JPH05245372A - Catalyst for catalytic reduction of nitrogen oxides - Google Patents

Abstract

PURPOSE:To obtain a catalyst capable of effective catalytic reduction of nitrogen oxides contained in an exhaust gas discharged from plants or the like in the presence of oxygen by depositing provskite multiple oxide having the specified structure consisting of various elements included with rare earth elements on solid-acid carrier. CONSTITUTION:The provskite multiple oxide expressed by a formula is deposited on the solid-acid carrier. (In the formula, A is an element selected from group of La, Y, Ce, Pr, Nd, Pm, Sm, Eu, Gd, B is an element selected from group of Na, K, Bi, Th, Ba, Sr, Ca, Mg, Pb, Zn, Ag, C is an element selected from group of Mn, Co, Fe, Ni, Cr, V, Cu, Mo, W, Ta, Li, Ti, Zr, Nb, Pd, Rh, Ru, Pt, 0<=x<=1.) The solid acid carrier is zeolite, metallosilicate, crystalline Al silicate phosphate, crystalline Al phosphate, crystalline metal Al phosphoric acid, alumina, titania, zirconia, silica-alumina or the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for catalytic reduction of nitrogen oxides, and more specifically, it is suitable for use in reducing and removing harmful nitrogen oxides contained in exhaust gas discharged from factories, automobiles and the like. The present invention relates to a catalyst for nitrogen oxidation catalytic reduction using a hydrocarbon and / or oxygen-containing compound as a reducing agent.

[0002]

2. Description of the Related Art Conventionally, nitrogen oxides contained in exhaust gas have been produced by oxidizing nitrogen oxides and then absorbing it in an alkali, or by using a reducing agent such as ammonia, hydrogen, carbon monoxide, or hydrocarbon. It is removed by a method such as conversion to nitrogen. However, according to the former method, it is necessary to treat the generated alkaline waste liquid to prevent pollution. On the other hand, according to the latter method, when ammonia is used as the reducing agent, it reacts with the sulfur oxide in the exhaust gas to form salts, and as a result, there is a problem that the reducing activity of the catalyst decreases. Even when hydrogen, carbon monoxide, hydrocarbon, etc. are used as a reducing agent, these react with oxygen present in a higher concentration than nitrogen oxide present in a low concentration. Has a problem that it requires a large amount of reducing agent.

For this reason, recently, a method of directly decomposing a nitrogen oxide with a catalyst in the absence of a reducing agent has also been proposed. However, such a conventionally known catalyst is a nitrogen oxide. There is a problem that it cannot be put to practical use because of its low decomposition activity. In addition, as a new catalyst for catalytic reduction of nitrogen oxides using a hydrocarbon or an oxygen-containing compound as a reducing agent, H 2
Type zeolite and Cu ion exchange ZSM-5 have been proposed. In particular, H type _{ZSM-5 (SiO 2 / Al} 2 O 3
The molar ratio = 30-40) is said to be optimal. However, even with such H-type ZSM-5, it is hard to say that it still has sufficient reducing activity, and a catalyst for catalytic reduction of nitrogen oxides having higher reducing activity is desired.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to use oxygen when a hydrocarbon or an oxygen-containing compound is used as a reducing agent. Nitrogen oxides react selectively with hydrocarbons and oxygen-containing compounds in the coexistence of nitrogen, so nitrogen oxides catalytic reduction that can efficiently reduce nitrogen oxides in exhaust gas without using large amounts of reducing agents To provide a catalyst for use.

[0005]

A catalyst for catalytic reduction of nitrogen oxides using a hydrocarbon and / or an oxygen-containing compound as a reducing agent according to the invention of claim 1 has a general formula:

[0006]

[Chemical 4]

(Where A is La, Y, Ce, Pr, N
d represents at least one element selected from the group consisting of d, Pm, Sm, Eu and Gd, and B represents Na, K, Bi, T
h, Ba, Sr, Ca, Mg, Pb, Zn, and at least one element selected from the group consisting of Ag, C is Mn, Co, Fe, Ni, Cr, Cu, V, Mo, W,
At least one element selected from the group consisting of Ta, Li, Ti, Zr, Nb, Pd, Rh, Ru, and Pt is shown, and 0 ≦ X ≦ 1. ) Is a perovskite type complex oxide represented by zeolite, metallosilicate, crystalline aluminum silicate phosphate (SAPO), crystalline aluminum phosphate (ALPO), crystalline aluminum metal phosphate (MAPO), alumina, titania, zirconia. ,
It is characterized in that it is supported on a solid acid carrier such as silica-alumina.

Hydrocarbons according to the invention of claim 2 and /
Alternatively, a catalyst for catalytic reduction of nitrogen oxides using an oxygen-containing compound as a reducing agent has a general formula

[0009]

[Chemical 5]

(In the formula, A represents at least one element selected from the group consisting of La, Y and Ce, B represents Na,
K, Bi, Th, Ba, Sr, Ca, Mg, Pb, Zn
And at least one element selected from the group consisting of Ag, C is Mn, Co, Fe, Ni, Cr, Cu,
V, Mo, W, Ta, Li, Ti, Zr, Nb, Pd,
At least one element selected from the group consisting of Rh, Ru, and Pt is shown, and 0 ≦ X ≦ 1. ) Is a perovskite-type composite oxide of zeolite, metallosilicate, crystalline aluminum silicate phosphate (SAP).
O), crystalline aluminum phosphate (ALPO), crystalline metal aluminum phosphate (MAPO), alumina, titania, zirconia, silica-alumina, and other solid acid carriers.

Hydrocarbons according to the invention as claimed in claim 3 and /
Alternatively, a catalyst for catalytic reduction of nitrogen oxides using an oxygen-containing compound as a reducing agent has a general formula

[0012]

[Chemical 6]

(In the formula, A represents La or Ce, and B represents B.
a, Sr, Ca, Mg, Pb, Zn or Ag, and C
Represents Mn or Co, C ′ represents Fe, Ni, Cr, C
u, V, Mo, W, Ti, Zr, Nb, Pd, Rh, R
u or Pt, and 0 ≦ X ≦ 1 and 0 ≦ Y ≦ 1. )
The perovskite type complex oxide represented by is zeolite, metallosilicate, crystalline aluminum silicate phosphate (SAPO), crystalline aluminum phosphate (ALP).
O), crystalline aluminum metal phosphate (MAPO), alumina, titania, zirconia, silica-alumina, or the like.

The solid acid carrier in the present invention means a carrier which exhibits solid acidity in the temperature range where the catalyst is used.
Solid acidity can be confirmed by the temperature programmed desorption method using ammonia,
In situ FTIR with ammonia or pyridine
(Fourier transform infrared absorption spectrum) method. Examples of the solid acid carrier include the following zeolite-based solid acid carriers and oxide-based solid acid carriers.

Zeolite-based solid acid carriers include Na-mordenite, Na-ZSM-5, Na-USY (USY: ultrastable or ultra-stable Y-type zeolite), and a part or all of aluminum in the zeolite to other metal elements. ,
In particular, a zeolite having excellent heat resistance such as iron, gallium, zinc, lanthanum, copper, molybdenum, chromium, germanium, titanium, boron, and the like, which is excellent in heat resistance, is used as an aqueous solution of ammonium salt such as ammonium sulfate, or an acid such as sulfuric acid. Can be obtained by ion-exchange of a part or all of the alkali metal in the zeolite with ammonium ion or hydrogen ion. In the case of the method of performing ion exchange with ammonium ions, a calcination treatment is finally required.

As an example of the zeolite-based solid acid carrier, for example, the following formula

[0017]

[Chemical 7]

Acid-type mordenite obtained by acid-treating the mordenite-type zeolite represented by
₂ / Al ₂ O ₃ molar ratio is 13 to 20, and Si
O ₂ / H ₂ O molar ratio can be exemplified acid type mordenite is 25 to 200. However, in the above formula, M represents an alkali metal ion, and r is a value that varies depending on the synthesis conditions of zeolite.

Another example of the zeolite-based solid acid carrier is, for example, the following formula

[0020]

[Chemical 8]

A zeolite obtained by exchanging a part or all of the ions M in the zeolite represented by the formula with titanium ions (Ti ⁴⁺ ), zirconium ions (Zr ⁴⁺ ) or tin ions (Sn ⁴⁺ ). You can However, in the above formula, M ′ represents an alkali metal ion, an alkaline earth metal ion, or a hydrogen ion, and nA = p (n is the valence of the ion M) and q / p ≧ 5.

The oxide solid acid carrier is Al
_{2 O 3, TiO 2, TiO} 2 / SO 4 -, ZrO 2, Z
rO ₂ / SO ₄ ^- or a single metal oxide such as, SiO ₂ / A
l ₂ O ₃ , TiO ₂ / Al ₂ O ₃ , TiO ₂ / ZrO ₂
And other complex oxides. Among these, from the viewpoint of heat resistance, Al ₂ O ₃ , ZrO ₂ , SiO ₂ / Al ₂
O ₃ is preferred.

As another example of the solid acid carrier, a kind of crystalline aluminum phosphate (ALPO) having a zeolite-like porous structure or a layered structure, and its related substance, crystalline aluminum silicate phosphate (SAPO). ), ALPO
The crystalline aluminum metal phosphate (MAPO) obtained by substituting a part of phosphorus or phosphorus-aluminum with a metal such as titanium, iron, magnesium, zinc, manganese, or cobalt can be given.

The ALPO-type phosphate is a so-called template such as amine, quaternary ammonium or the like in a desired combination selected from the above-mentioned phosphoric acid source and metal source and silica, silica sol, sodium silicate and the like. It can be prepared by a hydrothermal synthesis method from a mixed raw material under conditions similar to those for synthesizing zeolite. The main difference from the case of synthesizing zeolite is that it is generally synthesized at a higher temperature (approximately 150 ° C. or higher) in the acidic pH range.

The composition of the ALPO type phosphate is generally Al ₂ O _3. (0.8 to 1.2) .P ₂ O ₅ .nH ₂ O
It is represented by. In the case of SAPO or MAPO, the maximum amount of silica and metal to be replaced is about 1/10 of the total amount of aluminum and phosphorus, but the present invention does not always fall within this composition range. That is, that containing amorphous may be used.

When an ALPO type phosphate obtained by the hydrothermal synthesis method is used as a carrier, it is generally one that is washed with water, dried and then baked in the air to remove the remaining template by incineration. used. The catalyst according to the present invention can be prepared, for example, by the method (1), (2) or (3) shown below. (1) In a chiller in which a solid acid carrier is dispersed, La, C
e, Y, Pr, Nd, Pm, Sm, Eu, Gd, Na,
K, Bi, Th, Ba, Sr, Ca, Mg, Pb, Z
n, Ag, Mn, Co, Fe, Ni, Cr, Cu, V,
Mo, W, Ta, Li, Ti, Zr, Nb, Pd, R
A water-soluble salt such as a nitrate of h, Ru or Pt or an alcohol solution of these alkoxides is added to neutralize or hydrolyze these, or a solid acid is prepared by a spray drying method or a freeze drying method. The carrier is made to carry a precursor of a perovskite compound such as a hydroxide of these composite metal species, and then filtration, washing with water and repulping are repeatedly carried out, followed by drying and firing. (2) The solid acid carrier and the separately prepared perovskite compound are thoroughly wet-milled and mixed by a planetary mill or the like. (3) A precursor such as a water-soluble salt or hydroxide of a solid acid carrier, La, Ce, Y, Pr, Nd, Pm, Sm, Eu,
Gd, Na, K, Bi, Th, Ba, Sr, Ca, M
g, Pb, Zn, Ag, Mn, Co, Fe, Ni, C
r, Cu, V, Mo, W, Ta, Li, Ti, Zr, N
A precipitate is formed by a method of neutralizing or hydrolyzing a solution in which a water-soluble salt such as a nitrate of b, Pd, Rh, Ru or Pt or an alcohol solution of an alkoxide is neutralized and then hydrolyzed. The product is filtered, washed with water and repulped repeatedly, then dried and fired.

In the above method, it is preferable that the production temperature of the perovskite compound is low. The reason is that as the production temperature is lower, a perovskite compound having a larger specific surface area is obtained, and the solid acid of the solid acid carrier is altered by the reaction between the solid acid carrier and the elements constituting the perovskite compound, or the perovskite compound This is because it is possible to avoid a decrease in the activity of the catalyst due to a decrease in the production amount.

Therefore, when a solid acid carrier having a high reactivity with an element constituting the perovskite compound such as Al ₂ O ₃ or TiO ₂ is used, the element constituting the solid acid carrier and the perovskite compound are used. The method (3) for increasing the homogeneity with the elements constituting the is not preferable. Generally, the method (1) is preferable, but the method (2) can also give a catalyst having a considerably high activity.

The preferable loading amount of the perovskite compound is
The amount of the perovskite compound and the solid acid carrier is 0.1 to 60% by weight based on the total weight of the solid acid carrier.
It is 5 to 50% by weight. Even if the supported amount of the perovskite compound exceeds 60% by weight, not only the addition effect corresponding to such increase cannot be obtained, but also in the reaction system in which oxygen coexists, the consumption of hydrocarbons and oxygen-containing compounds by oxygen occurs. Will increase. On the other hand, when the supported amount is less than 0.1% by weight, the reducing activity of the catalyst cannot be sufficiently improved.

The catalyst according to the present invention can be formed into various shapes such as a honeycomb shape and a spherical shape by a conventionally known forming method. At the time of this molding, a molding aid, a molded body reinforcing material, an inorganic fiber, an organic binder and the like may be appropriately mixed. It is also possible to carry the coating on a preformed substrate by a washcoat method or the like. Furthermore,
It is also possible to use other conventionally known catalyst preparation methods.

In the practice of the present invention, specific examples of the hydrocarbon used as the reducing agent include those in a gaseous state,
Hydrocarbon gas such as methane, ethane, butylene, etc. in liquid form, such as pentane, hexane, octane, heptane, benzene, toluene, xylene, etc., single component hydrocarbons, gasoline, kerosene, light oil, heavy oil, etc. Mineral oil-based hydrocarbons and the like. Particularly preferred hydrocarbons include lower alkynes such as acetylene, methylacetylene and 1-butyne, lower alkenes such as ethylene, propylene, isobutylene, 1-butene and 2-butene, lower dienes such as butadiene and isoprene, propane and butane. And lower alkanes and the like.

The suitable amount of the hydrocarbon added varies depending on its kind, but is 0.1 to 2 in terms of molar ratio to nitrogen oxide.
It is a degree. When it is less than 0.1, sufficient reducing activity cannot be obtained, while when the molar ratio exceeds 2,
Since the amount of unreacted hydrocarbons emitted is large, a post-treatment for recovering the unreacted hydrocarbons is required. Further, the oxygen-containing compound used as the reducing agent in the practice of the present invention is an organic compound having an oxygen element in its molecule. Specific examples thereof include methyl alcohol, ethyl alcohol,
Alcohols such as propyl alcohol and octyl alcohol, ethers such as dimethyl ether, diethyl ether and dipropyl ether, methyl acetate, ethyl acetate,
Examples thereof include esters such as oils and fats and ketones such as acetone and methyl ethyl ketone. Suitable oxygen-containing compounds include lower alcohols such as methyl alcohol and ethyl alcohol.

The above hydrocarbons and oxygen-containing compounds may be used alone or in combination of two or more if necessary. Further, the hydrocarbon and the oxygen-containing compound may be used alone or in combination of two or more. It should be noted that unburned substances such as fuel and incomplete combustion products existing in the exhaust gas, that is, hydrocarbons and patty chelates are also effective as reducing agents, and these are also included in the hydrocarbon of the present invention. From this point of view, it can be said that the catalyst according to the present invention is also useful as a catalyst for reducing or removing hydrocarbons, patty chelates and the like in exhaust gas.

The temperature at which the reducing agent shows a selective reduction reaction with respect to nitrogen oxides increases in the order of oxygen-containing compound <alkyne <alkene <aromatic hydrocarbon <alkane. Further, in the hydrocarbons of the same system, the temperature becomes lower as the carbon number becomes larger. The optimum temperature at which the catalyst according to the present invention exhibits reduction activity for nitrogen oxides varies depending on the reducing agent and the catalyst species used, but is usually 100 to 800.
℃. In this temperature range, space velocity (SV)
It is preferable to circulate the exhaust gas at about 500 to 100,000. In the present invention, a particularly suitable temperature range is 200
~ 600 ° C.

[0035]

The present invention will be described below with reference to examples.
The present invention is not limited to these examples. (1) Preparation Example 1 of lanthanum nitrate hexahydrate catalyst _{(La (NO 3) 2 ·} 6H 2 O)
101.05 g, manganese acetate tetrahydrate (Mn (Ac) ₂ ·
4H ₂ O (Ac = CH ₃ COO, hereinafter the same)) 28.
60 g, strontium nitrate (Sr (NO ₃ ) ₂ ) 74.
08 g and cobalt nitrate hexahydrate (Co (NO ₃ ) ₂ ·
An aqueous solution was prepared by dissolving 135.83 g of (6H ₂ O) in 500 ml of water.

With sufficient stirring in this aqueous solution, a concentration of 1
Add 21 g / 1 of aqueous sodium hydroxide to adjust the pH to 10
And After completion of the precipitation reaction, stirring was continued for 18 hours for aging. Then, filtration, washing with water, and repulping were repeated until the conductivity of the filtrate was almost the same as that of the repulping water.
The obtained filter cake was dried at 120 ° C. for 18 hours and then calcined at 700 ° C. for 3 hours.

As a result of X-ray diffraction of the obtained fired product, perov
It was confirmed that the skylite crystal phase was generated. Well
In addition, the specific surface area of this fired product by the BET method (the following ratio table
The area is measured by the same method. ) Is 23.7m²/ G
(La_0.4Sr_0.6Co_0.8Mn _0.2O₃). like this
30 g of the perovskite compound obtained by
Metatitanic acid obtained from the titanium process (TiO₂・ H₂O)
Activated titanium oxide obtained by firing at 600 ° C. for 3 hours (comparative table
Area 104.2m²/ G) 100 g of water in a mixture with 100 g
, Crush and mix with a planetary mill for 30 minutes, and then with water
The viscosity was adjusted to obtain a slurry for washcoat. This
Of the slurry of 1.25 mm pitch made by Cordillite Co., Ltd.
Nicam (Hereinafter, this honeycomb is simply referred to as honeycomb.
It ) To support a catalyst, and a prototype sample (A-
1) was obtained. The amount of catalyst loaded at this time was 1 cc of honeycomb.
The amount was 0.116 g. Example 2 Lanthanum nitrate hexahydrate 89.5 g and manganese acetate tetrahydrate
Using 50.66 g, in the same manner as in Example 1, perovs
Kite compound (LaMnO₃) Got. This Perovska
Specific surface area of Ito compound is 29.1m²/ G.

Perovskite compound thus obtained
30 g and γ-alumina (A-11) 10 manufactured by Sumitomo Chemical Co., Ltd.
100 g of water was added to the mixture with 0 g to obtain a slurry.
This is applied to the honeycomb, the catalyst is supported, and the prototype sample
To obtain le (A-2). The supported amount of catalyst at this time is
It was 0.094 g per cc of cam. Example 3 71.60 g of lanthanum nitrate hexahydrate, lead nitrate (Pb (NO
₃)₂) 13.69 g and manganese acetate tetrahydrate 50.66
g except that they were mixed and baked at 800 ° C. for 3 hours.
In the same manner as in 1, the perovskite compound (La_0.8
Pb_0.2MnO ₃) Got. This perovskite compound
Has a specific surface area of 23.7 m²/ G.

Perovskite compound thus obtained
30 g and γ-alumina (A-11) 10 manufactured by Sumitomo Chemical Co., Ltd.
100 g of water was added to a mixture with 0 g to obtain a slurry.
Is applied to the honeycomb to support the catalyst, and a prototype sample
(A-3) was obtained. The supported amount of catalyst at this time is
It was 0.117 g per cc of aluminum. Example 4 88.07 g of lanthanum nitrate hexahydrate and cobalt nitrate 6 water
Japanese (Co (NO₃) ₂・ 6H₂O) Mix 59.19g
And the same as Example 1 except that it was baked at 800 ° C. for 3 hours.
Of the perovskite compound (LaCoO₃)
Obtained. The specific surface area of this perovskite compound is 17.4 m²
/ G.

Perovskite compound thus obtained
30g and Nippon Kagaku Co., Ltd. H type mordenite (HM-23)
Add 100 g of water to the mixture with 100 g to make a slurry.
We obtained this, applied it to a honeycomb, supported a catalyst, and made a prototype.
A sample (A-4) was obtained. Amount of catalyst supported at this time
Was 0.113 g per 1 cc of honeycomb. Example 5 Cerium nitrate hexahydrate (Ce (NO₃)₂・ 6H₂O)
70.65 g, barium nitrate (Ba (NO₃)₂) 10.63
g and 59.19 g of cobalt nitrate hexahydrate.
In the same manner as in 1, the perovskite compound (Ce_0.8
Ba_0.2CoO ₃) Got. This perovskite compound
Has a specific surface area of 23.0 m²/ G.

Perovskite compound thus obtained
30g and Nippon Kagaku Co., Ltd. H type mordenite (HM-23)
100 g of water was added to the mixture of and to obtain a slurry.
Sample coating by coating on honeycomb and supporting catalyst
(A-5) was obtained. The supported amount of catalyst at this time is
It was 0.130 g per cc of mu. Example 6 Lanthanum nitrate hexahydrate 90.84 g, manganese acetate tetrahydrate
25.71 g of a product and an aqueous titanium tetrachloride solution (as Ti: 14.
82 g / 100 ml aqueous solution) 339.0 ml
By the same method as in Example 1, the perovskite compound (L
aMn_0.5Ti _0.5O₃) Got. This perovskite
The specific surface area of the compound is 25.3m²/ G.

10 g of the perovskite compound obtained in this manner and silica-alumina (COK-
84) 100 g of water was added to a mixture with 100 g to obtain a slurry, which was applied to a honeycomb to support a catalyst,
A trial sample (A-5) was obtained. At this time, the supported amount of the catalyst was 0.098 g per 1 cc of the honeycomb. Example 7 (Preparation of perovskite compound) L manufactured by Shiramizu Chemical Industry Co., Ltd.
Ethanol solution of a-ethoxide (73 as La ₂ O ₃
g / l concentration solution) 100.0 ml, company's Ba ethoxide ethanol solution (BaO 79 g / l concentration solution) 21.74 ml, company Ni ethoxide ethanol solution (NiO 67 g / l concentration solution) ) 49.95 ml
And Co ethoxide in ethanol solution (9 as CoO
9.22 ml of a solution having a concentration of 1 g / l) was mixed, and a 1% by weight aqueous ammonia solution was gradually added dropwise thereto with sufficient stirring for hydrolysis.

Next, this was evaporated to dryness while uniformly mixing, and calcined at 600 ° C. for 3 hours to obtain a perovskite compound (La _0.8 Ba _0.2 Co _0.8 Ni _0.2 O ₃ ). The specific surface area of this perovskite compound is 36.9 m ² /
It was g. (Preparation of SAPO-34) To 129.6 g of water, 90.7 g of finely crushed aluminum isopropoxide was added little by little while stirring, and the mixture was stirred and mixed until uniform. To this mixed solution, 51.3 g of an 85% phosphoric acid aqueous solution was added dropwise, and the mixture was stirred and mixed until it became uniform. Then, 16.0 g of 50% silica sol was further added, and sufficiently stirred and mixed until it became uniform.

Next, 81.6 g of tetraethylammonium hydroxide was added, and the mixture was sufficiently stirred and mixed. This mixture was placed in an autoclave and reacted at 200 ° C. for 24 hours, then the product was separated by filtration, further washed with water and dried, and then 50
It was baked in air at 0 ° C. for 3 hours to obtain SAPO-34. This SAPO-34 contained 9.5% by weight, 18.0% by weight and 19.0% by weight of Si, Al and P, respectively.

100 g of water was added to a mixture of 25 g of the perovskite compound thus obtained and 100 g of the above SAPO-34 to obtain a slurry, which was coated on a honeycomb and supported with a catalyst to prepare a trial sample (A- 7) was obtained. At this time, the supported amount of catalyst was 0 per 1 cc of honeycomb.
It was 138 g. Example 8 101.05 g of lanthanum nitrate hexahydrate, 74.08 g of strontium nitrate (Sr (NO ₃ ) ₂ ), 135.83 g of cobalt nitrate hexahydrate and ferrous nitrate hexahydrate (Fe (NO
_{3) 2 · 6H 2 O)} 33.60g were mixed, in the same manner as in Example 1, a perovskite compound (La _0.4 Sr
_0.6 Co _0.8 Fe _0.2 O ₃ ) was obtained. The specific surface area of this perovskite compound was 21.6 m ² / g.

30 g of the perovskite compound thus obtained and γ-alumina (A-11) 10 manufactured by Sumitomo Chemical Co., Ltd.
100 g of water was added to a mixture with 0 g to obtain a slurry, which was applied to a honeycomb to carry a catalyst, and a trial sample (A-8) was obtained. The coating amount of the slurry at this time is
The amount was 0.098 g per 1 cc of honeycomb. Example 9 lanthanum nitrate hexahydrate 202.10G, zinc nitrate hexahydrate _{(Zn (NO 3) 2 ·} 6H 2 O) 28.41g, cobalt nitrate hexahydrate 135.83g and cupric nitrate 3 Hydrate (C
u (NO ₃ ) ₂ .3H ₂ O (28.19 g) was mixed, and the perovskite compound (La) was mixed in the same manner as in Example 1.
_0.8 Zn _0.2 Co _0.8 Cu _0.2 O ₃ ) was obtained. The specific surface area of this perovskite compound was 17.3 m ² / g.

Perovskite compound thus obtained
30 g and Sumitomo Chemical's γ-alumina (A-11) 100
100 g of water was added to the mixture with g to obtain a slurry.
Is applied to the honeycomb to support the catalyst, and a prototype sample
(A-9) was obtained. The supported amount of catalyst at this time is
It was 0.083 g per 1 cc of aluminum. Example 10 Lanthanum nitrate hexahydrate 202.10 g, silver nitrate (AgNO
₃) 19.82 g, cobalt nitrate hexahydrate 135.83 g and
And zirconium nitrate pentahydrate (Zr (NO₃) _Four・ 5H
₂O) 69.87 g are mixed and processed in the same manner as in Example 1.
The perovskite compound (La_0.8Ag_0.2Co_0.8
Zn_0.2O₃) Got. The ratio of this perovskite compound
Surface area is 17.3m²/ G.

30 g of the perovskite compound thus obtained and γ-alumina (A-11) 100 manufactured by Sumitomo Chemical Co., Ltd.
100 g of water was added to a mixture with g to obtain a slurry, which was applied on a honeycomb to carry a catalyst, and a trial sample (A-10) was obtained. The amount of the catalyst loaded at this time was 0.097 g per 1 cc of the honeycomb. Example 11 (Preparation of Perovskite Compound) Lanthanum nitrate hexahydrate 101.05 g, strontium nitrate 74.08 g, cobalt nitrate hexahydrate 135.83 g and chromium nitrate (Cr (N (N
27.79 g of O ₃ ) ₃ ) were mixed, and the perovskite compound (La _0.4 Sr _0.6 Co) was mixed in the same manner as in Example 1.
_0.8 Cr _0.2 O ₃ ) was obtained. The specific surface area of this perovskite compound was 20.3 m ² / g. (Preparation of ALPO-5) 85% phosphoric acid 69.2 g and water 17
Pseudo-boehmite powder (containing 67% alumina and 9.5% acetic acid) 45.8 g was added little by little to the mixture with 8 g, and the mixture was stirred and mixed until uniform. Tripropylamine (43.8 g) was added to this solution, and the mixture was stirred and mixed until uniform. This mixture was charged into an autoclave and reacted with stirring at 150 ° C. for 70 hours, then the product was separated by filtration, washed with water and dried. After this, burn in air at 500 ° C for 3 hours, and
PO-5 was obtained. This ALPO-5 had a composition containing 18.0% by weight and 22.0% by weight of Al and P, respectively.

100 g of water was added to a mixture of 30 g of the perovskite compound thus obtained and 100 g of the above-mentioned ALPO-5 to obtain a slurry, which was coated on a honeycomb and supported with a catalyst to prepare a trial sample (A -11) was obtained. At this time, the supported amount of catalyst was 0 per 1 cc of honeycomb.
It was 104 g. Example 12 (Preparation of Perovskite Compound) 101.05 g of lanthanum nitrate hexahydrate, 74.08 g of strontium nitrate, 135.83 g of cobalt nitrate hexahydrate and niobium pentachloride hydrochloric acid aqueous solution (aqueous hydrochloric acid solution having a concentration of 50 g / l as Nb). ) 216.8
1 ml was mixed, and the perovskite compound (La _0.4 Sr _0.6 Co _0.8 Nb _0.2 O ₃ ) was mixed in the same manner as in Example 1.
Got The specific surface area of this perovskite compound is 18.
It was 9 m ² / g. (Preparation of MAPO-5) Aluminum isopropoxide 56.3 finely crushed with stirring in a liquid prepared by dissolving 4.9 g of manganese acetate and 4.1 g of cupric acetate in 129 g of water.
g was added little by little and mixed with stirring until uniform.

A mixture of 85% phosphoric acid (55.4 g), diethylethanolamine (56.3 g) and water (55.5 g) was added little by little to this solution while stirring, and the mixture was stirred and mixed until uniform. This solution was charged into an autoclave and heated to 200 ° C.
After reacting for 25 hours, the product is separated by filtration, washed with water,
Dried. After this, calcination with air for 3 hours at 500 ° C
APO-5 was obtained. This MAPO-5 is made of Al, P, M
n and Cu are 19.0% by weight, 19.0% by weight, and 2.
It had a composition containing 8% by weight and 4.4% by weight.

A mixture of 25 g of the perovskite compound thus obtained and 100 g of the above MAPO-5 was added to 1 part of water.
00 g was added to obtain a slurry, which was applied onto a honeycomb to carry a catalyst, and a trial sample (A-12) was obtained. At this time, the supported amount of catalyst was 0 per 1 cc of honeycomb.
It was 116 g. Example 13 In the same manner as in Example 1, except that zirconium hydroxide (ZrO ₂ , specific surface area 148.3 m ² / g) obtained by firing zirconium hydroxide at 600 ° C. for 3 hours was used instead of the active titanium oxide. In the same manner as in Example 1, a prototype sample (A-1
3) was obtained. The amount of catalyst supported at this time is 0.1 per cc
It was 39 g. Example 14 (Preparation of perovskite compound) Lanthanum nitrate hexahydrate 88.07 g, strontium nitrate 10.76 g and cobalt acetate tetrahydrate 50.66 g were dissolved in 500 ml of water to prepare an aqueous solution. While stirring well in this aqueous solution,
An aqueous solution of sodium hydroxide having a concentration of 121 g / 1 was added dropwise to adjust the pH of the solution to 10. After completion of the precipitation reaction, stirring was continued for 18 hours for aging. Then, filtration, washing with water, and repulping were repeated until the conductivity of the filtrate was almost the same as that of the repulping water, and the obtained filter cake was heated at 120 ° C. for 18 hours.
Allowed to dry for hours.

The dried product was crushed, and a vanadyl oxalate aqueous solution (V: 100 g / 1 concentration aqueous solution) 25.
After adding 90 ml and thoroughly kneading, evaporate to dryness,
It was dried at 0 ° C. for 18 hours and then calcined at 850 ° C. for 3 hours to give a perovskite compound (La _0.8 Sr _0.2 Co).
_0.8 V _0.2 O ₃ ) was obtained. The specific surface area of this perovskite compound was 12.8 m ² / g. (Preparation of Silica-Zirconia) 100.0 g of silica sol O type (20 wt% concentration as SiO ₂ ) manufactured by Nissan Kagaku Co., Ltd. and 97.20 g of zirconium chloride (ZrCl ₄ ) were thoroughly mixed with stirring, and water was added. The total volume was 500 ml. A 121 g / 1 concentration aqueous sodium hydroxide solution was added dropwise to the solution to adjust the pH to 10. After completion of the precipitation reaction, stirring was continued for 18 hours, and then filtration, washing with water and repulping were repeated,
A filter cake was obtained. The filter cake was dried at 120 ° C. for 18 hours and calcined for 3 hours. The specific surface area of the obtained silica-zirconia was 297 m ² / g.

Perovskite compound thus obtained
In a mixture of 30 g and 100 g of the above silica-zirconia.
Add 100 g of water, crush and mix for 30 minutes with a planetary mill,
Furthermore, the viscosity is adjusted with water and the slurry for washcoat is used.
Got Apply this slurry to honeycomb to support catalyst
Then, a trial sample (A-14) was obtained. At this time
The supported amount of catalyst is 0.127 g per 1 cc of honeycomb.
It was Example 15 (Preparation of perovskite compound) In Example 14,
Replace the vanadyl oxalate aqueous solution with ammonium molybdate.
Ammoniacal aqueous solution of Ni (MoO₂As 25 g /
Example 1 except that 260.22 ml of a 1-concentration aqueous solution was used.
In the same manner as in No. 14, perovskite compound (La _0.8S
r_0.2Co_0.8Mo_0.2O₃) Got. This Perovska
The specific surface area of the ito compound is 11.4 m²/ G. (Preparation of Zr-mordenite) Namol manufactured by Nippon Kagaku Co., Ltd.
Denit (NM-100P) 100 g with zirconyl nitrate
Aqueous solution (ZrO₂As a 100 g / 1 concentration aqueous solution)
Immerse, hold at 70 ° C for 1 hour with stirring, and add Na to Z
It was ion-exchanged with r. Zeolite obtained by filtration and washing with water
The cake was dried and then baked at 650 ° C. for 4 hours. This
Zr content of the zeolite (Zr-mordenite) of 3.
3% by weight, and the specific surface area is 391 m²/ G
It was

Perovskite compound thus obtained
In a mixture of 30 g and 100 g of the above Zr-mordenite
Add 100 g of water and crush and mix for 30 minutes with a planetary mill
Then, adjust the viscosity with water on a dish, and then use the slurry for the washcoat.
Got Lee This slurry is applied to the honeycomb to apply the catalyst.
By carrying it, a trial sample (A-15) was obtained. This and
The supported amount of mushroom catalyst is 0.135 g per 1 cc of honeycomb.
Atsuta Example 16 Instead of the vanadyl oxalate aqueous solution in Example 14,
Ammonium metatungstate aqueous solution (WO₃When
50% by weight aqueous solution) except that 2.53 g was used.
In the same manner as in Example 14, the perovskite compound (La
_0.8Sr_0.2Co _0.8W_0.2O₃) Got. This perov
Specific surface area of the skylite compound is 13.6m²/ G.

Perovskite compound thus obtained
30 g and Sumitomo Chemical's γ-alumina (A-11) 100
100g of water is added to the mixture with g, and it is 30 minutes on a planetary mill.
Pulverize and mix, adjust viscosity with water in a dish, and
A slurry for polishing was obtained. Apply this slurry to honeycomb
Then, a catalyst is supported and a trial sample (A-16) is obtained.
It was At this time, the supported amount of catalyst was 0 per 1 cc of honeycomb.
It was 135 g. Example 17 173.20 g of lanthanum nitrate hexahydrate, strontium nitrate
126.98 g, cobalt nitrate hexahydrate 276.48 g
And chloroplatinic acid hexahydrate (H₂PtCl₆・ 6H ₂O) 2
Prepare an aqueous solution by dissolving 5.90 g in 1000 ml of water
It was With sufficient stirring in this aqueous solution, a concentration of 121 g /
The pH of the solution is adjusted to 10 by dropping the aqueous sodium hydroxide solution of 1.
And After completion of the hydrolysis reaction, stirring was continued for 18 hours.
Thereafter, in the same manner as in Example 1, the perovskite compound
(La_0.4Sr_0.6Co_0.95Pt_{0. 05}O₃) Got. This
The specific surface area of the perovskite compound is 27.6 m²/ G
Atsuta

30 g of the perovskite compound thus obtained and γ-alumina (A-11) 100 manufactured by Sumitomo Chemical Co., Ltd.
100 g of water was added to the mixture with g, and the mixture was pulverized and mixed in a planetary mill for 30 minutes, and the viscosity of the dish was adjusted with water to obtain a slurry for washcoat. This slurry was applied to a honeycomb to support a catalyst, and a trial sample (A-17) was obtained. At this time, the supported amount of catalyst was 0 per 1 cc of honeycomb.
It was 123 g. Example 18 In Example 17, instead of chloroplatinic acid hexahydrate, rhodium nitrate dihydrate (Rh (NO ₃ ) ₃ .2H ₂ O) 1
A perovskite compound (La _0.4 Sr _0.6 Co _0.95 Rh) was prepared in the same manner as in Example 17 except that 6.25 g was used.
_0.05 O ₃ ) was obtained. The specific surface area of this perovskite compound was 29.6 m ² / g.

30 g of the perovskite compound thus obtained and γ-alumina (A-11) 100 manufactured by Sumitomo Chemical Co., Ltd.
100 g of water was added to the mixture with g, and the mixture was pulverized and mixed in a planetary mill for 30 minutes, and the viscosity was adjusted with water to obtain a slurry for washcoat. This slurry was applied to a honeycomb to carry a catalyst, and a trial sample (A-18) was obtained. At this time, the supported amount of catalyst was 0 per 1 cc of honeycomb.
It was 129 g. Example 19 Example 17 was repeated except that 8.67 g of palladium chloride (PdCl ₂ ) was used instead of chloroplatinic acid hexahydrate.
In the same manner as in Example 17, the perovskite compound (La
_0.4 Sr _0.6 Co _0.95 Pd _0.05 O ₃ ) was obtained. The specific surface area of this perovskite compound was 28.5 m ² / g.

30 g of the perovskite compound thus obtained and γ-alumina (A-11) 100 manufactured by Sumitomo Chemical Co., Ltd.
100 g of water was added to the mixture with g, and the mixture was pulverized and mixed in a planetary mill for 30 minutes, and the viscosity was adjusted with water to obtain a slurry for washcoat. This slurry was applied to a honeycomb to support a catalyst to obtain a trial sample (A-19). At this time, the supported amount of catalyst was 0 per 1 cc of honeycomb.
It was 122 g. Example 20 In Example 17, instead of chloroplatinic acid hexahydrate, ruthenium chloride pentahydrate (RuCl ₄ .5H ₂ O) 16.1
Except for using 5g is perovskite compound in the same manner as in Example _{17 (La 0.4 Sr 0.6 Co 0.95} Ru
_0.05 O ₃ ) was obtained. The specific surface area of this perovskite compound was 25.3 m ² / g.

30 g of the perovskite compound thus obtained and γ-alumina (A-11) 100 manufactured by Sumitomo Chemical Co., Ltd.
100 g of water was added to the mixture with g, and the mixture was pulverized and mixed in a planetary mill for 30 minutes, and the viscosity was adjusted with water to obtain a slurry for washcoat. This slurry was applied to a honeycomb to carry a catalyst, and a trial sample (A-20) was obtained. At this time, the supported amount of catalyst was 0 per 1 cc of honeycomb.
It was 129 g. Example 21 In Example 4, the perovskite compound (LaCoO 2
₃ ) 1 g and H-type mordenite manufactured by Nippon Kagaku Co. (HM-2
3) A trial sample (A-21) was obtained in the same manner as in Example 4 except that 100 g was used. The amount of the catalyst loaded at this time was 0.929 g per 1 cc of the honeycomb. Example 22 In Example 4, the perovskite compound (LaCoO 2
₃ ) 10 g and H-type mordenite manufactured by Nippon Kagaku Co. (HM-2
3) A trial sample (A-22) was obtained in the same manner as in Example 4 except that 100 g was used. The amount of catalyst supported at this time was 0.948 g per 1 cc of honeycomb. Example 23 In Example 4, the perovskite compound (LaCoO 2
₃ ) 50 g and H-type mordenite manufactured by Nippon Kagaku Co. (HM-2
3) A prototype sample (A-23) was obtained in the same manner as in Example 4 except that 100 g was used. The amount of the catalyst loaded at this time was 0.109 g per 1 cc of the honeycomb. Example 24 In Example 4, the perovskite compound (LaCoO 2
₃ ) 50 g and H-type mordenite manufactured by Nippon Kagaku Co. (HM-2
3) In the same manner as in Example 4 except that 50 g was used,
A prototype sample (A-24) was obtained. The amount of catalyst supported at this time was 0.122 g per 1 cc of honeycomb. Example 25 Compositional formula Nax [(AlO ₂ ) _X. (SiO ₂ ) _Y ] .Z
0.02 of sodium-type ZSM-5 represented by H ₂ O (ZSM-5 manufactured by Nippon Mobile Co., Ltd., Y / X = 35) was added to 100 g.
It was dipped in 1 liter of a 5 mol / 1 TiOSO ₄ aqueous solution and sufficiently stirred.

While stirring this in an autoclave, the temperature was raised at a heating rate of 100 ° C./hour and kept at 125 ° C. for 1 hour to hydrolyze TiOSO ₄ to convert Na into Ti.
After being ion-exchanged with, the mixture was filtered and washed with water to obtain a cake of zeolite. Then, after drying the cake, 650
Calcination was performed for 4 hours to obtain zeolite. The Ti content in this zeolite was 2.4% by weight as TiO ₂ .

The Ti-ZSM-5 thus obtained was treated with H
A prototype sample (A-25) was obtained in the same manner as in Example 4 except that the type mordenite was used instead. The amount of catalyst supported at this time was 0.110 g per 1 cc of honeycomb. Example 26 nitrate yttrium tetrahydrate _{(Y (NO 3) 3 ·} 4H
₂ O) 173.49 g and cobalt nitrate hexahydrate 145.52
g was dissolved in 500 ml of water to prepare an aqueous solution.

With sufficient stirring in this aqueous solution, a concentration of 1
Add 21 g / 1 of aqueous sodium hydroxide to adjust the pH to 10
And After completion of the precipitation reaction, stirring was continued for 18 hours for aging. Then, filtration, washing with water, and repulping were repeated until the conductivity of the filtrate was almost the same as that of the repulping water.
The obtained filter cake was dried at 120 ° C. for 18 hours and then calcined at 700 ° C. for 3 hours.

As a result of X-ray diffraction of the obtained fired product, perov
It was confirmed that the skylite crystal phase was generated. Well
Also, the specific surface area of this fired product is 18.5 m²/ G (Y
CoO ₃). Perovskite compound thus obtained
30 g and H-type mordenite manufactured by Nippon Kagaku Co. (HM-2
3) Add 100g of water to the mixture with 100g, and add planetary mill.
Crush and mix for 30 minutes, and then adjust the viscosity with water and
A slurry for a wash coat was obtained. This slurry
Coated with a catalyst to support the catalyst, and the sample (A-2
6) was obtained. The amount of catalyst loaded at this time was 1 cc of honeycomb.
The amount was 0.102 g. Example 27 Lanthanum nitrate hexahydrate 89.5 g, cobalt acetate tetrahydrate
Using 41.19 g and 10.13 g of manganese acetate tetrahydrate
Then, in the same manner as in Example 1, the perovskite compound
(LaCo_0.8Mn_0.2O₃) Got. This Perovska
The specific surface area of the ito compound is 24.8 m²/ G.

30 g of the perovskite compound thus obtained and γ-alumina (A-11) 100 manufactured by Sumitomo Chemical Co., Ltd.
100 g of water was added to a mixture with g to obtain a slurry, which was applied to a honeycomb to carry a catalyst, and a trial sample (A-27) was obtained. The amount of catalyst supported at this time was 0.106 g per 1 cc of honeycomb. Example 28 lanthanum nitrate hexahydrate 135.80G, nitrate yttrium tetrahydrate _{(Y (NO 3) 3 ·} 4H 2 O) 108.82g,
Using 41.19 g of strontium nitrate, 156.23 g of cobalt acetate tetrahydrate and 38.43 g of manganese acetate tetrahydrate, a perovskite compound (La _0.4 Y _0.4 Sr _0.2 Co _{0.8) was} prepared in the same manner as in Example 26. Mn _0.2 O ₃ )
Got The specific surface area of this perovskite compound is 20.
It was 4 m ² / g.

30 g of the perovskite compound thus obtained and γ-alumina (A-11) 100 manufactured by Sumitomo Chemical Co., Ltd.
100 g of water was added to a mixture with g to obtain a slurry, which was applied to a honeycomb to carry a catalyst, and a trial sample (A-28) was obtained. The amount of the catalyst loaded at this time was 0.111 g per 1 cc of the honeycomb. Example 29 Lanthanum nitrate hexahydrate 17.90 g, yttrium nitrate 4
Hydrate 28.69 g, cerium nitrate hexahydrate (Ce (NO
_{3) 3 · 6H 2 O)} 35.90g and chromium nitrate 49.22
A perovskite compound (La _0.2 Y _0.4 Ce _0.4 CrO ₃ ) was obtained in the same manner as in Example 26, except that g was mixed and then calcined at 800 ° C. for 3 hours. The specific surface area of this perovskite compound was 21.6 m ² / g.

30 g of the perovskite compound thus obtained and H-type mordenite (HM-23) manufactured by Nippon Kagaku Co., Ltd.
100 g of water was added to a mixture with 100 g to obtain a slurry, which was applied to a honeycomb to carry a catalyst, and a trial sample (A-29) was obtained. At this time, the supported amount of the catalyst was 0.098 g per 1 cc of the honeycomb. Example 30 Cerium nitrate hexahydrate 70.65 g, barium nitrate (Ba
(NO ₃ ) ₂ ) 10.63 g, cupric nitrate trihydrate (Cu
_{(NO 3) 2 · 3H 2} O) 24.57g and chromium nitrate 2
Using 4.22 g, a perovskite compound (Ce _0.8 Ba _0.2 Cu _0.5 Cr _{0.5) was} prepared in the same manner as in Example 26.
O ₃ ) was obtained. The specific surface area of this perovskite compound was 19.3 m ² / g.

30 g of the perovskite compound thus obtained and H-type mordenite (HM-23) manufactured by Nippon Kagaku Co., Ltd.
100 g of water was added to a mixture with 100 g to obtain a slurry, which was applied to a honeycomb to carry a catalyst, and a trial sample (A-30) was obtained. The amount of the catalyst supported at this time was 0.126 g per 1 cc of the honeycomb. Example 31 Lanthanum nitrate hexahydrate 72.67 g, cerium nitrate hexahydrate 18.22 g, manganese acetate tetrahydrate 25.71 g and aqueous titanium tetrachloride solution (aqueous solution having a Ti concentration of 14.82 g / 100 ml) 339 Using 0.0 ml, the perovskite compound (La _0.8 Ce _0.2 M) was prepared in the same manner as in Example 26.
n _0.5 Ti _0.5 O ₃ ) was obtained. The specific surface area of this perovskite compound was 23.1 m ² / g.

10 g of the perovskite compound obtained in this manner and silica-alumina (COK-
84) 100 g of water was added to a mixture with 100 g to obtain a slurry, which was applied to a honeycomb to support a catalyst,
A prototype sample (A-31) was obtained. The amount of the catalyst loaded at this time was 0.095 g per 1 cc of the honeycomb. Example 32 101.05 g of lanthanum nitrate hexahydrate, 80.97 g of yttrium nitrate tetrahydrate, 24.69 g of strontium nitrate,
Nitrate nickel hexahydrate _{(Ni (NO 3) 2 ·} 6H 2 O)
135.72 g and ferrous nitrate hexahydrate 33.60 g were mixed, and a perovskite compound (La _0.4 Y _0.4 Sr _0.2 Ni _0.8 Fe _0.2 O ₃ ) was obtained in the same manner as in Example 26. The specific surface area of this perovskite compound is 24.0.
It was m ² / g.

Perovskite compound thus obtained
30 g and Sumitomo Chemical's γ-alumina (A-11) 100
100 g of water was added to the mixture with g to obtain a slurry.
Is applied to the honeycomb to support the catalyst, and a prototype sample
(A-32) was obtained. The supported amount of catalyst at this time is
It was 0.099 g per 1 cc of cam. Example 33 151.58 g of lanthanum nitrate hexahydrate, yttrium nitrate
Tetrahydrate 40.49 g, silver nitrate 19.82 g, cupric nitrate 3
Hydrate 112.77 g and zirconium nitrate pentahydrate (Z
r (NO₃)_Four・ 5H₂O) 69.87g was mixed and carried out
In the same manner as in Example 26, the perovskite compound (La
_0.6Y_0.2Ag_0.2Cu_0.8Zr_0.2O ₃) Got. This
The specific surface area of the perovskite compound is 17.8 m²/ G
Atsuta

30 g of the perovskite compound thus obtained and zirconium hydroxide obtained by firing zirconium hydroxide at 600 ° C. for 3 hours (ZrO ₂ , specific surface area 148.
Water (100 g) was added to a mixture of 100 g (3 m ² / g) to obtain a slurry, which was applied to a honeycomb to support a catalyst to obtain a trial sample (A-33). The amount of catalyst supported at this time was 0.094 g per 1 cc of honeycomb. Example 34 (Preparation of perovskite compound) Cerium nitrate hexahydrate 44.16 g, yttrium nitrate tetrahydrate 35.29 g, strontium nitrate 10.76 g and ferrous nitrate hexahydrate 5
An aqueous solution was prepared by dissolving 8.57 g in 500 ml of water. With sufficient stirring in this aqueous solution, a concentration of 121 g /
The pH of the solution is adjusted to 10 by dropping the aqueous sodium hydroxide solution of 1.
And After completion of the precipitation reaction, stirring was continued for 18 hours for aging. Then, after repeating filtration, washing with water, and repulp until the conductivity of the filtrate is almost the same as the water for repulp,
The obtained filter cake was dried at 120 ° C. for 18 hours.

The dried product was crushed, and an aqueous vanadyl oxalate solution (100 g / V concentration aqueous solution as V) 25.
After adding 90 ml and thoroughly kneading, evaporate to dryness,
The perovskite compound (Ce _0.4 Y _0.4 Sr was dried at 0 ° C. for 18 hours and then baked at 850 ° C. for 3 hours.
_0.2 Fe _0.8 V _0.2 O ₃ ) was obtained. The specific surface area of this perovskite compound was 13.7 m ² / g. (Preparation of Silica-Zirconia) 100.0 g of silica sol O type (20 wt% concentration as SiO ₂ ) manufactured by Nissan Kagaku Co., Ltd. and 97.20 g of zirconium chloride (ZrCl ₄ ) were thoroughly mixed with stirring, and water was added. The total volume was 500 ml. A 121 g / 1 concentration aqueous sodium hydroxide solution was added dropwise to the solution to adjust the pH to 10. After completion of the precipitation reaction, stirring was continued for 18 hours, and then filtration, washing with water and repulping were repeated,
A filter cake was obtained. The filter cake was dried at 120 ° C. for 18 hours and calcined for 3 hours. The specific surface area of the obtained silica-zirconia was 297 m ² / g.

100 g of water was added to a mixture of 30 g of the perovskite compound thus obtained and 100 g of the above silica-zirconia, and the mixture was ground and mixed for 30 minutes in a planetary mill,
Further, the viscosity was adjusted with water to obtain a slurry for washcoat. This slurry was applied to a honeycomb to carry a catalyst, and a trial sample (A-34) was obtained. The amount of the catalyst loaded at this time was 0.124 g per 1 cc of the honeycomb. Example 35 Lanthanum nitrate hexahydrate (173.20 g), strontium nitrate (126.98 g), cupric nitrate trihydrate (276.48 g) and chloroplatinic acid hexahydrate (25.90 g) were dissolved in water (1000 ml). An aqueous solution was prepared. The pH of the solution was adjusted to 10 by dropwise adding an aqueous solution of sodium hydroxide having a concentration of 121 g / 1 while sufficiently stirring the solution. After completion of hydrolysis reaction,
The mixture was agitated for 18 hours and aged. Thereafter, in the same manner as in Example 26, the perovskite compound (La _0.4 S
r _0.6 Cu _0.95 Pt _0.05 O ₃ ) was obtained. The specific surface area of this perovskite compound was 27.6 m ² / g.

30 g of the perovskite compound thus obtained and H-type mordenite manufactured by Nippon Kagaku Co. (HM-2
3) 100 g of water was added to a mixture with 100 g, and the mixture was pulverized and mixed in a planetary mill for 30 minutes, and the viscosity was adjusted with water to obtain a slurry for washcoat. This slurry was applied to a honeycomb to support a catalyst, and a prototype sample (A-3
5) was obtained. The amount of catalyst loaded at this time was 1 cc of honeycomb.
The amount was 0.123 g. Example 36 Compositional formula Nax [(AlO ₂ ) _X. (SiO ₂ ) _Y ] .Z
Commercial product of sodium-type mordenite represented by H ₂ O (ZSM-5, Y / X = 35, manufactured by Nippon Mobile Co., Ltd.) 100
g was immersed in 1 liter of 0.025 mol / 1 TiOSO ₄ aqueous solution, and stirred sufficiently.

While stirring this in an autoclave, the temperature was raised at a heating rate of 100 ° C./hour and kept at 125 ° C. for 1 hour to hydrolyze TiOSO ₄ to convert Na into Ti.
After being ion-exchanged with, the mixture was filtered and washed with water to obtain a cake of zeolite. Then, after drying the cake, 650
Calcination was performed for 4 hours to obtain zeolite. The Ti content in this zeolite was 2.4% by weight as TiO ₂ .

The Ti-ZSM-5 thus obtained was treated with H
A prototype sample (A-36) was obtained in the same manner as in Example 26, except that the prototype mordenite was used instead. The amount of catalyst supported at this time was 0.116 g per 1 cc of honeycomb. Example 37 (Preparation of perovskite compound) 72.67 g of lanthanum nitrate hexahydrate, 4.24 g of potassium nitrate (KNO ₃ ), 50.39 g of manganese acetate tetrahydrate and rhodium nitrate dihydrate (Rh (NO ₃ ). ₃ · 2H ₂ O) 1.36g water 250ml
To prepare an aqueous solution. The aqueous solution was evaporated to dryness Yamato Scientific Co. spray dryer "Parubisu GB22", which was calcined for 3 hours at 700 ° C., perovskite compound _{(La 0.8 K 0.2 Mn 0. 98} Rh 0.02 O
₃ ) got The specific surface area of this perovskite compound is 1
It was 8.3 m ² / g. (Preparation of H-Fe Silicate) While stirring, a mixture of 162 g of 50% silica sol and 500 g of water was prepared by first adding 9.23 g of ferric nitrate (Si / Fe atomic ratio of 60) to water 200.
Aqueous solution dissolved in g, then potassium hydroxide 22.
An aqueous solution prepared by dissolving 26 g in 200 g of water was added dropwise to the mixture over about 30 minutes.

Tetrapropylammonium bromide 3
5.19 g was dissolved and mixed. This mixture was placed in an autoclave and mixed by stirring at 160 ° C. for 16 hours. The reaction product is separated by filtration, washed with water and dried, and further at 500 ° C. for 3
By firing in air for a period of time, a ZSM-5 type Fe silicate (K exchanger) was obtained. 30 g of this Fe silicate was added to an aqueous solution of ammonium nitrate having a concentration of 0.5 mol / liter.
The mixture was added to 0 ml, stirred on an oil bath at 60 ° C. for 3 hours, and then separated by filtration. After repeating this operation 3 times, the filtered and separated product was washed with water, dried, and further calcined in the air at 500 ° C. for 3 hours to obtain a proton-type Fe silicate (H—Fe silicate).

100 g of water was added to a mixture of 45 g of the perovskite compound thus obtained and 55 g of the above H-Fe silicate, and the mixture was pulverized and mixed in a planetary mill for 30 minutes, and the viscosity was adjusted with water to prepare a washcoat. A slurry was obtained. This slurry was applied to a honeycomb to carry a catalyst, and a trial sample (A-37) was obtained. The amount of the catalyst supported at this time was 0.179 g per 1 cc of the honeycomb. Example 38 72.67 g of lanthanum nitrate hexahydrate, sodium nitrate (N
aNO ₃ ) 1.58 g and cobalt nitrate hexahydrate 54.27
g was dissolved in 250 ml of water to prepare an aqueous solution. Then, a perovskite compound (La _0.9 Na _0.1 CoO ₃ ) was obtained in the same manner as in Example 37. The specific surface area of this perovskite compound was 13.5 m ² / g.

40 g of the perovskite compound thus obtained and H-type mordenite (HM-2 manufactured by Nippon Kagaku Co., Ltd.)
3) 100 g of water was added to the mixture with 60 g, and the mixture was pulverized and mixed in a planetary mill for 30 minutes, and the viscosity was adjusted with water to obtain a slurry for wash coat. This slurry was applied to a honeycomb to support a catalyst, and a prototype sample (A-3
8) was obtained. The amount of catalyst loaded at this time was 1 cc of honeycomb.
The amount was 0.153 g. Example 39 lanthanum nitrate hexahydrate 72.67G, bismuth nitrate pentahydrate _{(Bi (NO 3) 3 ·} 5H 2 O) 9.05g, lithium nitrate (LiNO ₃₎ 7.71g and chloroplatinic acid hexahydrate Japanese 3
An aqueous solution was prepared by dissolving 8.63 g in 500 ml of water.
Then, a perovskite compound (La _0.9 Bi _0.1 Li _0.6 Pt _0.4 O ₃ ) was obtained in the same manner as in Example 37.
The specific surface area of this perovskite compound was 20.7 m ² / g. (Preparation of La-silicate) Example 37 was prepared except that lanthanum nitrate 11.27 g (Si / La atomic ratio = 30) was used in place of ferric nitrate in the preparation of H-Fe silicate of Example 37. H-La silicate was prepared in the same manner as in.

100 g of water was added to a mixture of 25 g of the perovskite compound thus obtained and 75 g of the above H-La silicate, and the mixture was pulverized and mixed in a planetary mill for 30 minutes, and the viscosity was adjusted with water to prepare a washcoat. A slurry was obtained. This slurry was applied to a honeycomb to carry a catalyst, and a trial sample (A-39) was obtained. The amount of catalyst supported at this time was 0.174 g per 1 cc of honeycomb. Example 40 Lanthanum nitrate hexahydrate 72.67 g, thorium nitrate tetrahydrate (Th (NO ₃ ) ₄ .4H ₂ O) 10.30 g, cupric nitrate trihydrate 4.50 g, nitric acid second Iron hexahydrate 48.33 g
And H-type mordenite (HM-23) 6 manufactured by Nippon Kagaku Co., Ltd.
300 ml of water was added to the mixture consisting of 6 g, and the mixture was thoroughly stirred and mixed.

The obtained slurry was evaporated to dryness with the same spray dryer as in Example 37 and calcined at 800 ° C. for 3 hours. The specific surface area of the obtained fired product was 241.3 m ² / g. 100 g of water was added to 100 g of this fired product, and the mixture was pulverized and mixed in a planetary mill for 30 minutes, and the viscosity was adjusted with water to obtain a slurry for washcoat. This slurry was applied to a honeycomb to support a catalyst, and a prototype sample (A
-40) was obtained. The amount of the catalyst supported at this time was 0.135 g per 1 cc of the honeycomb. Example 41 250 ml of water was added to a mixture consisting of 72.67 g of lanthanum nitrate hexahydrate, 32.44 g of cupric nitrate trihydrate and 7.42 g of tantalum oxide (Ta ₂ O ₅ ) and sufficiently stirred and mixed. ..

The obtained slurry was evaporated to dryness with the same spray dryer as in Example 37 and calcined at 800 ° C. for 3 hours to give a perovskite compound (LaCu _0.8 Ta _0.2).
O ₃ ) was obtained. The specific surface area of this perovskite compound is
It was 9.2 m ² / g. 40 g of the perovskite compound thus obtained and H-type mordenite (H
100 g of water was added to a mixture of 60 g of M-23), pulverized and mixed in a planetary mill for 30 minutes, and the viscosity was adjusted with water to obtain a slurry for washcoat. This slurry was applied to a honeycomb to support a catalyst, and a prototype sample (A
-41) was obtained. At this time, the loaded amount of the catalyst was 0.186 g per 1 cc of the honeycomb. Example 42 Praseodymium chloride heptahydrate (PrCl ₃ .7H ₂ O) 2
An aqueous solution was prepared by dissolving 24.02 g, lead nitrate 132.48 g and manganese acetate tetrahydrate 245.09 g in 500 ml of water.

With sufficient stirring in this aqueous solution, the concentration of 1
Add 21 g / 1 of aqueous sodium hydroxide to adjust the pH to 10
And After completion of the precipitation reaction, stirring was continued for 18 hours for aging. Then, filtration, washing with water, and repulping were repeated until the conductivity of the filtrate was almost the same as that of the repulping water.
The obtained filter cake was dried at 120 ° C. for 18 hours and then calcined at 700 ° C. for 3 hours.

As a result of X-ray diffraction of the obtained fired product, it was confirmed that a perovskite crystal phase was generated. The specific surface area of this fired product by the BET method is 25.9 m ² /
g (Pr _0.8 Pb _0.4 MnO ₃ ). 40 g of the perovskite compound thus obtained and H produced by Nippon Kagaku Co., Ltd.
100 g of water was added to a mixture with 60 g of mold mordenite (HM-23), pulverized and mixed in a planetary mill for 30 minutes, and the viscosity was adjusted with water to obtain a slurry for a washcoat. This slurry was applied to a honeycomb to support a catalyst, and a trial sample (A-42) was obtained. The amount of catalyst loaded at this time was 0.118 g per 1 cc of honeycomb. Example 43 neodymium nitrate hexahydrate _{(Nd (NO 3) 3 ·} 6H 2 O)
263.01 g, lead nitrate 132.48 g and manganese acetate 4
The perovskite compound (Nd _0.6 Pb _0.4 Mn) was prepared in the same manner as in Example 42 except that 245.09 g of the hydrate was used.
O ₃ ) was obtained. The specific surface area of this perovskite compound was 30.7 m ² / g.

40 g of the perovskite compound thus obtained and H-type mordenite (HM-23) manufactured by Nippon Kagaku Co., Ltd.
100 g of water was added to the mixture with 60 g to obtain a slurry,
This was applied to a honeycomb to support a catalyst, and a trial sample (A-43) was obtained. The loading amount of the catalyst at this time is
It was 0.133 g per 1 cc of honeycomb. Example 44 gadolinium nitrate hexahydrate _{(Gd (NO 3) 3 ·} 6H 2
O) 270.82 g, lead nitrate 132.48 g and manganese acetate tetrahydrate 245.09 g were mixed and then calcined at 700 ° C. for 3 hours in the same manner as in Example 42, except that the perovskite compound (Gd _0.6 Pb _0.4 MnO ₃ ) was obtained. The specific surface area of this perovskite compound is 24.2 m ² /
It was g.

40 g of the perovskite compound thus obtained and H type mordenite (HM-23) manufactured by Nippon Kagaku Co., Ltd.
100 g of water was added to the mixture with 60 g to obtain a slurry,
This was applied on a honeycomb to support a catalyst, and a trial sample (A-44) was obtained. The loading amount of the catalyst at this time is
It was 0.127 g per 1 cc of honeycomb. Example 45 samarium nitrate hexahydrate _{(Sm (NO 3) 3 ·} 6H
₂ O) 230.97 g, cobalt nitrate hexahydrate 291.03
A perovskite compound (SmCoO ₃ ) was obtained in the same manner as in Example 42, except that g and g were mixed and then calcined at 800 ° C. for 3 hours. The specific surface area of this perovskite compound was 16.4 m ² / g.

40 g of the perovskite compound thus obtained and H-type mordenite manufactured by Nippon Kagaku Co. (HM-23)
100 g of water was added to the mixture with 60 g to obtain a slurry,
This was applied to a honeycomb to support a catalyst, and a trial sample (A-45) was obtained. The loading amount of the catalyst at this time is
It was 0.112 g per 1 cc of honeycomb. Example 46 of europium nitrate hexahydrate _{(Eu (NO 3) 3 ·} 6H 2
O) 354.68 g, barium nitrate 52.27 g, and cobalt nitrate hexahydrate 291.03 g were used in the same manner as in Example 45 to perform the perovskite compound (Eu _0.8 Ba _0.2 Co).
O ₃ ) was obtained. The specific surface area of this perovskite compound was 18.5 m ² / g.

30 g of the perovskite compound thus obtained and H-type mordenite (HM-23) manufactured by Nippon Kagaku Co., Ltd.
100 g of water was added to a mixture with 100 g to obtain a slurry, which was applied to a honeycomb to support a catalyst, and a trial sample (A-46) was obtained. The amount of catalyst supported at this time was 0.119 g per 1 cc of honeycomb. Without the use of active titanium oxide in Comparative Example 1 Example 1, perovskite compound _{(La 0. 4 Sr 0.6 Co 0.8} Mn
_0.2 O ₃ ) was used alone to obtain a wash coat slurry, and otherwise the same as in Example 1 to obtain a honeycomb-shaped comparative sample (B-1) having a 1.25 mm pitch. The amount of the catalyst supported at this time was 0.132 g per 1 cc of the honeycomb. Comparative Example 2 Sodium-type mordenite (SiO manufactured by Nippon Mobile Co., Ltd.
_{A 2} / Al ₂ O ₃ molar ratio = 34) was treated in the same manner as in Example 2 to obtain a comparative sample (B-2) (H-type ZSM-5). At this time, the supported amount of the catalyst was 0.128 g per 1 cc of the honeycomb. (2) Evaluation test Regarding the samples (A-1) to (A-46) and the comparative samples (B-1) and (B-2), the nitrogen oxide catalytic reduction of the nitrogen oxide-containing gas under the following test conditions. It was carried out, the conversion to N ₂ of nitrogen oxides was calculated to quantify the N ₂ by gas chromatography. (Test conditions) (1) Gas composition NO 1 volume% O ₂ 10 volume% Reducing agent 1 volume% He balance (2) Space velocity 20000 (1 / Hr) (3) Reaction temperature 300 ° C, 400 ° C, 500 ° C or The results at 600 ° C. are shown in Tables 1 to 4.

[0088]

[Table 1]

[0089]

[Table 2]

[0090]

[Table 3]

[0091]

[Table 4]

As is clear from the results shown in Tables 1 to 4, the catalysts of the present invention (trial samples (A-1) to (A
-46)) has a high conversion rate of nitrogen oxides to nitrogen, while the comparative catalysts (comparative samples (B-1) and (B-2)) generally convert to nitrogen. The rate is low.

[0093]

As described above in detail, the catalyst for catalytic reduction of nitrogen oxides using the hydrocarbon or the oxygen-containing compound according to the present invention as a reducing agent is a nitrogen oxide in exhaust gas in the presence of oxygen. Can be efficiently catalytically reduced.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication location B01J 23/78 A 8017-4G 23/80 A 8017-4G 23/84 A 8017-4G 23/85 A 8017-4G 23/89 A 8017-4G 29/00 A 7038-4G 29/04 A 7038-4G 29/18 A 7038-4G 29/28 A 7038-4G (71) Applicant 000174541 Sakai Chemical Industry Co., Ltd. 1-23, 1-2-1, Nishinocho, Sakai-shi, Osaka (74) Attorney attorney Makoto Makino (72) Inventor, Tadao Nakatsuji 5-chome, Enoshima-cho, Sakai-shi, Osaka Sakai Chemical Industry Co., Ltd. (72) Inventor Hiromasu Shimizu 5-1, Ebishimacho, Sakai City, Osaka Prefecture Central Research Institute, Sakai Chemical Industry Co., Ltd. (72) Ritsu Yasukawa, 5-1, Ebishimacho, Sakai City, Osaka Prefecture Central Research, Sakai Chemical Industry Co., Ltd. In-house (72) Inventor Fujio Suganuma Saitama 228-16 Shinden, Shinjuku, Showa-cho, Kita-Katsushika-gun 228-16 (72) Akihiro Kitazume 2-15-36 Sugito, Sugito-cho, Kita-Katsushika-gun Saitama Prefecture Hiroshi Tsuchida 2-24-6 Kyo-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa (72) ) Inventor Takehiko Ito 1-1, East, Tsukuba City, Ibaraki Prefectural Institute of Chemical Technology (72) Inventor Hideaki Hamada 1-1, East, Tsukuba, Ibaraki Institute of Chemical Technology

Claims (3)

[Claims] 1. A general formula: (In the formula, A is La, Y, Ce, Pr, Nd, Pm, S
at least 1 selected from the group consisting of m, Eu and Gd
B represents Na, K, Bi, Th, Ba, S
r, Ca, Mg, Pb, Zn and at least one element selected from the group consisting of Ag, C is Mn, Co,
Fe, Ni, Cr, Cu, V, Mo, W, Ta, Li,
At least one element selected from the group consisting of Ti, Zr, Nb, Pd, Rh, Ru and Pt is shown, and 0 ≦ X ≦
It is 1. ) A catalyst for catalytic reduction of nitrogen oxides using a hydrocarbon and / or oxygen-containing compound as a reducing agent, characterized in that the perovskite-type composite oxide represented by the formula (4) is supported on a solid acid carrier. 2. A general formula: (In the formula, A represents at least one element selected from the group consisting of La, Y and Ce, and B represents Na, K, Bi and T.
h, Ba, Sr, Ca, Mg, Pb, Zn, and at least one element selected from the group consisting of Ag, C is Mn, Co, Fe, Ni, Cr, Cu, V, Mo, W,
At least one element selected from the group consisting of Ta, Li, Ti, Zr, Nb, Pd, Rh, Ru, and Pt is shown, and 0 ≦ X ≦ 1. ) A catalyst for catalytic reduction of nitrogen oxides using a hydrocarbon and / or oxygen-containing compound as a reducing agent, characterized in that the perovskite-type composite oxide represented by the formula (4) is supported on a solid acid carrier. 3. A general formula: (In the formula, A represents La or Ce, B represents Ba, Sr, C
a, Mg, Pb, Zn or Ag, and C is Mn or C
o, C'is Fe, Ni, Cr, Cu, V, Mo,
It represents W, Ti, Zr, Nb, Pd, Rh, Ru or Pt, and 0 ≦ X ≦ 1 and 0 ≦ Y ≦ 1. ) A catalyst for catalytic reduction of nitrogen oxides using a hydrocarbon and / or oxygen-containing compound as a reducing agent, characterized in that the perovskite-type composite oxide represented by the formula (4) is supported on a solid acid carrier.