JPH0970536A - Purifying material for exhaust gas and purifying method of exhaust gas - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently reduce and remove nitrogen oxides from combustion exhaust gas by disposing a mixture catalyst of a first catalyst and a second catalyst in the inlet side of the exhaust gas and disposing a mixture catalyst of a third catalyst and a fourth catalyst in the outlet side of the exhaust gas. SOLUTION: A mixture of a first catalyst and a second catalyst is disposed in the inlet side of the exhaust gas, while a mixture catalyst of a third catalyst and a fourth catalyst is disposed in the outlet side. The first catalyst carries one or more kinds of silver and/or silver compds. by 0.2-15wt.% on a porous inorg. oxide. The second catalyst carries a compd. of at least one element selected from W, V and Mo by 0.01-10wt.%. The third catalyst carries one or more kinds of element and/or compds. of copper, nickel and silver by 0.5-30wt.%, a compd. of one or more elements of W, V and Mo by <=30wt.% and one or more kinds of rare earth elements and alkali metal elements by <=5wt.%. The fourth catalyst carries at least one kind of element selected from Pt, Pd, Ru, Rh, Ir and Au by 0.01-5wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an exhaust gas purifying material capable of effectively reducing and removing nitrogen oxides from a combustion exhaust gas containing nitrogen oxides and excess oxygen, and a purification method using the same.

[0002]

2. Description of the Related Art Excessive combustion exhaust gas emitted from internal combustion engines such as automobile engines, combustion equipment installed in factories, household fan heaters, and the like is excessive. It contains nitrogen oxides such as nitric oxide and nitrogen dioxide together with oxygen. Here, "containing excess oxygen" means that the exhaust gas contains more oxygen than the theoretical amount of oxygen necessary to burn unburned components such as carbon monoxide, hydrogen, and hydrocarbons. I do. In the following, nitrogen oxide refers to nitric oxide and / or nitrogen dioxide.

[0003] This nitrogen oxide is one of the causes of acid rain and is a major environmental problem. Therefore, various methods for removing nitrogen oxides in exhaust gas discharged from various combustion equipments are being studied.

[0004] As a method for removing nitrogen oxides from a combustion exhaust gas containing excess oxygen, a selective catalytic reduction method using ammonia is used particularly for a large-scale fixed combustion device (a large-scale combustor in a factory or the like). Has been put to practical use.

However, in this method, ammonia used as a reducing agent for nitrogen oxides is expensive, and ammonia is toxic. Therefore, the nitrogen oxides in the exhaust gas must be removed so that unreacted ammonia is not discharged. There are problems that the amount of injected ammonia must be controlled while measuring the concentration, and that the apparatus generally becomes large.

As another method, there is a non-selective catalytic reduction method in which a nitrogen oxide is reduced by using a gas such as hydrogen, carbon monoxide, or a hydrocarbon as a reducing agent. In order to reduce and remove nitrogen oxides, it is necessary to add a reducing agent in an amount equal to or more than a theoretical reaction amount with oxygen in exhaust gas, and there is a disadvantage that a large amount of the reducing agent is consumed. For this reason, the non-selective catalytic reduction method is practically effective only for exhaust gas having a low residual oxygen concentration burned near the stoichiometric air-fuel ratio, and is not practical because of poor versatility.

In view of the above, a method has been proposed for removing nitrogen oxides by using a zeolite or a catalyst carrying a transition metal on the zeolite and adding a reducing agent having a theoretical reaction amount or less with oxygen in exhaust gas (for example, Japanese Patent Application Laid-Open No. H11-157572). Kaisho 63-100919, 63-283727
No., Japanese Patent Application Laid-Open No. 1-130735). Also, a method of decomposing nitrogen oxides in exhaust gas while supplying a hydrocarbon gas using a catalyst in which an alkaline earth metal and / or silver is supported on a carrier such as γ-alumina (JP-A-4-354536) A method of reducing and removing nitrogen oxides in exhaust gas by using a catalyst comprising alumina and silver-containing silica or zirconia while supplying a hydrocarbon or an oxygen-containing compound has been proposed (JP-A-7-24261).

However, according to these methods, effective removal of nitrogen oxides can be obtained only in a narrow temperature range, and in the case of exhaust gas from a vehicle or the like which contains water and whose exhaust gas temperature greatly changes depending on operating conditions, The nitrogen oxide removal rate is significantly reduced.

Accordingly, it is an object of the present invention to provide a method for producing nitrogen oxides, carbon monoxide, hydrogen, hydrocarbons, and the like, such as combustion exhaust gas from a fixed combustion device and a gasoline engine, a diesel engine, or the like, which burns under oxygen excess conditions. By providing an exhaust gas purifying material and an exhaust gas purifying method capable of efficiently reducing and removing nitrogen oxides from combustion exhaust gas containing oxygen in excess of the theoretical reaction amount with respect to unburned components and containing sulfur oxides and moisture. is there.

[0010]

Means for Solving the Problems In view of the above-mentioned problems, as a result of intensive studies, the present inventors have found that a catalyst comprising a porous inorganic oxide carrying a silver component and a porous inorganic oxide carrying a W-based component. An organic compound such as ethanol reacts with exhaust gas containing oxygen and nitrogen oxides on the mixed catalyst obtained by mixing the catalysts, and reduces nitrogen oxides to nitrogen gas even in exhaust gas containing moisture, sulfur dioxide, etc. In addition, they have found that nitrogen-containing compounds such as nitrites and ammonia and aldehydes are produced as by-products. One or more of silver, copper, and nickel capable of effectively reducing nitrogen-containing compounds to nitrogen under exhaust gas conditions containing nitrogen-containing compounds such as nitrites, ammonia, and aldehydes generated by a mixed catalyst of silver and W, and W A mixture of a catalyst carrying a system component and a rare earth element or an alkali metal element with a platinum-based or platinum-based or W-based catalyst, and using the exhaust gas purifying material in combination with the silver and W-mixed catalyst, in the exhaust gas Adding a hydrocarbon and any of oxygen-containing organic compounds having 2 or more carbon atoms or a fuel containing them;
If exhaust gas is brought into contact with the above-mentioned purifying material, nitrogen oxides can be effectively removed in a wide temperature range, and residual carbon monoxide, hydrocarbons and SOF (soluble organic components) in the exhaust gas.
The present inventors have found that oxidation of sulfur dioxide can be suppressed in an exhaust gas containing sulfur dioxide by using a platinum or W-based catalyst, and the present invention has been completed.

That is, the first exhaust gas purifying material of the present invention for reducing and removing nitrogen oxides from a combustion exhaust gas containing nitrogen oxides and oxygen in an amount larger than the theoretical reaction amount of coexisting unburned components is a first catalyst, It comprises a second catalyst, a third catalyst and a fourth catalyst. (1) The first catalyst comprises a porous inorganic oxide and one or more elements selected from the group consisting of silver and silver compounds and / or (2) The second catalyst is a group consisting of W, V, Mo, Mn, Nb, and Ta on a porous inorganic oxide. A compound of at least one element selected from
01 to 10% by weight (metal element conversion value)
(3) The third catalyst is a porous inorganic oxide which comprises (a)
One or more elements and / or compounds selected from the group consisting of copper, nickel, and silver 0.5 to 30% by weight (in terms of metal element) and (b) W, V, Mo, Mn, Nb, and Ta. A compound of at least one element selected from the group consisting of 30% by weight or less (in terms of a metal element) and (c) one or more elements selected from the group consisting of a rare earth element and an alkali metal element of 5% by weight or less (in terms of an element) And (4) the fourth catalyst comprises Pt, Pd, Ru, R
at least one selected from the group consisting of h, Ir and Au
A mixed catalyst that carries 0.01 to 5% by weight (converted to a metal element) of a seed element, and is formed by mixing the first catalyst and the second catalyst on the exhaust gas inflow side of the exhaust gas purifying material To
An outlet side is provided with a mixed catalyst obtained by mixing the third catalyst and the fourth catalyst.

Further, the second exhaust gas purifying material of the present invention for reducing and removing nitrogen oxides from a combustion exhaust gas containing nitrogen oxides and oxygen in an amount larger than a theoretical reaction amount for coexisting unburned components is a first catalyst, It comprises a second catalyst, a third catalyst and a fourth catalyst. (1) The first catalyst comprises a porous inorganic oxide and one or more elements selected from the group consisting of silver and silver compounds and / or (2) The second catalyst is a group consisting of W, V, Mo, Mn, Nb, and Ta on a porous inorganic oxide. A compound of at least one element selected from the group consisting of 0.01
-10% by weight (converted to metal element)
(3) The third catalyst is a porous inorganic oxide which comprises (a)
One or more elements and / or compounds selected from the group consisting of copper, nickel and silver, and 0.5 to 30% by weight (converted to metal elements); and (b) W, V, Mo, Mn, Nb, and Ta. A compound of at least one element selected from the group consisting of 30% by weight or less (in terms of a metal element) and (c) one or more elements selected from the group consisting of a rare earth element and an alkali metal element of 5% by weight or less (in terms of an element) And (4) the fourth catalyst comprises W, V, Mo, Mn,
0.2 to 10% by weight of a compound of at least one element selected from the group consisting of Nb and Ta (in terms of a metal element);
It carries at least one element selected from the group consisting of Pt, Pd, Ru, Rh, Ir, and Au in an amount of 0.01 to 5% by weight (in terms of a metal element), and the inflow of exhaust gas into the exhaust gas purifying material. And a mixed catalyst obtained by mixing the third catalyst and the fourth catalyst on the outflow side, and a mixed catalyst obtained by mixing the first catalyst and the second catalyst on the side. And

Further, an exhaust gas purifying method of the present invention for reducing and removing nitrogen oxides from a combustion exhaust gas containing nitrogen oxides and oxygen in excess of the theoretical reaction amount for coexisting unburned components uses the above exhaust gas purifying material. The exhaust gas purifying material is installed in the middle of an exhaust gas conduit, and the exhaust gas to which hydrocarbons and / or oxygen-containing organic compounds are added upstream of the purifying material is
The nitrogen oxides are removed by contacting the purifying material at 50 to 600 ° C. and reacting with the hydrocarbons and / or oxygen-containing organic compounds in the exhaust gas.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. [1] Exhaust gas purifying material The first and second exhaust gas purifying materials of the present invention comprise a first catalyst, a second catalyst, a third catalyst, and a fourth catalyst. There is a mixed catalyst obtained by mixing the first catalyst and the second catalyst, and a mixed catalyst obtained by mixing the third catalyst and the fourth catalyst on the outlet side.

In the present invention, the above-mentioned purifying material is installed in an exhaust gas conduit, and either hydrocarbon or an oxygen-containing organic compound having 2 or more carbon atoms or a fuel containing them is added upstream of the purifying material installation position. The exhaust gas is brought into contact with the purifying material to reduce and remove nitrogen oxides in the exhaust gas.

A first preferred embodiment of the exhaust gas purifying material of the present invention is a powdery porous inorganic oxide comprising a catalytically active species supported on a first, second, third and fourth catalyst. A purifying material obtained by coating one or more purifying material bases. As the ceramic material forming the base of the purifying material, cordierite, mullite, alumina and a composite thereof are preferably used. In addition, a known metal material can be used for the base of the exhaust gas purifying material.

The shape and size of the substrate of the exhaust gas purifying material are as follows:
Various changes can be made according to the purpose. Also, as its structure,
Examples include a honeycomb structure type, a foam type, a three-dimensional network structure type made of a fibrous refractory, a granular form, a pellet form, and the like. The catalyst may be coated on the substrate using a wash coat method, a powder method, or the like, or a wash coat method, a sol
After the porous inorganic oxide is coated on the substrate using a gel method or the like, the catalytically active species can be supported using a known impregnation method, an ion exchange method, or the like.

The second preferred form of the exhaust gas purifying material of the present invention is a catalyst comprising a porous inorganic oxide in the form of pellets, granules, powders, honeycombs or plates carrying a catalytically active species, or a catalyst. It is a purifying material obtained by molding a powdery porous inorganic oxide carrying each active species into pellets or granules and filling the resultant into a casing having a desired shape.

The following catalyst is formed on the purifying material of the present invention. (1) First catalyst The first catalyst comprises a porous inorganic oxide carrying one or more elements and / or compounds selected from the group consisting of silver and silver compounds, and performs nitrogen oxidation in a wide temperature range. Acts on object removal. As the porous inorganic oxide, alumina alone, or titania, silica, zirconia, zinc oxide, tin oxide,
A composite or mixed oxide of either magnesium oxide or zeolite and alumina can be used. It is preferable that the alumina content is 50% by weight or more. The use of alumina or a composite or mixed oxide of alumina improves the heat resistance and durability of the catalyst. Here, the tin oxide includes tin oxide in various oxidation states, and examples of the main tin oxide include stannous oxide and stannic oxide.

The specific surface area of the porous inorganic oxide such as alumina used for the first catalyst is preferably 10 m ² / g or more. If the specific surface area is less than 10 m ² / g, the dispersion of the silver component is reduced, and good removal of nitrogen oxides cannot be performed.
More preferable specific surface area of the porous inorganic oxide is 30 m ² /
g or more.

The silver compound is at least one selected from the group consisting of silver oxide, silver halide, silver sulfate and silver phosphate, and preferably at least one of silver oxide, silver chloride and silver sulfate. And more preferably silver oxide and / or silver chloride. The supported amount of the silver component is 0.2 to 15% by weight (in terms of silver element) based on 100% by weight of the porous inorganic oxide. If the amount is less than 0.2% by weight, the removal rate of nitrogen oxides decreases. If the silver component is carried in an amount exceeding 15% by weight, the combustion of the hydrocarbon and / or the oxygen-containing organic compound itself tends to occur, and the nitrogen oxide removal rate is rather lowered. A preferable loading amount of the silver component is 0.5 to 12% by weight.
It is.

As a method for supporting silver on an inorganic oxide such as alumina, a known impregnation method, precipitation method, or the like can be used. When using the impregnation method, the porous inorganic oxide is immersed in an aqueous solution of silver nitrate, chloride, sulfate, carbonate, or the like, or an aqueous ammonia solution. Alternatively, the porous inorganic oxide is immersed in an aqueous solution of silver nitrate, dried, and then immersed again in an aqueous solution of ammonium chloride or ammonium sulfate. To prepare silver halide by the precipitation method, silver nitrate and ammonium halide are reacted to precipitate silver halide on the porous inorganic oxide. After drying at 50 to 150 ° C., particularly at about 70 ° C., it is preferable to raise the temperature stepwise at 100 to 600 ° C. for firing. The calcination is preferably performed in air, under a stream of nitrogen containing oxygen or under a stream of hydrogen gas. When the treatment is performed under a hydrogen gas stream, it is preferable to perform the oxidation treatment at 300 to 650 ° C. at last.

(2) Second catalyst The second catalyst comprises W, V, Mo, M
It supports a compound of at least one element selected from the group consisting of n, Nb, and Ta. As the porous inorganic oxide, any of alumina, titania, zeolite, silica, and zirconia, or a composite or mixed oxide containing them can be used. Various zeolites such as ferrierite, mortenite, and ZSM-5 can be used as the zeolite. Similar to the first catalyst, the specific surface area of the porous inorganic oxide is preferably 10 m ² / g or more.

The compound of W, V, Mo, Mn, Nb and Ta is preferably an oxide. 10 porous inorganic oxides
Assuming 0% by weight, the loading amount of the W-based component is 0.01 to 10% by weight (in terms of a metal element), preferably 0.05 to 10%.
It is 8% by weight (in terms of metal element).

W, V, Mo, inorganic oxides such as alumina
As a method for supporting Mn, Nb, and Ta, a known impregnation method, precipitation method, or the like can be used. Specifically, a porous inorganic oxide is immersed and used in a solution of a salt compound of each element, for example, a solution obtained by adding oxalic acid to an ammonium salt. After drying at 50 to 150 ° C., particularly at about 70 ° C., it is preferable to raise the temperature stepwise at 100 to 600 ° C. for firing. This calcination is performed in air under a nitrogen stream containing oxygen. It is also an effective method to use metatitanic acid (hydrous titanium oxide) as a starting material instead of titania and to carry V, W, and Mo. When zeolite is used as the inorganic oxide, it is preferable to support the zeolite by an impregnation method or a known ion exchange method.

In the present invention, a mixed catalyst obtained by mixing the first catalyst and the second catalyst is used. This mixing allows the catalysis of the first catalyst and the catalysis of the second catalyst to proceed simultaneously without affecting each other. The weight ratio of the first catalyst to the second catalyst (the ratio of the total weight of the porous inorganic oxide and the catalytically active species) is preferably 1:10 to 20: 1. More preferably, the weight ratio of the first catalyst to the second catalyst is 1: 5 to 10: 1.

In the case where the form of the purifying material is the first preferred embodiment described above, the thickness of the mixed catalyst provided on the purifying material base generally depends on the difference in thermal expansion characteristics between the base material and the mixed catalyst. Is often restricted from. The thickness of the catalyst provided on the purifying material base is preferably 300 μm or less. With such a thickness, it is possible to prevent the purifying material from being damaged by thermal shock or the like during use. A method for forming a catalyst on the surface of the purifying material base is performed by a known wash coat method or the like.

The amount of the mixed catalyst provided on the surface of the purifying material base is preferably 20 to 300 g / liter of the purifying material base. If the amount of the catalyst is less than 20 g / liter, good NOx removal cannot be performed. On the other hand, when the amount of the catalyst is 300
When the amount exceeds g / liter, the removal characteristics do not increase so much.
Pressure loss increases. More preferably, the mixed catalyst provided on the surface of the purification material substrate is 50 to 200 g of the purification material substrate.
/ Liter.

(3) Third catalyst The third catalyst comprises a porous inorganic oxide, as a catalytically active species, (a) one or more elements and / or compounds selected from the group consisting of copper, nickel and silver; (B) W, V, Mo, M
It carries one or more compounds of one or more elements selected from the group consisting of n, Nb, and Ta, and (c) one or more elements selected from the group consisting of rare earth elements and alkali metal elements. As the porous inorganic oxide, alumina, titania,
Either zeolite, silica, zirconia, or the like, or a composite or mixed oxide containing them is used. Various zeolites such as ferrierite, mortenite, and ZSM-5 can be used as the zeolite. Similar to the first catalyst, the specific surface area of the porous inorganic oxide is preferably 10 m ² / g or more.

The nickel compound is at least one selected from the group consisting of nickel oxides, halides, sulfates and the like. The silver compound is silver oxide, silver halide,
It is at least one selected from the group consisting of silver sulfate and silver phosphate. The copper compound is at least one selected from the group consisting of copper oxides, halides, sulfates and the like. With the porous inorganic oxide being 100% by weight, silver, copper,
The total supported amount of nickel is 0.5 to 30% by weight (converted to metal element), and the preferable total supported amount is 0.5 to 25% by weight (converted to metal element).

When the nickel component and the silver component are used simultaneously, the weight ratio of the nickel element to the silver element is 1: 5 to 5: 1.
Similarly, the weight ratio between the nickel element and the copper element is 1: 5.
５5: 1, and the weight ratio of silver element to copper element is 1: 5
The ratio is preferably 5: 1.

The compound of W, V, Mo, Mn, Nb and Ta is preferably an oxide. 10 porous inorganic oxides
Assuming 0% by weight, the loading amount of the W-based component is 30% by weight or less (in terms of a metal element), preferably 0.05 to 20%.
% By weight (in terms of metal element).

Preferred rare earth elements are La, Ce, Y, N
d, and preferred alkali metal elements are Na, K, C
s and Li. Alkali metal elements and / or
Alternatively, by using a rare earth element, the durability of the catalyst is improved, and the characteristic of removing nitrogen oxides by residual hydrocarbons is improved. Assuming that the porous inorganic oxide is 100% by weight, the total carrying amount of the rare earth element and the alkali metal element is 5% by weight or less (element conversion value), preferably 4% by weight or less (element conversion value).

The active species can be supported by a known impregnation method, precipitation method,
An ion exchange method or the like can be used. First, a W-based component is supported, dried at 50 to 150 ° C., particularly 70 ° C., and then dried.
After the temperature is increased stepwise at 0 to 600 ° C. and calcined, copper, nickel, a silver component, a rare earth element, and an alkali metal element are supported, and after drying at 50 to 150 ° C., particularly 70 ° C., 10
It is carried out by raising the temperature stepwise at 0 to 600 ° C. and firing. This calcination is performed in air under a nitrogen stream containing oxygen. When using the impregnation method, the porous inorganic oxide is immersed in an aqueous solution of a carbonate, nitrate, acetate, sulfate or the like of the catalytically active species element. In the case of copper, nickel, silver components, rare earth elements and alkali metal elements, aqueous solutions of acetate, sulfate, nitrate and the like are used. In the case of W, V, Mo, Mn, Nb, Ta,
The porous inorganic oxide is immersed in a solution of a salt compound of each element, for example, a solution obtained by adding and dissolving oxalic acid to an ammonium salt. Also, metatitanic acid (hydrous titanium oxide) is used as a starting material instead of titania, and V, W, M
Carrying o is also an effective method. When zeolite is used as the inorganic oxide, it is effective to carry the zeolite by an impregnation method or a known ion exchange method. The loading of the silver catalyst can be carried out in the same manner as in the first catalyst. On the third catalyst thus prepared, silver, nickel, and copper are present in the form of silver, nickel, copper, or oxides, halides, and sulfates thereof, respectively.

The weight ratio of the mixed catalyst of the first catalyst and the second catalyst to the third catalyst (the ratio of the total weight of the porous inorganic oxide to the catalytically active species) is 1: 5 to 20: It is preferably set to 1. More preferably, the weight ratio of the mixed catalyst of the first catalyst and the second catalyst to the third catalyst is 1: 2 to 10: 1.

(4) Fourth Catalyst The fourth catalyst comprises a porous inorganic oxide carrying a catalytically active species, acts to remove nitrogen oxides in a low temperature range, and acts on carbon monoxide and carbon dioxide. It acts on the oxidative removal of hydrogen. As the porous inorganic oxide, it is preferable to use any of alumina, titania, zeolite, silica, zirconia and the like, or a composite or mixed oxide containing them. Similar to the first catalyst, the specific surface area of the porous inorganic oxide is preferably 10 m ² / g or more.

In the first exhaust gas purifying material of the present invention, at least one element selected from the group consisting of Pt, Pd, Ru, Rh, Ir and Au is used as the active species of the fourth catalyst. Among Pt, Pd, Ru, Rh and Au, it is particularly preferable to use at least one of Pt, Pd and Au. Assuming that the porous inorganic oxide is 100% by weight, the supported amount of the platinum component is 0.01 to 5% by weight (in terms of a metal element).
And preferably 0.01 to 4% by weight (in terms of a metal element).

In the second exhaust gas purifying material of the present invention, the active species of the fourth catalyst is W, V, Mo, Mn, Nb, Ta.
And at least one element selected from the group consisting of Pt, Pd, Ru, Rh, Ir, and Au. W,
Of V, Mo, Mn, Nb and Ta, it is preferable to use W and / or V, and Pt, Pd, Ru, Rh and Au
Among them, it is particularly preferable to use at least one of Pt, Pd and Au. Assuming that the porous inorganic oxide is 100% by weight, the supported amount of the W-based component is 0.2 to 10% by weight (in terms of a metal element), and the supported amount of the platinum-based component is 0.01 to 5%.
% By weight (in terms of metal element). The preferred amount of the W-based component is 0.2 to 9% by weight (in terms of a metal element),
The preferable loading amount of the platinum component is 0.01 to 4% by weight (in terms of metal element).

By using a Pt-based or Pt / W-based catalyst, residual carbon monoxide, hydrocarbons, SOF and the like in exhaust gas can be effectively oxidized and removed. In particular, when a Pt or W-based catalyst is used, even in an exhaust gas containing sulfur dioxide, the oxidation of sulfur dioxide is suppressed, and residual carbon monoxide, hydrocarbons,
SOF and the like can be effectively oxidized and removed.

For supporting the active species on the fourth catalyst, a known impregnation method, precipitation method or the like can be used. When the impregnation method is used, the porous inorganic oxide is immersed in an aqueous solution of a carbonate, nitrate, acetate, sulfate, chloride, hexachlorometal acid, or dinitrodiamine metal compound of a catalytically active species element. After drying at 50-150 ° C, especially 70 ° C, 100-6
It is carried out by raising the temperature stepwise at 00 ° C. and firing. This calcination is performed in air under a nitrogen stream containing oxygen.
In the case of W, V, Mo, Mn, Nb, and Ta, loading can be performed by the method described for the second catalyst.

The ratio of the weight of the mixed catalyst of the first catalyst and the second catalyst to the weight of the fourth catalyst (ratio of the total weight of the porous inorganic oxide and the catalytically active species) is 1: 2. It is preferably set to 20: 1. When the ratio is less than 1: 2, the purification rate of nitrogen oxides decreases. On the other hand, when the ratio exceeds 20: 1 and the amount of the fourth catalyst is small, the oxidation characteristics of hydrocarbons, carbon monoxide, and SOF deteriorate. More preferably, the ratio of the weight of the mixed catalyst of the first catalyst and the second catalyst to the weight of the fourth catalyst is from 1: 1 to 15: 1.

In the present invention, the third catalyst and the fourth catalyst are mixed and used. By this mixing, the catalytic action of converting the nitrogen-containing oxide of the third catalyst into nitrogen and the oxidizing action of the fourth catalyst can proceed simultaneously without affecting each other.
When the purifying material is the first preferred embodiment, the thickness of the mixed catalyst of the third catalyst and the fourth catalyst provided on the purifying material base is preferably 300 μm or less. In addition, the amount of the mixed catalyst of the third catalyst and the fourth catalyst provided on the surface of the purifying material base is preferably 20 to 300 g / liter with respect to the purifying material base.

The weight ratio of the third catalyst to the fourth catalyst (the ratio of the total weight of the porous inorganic oxide to the catalytically active species) is 10
The ratio is preferably set to 0: 1 to 100: 50. If the amount of the fourth catalyst is less than 1 part by weight based on 100 parts by weight of the third catalyst, the removal rate of hydrocarbons and carbon monoxide decreases. On the other hand, 50 parts of the fourth catalyst is added to 100 parts by weight of the third catalyst.
If the amount is more than 100 parts by weight, the purification rate of nitrogen oxides is generally lowered in a wide temperature range of 150 to 600 ° C. More preferably, the weight ratio of the third catalyst to the fourth catalyst is 100: 1 to 10
0:30. The mixing of the third catalyst and the fourth catalyst can be performed by a known method.

In the present invention, the weight ratio of the mixed catalyst of the first catalyst and the second catalyst and the mixed catalyst of the third catalyst and the fourth catalyst (the porous inorganic oxide and the catalytically active species and Is preferably 1: 7 to 40: 1. When the ratio is less than 1: 7 (the amount of the mixed catalyst of the first catalyst and the second catalyst is small), the purification rate of nitrogen oxides is reduced overall in a wide temperature range of 150 to 600 ° C. On the other hand, when the ratio exceeds 40: 1, nitrogen-containing compounds such as nitrites and ammonia formed on the first catalyst are discharged without becoming nitrogen, and the removal rates of carbon monoxide and hydrocarbons decrease. I do. More preferably, the weight ratio of the mixed catalyst of the first and second catalysts to the mixed catalyst of the third catalyst and the fourth catalyst is 1: 3 to 2
5: 1.

If the purifying material having the above-described structure is used, 150
In a wide temperature range of up to 600 ° C., good removal of nitrogen oxides can be performed even with an exhaust gas containing about 10% of moisture and sulfur oxides.

[2] Exhaust Gas Purification Method Next, the method of the present invention will be described. First, in the first purification material and the second purification material of the present invention, the exhaust gas purification material is a mixed catalyst of the first catalyst and the second catalyst facing the exhaust gas inflow side, the third catalyst and the The mixed catalyst with the fourth catalyst is installed in the exhaust gas conduit so as to face the outflow side.

Although the exhaust gas contains ethylene, propylene and the like to some extent as residual hydrocarbons, it is generally not enough to reduce NOx in the exhaust gas. Preferably, an oxygen-containing organic compound or a reducing agent obtained by mixing the compound with a hydrocarbon fuel is introduced into the exhaust gas. The position where the reducing agent is introduced is upstream of the position where the purifying material is installed.

As the hydrocarbon introduced from the outside, gaseous or liquid alkanes, alkenes and / or alkynes can be used under standard conditions. In particular, alkanes preferably have 2 or more carbon atoms. Specific examples of the hydrocarbon in a liquid state in a standard state include hydrocarbons such as light oil, cetane, heptane, kerosene, and gasoline. Among them, boiling point 5
Hydrocarbons at 0-350 ° C are particularly preferred. As the oxygen-containing organic compound introduced from the outside, alcohols such as ethanol and isopropyl alcohol having 2 or more carbon atoms, or a fuel containing them can be used.

The amount of the hydrocarbon and / or oxygen-containing organic compound introduced from the outside is determined by the weight ratio (weight of the reducing agent to be added / weight).
(Weight of nitrogen oxides in the exhaust gas) is preferably 0.1 to 5. If the weight ratio is less than 0.1, the removal rate of nitrogen oxides does not increase. On the other hand, if it exceeds 5, fuel efficiency will be degraded.

When a fuel containing a hydrocarbon or an oxygen-containing organic compound is added, it is preferable to use gasoline, light oil, kerosene or the like as the fuel. In this case, the amount of the reducing agent is set such that the weight ratio (the weight of the reducing agent to be added / the weight of the nitrogen oxide in the exhaust gas) is 0.1 to 5 in the same manner as described above.

In the present invention, the space velocity of the mixed catalyst of the first catalyst and the second catalyst is 200,000 h in order to efficiently promote the reduction and removal of nitrogen oxides by oxygen-containing organic compounds, hydrocarbons and the like. ^-1 or less, preferably 150,000 h ^-1 or less. The space velocity of the mixed catalyst of the third catalyst and the fourth catalyst is
200,000 ^-1 or less, preferably 150,000H ^-1 or less.

Further, in the present invention, the temperature of the exhaust gas at the purification material installation site where the hydrocarbon and / or the oxygen-containing organic compound reacts with the nitrogen oxide is set to 150 to 600 ° C.
To keep. If the temperature of the exhaust gas is lower than 150 ° C., the reaction between the reducing agent and the nitrogen oxide does not proceed, and it is not possible to remove the nitrogen oxide satisfactorily. On the other hand, if the temperature exceeds 600 ° C., the combustion of the hydrocarbon and / or the oxygen-containing organic compound itself starts, and the reduction and removal of nitrogen oxides cannot be performed. The preferred exhaust gas temperature is from 200 to 550 ° C, more preferably from 250 to 550 ° C.

[0053]

The present invention will be described in more detail with reference to the following specific examples. Example 1 Commercially available silica-alumina powder (silica content 5% by weight,
^3. Using an aqueous solution of silver nitrate to a specific surface area of 350 m ² / g).
1% by weight (in terms of metal element) of silver was supported, dried, and fired stepwise in air to 600 ° C. to prepare a silver-based silver catalyst (first catalyst).

Put ammonium tungstate in water,
A commercially available powdery γ-
After injecting and impregnating alumina (specific surface area: 200 m ² / g), the γ-alumina powder is separated from the solution, heated to 600 ° C. in air in a stepwise manner, and calcined to obtain 4.3 wt. % (Converted to metal element), to prepare a W-based catalyst (second catalyst).

After 0.2 g of the first catalyst and 0.06 g of the second catalyst were mixed and slurried, a commercially available cordierite honeycomb-shaped formed body (diameter: 20 mm, length: 8.3 m)
m, 400 cells / inch ² ) and after drying 600
By sintering stepwise to ° C., a W and silver-based exhaust gas purifying material (a purifying material coated with a first catalyst and a second catalyst) was prepared.

Tungsten oxide was supported on powdered silica / alumina in an amount of 3.0% by weight (in terms of a metal element) in the same manner as in the second catalyst, and then an aqueous solution of copper nitrate, lanthanum nitrate and cesium nitrate was used. 4.4 in the same manner as the silver-based catalyst
% By weight of copper, 0.3% by weight of lanthanum and 0.3% by weight
Of cesium (each converted to a metal element), W,
A copper-based catalyst (third catalyst) was prepared.

Powdered titania (specific surface area 35 m ² / g)
Is immersed in chloroplatinic acid aqueous solution for 20 minutes,
Dried at 0 ° C. for 2 hours, under a nitrogen stream at 120 ° C. for 2 hours,
It was baked stepwise for 1 hour from 200 to 400 ° C. Then, under a nitrogen stream containing 4% of hydrogen gas, at 50 ° C. to 400 ° C.
And then calcined at 400 ° C. for 4 hours, and further heated to 50 ° C. to 500 ° C. under a nitrogen stream containing 10% oxygen.
And then calcined at 500 ° C. for 5 hours to carry 1% by weight (in terms of metal element) of platinum with respect to titania to prepare a platinum-based catalyst (fourth catalyst).

After 0.26 g of the third catalyst and 0.05 g of the fourth catalyst were mixed and slurried, a honeycomb-shaped formed body (diameter 20 mm, length 8.8) was prepared in the same manner as W and silver-based purifying materials. 3
mm, 400 cells / inch ² ) and after drying 60
It was fired stepwise to 0 ° C. to prepare a W, copper, platinum-based exhaust gas purifying material (an exhaust gas purifying material coated with a third and fourth catalyst).

W and silver purifying materials were set on the inflow side of the exhaust gas in the reaction tube, and W, copper and platinum purifying materials were set on the outflow side. Next, a gas (nitrogen monoxide, oxygen, ethanol, nitrogen and water) having a composition shown in Table 1 was flowed at a flow rate of 3.48 liters per minute (standard state) (the apparent space velocity of each purification material was about 80,000 h ⁻¹ ), and the temperature of the exhaust gas in the reaction tube was kept in the range of 250 to 550 ° C., and ethanol and nitrogen oxide were reacted.

The concentration of nitrogen oxides in the gas after passing through the reaction tube was measured with a chemiluminescent nitrogen oxide analyzer to determine the nitrogen oxide removal rate. Table 2 shows the results.

Table 1 Component concentration Nitric oxide 800 ppm Oxygen 10% by volume Ethanol 1560 ppm Nitrogen Residual water 10% by volume (based on the total volume of the above components)

Example 2 A commercially available powdery alumina (specific surface area: 200 m ² / g) was loaded with 3.0% by weight (in terms of a metal element) of silver using an aqueous silver nitrate solution, dried, and stepwise dried in air. Was fired to 600 ° C. to prepare a silver-based catalyst (first catalyst) supporting silver.

In the same manner as in Example 1, commercially available powdered alumina (specific surface area: 200
m ² / g), molybdenum of 3.0% by weight (in terms of metal element) was supported, dried, and calcined in air stepwise to 600 ° C. to prepare a Mo-based catalyst (second catalyst). .

After 0.2 g of the first catalyst and 0.06 g of the second catalyst were mixed and slurried, a commercially available cordierite honeycomb molded body (diameter: 20 mm, length: 8.3 m)
m, 400 cells / inch ² ) and after drying 600
The resultant was baked stepwise to ℃ to prepare Mo and silver-based exhaust gas purifying materials (purifying materials coated with a first catalyst and a second catalyst).

In the same manner as in Example 1, 3.2% by weight of a vanadium oxide (in terms of a metal element) was loaded on a commercially available alumina powder (specific surface area: 200 m ² / g) using ammonium vanadate, and then nitric acid was added. Using copper, cerium nitrate, and potassium nitrate aqueous solution, carry 7.0% by weight of copper, 0.3% by weight of cerium, and 0.4% by weight of potassium (each converted to a metal element) in the same manner as in Example 1. Then, V, a copper-based catalyst (third catalyst) was prepared.

After 0.26 g of the third catalyst and 0.06 g of the fourth catalyst of Example 1 were mixed and slurried, M
o, like a silver-based purifying material, a honeycomb-shaped formed body (20 m in diameter)
m, length 8.3 mm, 400 cells / inch ² ), dried and baked stepwise to 600 ° C, V, copper, platinum-based exhaust gas purifying material (exhaust gas coated with third and fourth catalysts) Purification material).

Mo and silver-based purifying materials were set on the inflow side of the exhaust gas in the reaction tube, and V, copper and platinum-based purifying materials were set on the outflow side.
Evaluation was performed using the gas having the composition shown in Table 1 under the same reaction conditions as in Example 1 (the apparent space velocity of each purification material was about 80,000 h ^-1 ). Table 2 shows the results.

Example 3 In the same manner as in Example 1, 1.2% by weight (converted to metal element) of vanadium oxide was supported on commercially available powdered alumina (specific surface area: 200 m ² / g) using ammonium vanadate. Then, after drying, the mixture was calcined in air stepwise to 600 ° C. to prepare a V-based catalyst (second catalyst).

0.2 g of the first catalyst of Example 2 and 0.0
After 6 g of the second catalyst was mixed and slurried, a commercially available cordierite honeycomb-shaped formed body (20 m in diameter) was obtained.
m, length 8.3 mm, 400 cells / inch ² ), dried and baked stepwise to 600 ° C, V, silver-based exhaust gas purifying material (purification coated with first and second catalysts) Material) was prepared.

In the same manner as in Example 1, 2.3 of tungsten oxide was added to powdery titania (specific surface area: 35 m ² / g).
After loading, the same method as in Example 1 was used to prepare 4.5% by weight of an aqueous copper nitrate, nickel nitrate, or lanthanum nitrate solution.
, 2.5% by weight of nickel, and 0.4% by weight of lanthanum (each converted to a metal element) to prepare a W, copper, nickel-based catalyst (third catalyst).

In the same manner as in Example 1, powdery titania (specific surface area: 35 m ² / g) was loaded with 1% by weight (converted to metal element) of Pt with respect to titania using an aqueous solution of chloroplatinic acid. 3.3 wt% (converted to a metal element) of V oxide is supported on powdered titania on which platinum is supported in the same manner as the second catalyst using ammonium, and a V-platinum-based catalyst (fourth catalyst) ) Was prepared.

After 0.26 g of the third catalyst and 0.06 g of the fourth catalyst were mixed and slurried, a honeycomb formed body (diameter 20 mm, length 8 0.3 mm, 400 cells / inch ² ), dried and baked stepwise to 600 ° C. to prepare a copper- and platinum-based exhaust gas purifying material (an exhaust gas purifying material coated with third and fourth catalysts).

V and silver-based purifying materials were set on the inflow side of the exhaust gas in the reaction tube, and copper and platinum-based purifying materials were set on the outflow side. Evaluation was performed using the gas having the composition shown in Table 1 under the same reaction conditions as in Example 1 (the apparent space velocity of each purification material was about 80,000 h ^-1 ). Table 2 shows the results.

Example 4 In the same manner as in Example 1, powdered alumina (specific surface area 200
m ² / g), after supporting 4.0% by weight of a tungsten oxide, copper nitrate, nickel nitrate,
An aqueous solution of sodium nitrate is used to carry 4.4% by weight of copper, 5.0% by weight of nickel and 0.2% by weight of sodium (respectively in terms of metal elements). Was prepared.

After 0.26 g of the third catalyst and 0.06 g of the fourth catalyst of Example 1 were mixed and slurried, a honeycomb formed body (diameter: 20 mm, length: 8.3 mm, 400 cells / inch ² ), dried and baked stepwise to 600 ° C. to prepare copper and platinum based exhaust gas purifying materials (exhaust gas purifying materials coated with third and fourth catalysts). .

The W and silver purifying materials of Example 1 were set on the inflow side of the exhaust gas in the reaction tube, and the copper and platinum purifying materials were set on the outflow side. Under the same reaction conditions as in Example 1 (the apparent space velocity of each purification material is about 80,000 h ^-1 ),
Evaluation was performed using a gas having a composition shown in Table 1. Table 2 shows the results.

Example 5 A commercially available powdered alumina (specific surface area: 200 m ² / g) and powdered stannic oxide (specific surface area: 71 m ² / g) were mixed in a ratio of 95: 5.
In the same manner as in Example 1, 4.1 wt% (in terms of a metal element) of silver was supported on the powder mixed in the same weight ratio as in Example 1, and after drying, it was gradually heated to 600 ° C. in air. By calcining, a silver-based catalyst (first catalyst) carrying silver was prepared.

After mixing 0.2 g of the first catalyst and 0.06 g of the second catalyst of Example 1 to form a slurry, a commercially available cordierite honeycomb-shaped molded product (20 mm in diameter,
8.3 mm long, 400 cells / inch ² )
After drying, it is baked step by step to 600 ° C, W, silver-based exhaust gas purifying material (purifying material coated with first catalyst and second catalyst)
Was prepared.

The W, silver-based purifying material, W, copper, and platinum-based purifying material of Example 1 were set in order from the inflow side to the outflow side of the exhaust gas in the reaction tube. Under the same reaction conditions as in Example 1 (the apparent space velocities of W, a silver-based purifying material and W, copper, and a platinum-based purifying material are each about 80,000 h ^-1 ), a gas having a composition shown in Table 1 was used. The evaluation was carried out. Table 2 shows the results.

Comparative Example 1 A commercially available alumina powder (specific surface area: 200 m ² / g) was loaded with 3.0% by weight (in terms of metal element) of silver using an aqueous silver nitrate solution, dried, and stepwise in air. By baking to 600 ° C., a silver-based catalyst (first catalyst) was prepared. 0.54 g of the first catalyst was used in the same manner as in Example 1 to obtain a commercially available cordierite honeycomb-shaped formed body (diameter: 20 mm, length: 16.6 m)
m, 400 cells / inch ² ) to prepare a silver-based exhaust gas purifying material.

After slurrying 0.18 g of the fourth catalyst of Example 1, the formed honeycomb body (diameter 20 mm, length 6.
6 mm, 400 cells / inch ² ) was coated in the same manner as in Example 1, dried and fired to prepare a platinum-based purifying material.

A silver-based purifying material is provided on the exhaust gas inflow side in the reaction tube.
A platinum-based purifying material was set on the outflow side. The same reaction conditions as in Example 1 (the apparent space velocity of the silver-based purifying material was about 40,00
0h ^-1 and the apparent space velocity of the platinum-based purifying material is about 10
(At 0000 h ⁻¹ )), and the evaluation was performed using a gas having a composition shown in Table 1. Table 2 shows the results.

Table 2 Removal rate of nitrogen oxides (NOx) Removal rate of nitrogen oxides (%) Reaction temperature (° C.) 250 300 350 400 450 500 550 Example 1 78.8 91.8 82.4 66.0 53.4 39.1 33.4 Example 2 77.4 93.0 82.6 67.0 53.0 38.8 33.0 Example 3 77.9 90.0 81.0 62.0 51.6 43.0 36.6 Example 4 76.4 99.7 80.4 66.0 52.0 40.8 34.0 Example 5 78.5 90.6 80.5 68.3 53.5 38.6 34.4 Comparative Example 1 25.6 56.5 60.6 58.6 55.9 43.3 35.7

As can be seen from Table 2, as compared with Comparative Example 1 using a purifying material composed of a silver-based or Pt-based catalyst, in Examples 1 to 5 using the purifying material of the present invention, nitrogen in a wide exhaust gas temperature range was used. Good removal of oxides was observed.

[0085]

As described above in detail, the use of the exhaust gas purifying material of the present invention makes it possible to efficiently remove nitrogen oxides in exhaust gas containing excess oxygen in a wide temperature range. INDUSTRIAL APPLICABILITY The exhaust gas purifying material and the purification method of the present invention can be widely used for purifying exhaust gas of various types of combustors, automobiles and the like.

Claims (7)

[Claims] 1. An exhaust gas purifying material for reducing and removing nitrogen oxides from a combustion exhaust gas containing nitrogen oxides and oxygen in an amount larger than a theoretical reaction amount of coexisting unburned components, wherein the exhaust gas purifying material is a first catalyst, It comprises a second catalyst, a third catalyst and a fourth catalyst. (1) The first catalyst comprises a porous inorganic oxide and one or more elements selected from the group consisting of silver and silver compounds and / or (2) The second catalyst comprises a porous inorganic oxide containing W, V, Mo, Mn, Nb, and Ta.
And (3) the third catalyst comprises a porous inorganic oxide containing (a) a compound of at least one element selected from the group consisting of ) One or more elements and / or compounds selected from the group consisting of copper, nickel and silver, 0.5 to 30% by weight (in terms of metal elements), and (b) W, V, Mo, Mn, Nb, Ta
And 30% by weight or less (in terms of a metal element) of a compound of one or more elements selected from the group consisting of: (c) 5% by weight or less of one or more elements selected from the group consisting of a rare earth element and an alkali metal element (element Conversion value) and
(4) The fourth catalyst contains Pt and P on the porous inorganic oxide.
At least one element selected from the group consisting of d, Ru, Rh, Ir and Au is carried in an amount of 0.01 to 5% by weight (in terms of a metal element), and the above-mentioned exhaust gas purifying material is provided on the exhaust gas inflow side of the exhaust gas purifying material. An exhaust gas comprising: a mixed catalyst obtained by mixing a first catalyst and the second catalyst; and a mixed catalyst obtained by mixing the third catalyst and the fourth catalyst on an outflow side. Purifying material. 2. An exhaust gas purifying material for reducing and removing nitrogen oxides from a combustion exhaust gas containing nitrogen oxides and oxygen in an amount larger than a theoretical reaction amount of coexisting unburned components, wherein the exhaust gas purifying material is a first catalyst, It comprises a second catalyst, a third catalyst and a fourth catalyst. (1) The first catalyst comprises a porous inorganic oxide and one or more elements selected from the group consisting of silver and silver compounds and / or (2) The second catalyst comprises a porous inorganic oxide containing W, V, Mo, Mn, Nb, and Ta.
And (3) the third catalyst comprises a porous inorganic oxide containing (a) a compound of at least one element selected from the group consisting of ) One or more elements and / or compounds selected from the group consisting of copper, nickel and silver, 0.5 to 30% by weight (in terms of metal elements), and (b) W, V, Mo, Mn, Nb, Ta
And 30% by weight or less (in terms of a metal element) of a compound of one or more elements selected from the group consisting of: (c) 5% by weight or less of one or more elements selected from the group consisting of a rare earth element and an alkali metal element (element Conversion value) and
(4) The fourth catalyst comprises W, V, M on the porous inorganic oxide.
0.2 to 10% by weight of a compound of at least one element selected from the group consisting of o, Mn, Nb, and Ta (in terms of a metal element) and a group consisting of Pt, Pd, Ru, Rh, Ir, and Au. At least one selected element of 0.01 to 5
Wt.% (In terms of metal element), and a mixed catalyst obtained by mixing the first catalyst and the second catalyst on the exhaust gas inflow side of the exhaust gas purifying material and the second catalyst on the outflow side. An exhaust gas purifying material comprising a mixed catalyst obtained by mixing a third catalyst and the fourth catalyst. 3. The exhaust gas purifying material according to claim 1, wherein the compound of W, V, Mo, Mn, Nb, and Ta is an oxide, and the silver compound is an oxide of silver or silver halide. , At least one selected from the group consisting of silver sulfate and silver phosphate, wherein the nickel compound is nickel oxide and / or nickel sulfate, and the copper compound is copper oxide and / or copper sulfate. An exhaust gas purifying material characterized by the following. 4. The exhaust gas purifying material according to claim 1, wherein the porous inorganic oxide is alumina alone in the first catalyst, or titania, silica, zirconia, zinc oxide, tin oxide, Magnesium oxide, a composite or mixed oxide of either zeolite and alumina,
An exhaust gas purifying material, wherein the second catalyst, the third catalyst, and the fourth catalyst are each one of alumina, titania, zeolite, silica, and zirconia, or a composite or mixed oxide containing them. 5. The exhaust gas purifying material according to claim 1, wherein at least one of the first, second, third, and fourth catalysts is a ceramic or metal substrate. An exhaust gas purifying material characterized by being coated on the surface. 6. The exhaust gas purifying material according to claim 1, wherein at least one of the first, second, third, and fourth catalysts is in the form of a pellet, a granule, or a honeycomb. Or an exhaust gas purifying material having a plate shape. 7. A method for reducing nitrogen oxides from a combustion exhaust gas containing nitrogen oxides and oxygen which is larger than a theoretical reaction amount of unexisting unburned components using the exhaust gas purifying material according to claim 1. In the exhaust gas purifying method for removing, the exhaust gas purifying material is installed in the middle of an exhaust gas conduit, and the exhaust gas to which hydrocarbons and / or oxygen-containing organic compounds are added on the upstream side of the purifying material is subjected to the purifying material at 150 to 600 ° C. Exhaust gas purifying method, wherein the nitrogen oxides are removed by contact with a hydrocarbon and / or an oxygen-containing organic compound in the exhaust gas.