide catalyst supporting an inorganic oxide having heat resistance and a catalyst of an alkali metal sulfate are individually provided to increase the catalyst surface area, thereby increasing the contact points with particulates in diesel exhaust gas. To increase the catalytic activity. (8) By providing a heat-resistant inorganic oxide-supported transition metal oxide catalyst and an alkali metal sulfate catalyst individually, the necessary and sufficient amounts of the transition metal oxide and the alkali metal sulfate can be reduced. It is possible to obtain an exhaust gas purifying material at low cost, and it is economical. (9) By providing a heat-resistant inorganic oxide-supported transition metal oxide catalyst and an alkali metal sulfate catalyst individually, the reaction between the catalysts due to heat such as that observed during particulate combustion can be prevented. Thus, different catalyst characteristics can be sufficiently exhibited, and the catalyst activity can be prevented from deteriorating to enhance the durability.

Here, as the three-dimensional structure having heat resistance, a material such as metal or ceramic is used.

As the metal, metals such as iron, copper, nickel and chromium can be used alone or in combination of two or more kinds.

As the material of the ceramic, cordierite, aluminum titanate, mullite, α-alumina, zirconia, titania, silicon carbide, silica, silica-alumina, alumina-zirconia and the like can be used.

The heat-resistant three-dimensional structure on which the layer of the exhaust gas purifying catalyst is formed is a wall-through type ceramic honeycomb, a ceramic foam, a wall-through type metal honeycomb, a metal foam, A metal mesh or the like is used, but a wall-through type ceramic honeycomb is preferably used.

The method for forming the exhaust gas purifying catalyst according to claim 1 on the three-dimensional structure having heat resistance is not particularly limited, and any method can be used. There are methods such as methods.

An exhaust gas purifying material according to a twelfth aspect of the present invention includes a three-dimensional structure having heat resistance, and a layer of the exhaust gas purifying catalyst according to the second aspect formed on the three-dimensional structure. , Is provided.

With this configuration, the following operation can be obtained. (1) By providing a heat-resistant inorganic oxide-supported transition metal oxide catalyst, a heat-resistant inorganic oxide-supported noble metal catalyst, and an alkali metal sulfate catalyst individually, The reaction between the three-dimensional structure and the catalyst component can be suppressed, the catalyst activity can be increased, and the catalyst can be prevented from being deteriorated, resulting in excellent durability. (2) A transition metal oxide catalyst having a heat-resistant inorganic oxide supported thereon, a noble metal catalyst layer having a heat-resistant inorganic oxide supported thereon, and a catalyst of an alkali metal sulfate are individually provided to provide a transition metal oxidation catalyst. It is possible to reduce the necessary and sufficient amount of the product and the alkali metal sulfate, and to obtain an exhaust gas purifying material at low cost, which is excellent in economy. (3) The required amount of expensive noble metal can be reduced, and a low-cost realized exhaust gas purifying material with excellent economy can be obtained. (4) By having different catalysts with different functions,
A reaction between the three-dimensional structure having heat resistance and the catalyst component is suppressed, and a highly active exhaust gas purifying material can be obtained. (5) By having different catalysts with different functions,
It is possible to sufficiently bring out different catalyst characteristics from each other, and it is possible to suppress the deterioration due to the reaction between the catalysts. As a result, it is possible to prevent the deterioration of the activity of the catalyst,
A highly active exhaust gas purifying material can be obtained. (6) By forming the catalyst component on the surface of the inorganic oxide having heat resistance, the catalyst surface area is increased, and as a result, the contact points with the particulates in the diesel exhaust gas are increased,
A highly active exhaust gas purifying material can be obtained. (7) By forming the catalyst component on the surface of the inorganic oxide having heat resistance, the required amount of the catalyst can be reduced, the exhaust gas purifying material can be obtained at low cost, and the economy is excellent. (8) A transition metal oxide catalyst supporting an inorganic oxide having heat resistance, a noble metal catalyst layer supporting an inorganic oxide having heat resistance, and a catalyst of an alkali metal sulfate are individually provided to increase the catalyst surface area. Thereby, the contact point with the particulates in the diesel exhaust gas can be increased and the catalytic activity can be increased. (9) Particulate combustion by separately providing a heat-resistant inorganic oxide-supported transition metal oxide catalyst, a heat-resistant inorganic oxide-supported noble metal catalyst layer, and an alkali metal sulfate catalyst The reaction between the catalysts due to heat, which is sometimes observed, can be prevented, and different catalyst characteristics can be sufficiently exhibited, and the catalyst activity can be prevented from deteriorating and durability can be increased.

Here, as the three-dimensional structure having heat resistance, a material such as metal or ceramic is used.

As the metal, metals such as iron, copper, nickel, and chromium can be used alone or in combination of two or more kinds.

As the ceramic material, cordierite, aluminum titanate, mullite, α-alumina, zirconia, titania, silicon carbide, silica, silica-alumina, alumina-zirconia and the like can be used.

The heat-resistant three-dimensional structure on which the layer of the exhaust gas purifying catalyst is formed is a wall-through type ceramic honeycomb, a ceramic foam, a wall-through type metal honeycomb, a metal foam, A metal mesh or the like is used, but a wall-through type ceramic honeycomb is preferably used.

The method for forming the exhaust gas purifying catalyst according to claim 2 on the three-dimensional structure having heat resistance is not particularly limited, and any method can be used. There are methods such as methods.

According to a thirteenth aspect of the present invention, there is provided an exhaust gas purifying material comprising: a three-dimensional structure having heat resistance; and the third exhaust gas purifying catalyst according to the first aspect formed on the three-dimensional structure. It has a configuration including a first catalyst layer and the second catalyst layer formed on the upper surface of the layer.

With this configuration, the following operation is obtained. (1) By providing a heat-resistant inorganic oxide-supported transition metal oxide catalyst and an alkali metal sulfate catalyst individually, the reaction between the heat-resistant three-dimensional structure and the catalyst component is suppressed. In addition, the catalyst can be prevented from deteriorating and has excellent durability. (2) By separately disposing the catalysts having the respective functions, the surface area of the catalyst can be increased, the contact point with the particulates in the diesel exhaust gas can be increased, and the catalytic activity can be enhanced. (3) By having different catalysts with different functions,
The required and sufficient amount of each catalyst can be reduced, the exhaust gas purifying material can be manufactured at low cost, and the economy is excellent. (4) By having different catalysts with different functions,
It is possible to sufficiently bring out different catalyst characteristics from each other, and it is possible to suppress the deterioration due to the reaction between the catalysts. As a result, it is possible to prevent the deterioration of the activity of the catalyst,
A highly active exhaust gas purifying material can be obtained.

Here, as the three-dimensional structure having heat resistance, a material such as metal or ceramic is used.

As the metal, metals such as iron, copper, nickel, and chromium can be used alone or in combination of two or more kinds.

As the material of the ceramic, cordierite, aluminum titanate, mullite, α-alumina, zirconia, titania, silicon carbide, silica, silica-alumina, alumina-zirconia and the like can be used.

As the heat-resistant three-dimensional structure on which the first catalyst layer is formed, a wall-through type ceramic honeycomb, a ceramic foam, a flow-through type metal honeycomb, a metal foam, a metal mesh, or the like is used. However, a wall-through type ceramic honeycomb is preferably used.

The method for forming the catalyst is not particularly limited, and any method can be used. Examples thereof include an impregnation method and a wash coat method.

The exhaust gas purifying material according to claim 14 of the present invention is a heat-resistant three-dimensional structure, and the exhaust gas purifying catalyst according to claim 2 formed on the three-dimensional structure. It has a configuration including a layer composed of one catalyst and the third catalyst, and a layer of the second catalyst formed on the upper surface of the layer.

With this configuration, the following operation can be obtained. (1) By adding a noble metal, carbon monoxide, nitrogen oxides, hydrocarbons and the like in the exhaust gas coexisting with the particulates can be reduced, and pollution due to air pollution can be prevented. (2) A three-dimensional heat-resistant material is provided by individually providing a heat-resistant inorganic oxide-supported transition metal oxide catalyst, a heat-resistant inorganic oxide-supported noble metal catalyst, and an alkali metal sulfate catalyst. The reaction between the structure and the catalyst component is suppressed, and deterioration of the catalyst can be prevented, resulting in excellent durability. (3) By separately disposing the catalysts having the respective functions, the catalyst surface area can be increased, the contact point with the particulates in the diesel exhaust gas can be increased, and the catalytic activity can be enhanced. (4) By having different catalysts with different functions,
The required and sufficient amount of each catalyst can be reduced, the exhaust gas purifying material can be manufactured at low cost, and the economy is excellent. (5) By having different catalysts with different functions,
It is possible to sufficiently bring out different catalyst characteristics from each other, and it is possible to suppress the deterioration due to the reaction between the catalysts. As a result, it is possible to prevent the deterioration of the activity of the catalyst,
A highly active exhaust gas purifying material can be obtained.

Here, as the three-dimensional structure having heat resistance, a material such as metal or ceramic is used.

As the metal, metals such as iron, copper, nickel and chromium can be used alone or in combination of two or more kinds.

As the material of the ceramic, cordierite, aluminum titanate, mullite, α-alumina, zirconia, titania, silicon carbide, silica, silica-alumina, alumina-zirconia and the like can be used.

The heat-resistant three-dimensional structure on which the first catalyst layer and the third catalyst layer are formed includes wall-through type ceramic honeycombs, ceramic foams, flow-through type metal honeycombs, metal foams, and metal foams. A mesh or the like is used, but a wall-through type ceramic honeycomb is preferably used.

The method for forming the catalyst is not particularly limited, and any method can be used. Examples thereof include an impregnation method and a wash coat method.

According to a fifteenth aspect of the present invention, an exhaust gas purifying material comprises a three-dimensional structure having heat resistance, and the third exhaust gas purifying catalyst of the first aspect formed on the three-dimensional structure. The exhaust gas purifying catalyst according to claim 1, which is contained in the second catalyst layer and the first catalyst powder particles contained in the second catalyst layer. .

With this configuration, the following operation can be obtained. (1) By forming a layer of an alkali metal sulfate on the powder surface of a transition metal oxide catalyst supporting an inorganic oxide having heat resistance, a transition metal oxide or an alkali metal An ideal catalyst composition can be easily synthesized by preventing a change in the catalyst composition due to a reaction between a sulfate and a noble metal. (2) By separately providing a heat-resistant inorganic oxide-supported transition metal oxide catalyst and an alkali metal sulfate catalyst, the reaction between the heat-resistant three-dimensional structure and the catalyst component can be suppressed. In addition, the catalyst can be prevented from deteriorating and has excellent durability. (3) By separately disposing the catalysts having the respective functions, the catalyst surface area can be increased, the contact point with the particulates in the diesel exhaust gas can be increased, and the catalytic activity can be enhanced. (4) By having different catalysts with different functions,
The required and sufficient amount of each catalyst can be reduced, the exhaust gas purifying material can be manufactured at low cost, and the economy is excellent. (5) By having different catalysts with different functions,
It is possible to sufficiently bring out different catalyst characteristics from each other, and it is possible to suppress the deterioration due to the reaction between the catalysts. As a result, it is possible to prevent the deterioration of the activity of the catalyst,
A highly active exhaust gas purifying material can be obtained.

Here, as the three-dimensional structure having heat resistance, a material such as metal or ceramic is used.

As the metal, metal such as iron, copper, nickel, chromium, etc. can be used alone or in combination of two or more kinds.

As the material of the ceramic, cordierite, aluminum titanate, mullite, α-alumina, zirconia, titania, silicon carbide, silica, silica-alumina, alumina-zirconia and the like can be used.

As the heat-resistant three-dimensional structure on which the first catalyst layer is formed, a wall-through type ceramic honeycomb, a ceramic foam, a flow-through type metal honeycomb, a metal foam, a metal mesh, or the like is used. However, a wall-through type ceramic honeycomb is preferably used.

The method for forming the catalyst is not particularly limited, and any method can be used. Examples of the method include an impregnation method and a wash coat method.

The exhaust gas purifying material according to claim 16 of the present invention has a three-dimensional structure having heat resistance, and the exhaust gas purifying catalyst according to claim 1 formed on the three-dimensional structure. 2. The exhaust gas purifying catalyst according to claim 1, wherein the first catalyst layer is contained in a second catalyst layer and the second catalyst layer.
And the third catalyst powder particles.

With this configuration, the following operation is obtained. (1) By forming a layer of an alkali metal sulfate on the surface of a powder of a heat-resistant inorganic oxide-supported transition metal oxide catalyst and a heat-resistant inorganic oxide-supported noble metal catalyst, an ideal layer is formed. A catalyst composition can be synthesized, and a highly active exhaust gas purifying material can be obtained. (2) By adding a noble metal, carbon monoxide, nitrogen oxides, hydrocarbons and the like in the exhaust gas coexisting with the particulates can also be reduced, and pollution due to air pollution can be prevented. (3) A three-dimensional heat-resistant catalyst is provided by individually providing a heat-resistant inorganic oxide-supported transition metal oxide catalyst, a heat-resistant inorganic oxide-supported noble metal catalyst, and an alkali metal sulfate catalyst. The reaction between the structure and the catalyst component is suppressed, and deterioration of the catalyst can be prevented, resulting in excellent durability. (4) By separately disposing the catalysts having the respective functions, the surface area of the catalyst can be increased, the contact point with the particulates in the diesel exhaust gas can be increased, and the catalytic activity can be enhanced. (5) By having different catalysts with different functions,
The required and sufficient amount of each catalyst can be reduced, the exhaust gas purifying material can be manufactured at low cost, and the economy is excellent. (6) By separately presenting catalysts having different functions,
It is possible to sufficiently bring out different catalyst characteristics from each other, and it is possible to suppress the deterioration due to the reaction between the catalysts. As a result, it is possible to prevent the deterioration of the activity of the catalyst,
A highly active exhaust gas purifying material can be obtained.

Here, as the three-dimensional structure having heat resistance, a material such as metal or ceramic is used.

As the metal, metals such as iron, copper, nickel and chromium can be used alone or in combination of two or more kinds.

As the material of the ceramic, cordierite, aluminum titanate, mullite, α-alumina, zirconia, titania, silicon carbide, silica, silica-alumina, alumina-zirconia and the like can be used.

The heat-resistant three-dimensional structure on which the first catalyst layer and the third catalyst layer are formed is a wall-through type ceramic honeycomb, a ceramic foam, a flow-through type metal honeycomb, a metal foam, a metal foam, or the like. A mesh or the like is used, but a wall-through type ceramic honeycomb is preferably used.

The method for forming the catalyst is not particularly limited, and any method can be used. Examples of the method include an impregnation method and a wash coat method.

An exhaust gas purifying material according to a seventeenth aspect of the present invention has a structure according to any one of the twelfth, fourteenth, and sixteenth aspects, wherein the noble metal contains Pt.

According to this configuration, claims 12, 14, 16
The following operation is obtained in addition to the operation of any one of the above. (1) Since the noble metal contains Pt, the SOF component other than the carbon component in the particulate by the noble metal catalyst can be burned and purified most efficiently and stably,
Extremely excellent exhaust gas purification capacity.

An exhaust gas purifying material according to claim 18 of the present invention is the exhaust gas purifying material according to any one of claims 11 to 17, wherein the transition metal oxide is Cu, Mn, Co, V, Mo, W
It has a configuration containing at least one metal oxide selected from the group consisting of:

According to this configuration, the following operation is obtained in addition to the operation of any one of the eleventh to seventeenth aspects. (1) The transition metal oxide is Cu, Mn, Co, V, M
Since it contains at least one metal oxide selected from o and W, it is possible to obtain an exhaust gas purifying material having high catalytic activity when burning particulates.

According to a nineteenth aspect of the present invention, in the exhaust gas purifying material according to any one of the eleventh to eighteenth aspects, the oxide of Cu is selected from CuO, Cu ₂ O, and Cu ₂ O _3. It has at least one type of configuration.

With this configuration, the following operation can be obtained in addition to the operation of any one of the eleventh to eighteenth aspects. (1) The transition metal oxide is CuO, Cu ₂ O, Cu ₂ O ₃
Since it is at least one member selected from the group consisting of :, it is possible to obtain an exhaust gas purifying material having high catalytic activity when burning particulates.

The exhaust gas purifying material according to claim 20 of the present invention is the exhaust gas purifying material according to any one of claims 11 to 19, wherein the oxide of the transition metal contains a composite metal oxide composed of Cu and V. have.

With this configuration, the following operation is obtained in addition to the operation of any one of the eleventh to nineteenth aspects. (1) Since the oxide of the transition metal contains a composite metal oxide composed of Cu and V, the particulates can be efficiently burned and removed, and the catalytic activity can be enhanced. (2) Particulates can be removed by an oxidation reaction at a predetermined exhaust gas temperature.

An exhaust gas purifying material according to claim 21 of the present invention.
Is the preamble of any one of claims 11 to 20,
The composite metal oxide is Cu_FiveV_TwoO_Ten, CuV_TwoO₆, Cu_Three
V_TwoO ₈Having a configuration that is at least one selected from
ing.

With this configuration, the following operation can be obtained in addition to the operation of any one of the eleventh to twentieth aspects. (1) a composite metal oxide _{Cu 5 V 2 O 10, CuV} 2 O 6, C
at least one selected from u ₃ V ₂ O ₈
An exhaust gas purifying material having a higher catalytic activity when burning particulates can be obtained.

The exhaust gas purifying material according to claim 22 of the present invention, in any one of claims 11 to 21, has a structure in which the alkali metal sulfate contains cesium sulfate.

With this configuration, the following operation can be obtained in addition to the operation of any one of the eleventh to twenty-first aspects. (1) Since the alkali metal sulfate contains cesium sulfate, the catalytic activity is enhanced and the particulates can be efficiently burned, and the exhaust gas purifying ability is extremely excellent.

An exhaust gas purifying material according to claim 23 of the present invention is the exhaust gas purifying material according to any one of claims 11 to 22, wherein the alkali metal sulfate contains a mixture of cesium sulfate and potassium sulfate. Have.

According to this configuration, the following operation is obtained in addition to the operation of any one of the eleventh to twenty-second aspects. (1) Since the alkali metal sulfate contains a mixture of cesium sulfate and potassium sulfate, it is possible to obtain an exhaust gas purifying material having extremely high catalytic activity when burning particulates.

The exhaust gas purifying material according to claim 24 of the present invention is the exhaust gas purifying material according to any one of claims 11 to 23, wherein the heat-resistant inorganic oxide is Ta ₂ O ₅ , Nb ₂ O ₅ , WO _3. ,
It has a configuration containing at least one inorganic oxide selected from SnO ₂ , SiO ₂ , TiO ₂ , Al ₂ O ₃ , and ZrO ₂ .

According to this configuration, the following operation is obtained in addition to the operation of any one of claims 11 to 23. (1) Ta ₂ as a carrier for supporting a transition metal oxide
O ₅ , Nb ₂ O ₅ , WO ₃ , SnO ₂ , SiO ₂ , TiO ₂ ,
Since it contains at least one kind of inorganic oxide selected from Al ₂ O ₃ and ZrO ₂ , the surface area of the transition metal oxide catalyst is increased, and as a result, the number of contacts with the particulates is increased. Performance can be exhibited most efficiently and stably.

The exhaust gas purifying material according to claim 25 of the present invention is the exhaust gas purifying material according to any one of claims 11 to 24, wherein the heat-resistant three-dimensional structure is a wall-through type honeycomb filter or a flow filter. It has a configuration that is a through-type foam or a metal filter.

According to this configuration, the following operation is obtained in addition to the operation of any one of the eleventh to twenty-fourth aspects. (1) Since the tertiary structure having heat resistance is formed of a honeycomb filter or foam of a wall-through type, approximately 100% of the particulate components can be collected by the filter, and the collection efficiency can be improved. Can be maximized. (2) Since the three-dimensional structure is formed of a honeycomb filter, a foam or a metal film, the contact area between the exhaust gas purifying catalyst and the particulates increases,
Particulates can be burned and removed efficiently,
An exhaust gas purifying material having extremely excellent exhaust gas purifying ability can be obtained.

Here, the material of the honeycomb filter is as follows.
Although not particularly limited, metal, ceramic, or the like is used.

The foam may be in any shape, such as a foam filter having three-dimensionally continuous holes.

The material of the foam is not particularly limited, such as metal and ceramic, but cordierite ceramic foam is preferably used.

The expansion ratio of the foam is from 5 to 5 in terms of the number of pores.
50 pieces / square inch are preferred, more preferably 10
Pieces to 30 pieces / square inch.

The present invention is applicable not only to the exhaust gas of the engine of a car, but also to the engine of a transportation engine such as a cultivator, a ship, a train, etc.
It can be used for removing particulates in industrial engines, combustion furnaces, boilers and the like.

The present invention is not limited to the above-described embodiment, and various changes can be made without departing from the gist of the present invention.

[0116]

Embodiments Hereinafter, more specific embodiments will be described.

Example 1 Titania powder (manufactured by Ishihara Sangyo Co., Ltd.)
MC-90), 1000 g, copper sulfate pentahydrate (manufactured by Wako Pure Chemical) as a copper salt, and 95 g vanadium oxide (manufactured by Wako Pure Chemical) as a vanadium salt purified water 33
Then, the mixture was thoroughly dried under reduced pressure with a cold evaporator, and the obtained powder was dried in an electric furnace at 900.degree.
C. for 5 hours to obtain a powder in which the copper-vanadium composite oxide was supported on titania.

10 g of the powder thus obtained and 10 g of a cesium sulfate reagent were mixed in a powder mortar in an agate mortar, and the powder having copper-vanadium composite oxide supported on titania and cesium sulfate were mixed. A powder catalyst was obtained.

Example 2 Titania powder (manufactured by Ishihara Sangyo Co., Ltd.)
MC-90), 1000 g, copper sulfate pentahydrate (manufactured by Wako Pure Chemical) as a copper salt, and 95 g vanadium oxide sulfate (manufactured by Wako Pure Chemical) as a vanadium salt purified water 33
Then, the mixture was thoroughly dried under reduced pressure by a cold evaporator, and the obtained powder was dried in an electric furnace at 900.degree.
Calcination was performed at 5 ° C. for 5 hours to obtain a powder in which the copper-vanadium composite oxide was supported on titania.

On the other hand, titania powder (manufactured by Ishihara Sangyo, MC-
90) 1000 g and 36 g of tetraminedichloroplatinum (manufactured by Soekawa Chemical) as a salt of platinum were added to 3300 g of purified water, stirred sufficiently, dried under reduced pressure with a cold evaporator, and the obtained powder was dried in an electric furnace for 600 minutes. Calcination was performed at 5 ° C. for 5 hours to obtain a powder in which platinum was supported on titania.

A powder of 10 g of the above-obtained copper-vanadium composite oxide supported on titania, 10 g of the obtained powder of platinum supported on titania, and 10 g of a cesium sulfate reagent were mixed with the powder. The mixture was mixed in an agate mortar in this state to obtain a powder catalyst containing a powder in which a copper-vanadium composite oxide was supported on titania, a powder in which platinum was supported on titania, and cesium sulfate.

Comparative Example 1 Titania powder (manufactured by Ishihara Sangyo Co., Ltd.)
MC-90) 1000 g, copper sulfate pentahydrate (a product of Wako Pure Chemical Industries) 350 g as a copper salt, vanadium sulfate (available from Wako Pure Chemical) 95 g as a vanadium salt, and cesium sulfate (available from Soekawa Chemical) 220 g Was added to 3300 g of purified water, and the mixture was sufficiently stirred and dried under reduced pressure by a cold evaporator. The obtained powder was calcined in an electric furnace at 900 ° C. for 5 hours to obtain a copper-vanadium composite oxide and cesium sulfate. A powder supported on titania was obtained.

Comparative Example 2 Titania powder (manufactured by Ishihara Sangyo Co., Ltd.)
MC-90) 1000 g, copper sulfate pentahydrate (a product of Wako Pure Chemical) as a copper salt, 350 g, vanadium oxide sulfate (a product of Wako Pure Chemical) 95 g as a vanadium salt, and cesium sulfate (a product of Soekawa Chemical) 220 g And 36 g of tetraminedichloroplatinum (manufactured by Soekawa Chemical) as a salt of platinum were purified water 330
Then, the mixture was sufficiently dried under reduced pressure by a cold evaporator, and the obtained powder was dried in an electric furnace at 900.degree.
C. for 5 hours to obtain a powder in which a copper-vanadium composite oxide, cesium sulfate and platinum were supported on titania.

(Evaluation Example 1) The particulate catalysts obtained in Example 1, Example 2, Comparative Example 1, and Comparative Example 2 were subjected to the following particulate combustion experiments.

Each powder catalyst and powder of simulated particulates (carbon made by Nakarai) were mixed in a mortar at a weight ratio of 1: 1 and the mixture was filled in a quartz glass reaction tube having an inner diameter of 12 mm. 5 vol% oxygen and 50 pp in the reaction tube
The temperature of the inside of the reaction tube was raised at a constant speed by a tubular electric furnace arranged on the outer periphery of the reaction tube while a test gas consisting of a nitrogen gas containing SO ₂ and 250 ppm of NO gas was passed at a flow rate of 500 cc / min. did. At this time, the concentration of carbon dioxide in the test gas is detected by a carbon dioxide sensor disposed at a position on the exhaust gas side, and the temperature at which 5% of the particulates burn (hereinafter abbreviated as 5% combustion temperature). It was determined. The burning rate was calculated from the carbon amount (known amount) of the filled particulates and the generated CO + CO ₂ amount (measured value).
Table 1 shows the 5% combustion temperature of each exhaust gas purifying catalyst in the above combustion test.

[0126]

[Table 1]

As is clear from Table 1, even when the same type of catalyst composition is used, the exhaust gas purifying catalyst obtained in Example 1 is more effective than the exhaust gas purifying catalyst obtained in Comparative Example 1 as the exhaust gas purifying catalyst. However, it was found that the exhaust gas purifying catalyst obtained in Example 2 could burn particulates at a lower temperature than the exhaust gas purifying catalyst obtained in Comparative Example 2.

Example 3 Titania powder (manufactured by Ishihara Sangyo Co., Ltd.)
MC-90), 1000 g, copper sulfate pentahydrate (manufactured by Wako Pure Chemical) as a copper salt, and 95 g vanadium oxide (manufactured by Wako Pure Chemical) as a vanadium salt purified water 33
Then, the mixture was thoroughly dried under reduced pressure with a cold evaporator, and the obtained powder was dried in an electric furnace at 900.degree.
C. for 5 hours to obtain a powder in which the copper-vanadium composite oxide was supported on titania.

70 g of the powder thus obtained, 1.6 g of POLITY (manufactured by Lion) as a dispersant, 500 g of purified water, and 1000 g of 2 mm zirconia balls were added to each.
The mixture was placed in a 1-liter closed container and dispersed for 2 hours with a slurry disperser (manufactured by Red Devil) to obtain a slurry containing a powder in which the copper-vanadium composite oxide was supported on titania.

Next, as a heat-resistant three-dimensional structure, a wall flow type cordierite filter (manufactured by NGK, 5.66 inches, 100 cells / inch) was used.
The cell is cut into 5 cells x 15 mm, impregnated with the slurry solution obtained above, excess slurry is removed by an air gun, and then heat-treated at 600 ° C for 5 hours in an electric furnace.

On the other hand, 40 g of cesium sulfate (manufactured by Soekawa Chemical)
Was added to 500 g of purified water and sufficiently stirred to obtain an aqueous solution containing cesium sulfate. This aqueous solution is impregnated with the filter obtained above, excess solution is removed with an air gun, and then dried with a drier.
An exhaust gas purifying material was produced by heat treatment at 0 ° C. for 5 hours.

Example 4 Titania powder (manufactured by Ishihara Sangyo Co., Ltd.)
MC-90), 1000 g, copper sulfate pentahydrate (manufactured by Wako Pure Chemical) as a copper salt, and 95 g vanadium oxide (manufactured by Wako Pure Chemical) as a vanadium salt purified water 33
Then, the mixture was thoroughly dried under reduced pressure with a cold evaporator, and the obtained powder was dried in an electric furnace at 900.degree.
C. for 5 hours to obtain a powder in which the copper-vanadium composite oxide was supported on titania.

On the other hand, titania powder (manufactured by Ishihara Sangyo, MC-
90) 1000 g and 36 g of tetraminedichloroplatinum (manufactured by Soekawa Chemical) as a salt of platinum were added to 3300 g of purified water, stirred sufficiently, dried under reduced pressure with a cold evaporator, and the obtained powder was dried in an electric furnace for 600 minutes. Calcination was performed at 5 ° C. for 5 hours to obtain a powder in which platinum was supported on titania.

70 g of the above-obtained powder of copper-vanadium composite oxide supported on titania, 40 g of the above-obtained powder of platinum supported on titania, and Polyty (manufactured by Lion) as a dispersant 1.6g and purified water 500g
And 1000 g of 2 mm zirconia balls in a 1 liter sealed container, and a slurry disperser (manufactured by Red Devil)
For 2 hours to obtain a slurry containing a powder of copper-vanadium composite oxide supported on titania and a powder of platinum supported on titania.

Next, as a heat-resistant three-dimensional structure, a wall flow type cordierite filter (manufactured by NGK, 5.66 inches, 100 cells / inch) was used.
The cell is cut into 5 cells x 15 mm, impregnated with the slurry solution obtained above, excess slurry is removed by an air gun, and then heat-treated at 600 ° C for 5 hours in an electric furnace.

In addition, 40 g of cesium sulfate (manufactured by Soekawa Chemical)
Was added to 500 g of purified water and sufficiently stirred to obtain an aqueous solution containing cesium sulfate. This aqueous solution was impregnated with the filter obtained above, excess solution was removed with an air gun, and then dried with a dryer.
An exhaust gas purifying material was produced by heat treatment at 00 ° C. for 5 hours.

Example 5 Titania powder (manufactured by Ishihara Sangyo Co., Ltd.)
MC-90), 1000 g, copper sulfate pentahydrate (manufactured by Wako Pure Chemical) as a copper salt, and 95 g vanadium oxide (manufactured by Wako Pure Chemical) as a vanadium salt purified water 33
Then, the mixture was thoroughly dried under reduced pressure with a cold evaporator, and the obtained powder was dried in an electric furnace at 900.degree.
C. for 5 hours to obtain a powder in which the copper-vanadium composite oxide was supported on titania.

70 g of the powder thus obtained, 40 g of cesium sulfate (manufactured by Soekawa Chemical), 1.6 g of Polyty (manufactured by Lion) as a dispersant, 500 g of purified water,
zirconia balls of 1000 mm in a 1 liter closed container, and a slurry disperser (manufactured by Red Devil) is used for 2 g.
The slurry was dispersed for a time to obtain a slurry containing a powder in which the copper-vanadium composite oxide was supported on titania and cesium sulfate.

Next, as a heat-resistant three-dimensional structure, a wall flow type cordierite filter (manufactured by NGK, 5.66 inches, 100 cells / inch) was used.
The cell was cut into 5 cells x 15 mm, which was impregnated with the slurry solution obtained above, and excess slurry was removed with an air gun. Thereafter, the filter was dried in a dryer, and the filter was heat-treated in an electric furnace at 600 ° C. for 5 hours to produce an exhaust gas purifying material.

Example 6 Titania powder (manufactured by Ishihara Sangyo Co., Ltd.)
MC-90), 1000 g, copper sulfate pentahydrate (manufactured by Wako Pure Chemical) as a copper salt, and 95 g vanadium oxide (manufactured by Wako Pure Chemical) as a vanadium salt purified water 33
Then, the mixture was thoroughly dried under reduced pressure with a cold evaporator, and the obtained powder was dried in an electric furnace at 900.degree.
C. for 5 hours to obtain a powder in which the copper-vanadium composite oxide was supported on titania.

On the other hand, titania powder (manufactured by Ishihara Sangyo, MC-
90) 1000 g and 36 g of tetraminedichloroplatinum (manufactured by Soekawa Chemical) as a salt of platinum were added to 3300 g of purified water, stirred sufficiently, dried under reduced pressure with a cold evaporator, and the obtained powder was dried in an electric furnace for 600 minutes. Calcination was performed at 5 ° C. for 5 hours to obtain a powder in which platinum was supported on titania.

70 g of the powder obtained above, 40 g of the powder obtained above, and 40 g of cesium sulfate (manufactured by Soekawa Chemical)
1.6 g of Politi (made by Lion) as a dispersant,
500 g of purified water and 1000 zirconia balls of 2 mm
g was placed in a 1-liter closed container, and dispersed in a slurry disperser (manufactured by Red Devil) for 2 hours to obtain a powder in which a copper-vanadium composite oxide was supported on titania and a powder in which platinum was supported on titania. A slurry containing the powder and cesium sulfate was obtained.

Next, a wall flow type cordierite filter (5.66 inches, 100 cells / inch, made by NGK) was used as a heat-resistant three-dimensional structure, 2 cells × 5 cells.
The cell is cut into a cell having a size of 15 mm, and the cell is impregnated with the slurry solution obtained above, and excess slurry is removed with an air gun. Thereafter, the filter was dried in a dryer, and the filter was heat-treated in an electric furnace at 600 ° C. for 5 hours to produce an exhaust gas purifying material.

(Comparative Example 3) 70 g of copper sulfate pentahydrate (manufactured by Wako Pure Chemical) as a copper salt, 20 g of vanadium oxide (manufactured by Wako Pure Chemical) as a vanadium salt, and cesium sulfate (manufactured by Soekawa Chemical) 40 g was added to 500 g of purified water and sufficiently stirred to obtain an aqueous solution containing copper sulfate, vanadium oxide sulfate, and cesium sulfate.

Next, a wall-flow type cordierite filter (5.66 inches, 100 cells / inch, made by NGK) was used as a heat-resistant three-dimensional structure.
The cell is cut into 5 cells × 15 mm, which is impregnated with the solution obtained above, and an excess solution is removed with an air gun.
Thereafter, the filter was dried in a dryer, and the filter was heat-treated in an electric furnace at 900 ° C. for 5 hours to produce an exhaust gas purifying material.

(Comparative Example 4) 70 g of copper sulfate pentahydrate (manufactured by Wako Pure Chemical) as a copper salt, 20 g of vanadium oxide (manufactured by Wako Pure Chemical) as a vanadium salt, and cesium sulfate (manufactured by Soekawa Chemical) 40 g and 1.5 g of tetraminedichloroplatinum as a salt of platinum were added to 500 g of purified water and sufficiently stirred to obtain an aqueous solution containing copper sulfate, vanadium oxide sulfate, cesium sulfate, and tetraminedichloroplatinum.

Next, a wall-flow type cordierite filter (5.66 inches, 100 cells / inch, made by NGK) was used as a heat-resistant three-dimensional structure.
The cell is cut into 5 cells × 15 mm, which is impregnated with the solution obtained above, and an excess solution is removed with an air gun.
Thereafter, the filter was dried in a dryer, and the filter was heat-treated in an electric furnace at 900 ° C. for 5 hours to produce an exhaust gas purifying material.

Comparative Example 5 Titania powder (manufactured by Ishihara Sangyo Co., Ltd.)
MC-90) 1000 g, copper sulfate pentahydrate (a product of Wako Pure Chemical Industries) 350 g as a copper salt, vanadium sulfate (available from Wako Pure Chemical) 95 g as a vanadium salt, and cesium sulfate (available from Soekawa Chemical) 220 g Was added to 3300 g of purified water, and the mixture was sufficiently stirred and dried under reduced pressure by a cold evaporator. The obtained powder was calcined in an electric furnace at 900 ° C. for 5 hours to obtain a copper-vanadium composite oxide and cesium sulfate. A powder supported on titania was obtained.

70 g of the powder thus obtained, 1.6 g of POLITY (manufactured by Lion) as a dispersant, 500 g of purified water and 1000 g of 2 mm zirconia balls were placed in a 1-liter closed vessel, and a slurry disperser ( (Red Devil) for 2 hours to obtain a slurry containing a powder of cesium and copper-vanadium composite oxide supported on titania.

Next, as a heat-resistant three-dimensional structure, a wall flow type cordierite filter (manufactured by NGK, 5.66 inches, 100 cells / inch) was used.
The cell is cut into 5 cells × 15 mm, which is impregnated with the slurry obtained above, and excess slurry is removed with an air gun. Thereafter, the filter was dried in a dryer, and the filter was heat-treated in an electric furnace at 600 ° C. for 5 hours to produce an exhaust gas purifying material.

Comparative Example 6 Titania powder (manufactured by Ishihara Sangyo Co., Ltd.)
MC-90) 1000 g, copper sulfate pentahydrate (a product of Wako Pure Chemical) as a copper salt, 350 g, vanadium oxide sulfate (a product of Wako Pure Chemical) 95 g as a vanadium salt, and cesium sulfate (a product of Soekawa Chemical) 220 g And 36 g of tetraminedichloroplatinum (manufactured by Soekawa Chemical) as a salt of platinum were purified water 330
Then, the mixture was sufficiently dried under reduced pressure by a cold evaporator, and the obtained powder was dried in an electric furnace at 900.degree.
C. for 5 hours to obtain a powder in which a copper-vanadium composite oxide, cesium sulfate and platinum were supported on titania.

70 g of the powder thus obtained, 1.6 g of POLITY (manufactured by Lion) as a dispersant, 500 g of purified water, and 1000 g of 2 mm zirconia balls were added to each.
The mixture was placed in a liter closed container and dispersed for 2 hours with a slurry disperser (manufactured by Red Devil) to obtain a slurry containing a powder in which cesium, a copper-vanadium composite oxide, and platinum were supported on titania.

Next, as a heat-resistant three-dimensional structure, a wall flow type cordierite filter (NGK) was used.
5.66 inches, 100 cells / inch) x 2 cells
The cell is cut into 5 cells × 15 mm, which is impregnated with the slurry obtained above, and excess slurry is removed with an air gun. Thereafter, the filter was dried in a dryer, and the filter was heat-treated in an electric furnace at 600 ° C. for 5 hours to produce an exhaust gas purifying material.

Comparative Example 7 Titania powder (manufactured by Ishihara Sangyo Co., Ltd.)
MC-90), 40 g of Polity (manufactured by Lion) as a dispersant, 500 g of purified water, and 1000 g of 2 mm zirconia balls are placed in a 1-liter closed container.
The slurry was dispersed in a slurry disperser (manufactured by Red Devil) for 2 hours to obtain a slurry containing titania powder.

Next, a wall flow type cordierite filter (5.66 inches, 100 cells / inch, made by NGK) was used as a heat-resistant three-dimensional structure.
The cell is cut into 5 cells x 15 mm, impregnated with the slurry solution obtained above, excess slurry is removed by an air gun, and then heat-treated at 600 ° C for 5 hours in an electric furnace.

Also, 70 g of copper sulfate pentahydrate (manufactured by Wako Pure Chemical) as a copper salt, 20 g of vanadium oxide sulfate (manufactured by Wako Pure Chemical) as a salt of vanadium, and 40 g of cesium sulfate (manufactured by Soekawa Chemical) are used. 500 g of purified water was added and sufficiently stirred to obtain an aqueous solution containing copper sulfate, vanadium oxide sulfate, and cesium sulfate.

The filter obtained above was impregnated with this aqueous solution, the excess solution was removed with an air gun, dried with a dryer, and the filter was heat-treated at 900 ° C. for 5 hours in an electric furnace. Manufactured exhaust gas purifying materials.

Comparative Example 8 Titania powder (manufactured by Ishihara Sangyo Co., Ltd.)
MC-90), 40 g of Polity (manufactured by Lion) as a dispersant, 500 g of purified water, and 1000 g of 2 mm zirconia balls are placed in a 1-liter closed container.
The slurry was dispersed in a slurry disperser (manufactured by Red Devil) for 2 hours to obtain a slurry containing titania powder.

Next, a wall flow type cordierite filter (5.66 inches, 100 cells / inch, made by NGK) was used as a heat-resistant three-dimensional structure.
The cell is cut into 5 cells x 15 mm, impregnated with the slurry solution obtained above, excess slurry is removed by an air gun, and then heat-treated at 600 ° C for 5 hours in an electric furnace.

Also, 70 g of copper sulfate pentahydrate (manufactured by Wako Pure Chemical) as a copper salt, 20 g of vanadium oxide sulfate (manufactured by Wako Pure Chemical) as a salt of vanadium, 40 g of cesium sulfate (manufactured by Soekawa Chemical), 1.5 g of tetraminedichloroplatinum as a salt of platinum was added to 500 g of purified water and sufficiently stirred,
An aqueous solution containing copper sulfate, vanadium oxide sulfate, cesium sulfate, and tetraminedichloroplatinum was obtained.

The filter obtained above was impregnated with this aqueous solution, the excess solution was removed with an air gun, dried with a dryer, and the filter was heat-treated at 900 ° C. for 5 hours in an electric furnace. Manufactured exhaust gas purifying materials.

Comparative Example 9 Titania powder (manufactured by Ishihara Sangyo Co., Ltd.)
MC-90) 1000 g and 36 g of platinum salt of tetraminedichloroplatinum (manufactured by Soekawa Chemical) as purified water 3300
g, sufficiently stirred, dried under reduced pressure with a cold evaporator, and the obtained powder was heated at 600 ° C. in an electric furnace.
Firing was performed for 5 hours to obtain a powder in which platinum was supported on titania.

40 g of the powder thus obtained, 1.6 g of Polyty (manufactured by Lion) as a dispersing agent, 500 g of purified water, and 1000 g of 2 mm zirconia balls were added to each.
The mixture was placed in a 1 liter closed container and dispersed for 2 hours with a slurry disperser (manufactured by Red Devil) to obtain a slurry containing a powder in which platinum was supported on titania.

Next, a wall-flow type cordierite filter (5.66 inches, 100 cells / inch, made by NGK) was used as a heat-resistant three-dimensional structure.
The cell is cut into 5 cells x 15 mm, impregnated with the slurry solution obtained above, excess slurry is removed by an air gun, and then heat-treated at 600 ° C for 5 hours in an electric furnace.

Also, 70 g of copper sulfate pentahydrate (manufactured by Wako Pure Chemical Industries) as a copper salt, 20 g of vanadium oxide sulfate (manufactured by Wako Pure Chemical Industries) as a vanadium salt, and 40 g of cesium sulfate (manufactured by Soekawa Chemical) are used. 500 g of purified water was added and sufficiently stirred to obtain an aqueous solution containing copper sulfate, vanadium oxide sulfate, and cesium sulfate.

The filter obtained above was impregnated with this aqueous solution, the excess solution was removed with an air gun, dried with a dryer, and the filter was heat-treated at 900 ° C. for 5 hours in an electric furnace. Manufactured exhaust gas purifying materials.

(Comparative Example 10) 1000 g of titania powder (MC-90, manufactured by Ishihara Sangyo) and 36 g of tetraminedichloroplatinum (manufactured by Soegawa Chemical) as a platinum salt were purified water 33
After the mixture was sufficiently stirred and dried under reduced pressure with a cold evaporator, the obtained powder was dried in an electric furnace for 600 minutes.
Calcination was performed at 5 ° C. for 5 hours to obtain a powder in which platinum was supported on titania.

40 g of the powder thus obtained, 70 g of copper sulfate pentahydrate (manufactured by Wako Pure Chemical Industries) as a copper salt, and vanadium oxide sulfate (manufactured by Wako Pure Chemical Industries) as a vanadium salt
20 g, cesium sulfate (manufactured by Soekawa Chemical) 40 g, Polity (manufactured by Lion) 1.6 g as a dispersant, and purified water 5
00 g and 1000 g of 2 mm zirconia balls were placed in a 1 liter sealed container and dispersed with a slurry disperser (manufactured by Red Devil) for 2 hours. A slurry containing vanadium and cesium sulfate was obtained.

Next, as a heat-resistant three-dimensional structure, a wall flow type cordierite filter (manufactured by NGK, 5.66 inches, 100 cells / inch) was used.
The cell is cut into 5 cells × 15 mm, which is impregnated with the slurry obtained above, and excess slurry is removed with an air gun. Thereafter, the filter was dried in a dryer, and the filter was heat-treated in an electric furnace at 900 ° C. for 5 hours to produce an exhaust gas purifying material.

(Evaluation Example 2) The following particulate combustion experiments were performed on the exhaust gas purifying materials obtained in Examples 3 to 6 and Comparative Examples 3 to 10.

Examples 3 to 6, Comparative Examples 3 to 1
In one of the exhaust gas purifying materials obtained in Step No. 0, powder of simulated particulates (carbon made by Nakarai) was carried on the filter surface, and filled into a quartz glass reaction tube having an inner diameter of 12 mm.

In the reaction tube, 5 vol% of oxygen and 50 pp
The temperature of the inside of the reaction tube was raised at a constant speed by a tubular electric furnace arranged on the outer periphery of the reaction tube while a test gas consisting of a nitrogen gas containing 250 m ₂ of SO ₂ and 250 ppm of NO gas was passed at a flow rate of 500 cc / min. At this time, the concentration of carbon dioxide in the test gas is detected by a carbon dioxide sensor disposed at a position on the gas outflow side, and the temperature at which 5% of particulates are burned (hereinafter abbreviated as 5% combustion temperature). To do). The burning rate was calculated from the carbon amount (known amount) of the filled particulates and the generated CO + CO ₂ amount (measured value).
Table 2 shows the 5% combustion temperature of each exhaust gas purifying material in the above combustion test.

[0173]

[Table 2]

As is clear from Table 2, even when the same type of catalyst composition was used, the exhaust gas purifying materials obtained in Examples 3 to 6 were more excellent in Comparative Examples 3 to 10. It was found that particulates could be burned at a lower temperature than the exhaust gas purifying material used.

(Example 7) Cu as an oxide of a transition metal
Except for using V ₂ O ₆ , an exhaust gas purifying material was produced in the same manner as in Example 4.

Example 8 Cu as transition metal oxide
Except for using O, an exhaust gas purifying material was manufactured in the same manner as in Example 4.

(Example 9) V ₂ as a transition metal oxide
Except for using O ₅ , an exhaust gas purifying material was produced in the same manner as in Example 4.

(Example 10) As an oxide of a transition metal, C was used.
Except for using uMoO ₄ , an exhaust gas purifying material was produced in the same manner as in Example 4.

(Example 11) As an oxide of a transition metal, C was used.
Except for using oO ₃ , an exhaust gas purifying material was produced in the same manner as in Example 4.

(Example 12) As an oxide of a transition metal, M
Except that nO ₂ was used, an exhaust gas purifying material was produced in the same manner as in Example 4.

(Example 13) As a transition metal oxide,
Except for using oO ₃ , an exhaust gas purifying material was produced in the same manner as in Example 4.

(Example 14) As a transition metal oxide, W
Except that O ₃ was used, an exhaust gas purifying material was produced in the same manner as in Example 4.

(Comparative Example 11) As a transition metal oxide,
Except for using aMnCoO ₃ , an exhaust gas purifying material was produced in the same manner as in Example 4.

(Evaluation Example 3) In Examples 7 to 14 and Comparative Example 11, a particulate combustion experiment was performed in the same manner as in (Evaluation Example 2). Table 3 shows the 5% combustion temperature of each exhaust gas purifying material in the above combustion test.

[0185]

[Table 3]

As is clear from Table 3, when the exhaust gas purifying materials having the same structure were used, Examples 4 and 7 to 14 show transition metal oxides to be carried on the exhaust gas purifying materials. It has been found that the exhaust gas purifying material carrying the compound can burn particulates at a lower temperature.
In particular, it was found that high catalytic activity was obtained when a composite oxide of copper and vanadium and a copper oxide were used.

Example 15 An exhaust gas purifying material was produced in the same manner as in Example 4, except that sulfuric acid K + sulfuric acid Cs was used as the alkali metal sulfate.

Example 16 An exhaust gas purifying material was produced in the same manner as in Example 4 except that sulfuric acid Rb was used as a sulfate of an alkali metal.

Example 17 An exhaust gas purifying material was produced in the same manner as in Example 4, except that sulfuric acid K was used as the sulfate of the alkali metal.

Example 18 An exhaust gas purifying material was produced in the same manner as in Example 4 except that sodium sulfate was used as a sulfate of an alkali metal.

Example 19 An exhaust gas purifying material was produced in the same manner as in Example 4 except that Li sulfate was used as a sulfate of an alkali metal.

Comparative Example 12 An exhaust gas purifying material was produced in the same manner as in Example 4, except that Ca sulfate was used as a sulfate of an alkali metal.

(Evaluation Example 4) In Examples 15 to 19 and Comparative Example 12, a particulate combustion experiment was performed in the same manner as in (Evaluation Example 2). (Table 4) shows the 5% combustion temperature of each exhaust gas purifying material in the above combustion test.

[0194]

[Table 4]

As is clear from Table 4, when the exhaust gas purifying materials having the same structure are used, the alkali metal sulfates to be carried on the exhaust gas purifying materials are described in Examples 4 and 15 to
It was found that the exhaust gas purifying material carrying the compound shown in Example 19 could burn particulates at a lower temperature. In particular, it was found that high catalytic activity was obtained when cesium sulfate or cesium sulfate + potassium sulfate was used.

Example 20 An exhaust gas purifying material was produced in the same manner as in Example 4 except that Pt + Pd was used as a noble metal.

Example 21 An exhaust gas purifying material was produced in the same manner as in Example 4 except that Pd was used as a noble metal.

(Evaluation Example 5) In Examples 20 and 21, a particulate combustion experiment was conducted in the same manner as in (Evaluation Example 2). Table 5 shows the 5% combustion temperature of each exhaust gas purifying material in the above combustion test.

[0199]

[Table 5]

As is clear from Table 5, when the exhaust gas purifying materials having the same structure are used, when the compounds shown in Examples 20 and 21 are supported as the noble metals to be supported on the exhaust gas purifying materials. It was found that particulates could be burned at lower temperatures. In particular, those containing platinum were found to be highly active.

Example 22 An exhaust gas purifying material was produced in the same manner as in Example 4 except that TaO ₂ was used as a heat-resistant inorganic oxide for supporting a transition metal oxide.

Example 23 An exhaust gas purifying material was produced in the same manner as in Example 4 except that Nb ₂ O ₅ was used as a heat-resistant inorganic oxide for supporting a transition metal oxide.

Example 24 An exhaust gas purifying material was produced in the same manner as in Example 4, except that WO ₃ was used as a heat-resistant inorganic oxide for supporting a transition metal oxide.

Example 25 An exhaust gas purifying material was produced in the same manner as in Example 4 except that SnO ₂ was used as a heat-resistant inorganic oxide for supporting a transition metal oxide.

Example 26 An exhaust gas purifying material was produced in the same manner as in Example 4, except that SiO ₂ was used as a heat-resistant inorganic oxide for supporting a transition metal oxide.

Example 27 An exhaust gas purifying material was produced in the same manner as in Example 4, except that Al ₂ O ₃ was used as a heat-resistant inorganic oxide for supporting a transition metal oxide.

Example 28 An exhaust gas purifying material was produced in the same manner as in Example 4, except that ZrO ₂ was used as a heat-resistant inorganic oxide for supporting a transition metal oxide.

(Evaluation Example 6) In Examples 22 to 28, a particulate combustion experiment was conducted in the same manner as in (Evaluation Example 2). (Table 6) shows the 5% combustion temperature of each exhaust gas purifying material in the above combustion test.

[0209]

[Table 6]

As is clear from Table 6, when exhaust gas purifying materials having the same structure were used, Examples 4 and 22 were used as heat-resistant inorganic oxides supporting oxides of transition metals.
-It was found that when the compounds shown in Example 28 were used, particulates could be burned at a lower temperature. In particular, those containing titania were found to be highly active.

Example 29 An exhaust gas purifying material was produced in the same manner as in Example 4 except that TaO ₂ was used as a heat-resistant inorganic oxide for supporting a noble metal.

Example 30 An exhaust gas purifying material was produced in the same manner as in Example 4 except that Nb ₂ O ₅ was used as a heat-resistant inorganic oxide for supporting a noble metal.

Example 31 An exhaust gas purifying material was produced in the same manner as in Example 4, except that WO ₃ was used as a heat-resistant inorganic oxide for supporting a noble metal.

Example 32 An exhaust gas purifying material was produced in the same manner as in Example 4, except that SnO ₂ was used as a heat-resistant inorganic oxide for supporting a noble metal.

Example 33 An exhaust gas purifying material was produced in the same manner as in Example 4, except that SiO ₂ was used as a heat-resistant inorganic oxide for supporting a noble metal.

Example 34 An exhaust gas purifying material was produced in the same manner as in Example 4 except that Al ₂ O ₃ was used as a heat-resistant inorganic oxide for supporting a noble metal.

Example 35 An exhaust gas purifying material was produced in the same manner as in Example 4, except that ZrO ₂ was used as a heat-resistant inorganic oxide for supporting a noble metal.

(Evaluation Example 7) In Examples 29 to 35, a particulate combustion experiment was performed in the same manner as in (Evaluation Example 2). (Table 7) shows the 5% combustion temperature of each exhaust gas purifying material in the above combustion test.

[0219]

[Table 7]

As is clear from (Table 7), when exhaust gas purifying materials having the same structure were used, Examples 4 and 29 to 3 were used as heat-resistant inorganic oxides for supporting noble metals.
It was found that when the compound shown in No. 5 was used, particulates could be burned at a lower temperature. In particular, those containing titania were found to be highly active.

[0221]

As described above, according to the exhaust gas purifying catalyst of the present invention and the exhaust gas purifying material using the same, the following advantageous effects can be obtained.

According to the first aspect of the present invention, (1) the catalysts having different functions are separately present,
It is possible to sufficiently bring out different catalyst characteristics from each other, and it is possible to suppress the deterioration due to the reaction between the catalysts. As a result, it is possible to prevent the deterioration of the activity of the catalyst,
A highly active exhaust gas purifying catalyst can be obtained. (2) By forming the catalyst component on the surface of the inorganic oxide having heat resistance, the catalyst surface area is increased, and as a result, the contact points with the particulates in diesel exhaust gas are increased,
A highly active exhaust gas purifying catalyst can be obtained. (3) By forming a catalyst component on the surface of the inorganic oxide having heat resistance, the required amount of the catalyst can be reduced, and an exhaust gas purifying catalyst can be obtained at low cost, which is excellent in economy. (4) An inorganic oxide-supported transition metal oxide catalyst having heat resistance and an alkali metal sulfate catalyst are separately provided to increase the catalyst surface area, thereby increasing the contact points with particulates in diesel exhaust gas. To increase the catalytic activity. (5) By individually providing a transition metal oxide catalyst supporting an inorganic oxide having heat resistance and a catalyst of an alkali metal sulfate, the necessary and sufficient amounts of the transition metal oxide and the alkali metal sulfate can be reduced. It is possible to obtain an exhaust gas purifying catalyst at low cost, and it is economical. (6) By individually providing a transition metal oxide catalyst supporting an inorganic oxide having heat resistance and a catalyst of an alkali metal sulfate, a reaction between the catalysts due to heat as seen during particulate combustion or the like can be prevented. Thus, different catalyst characteristics can be sufficiently exhibited, and the catalyst activity can be prevented from deteriorating to enhance the durability.

According to the second aspect of the invention, (1) harmful components such as carbon monoxide, nitrogen oxides and hydrocarbons can be reduced by adding a noble metal;
Air pollution can be prevented. (2) By having different catalysts with different functions,
The required and sufficient amount of the noble metal can be reduced, and an exhaust gas purifying catalyst can be obtained at low cost, which is economical. (3) The catalyst surface area can be increased by forming the catalyst component on the surface of the inorganic oxide having heat resistance.
As a result, the number of contact points with the particulates in the diesel exhaust gas increases, and a highly active exhaust gas purifying catalyst can be obtained. (4) By forming the catalyst component on the surface of the inorganic oxide having heat resistance, the required amount of the catalyst can be reduced, and a low-cost exhaust gas purification catalyst having excellent purification performance can be obtained. (5) By having different catalysts with different functions,
It is possible to sufficiently bring out different catalyst characteristics from each other, and it is possible to suppress the deterioration due to the reaction between the catalysts. As a result, it is possible to prevent the deterioration of the activity of the catalyst,
A highly active exhaust gas purifying catalyst can be obtained. (6) To individually provide a heat-resistant inorganic oxide-supported transition metal oxide catalyst, a heat-resistant inorganic oxide-supported noble metal catalyst layer, and an alkali metal sulfate catalyst to increase the catalyst surface area. Thereby, the contact point with the particulates in the diesel exhaust gas can be increased and the catalytic activity can be increased. (7) A transition metal oxide catalyst supporting an inorganic oxide having heat resistance, a noble metal catalyst layer supporting an inorganic oxide having heat resistance, and a catalyst of an alkali metal sulfate are separately provided, whereby a transition metal oxidation catalyst is provided. It is possible to reduce the necessary and sufficient amounts of the substance, the noble metal catalyst layer and the alkali metal sulfate, and it is possible to obtain an exhaust gas purifying catalyst at low cost and to be excellent in economic efficiency. (8) Particulate combustion by separately providing a heat-resistant inorganic oxide-supported transition metal oxide catalyst, a heat-resistant inorganic oxide-supported noble metal catalyst layer, and an alkali metal sulfate catalyst The reaction between the catalysts due to heat, which is sometimes observed, can be prevented, and different catalyst characteristics can be sufficiently exhibited, and the catalyst activity can be prevented from deteriorating and durability can be increased.

According to the invention set forth in claim 3, according to claim 2
(1) Since the noble metal contains Pt, the SOF component other than the carbon component in the particulate by the noble metal catalyst can be burned and purified most efficiently and stably, and the exhaust gas purification ability is improved. Very good.

According to the invention set forth in claim 4, according to claim 1
In addition to the effects of any one of (1) to (3), (1) Since the transition metal oxide contains at least one metal oxide selected from Cu, Mn, Co, V, Mo, and W,
An exhaust gas purifying catalyst having a high catalytic activity when burning particulates can be obtained.

According to the invention set forth in claim 5, claim 1 is provided.
In addition to the effect of any one of (1) to (4), (1) since the oxide of Cu is at least one selected from CuO, Cu ₂ O, and Cu ₂ O ₃ , a high catalytic activity can be obtained when burning particulates. An exhaust gas purifying catalyst having the same can be obtained.

According to the invention of claim 6, according to claim 1,
In addition to the effects of any one of (1) to (5), (1) Since the transition metal oxide contains a composite metal oxide composed of Cu and V, the particulates can be efficiently burned and removed, and the catalytic activity can be reduced. Can be enhanced. (2) Particulates can be removed by an oxidation reaction at a predetermined exhaust gas temperature.

According to the invention of claim 7, according to claim 1,
Or in addition to any one of the effects of 6, since (1) is at least one oxide of a composite metal is selected from _{Cu 5 V 2 O 10, CuV} 2 O 6, Cu 3 V 2 O 8, An exhaust gas purifying catalyst having higher catalytic activity during particulate combustion can be obtained.

According to the invention described in claim 8, according to claim 1,
In addition to the effects of any one of (1) to (7), (1) Since the alkali metal sulfate contains cesium sulfate, the catalytic activity can be increased and particulates can be burned efficiently, and the exhaust gas purification ability is extremely excellent.

According to the ninth aspect of the present invention, the first aspect is provided.
In addition to the effects of any one of (1) to (8), (1) to obtain an exhaust gas purifying catalyst having extremely high catalytic activity in burning particulates because the alkali metal sulfate contains a mixture of cesium sulfate and potassium sulfate Can be.

According to the tenth aspect, in addition to the effect of any one of the first to ninth aspects, (1) Ta ₂ O ₅ , Nb ₂ O is used as a carrier for supporting a transition metal oxide. ₅ ,
WO ₃ , SnO ₂ , SiO ₂ , TiO ₂ , Al ₂ O ₃ , ZrO
_Since at least one inorganic oxide selected from ₂ is contained, the surface area of the transition metal oxide catalyst is increased, and as a result, the number of contacts with the particulates is increased. It can be exhibited stably.

According to the eleventh aspect of the present invention, (1) by separately providing catalysts having different functions,
The reaction between the heat-resistant three-dimensional structure and the catalyst component is suppressed, and a highly active exhaust gas purifying material can be obtained. (2) By providing a heat-resistant inorganic oxide-supported transition metal oxide catalyst and an alkali metal sulfate catalyst individually, the reaction between the heat-resistant three-dimensional structure and the catalyst component is suppressed, The catalyst can be prevented from deteriorating and has excellent catalytic activity. (3) By having different catalysts with different functions,
A reaction between the three-dimensional structure having heat resistance and the catalyst component is suppressed, and a highly active exhaust gas purifying material can be obtained. (4) By having different catalysts with different functions,
It is possible to sufficiently bring out different catalyst characteristics from each other, and it is possible to suppress the deterioration due to the reaction between the catalysts. As a result, it is possible to prevent the deterioration of the activity of the catalyst,
A highly active exhaust gas purifying material can be obtained. (5) By forming the catalyst component on the surface of the inorganic oxide having heat resistance, the catalyst surface area is increased, and as a result, the contact points with the particulates in the diesel exhaust gas are increased,
A highly active exhaust gas purifying material can be obtained. (6) By forming the catalyst component on the surface of the inorganic oxide having heat resistance, the required amount of the catalyst can be reduced, the exhaust gas purifying material can be obtained at low cost, and the economy is excellent. (7) A transition metal oxide catalyst supporting an inorganic oxide having heat resistance and a catalyst of an alkali metal sulfate are individually provided to increase the catalyst surface area, thereby increasing the contact points with particulates in diesel exhaust gas. To increase the catalytic activity. (8) By providing a heat-resistant inorganic oxide-supported transition metal oxide catalyst and an alkali metal sulfate catalyst individually, the necessary and sufficient amounts of the transition metal oxide and the alkali metal sulfate can be reduced. It is possible to obtain an exhaust gas purifying material at low cost, and it is economical. (9) By providing a heat-resistant inorganic oxide-supported transition metal oxide catalyst and an alkali metal sulfate catalyst individually, the reaction between the catalysts due to heat such as that observed during particulate combustion can be prevented. Thus, different catalyst characteristics can be sufficiently exhibited, and the catalyst activity can be prevented from deteriorating to enhance the durability.

According to the twelfth aspect of the present invention, (1) a transition metal oxide catalyst supporting an inorganic oxide having heat resistance, a noble metal catalyst supporting an inorganic oxide having heat resistance, and an alkali metal sulfate By individually providing the above catalyst, the reaction between the heat-resistant three-dimensional structure and the catalyst component can be suppressed, the catalyst activity can be increased, and the catalyst can be prevented from being deteriorated, and the durability is excellent. (2) A transition metal oxide catalyst having a heat-resistant inorganic oxide supported thereon, a noble metal catalyst layer having a heat-resistant inorganic oxide supported thereon, and a catalyst of an alkali metal sulfate are individually provided to provide a transition metal oxidation catalyst. It is possible to reduce the necessary and sufficient amount of the product and the alkali metal sulfate, and to obtain an exhaust gas purifying material at low cost, which is excellent in economy. (3) The required amount of expensive noble metal can be reduced, and a low-cost realized exhaust gas purifying material with excellent economy can be obtained. (4) By having different catalysts with different functions,
A reaction between the three-dimensional structure having heat resistance and the catalyst component is suppressed, and a highly active exhaust gas purifying material can be obtained. (5) By having different catalysts with different functions,
It is possible to sufficiently bring out different catalyst characteristics from each other, and it is possible to suppress the deterioration due to the reaction between the catalysts. As a result, it is possible to prevent the deterioration of the activity of the catalyst,
A highly active exhaust gas purifying material can be obtained. (6) By forming the catalyst component on the surface of the inorganic oxide having heat resistance, the catalyst surface area is increased, and as a result, the contact points with the particulates in the diesel exhaust gas are increased,
A highly active exhaust gas purifying material can be obtained. (7) By forming the catalyst component on the surface of the inorganic oxide having heat resistance, the required amount of the catalyst can be reduced, the exhaust gas purifying material can be obtained at low cost, and the economy is excellent. (8) A transition metal oxide catalyst supporting an inorganic oxide having heat resistance, a noble metal catalyst layer supporting an inorganic oxide having heat resistance, and a catalyst of an alkali metal sulfate are individually provided to increase the catalyst surface area. Thereby, the contact point with the particulates in the diesel exhaust gas can be increased and the catalytic activity can be increased. (9) Particulate combustion by separately providing a heat-resistant inorganic oxide-supported transition metal oxide catalyst, a heat-resistant inorganic oxide-supported noble metal catalyst layer, and an alkali metal sulfate catalyst The reaction between the catalysts due to heat, which is sometimes observed, can be prevented, and different catalyst characteristics can be sufficiently exhibited, and the catalyst activity can be prevented from deteriorating and durability can be increased.

According to the thirteenth aspect of the present invention, (1) heat resistance is improved by separately providing an inorganic oxide-supported transition metal oxide catalyst having heat resistance and an alkali metal sulfate catalyst. The reaction between the three-dimensional structure and the catalyst component is suppressed, and deterioration of the catalyst can be prevented, resulting in excellent durability. (2) By separately disposing the catalysts having the respective functions, the surface area of the catalyst can be increased, the contact point with the particulates in the diesel exhaust gas can be increased, and the catalytic activity can be enhanced. (3) By having different catalysts with different functions,
The required and sufficient amount of each catalyst can be reduced, the exhaust gas purifying material can be manufactured at low cost, and the economy is excellent. (4) By having different catalysts with different functions,
It is possible to sufficiently bring out different catalyst characteristics from each other, and it is possible to suppress the deterioration due to the reaction between the catalysts. As a result, it is possible to prevent the deterioration of the activity of the catalyst,
A highly active exhaust gas purifying material can be obtained.

According to the fourteenth aspect of the present invention, (1) By adding a noble metal, carbon monoxide, nitrogen oxides, hydrocarbons and the like in exhaust gas coexisting with particulates can be reduced. Pollution due to pollution can be prevented. (2) A three-dimensional heat-resistant material is provided by individually providing a heat-resistant inorganic oxide-supported transition metal oxide catalyst, a heat-resistant inorganic oxide-supported noble metal catalyst, and an alkali metal sulfate catalyst. The reaction between the structure and the catalyst component is suppressed, and deterioration of the catalyst can be prevented, resulting in excellent durability. (3) By separately disposing the catalysts having the respective functions, the catalyst surface area can be increased, the contact point with the particulates in the diesel exhaust gas can be increased, and the catalytic activity can be enhanced. (4) By having different catalysts with different functions,
The required and sufficient amount of each catalyst can be reduced, the exhaust gas purifying material can be manufactured at low cost, and the economy is excellent. (5) By having different catalysts with different functions,
It is possible to sufficiently bring out different catalyst characteristics from each other, and it is possible to suppress the deterioration due to the reaction between the catalysts. As a result, it is possible to prevent the deterioration of the activity of the catalyst,
A highly active exhaust gas purifying material can be obtained.

According to the fifteenth aspect of the present invention, (1) an alkali metal sulfate layer is formed on the powder surface of a transition metal oxide catalyst supporting inorganic oxide having heat resistance, At the time of catalyst synthesis, it is possible to prevent a change in catalyst composition due to a reaction between a transition metal oxide or a sulfate of an alkali metal and a noble metal, and to easily synthesize an ideal catalyst composition. (2) By separately providing a heat-resistant inorganic oxide-supported transition metal oxide catalyst and an alkali metal sulfate catalyst, the reaction between the heat-resistant three-dimensional structure and the catalyst component can be suppressed. In addition, the catalyst can be prevented from deteriorating and has excellent durability. (3) By separately disposing the catalysts having the respective functions, the catalyst surface area can be increased, the contact point with the particulates in the diesel exhaust gas can be increased, and the catalytic activity can be enhanced. (4) By having different catalysts with different functions,
The required and sufficient amount of each catalyst can be reduced, the exhaust gas purifying material can be manufactured at low cost, and the economy is excellent. (5) By having different catalysts with different functions,
It is possible to sufficiently bring out different catalyst characteristics from each other, and it is possible to suppress the deterioration due to the reaction between the catalysts. As a result, it is possible to prevent the deterioration of the activity of the catalyst,
A highly active exhaust gas purifying material can be obtained.

According to the sixteenth aspect of the present invention, (1) the powder surface of the heat-resistant inorganic oxide-supported transition metal oxide catalyst and the heat-resistant inorganic oxide-supported noble metal catalyst has an alkali By forming a metal sulfate layer, an ideal catalyst composition can be synthesized, and a highly active exhaust gas purifying material can be obtained. (2) By adding a noble metal, carbon monoxide, nitrogen oxides, hydrocarbons and the like in the exhaust gas coexisting with the particulates can also be reduced, and pollution due to air pollution can be prevented. (3) A three-dimensional heat-resistant catalyst is provided by individually providing a heat-resistant inorganic oxide-supported transition metal oxide catalyst, a heat-resistant inorganic oxide-supported noble metal catalyst, and an alkali metal sulfate catalyst. The reaction between the structure and the catalyst component is suppressed, and deterioration of the catalyst can be prevented, resulting in excellent durability. (4) By separately disposing the catalysts having the respective functions, the surface area of the catalyst can be increased, the contact point with the particulates in the diesel exhaust gas can be increased, and the catalytic activity can be enhanced. (5) By having different catalysts with different functions,
The required and sufficient amount of each catalyst can be reduced, the exhaust gas purifying material can be manufactured at low cost, and the economy is excellent. (6) By separately presenting catalysts having different functions,
It is possible to sufficiently bring out different catalyst characteristics from each other, and it is possible to suppress the deterioration due to the reaction between the catalysts. As a result, it is possible to prevent the deterioration of the activity of the catalyst,
A highly active exhaust gas purifying material can be obtained.

According to the seventeenth aspect of the present invention, in addition to the fruit of any one of the twelfth, twelfth and thirteenth aspects, (1) since the noble metal contains Pt, the carbon component in the particulate by the noble metal catalyst SOF components other than the above can be burned and purified most efficiently and stably, and the exhaust gas purification ability is extremely excellent.

According to the eighteenth aspect of the present invention, in addition to the effect of any one of the eleventh to seventeenth aspects, (1) the transition metal oxide is made of Cu, Mn, Co, V, Mo, W. Since it contains at least one selected metal oxide, it is possible to obtain an exhaust gas purifying material having high catalytic activity when burning particulates.

According to the nineteenth aspect, in addition to the effect of any one of the eleventh to eighteenth aspects, (1) Cu
Is at least one selected from CuO, Cu ₂ O, and Cu ₂ O ₃ , so that an exhaust gas purifying material having high catalytic activity in burning particulates can be obtained.

According to the twentieth aspect, in addition to the effects of any one of the eleventh to nineteenth aspects, (1) the transition metal oxide contains a composite metal oxide composed of Cu and V Therefore, the particulates can be efficiently burned and removed, and the catalytic activity can be enhanced. (2) Particulates can be removed by an oxidation reaction at a predetermined exhaust gas temperature.

According to the twenty-first aspect of the present invention, in addition to the effects of any one of the eleventh to twentieth aspects, (1) the composite metal oxide is made of Cu ₅ V ₂ O ₁₀ , CuV ₂ O ₆ , Cu ₃ V ₂ O ₈
Since it is at least one selected from the group consisting of :, it is possible to obtain an exhaust gas purifying material having a higher catalytic activity when burning particulates.

According to the twenty-second aspect of the present invention, in addition to the effects of any one of the eleventh to twenty-first aspects, (1) the alkali metal sulfate contains cesium sulfate, so that the catalytic activity is enhanced and the particulate matter is increased. Can be burned efficiently, and the exhaust gas purification ability is extremely excellent.

According to the invention of claim 23, in addition to the effect of any one of claims 11 to 22, (1) the alkali metal sulfate contains a mixture of cesium sulfate and potassium sulfate. An exhaust gas purifying material having extremely high catalytic activity when burning particulates can be obtained.

According to the invention of the twenty-fourth aspect, in addition to the effect of any one of the eleventh to twenty- _third aspects, (1) Ta ₂ O ₅ , Nb _{2 is used} as a carrier for supporting a transition metal oxide.
O ₅ , WO ₃ , SnO ₂ , SiO ₂ , TiO ₂ , Al ₂ O ₃ ,
Since it contains at least one inorganic oxide selected from ZrO _2, the surface area of the transition metal oxide catalyst is increased, and as a result, the number of contacts with the particulates is increased. And it can be stably exhibited.

According to the twenty-fifth aspect, in addition to the effects of any one of the eleventh to twenty-fourth aspects, (1) the tertiary structure having heat resistance is a wall-through type honeycomb filter or Since it is formed of a foam, approximately 100% of the particulate component can be collected by the filter, and the collection efficiency can be maximized. (2) Since the three-dimensional structure is formed of a honeycomb filter, a foam or a metal film, the contact area between the exhaust gas purifying catalyst and the particulates increases,
Particulates can be burned and removed efficiently,
An exhaust gas purifying material having extremely excellent exhaust gas purifying ability can be obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) F01N 3/02 301 F01N 3/02 301D 321A 321 B01D 53/36 104B (72) Inventor Nobuyuki Tokubuchi Kadoma, Osaka Matsushita Electric Industrial Co., Ltd. (72) Inventor Masaaki Arita 1006 Ojimon Kadoma, Kadoma City, Osaka Pref. Matsushita Electric Industrial Co., Ltd. F term (reference) 3G090 AA03 BA01 CA03 4D019 AA01 BA02 BA05 BB06 BB07 BC07 CA01 CA10 4D048 AA14 AB01 BA03X BA06X BA07X BA08X BA10X BA14X BA18Y BA21X BA23X BA24X BA26X BA27X BA28Y BA30 BAY BAY BAY BAY BAY BB09 BB14 BB16 CC38 CC45 CC50 4G069 AA03 BA01A BA01B BA02A BA02B BA04A BA04B BA05A BA05B BA13A BA17 BB02B BB04A BB04B BB06A BB06B BB10A BB10B BC01A BC02A BC02B BC03A BC03B BC04A BC04B BC05A BC05B BC06A BC06B BC22A BC22B BC31A BC54A BC54B BC55A BC55B BC56A BC56B BC59A BC59B BC60A BC60B BC62A BC62B BC67A BC67B BC69A BC70A BC71A BC72A BC72B BC75A BC75B CA02 CA03 CA07 CA18 EA01X EA18 EA19 EA27 EB11 EC28 EC29 EE08

Claims (25)

[Claims] 1. A first catalyst comprising a heat-resistant inorganic oxide, a transition metal oxide catalyst layer supported on the surface of the inorganic oxide, and a first catalyst comprising at least one alkali metal sulfate. 2. An exhaust gas purifying catalyst comprising: 2. A first catalyst having a heat-resistant inorganic oxide and a transition metal oxide catalyst layer carried on the surface of the inorganic oxide, a heat-resistant inorganic oxide and the inorganic oxide An exhaust gas purifying catalyst comprising: a third catalyst having a noble metal catalyst layer supported on the surface of a catalyst; and a second catalyst having at least one kind of alkali metal sulfate. 3. The exhaust gas purifying catalyst according to claim 2, wherein the noble metal contains Pt. 4. The oxide of a transition metal is Cu, Mn, C
The exhaust gas purifying catalyst according to any one of claims 1 to 3, further comprising at least one metal oxide selected from o, V, Mo, and W. 5. The oxide of Cu is CuO, Cu ₂ O, Cu
Exhaust gas purifying catalyst according to any one of claims 1 to 4, characterized in that from ₂ O ₃ is at least one selected. 6. The exhaust gas purifying catalyst according to claim 1, wherein the oxide of the transition metal contains a composite metal oxide consisting of Cu and V. 7. The composite metal oxide is composed of Cu ₅ V ₂ O ₁₀ , Cu
_{V 2 O 6, Cu 3 V} 2 exhaust gas purifying catalyst according to any one of claims 1 to 6, characterized in that the O ₈ is at least one selected. 8. The exhaust gas purifying catalyst according to claim 1, wherein said alkali metal sulfate contains cesium sulfate. 9. The exhaust gas purifying catalyst according to claim 1, wherein the sulfate of the alkali metal contains a mixture of cesium sulfate and potassium sulfate. 10. The heat-resistant inorganic oxide is Ta ₂ O ₅ , N
b ₂ O ₅ , WO ₃ , SnO ₂ , SiO ₂ , TiO ₂ , Al
₂ O _3, at least one exhaust gas purification catalyst according to any one of claims 1 to 9, characterized in that it contains an inorganic oxide selected from ZrO _2. 11. A three-dimensional structure having heat resistance, and
An exhaust gas purifying material comprising: a layer of the exhaust gas purifying catalyst according to claim 1 formed on a three-dimensional structure. 12. A three-dimensional structure having heat resistance, wherein
An exhaust gas purifying material comprising: a layer of the exhaust gas purifying catalyst according to claim 2 formed on a three-dimensional structure. 13. A three-dimensional structure having heat resistance, wherein:
2. The exhaust gas purifying catalyst according to claim 1, wherein the first catalyst layer is formed on a three-dimensional structure, and the second catalyst layer is formed on an upper surface of the layer. Exhaust gas purifying material. 14. A three-dimensional structure having heat resistance;
3. The exhaust gas purifying catalyst according to claim 2, wherein the first catalyst and the third catalyst are formed on a three-dimensional structure, and the second catalyst is formed on an upper surface of the layer. An exhaust gas purifying material comprising: 15. A three-dimensional structure having heat resistance, wherein
The exhaust gas purifying catalyst according to claim 1, wherein the second catalyst layer of the exhaust gas purifying catalyst according to claim 1 formed on a three-dimensional structure, and the second catalyst layer is contained in the second catalyst layer. And a powder particle of the first catalyst. 16. A three-dimensional structure having heat resistance;
2. The exhaust gas purification catalyst according to claim 1, wherein the second catalyst layer of the exhaust gas purification catalyst according to claim 1 formed on a three-dimensional structure, and the second catalyst layer is included in the second catalyst layer. An exhaust gas purifying material comprising: powder particles of the first catalyst and powder particles of the third catalyst. 17. The exhaust gas purifying material according to claim 12, wherein the noble metal contains Pt. 18. The method according to claim 18, wherein the oxide of the transition metal is Cu, Mn, C
18. A semiconductor device comprising at least one metal oxide selected from the group consisting of o, V, Mo, and W.
The exhaust gas purifying material according to any one of the above. 19. The method according to claim 19, wherein the Cu oxide is CuO, Cu ₂ O,
Exhaust gas purification material according to any one of claims 11 to 18, characterized in that the Cu ₂ O ₃ is at least one selected. 20. The method according to claim 1, wherein the oxide of the transition metal contains a composite metal oxide comprising Cu and V.
An exhaust gas purifying material according to any one of 1 to 19. 21. The composite metal oxide is Cu_FiveV_TwoO_Ten, C
uV_TwoO₆, Cu_ThreeV_TwoO ₈At least one selected from
21. Any of claims 11 to 20, wherein
2. The exhaust gas purifying material according to claim 1. 22. The exhaust gas purifying material according to claim 11, wherein the alkali metal sulfate contains cesium sulfate. 23. The exhaust gas purifying material according to claim 11, wherein the alkali metal sulfate contains a mixture of cesium sulfate and potassium sulfate. 24. The heat-resistant inorganic oxide is Ta ₂ O ₅ , N
b ₂ O ₅ , WO ₃ , SnO ₂ , SiO ₂ , TiO ₂ , Al
₂ O _3, the exhaust gas purifying material according to any one of claims 11 to 23, characterized in that it contains at least one inorganic oxide selected from ZrO _2. 25. The method according to claim 11, wherein the heat-resistant three-dimensional structure is a wall-type honeycomb filter, a flow-through type foam or a metal filter. Exhaust gas purifying material according to Item.