JPH0819739A - Exhaust gas purifying catalyst and producing method therefor - Google Patents

Abstract

PURPOSE:To provide a catalyst for exhaust gas purification and a producing method of the catalyst whose NOX purifying function under lean atmosphere under which a prior art catalyst does not have activity is improved and which can purify NOX in an exhaust gas in a wide temperature range from low temperature to high temperature. CONSTITUTION:A catalyst for exhaust gas purification consists of multicomponents-based composite oxide containing copper, cobalt, and aluminum and expressed by a general formula; CuaCobAdOg wherein a, b, and d stand for the atomic ratio of respective elements and in the case d=2.0, a=0.01-0.3 and b=0.05-0.4, and g stands for the number of oxygen atoms to satisfy the valence of each component.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an exhaust gas purifying catalyst, and more particularly to an exhaust gas purifying catalyst excellent in NOx purification performance in an oxygen excess atmosphere (hereinafter referred to as "lean atmosphere") and a method for producing the same. .

[0002]

2. Description of the Related Art Conventionally, as an exhaust gas purifying catalyst for cleaning exhaust gas emitted from an internal combustion engine of an automobile or the like, platinum (Pt), palladium (Pd), rhodium (Rh), etc. are added to alumina, cerium oxide, etc. Carrying noble metal of
A monolith carrier coated with this is used. Since this catalyst mainly focuses on improving the exhaust gas purifying ability in stoichiometric conditions, sufficient performance for purifying nitrogen oxides (NOx) was not obtained in a lean atmosphere.

On the other hand, many catalysts that improve the NOx purification performance in a lean atmosphere have been reported. In particular,
Many proposals have been made for exhaust gas purifying catalysts using alumina, for example, JP-A-4-284848.
It is disclosed in Japanese Patent Laid-Open No. 4-358525. Exhaust gas purifying catalyst using alumina described in the patent publication, by using a metal-supported alumina, a metal aluminate that is a composite oxide of metal and alumina as a catalyst, the catalytic performance in a high temperature range. Not only can NOx in the exhaust gas be reduced and removed in a lean atmosphere in a high temperature region, but also N
It can purify Ox, carbon monoxide (CO) and hydrocarbons (HC).

[0004]

However, in the above-mentioned conventional catalyst containing alumina as a main component, among the harmful components (HC, CO, NOx) in the waste gas, especially the exhaust gas composition (HC species) and the temperature. Furthermore, the purification performance of NOx that is strongly affected by the water contained in the exhaust gas is not sufficiently expressed unless it is in a high temperature range of 500 ° C. or higher. Therefore, improvement of catalytic activity in a wide temperature range from low temperature to high temperature, in particular, improvement of NOx purification performance has been a major issue.

Therefore, the object of the present invention is to improve the NOx purification performance in a lean atmosphere, which was not active with conventional catalysts, and to reduce NOx in exhaust gas in a wide temperature range from low temperature to high temperature. An object is to provide a catalyst for purifying exhaust gas that can be purified.

[0006]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventor has found that a catalyst prepared by coating a catalyst carrier with a multi-component composite oxide containing copper, cobalt and aluminum components is The present inventors have found that the present invention has sufficient NOx purification performance in a low temperature range to a high temperature range even in a lean atmosphere, and reached the present invention.

The exhaust gas purifying catalyst according to the present invention has the following general formula: Cu _a Co _b Al _d O _g (where a, b, c and d represent the atomic ratio of each element,
When d = 2.0, a = 0.01 to 0.3, b = 0.0
5 to 0.4, and g is the number of oxygen atoms required to satisfy the valences of the above components) and is composed of a multi-component composite oxide containing copper, cobalt and aluminum. It is a feature.

Further, in order to further control the HC oxidation activity of the catalyst, another exhaust gas purifying catalyst according to the present invention comprises:
The following general formula: Cu _a Co _b Al _d X _e O _g (wherein X is at least one element selected from the group consisting of chromium, manganese and iron, and a, b, d and e).
Indicates the atomic ratio of each element, and when d = 2.0, a =
0.01-0.3, b = 0.05-0.4, e ≦ 0.2
And g is the number of oxygen atoms required to satisfy the valences of the above components), and is composed of a multi-component composite oxide containing copper, cobalt and aluminum. is there.

In order to further improve the NOx purification performance of the above catalyst, another exhaust gas purification catalyst according to the present invention has the following general formula: Cu _a Co _b Al _d Y _f O _g (wherein Y is at least one element selected from the group consisting of boron, silicon, phosphorus, titanium, vanadium, gallium, yttrium, zirconium, molybdenum, silver, indium, tin, lanthanum, cerium, praseodymium, neodymium and tungsten, and a , B, d and f represent the atomic ratio of each element, and when d = 2.0, a =
0.01-0.3, b = 0.05-0.4, f = ≦ 0.
2 and g is the number of oxygen atoms required to satisfy the valences of the above components) and is composed of a multi-component composite oxide containing copper, cobalt and aluminum. Is.

Further, the HC oxidation activity and NOx of the above catalyst
In order to further improve the purification performance, another exhaust gas purification catalyst according to the present invention has the following general formula: Cu _a Co _b Al _d X _e Y _f O _g (where X is chromium, manganese, and iron). Is at least one element selected from the group consisting of, Y is boron,
Silicon, phosphorus, titanium, vanadium, gallium, yttrium, zirconium, molybdenum, silver, indium,
At least one selected from the group consisting of tin, lanthanum, cerium, praseodymium, neodymium and tungsten.
The seed elements a, b, d, e and f represent the atomic ratio of each element, and when d = 2.0, a = 0.01 to 0.3,
b = 0.05 to 0.4, e ≦ 0.2, f = ≦ 0.2, and g is the number of oxygen atoms required to satisfy the valences of the above components). It is characterized by comprising a multi-component complex oxide containing copper, cobalt and aluminum.

In order to finely adjust the adsorption state of HC and NOx on the catalyst by modifying the adsorption active points on the catalyst surface of the above catalyst, another catalyst for purifying exhaust gas according to the present invention is an alkali metal catalyst. And at least one element selected from the group of alkaline earth metals, preferably selected from the group consisting of potassium, cesium, magnesium, strontium, calcium and barium in a multi-component composite oxide containing copper, cobalt and aluminum. It is characterized in that at least one element is added.

The catalyst according to the present invention comprises alumina (A1 ₂ O
_By using a cobalt aluminate catalyst (hereinafter, referred to as "cobalt-aluminum-based composite oxide") in which a specific composition ratio of cobalt is added to ₃ ), a cobalt-aluminum-based composite oxide having a stoichiometric ratio can be obtained. The catalytic activity (both the activity of HC and NOx) can be significantly improved. The optimum composition ratio of cobalt is d = 2.
0 is in the range of b = 0.05 to 0.4. b is 0.
When it is less than 05, the catalytic activity for both HC and NOx activity is lowered, and when b is more than 0.4, NOx is activated.
Purification performance decreases.

Further, in the present invention, the composition ratio of copper is
A = 0.01 to 0.3 for d = 2.0 in the above general formula
Range. By adding copper in such a range,
It shows a remarkable effect in improving the activity of the cobalt-aluminum composite oxide limited to the above composition. In particular, high activity from low temperatures can be obtained without reducing the NO conversion performance (selectivity from NO to N ₂ ). However, the composition of copper is d = 2.
When a is smaller than 0.01 with respect to 0, the original effect of the catalyst is not exhibited, and conversely, when a is larger than 0.3, the NO conversion performance is deteriorated. It is considered that copper enters the crystal structure of alumina like cobalt and forms a spinel structure.

Further, the X component can be used as necessary when it is desired to further improve the HC oxidation activity of the copper-cobalt-aluminum composite oxide. The composition of the X component is such that d is 2.0 and e is at most 0.2, and the X component is the above-mentioned copper-cobalt-cobalt when the HC oxidation activity is sufficiently obtained under the conditions of use of the catalyst. The aluminum-based composite oxide can be used as it is, and it is not particularly necessary to add it. Therefore, X component is catalytic performance, especially H
It may be added if it is necessary to improve the C oxidation activity, but if the added amount of d exceeds 2.0 and e exceeds 0.2, the basic composition is a copper-cobalt-aluminum composite oxide. However, the catalyst performance is rather deteriorated, which is not preferable.

The Y component can be used as needed when it is desired to further improve the NOx purification performance of the copper-cobalt-aluminum composite oxide. The composition of this Y component is d = 2.0, but f is at most 0.2.
As the Y component, the above copper-cobalt-aluminum composite oxide can be used as it is, if the NOx removing activity is sufficiently obtained under the use condition of the catalyst, and it is not particularly necessary to add it. Therefore, the Y component is catalytic performance, especially NO.
x may be added when it is necessary to improve the purification performance, but when the added amount is more than d = 2.0 and f exceeds 0.2, the basic composition of the copper-cobalt-aluminum composite oxide is improved. The catalyst performance is rather deteriorated, which is not preferable.

The X component and the Y component are the above-mentioned copper-cobalt-
When it is desired to further improve the HC oxidation activity and the NOx purification performance of the aluminum-based composite oxide, they can be used in combination as needed. The composition of the X component and the Y component is such that e is at most 0.2 and f is at most 0.2 with respect to d = 2.0, and the reason for limiting the numerical values is the same as that described above. The above-mentioned copper-cobalt-aluminum composite oxide can be used as the X component and the Y component, if HC oxidation activity and NOx purification performance are sufficiently obtained under the use conditions, and it is not particularly necessary to add them. Therefore, the X component and the Y component have catalytic performance, especially H
It may be added when it is necessary to improve the C oxidation activity and the NOx purification performance at the same time.

In other words, on the catalyst according to the present invention, H
A selective reduction reaction of NOx using C as a reducing agent occurs,
The NOx purification efficiency, which is how effective the reducing agent HC contributes to the NOx purification reaction, is important. Therefore, when the activation of HC does not occur and it does not act effectively on the purification of NOx, the HC oxidation activity is improved, while when the complete oxidation of HC (generation of CO ₂ ) proceeds too much, the HC oxidation activity is increased. It is necessary to reduce the X component and / or
Alternatively, by adding a Y component and adjusting the HC activity, N
The HC activity is changed by changing the Ox purification selectivity and, conversely, adjusting the NOx purification selectivity.

Further, in the present invention, when it is desired to finely adjust the adsorption state of HC and NO on the catalyst by modifying the adsorption active point on the catalyst surface of the above copper-cobalt-aluminum composite oxide. And alkaline earth metals can be used if desired. As for the alkali metal and the alkaline earth metal, the above copper-cobalt-aluminum composite oxide can be used as it is, if sufficient NOx purification performance and HC oxidation activity can be obtained under the use conditions, and it is not particularly necessary to add it. . Particularly preferred alkali metals include potassium and cesium, and alkaline earth metals include magnesium, strontium, calcium and barium, and one or more of these elements can be added. The amount of addition is preferably 3.0% by weight or less based on the powder of the copper-cobalt-aluminum composite oxide, which is the basic composition. If it exceeds 3.0% by weight, conversely, the HC oxidation activity and NOx conversion activity and the selectivity are lowered, which is not preferable.

Regarding the number of oxygen atoms, it is necessary to identify the atoms of all elements, but in the multi-component catalyst, the valence of the element varies depending on the structure and coordination state of the oxide formed, so it is not possible to specify it. Very difficult.

As the raw material compound for preparing the catalyst used in the present invention, nitrates, carbonates, ammonium salts, acetates, halides, oxides and the like of each element can be used in any combination. It is preferable to use the organic salt from the viewpoint of improving the catalyst performance.

The method for preparing the catalyst according to the present invention is not limited to a special method, and various known methods such as a dry evaporation method, a precipitation method and an impregnation method may be used as long as the components are not unevenly distributed. Can be appropriately selected from the above, and particularly, a precipitation method in which an aqueous solution of at least one compound selected from the group consisting of ammonia water, ammonium carbonate, ammonium hydrogen carbonate, ammonium sulfate and ammonium hydrogen sulfate is used as a precipitant is used. That copper-cobalt-
It is preferable because the surface area of the multi-component composite oxide containing aluminum can be sufficiently secured and a sufficient amount of the supported metal can be obtained with good dispersibility.

In producing the exhaust gas purifying catalyst according to the present invention, first, a catalyst raw material containing copper, cobalt and aluminum components is added to pure water and stirred. At this time, a liquid in which each catalyst raw material is dissolved simultaneously or separately may be added.
Further, a liquid in which the catalyst raw materials containing the X component and / or the Y component are dissolved simultaneously or separately may be added. Then, an aqueous solution of at least one compound selected from the group consisting of aqueous ammonia, ammonium carbonate, ammonium hydrogen carbonate, ammonium sulfate and ammonium hydrogen sulfate is gradually added to the mixed solution containing the catalyst raw material to adjust the pH of the solution to 7 After adjusting to a range of 0.0 to 9.0, the residue is heat treated to obtain the desired catalyst.

In the exhaust gas purifying catalyst according to the present invention, the fine pore structure and large surface area of the oxide obtained by the precipitation method play an important role in exhibiting low temperature activity. On the other hand, the catalyst obtained without using the above-mentioned precipitating agent lacks a fine pore structure, and the surface area effective for the reaction becomes small, so that the catalytic activity decreases, so that it is preferable to use the precipitation method. If the above-mentioned ammonia water or ammonium compound is used as the precipitant used in this precipitation method, the metal element does not remain even if the cleaning is insufficient, and even if the ammonium compound (mainly ammonium nitrate etc. after dropping) remains. It can be easily decomposed and removed by firing. On the other hand, when a metal salt such as sodium hydroxide or sodium carbonate is used, metal elements such as sodium remain in the obtained precipitate, and these residual elements adversely affect the catalyst performance, so these are removed. Therefore, a cleaning process is required.

When carrying out the above-mentioned precipitation method, the pH of the solution can be adjusted to a range of 7.0 to 9.0 to form precipitates in various metal salts. pH is 7.
When it is lower than 0, various elements do not form a precipitate sufficiently, and conversely p
When H is higher than 9.0, some of the precipitated components may be redissolved.

The water can be removed by appropriately selecting from known methods such as filtration and evaporation to dryness.
The heat treatment is not particularly limited, but is, for example, 500 to 100.
It is preferable to carry out at a temperature in the range of 0 ° C. in air and / or under air flow until copper and cobalt are solid-dissolved in alumina to form a copper-cobalt-aluminum compound as a basic composition.

Examples of the method for adding the Y component or the alkali metal and alkaline earth metal, which hardly form a precipitate in the pH range of 7.0 to 9.0, together with the copper-cobalt-aluminum component, include the impregnation method and the kneading method. The method can be appropriately selected from known methods, and the impregnation method is particularly preferably used. The heat treatment after the addition is not particularly limited as in the above, but is preferably performed in the air and / or in the air flow at a temperature in the range of 500 to 1000 ° C, for example.

The thus obtained exhaust gas purifying catalyst according to the present invention can be effectively used without a carrier, but it is pulverized and slurried and coated on a catalyst carrier,
It is preferable to use it after firing at 400 to 900 ° C. The catalyst carrier can be appropriately selected and used from known catalyst carriers, and examples thereof include a monolith carrier and a metal carrier.

The shape of the catalyst carrier is not particularly limited, but it is usually preferable to use it in a honeycomb shape, and the catalyst powder is applied to various honeycomb-shaped base materials.
As the honeycomb material, a cordierite material is generally used, but a honeycomb made of a metal material can be used, and the catalyst powder itself may be formed into a honeycomb shape. By making the shape of the catalyst honeycomb, the contact area between the catalyst and the exhaust gas becomes large and the pressure loss can be suppressed, which is extremely effective when used for automobiles.

The present invention will be described below with reference to the following examples and comparative examples, but the present invention is not limited thereto. Unless otherwise specified in Examples and Comparative Examples,
The parts are parts by weight and the% is% by weight.

Example 1 1.6 parts of copper nitrate, 3.9 parts of cobalt nitrate and 50 parts of aluminum nitrate were added to 400 parts of pure water and stirred and dissolved.
Next, while stirring this solution, 5% ammonia water was gradually added dropwise so that the pH of the solution was between 7.0 and 9.0. The precipitate formed is filtered off and
After drying at 150 ° C. for 12 hours, it was baked in air at 800 ° C. for 2 hours. 500 parts of the powder thus obtained and 1000 parts of pure water were mixed by a ball mill and then pulverized, and the obtained slurry was adhered to a monolith carrier substrate and calcined at 400 ° C. for 1 hour. The adhesion amount at this time was set to 200 g / L. The composition of the components other than oxygen of the obtained catalyst was Cu.
_{It was 0.1} Co _0.2 Al _2.0 .

Example 2 The procedure of Example 1 was repeated except that a 5% aqueous solution of ammonium carbonate was used instead of the 5% aqueous ammonia. The composition of components other than oxygen of the obtained catalyst was Cu _0.1 Co.
It was _0.2 Al _2.0 .

Example 3 Example 3 was repeated except that 5% aqueous ammonium hydrogen carbonate solution was used instead of 5% aqueous ammonia. The composition of the components other than oxygen of the obtained catalyst was Cu _0.1
It was Co _0.2 Al _2.0 .

Example 4 Example 4 was repeated except that a 5% aqueous ammonium sulfate solution was used instead of the 5% aqueous ammonia. The composition of components other than oxygen of the obtained catalyst was Cu _0.1 Co.
It was _0.2 Al _2.0 .

Example 5 5% instead of 5% aqueous ammonia
% Aqueous ammonium hydrogen sulfate solution was used, and the same procedure as in Example 1 was performed. The composition of components other than oxygen of the obtained catalyst was Cu _0.1 Co _0.2 Al _2.0 .

Example 6 The procedure of Example 1 was repeated, except that cobalt nitrate was changed to 1.95 parts. The composition of components other than oxygen of the obtained catalyst was Cu _0.1 Co _0.1 Al _2.0 .

Example 7 The procedure of Example 1 was repeated, except that cobalt nitrate was changed to 7.8 parts. The composition of components other than oxygen of the obtained catalyst was Cu _0.1 Co _0.4 Al _2.0 .

Example 8 Example 8 was repeated except that the amount of copper nitrate was changed to 0.8 part. The composition of components other than oxygen of the obtained catalyst was Cu _0.05 Co _0.2 Al _2.0 .

Example 9 Example 9 was repeated except that copper nitrate was changed to 2.4 parts. The composition of components other than oxygen of the obtained catalyst was Cu _0.15 Co _0.2 Al _2.0 .

Example 10 Example 1 was repeated except that 0.04 part of boric acid and 0.29 part of lanthanum nitrate were added. The composition of components other than oxygen of the obtained catalyst was B _0.01 La _0.01 Cu _0.1 Co _0.1.
It was Al _2.0 .

Example 11 0.12 parts of ammonium molybdate, silica sol 0.
Example 1 was repeated except that 2 parts and 0.29 part of cerium nitrate were added. The composition of components other than oxygen of the obtained catalyst was Mo _0.01 Si _0.01 Ce _0.01 Cu _0.1 Co _0.2 A.
It was l _2.0 .

Example 12 The procedure of Example 1 was repeated except that 0.11 part of silver nitrate, 0.08 part of phosphoric acid and 0.28 part of praseodymium nitrate were added. The composition of components other than oxygen of the obtained catalyst was Ag.
_{It was 0.01} P _0.01 Pr _0.01 Cu _0.1 Co _0.2 Al _2.0 .

Example 13 Example 13 was repeated except that 0.24 part of indium nitrate, 0.13 part of titanium chloride and 0.29 part of neodymium nitrate were added. The composition of components other than oxygen of the obtained catalyst was In _0.01 Ti _0.01 Nd _0.01 Cu _0.1 Co _0.2 Al.
It was _2.0 .

Example 14 The same procedure as in Example 1 was carried out except that 0.29 part of zirconium nitrate, 0.08 part of ammonium metavanadate and 0.27 part of gallium nitrate were added. The composition of components other than oxygen of the obtained catalyst was Zr _0.01 V _0.01 Ga _0.01 Cu _0.1 C.
It was _0.2 Al _2.0 .

Example 15 The same procedure as in Example 1 was carried out except that 0.15 part of tin chloride, 0.26 part of yttrium nitrate and 0.17 part of ammonium tungstate were added. The composition of components other than oxygen of the obtained catalyst was Sn _0.01 Y _0.01 W _0.01 Cu _0.1 Co _0.2 A.
It was l _2.0 .

Example 16 Using potassium nitrate, converted to potassium oxide, 0.01
% Equivalent amount was impregnated into the catalyst of Example 1.

Example 17 Using cesium nitrate, 0.01 was calculated in terms of cesium oxide.
% Equivalent amount was impregnated into the catalyst of Example 11.

Example 18 The catalyst of Example 13 was impregnated with magnesium nitrate in an amount of 0.01% equivalent to magnesium oxide.

Example 19 The catalyst of Example 1 was impregnated with strontium nitrate in an amount equivalent to 0.01% in terms of strontium oxide.

Example 20 Using calcium nitrate, it was converted to calcium oxide and converted to 0.
The catalyst of Example 15 was impregnated with an amount equivalent to 01%.

Example 21 Using barium acetate, 0.01% in terms of barium oxide
A considerable amount was impregnated with the catalyst of Example 1.

Example 22 The procedure of Example 1 was repeated except that 0.53 part of chromium nitrate and 0.38 part of manganese nitrate were added. The composition of the components other than oxygen of the obtained catalyst was Cr _0.02 Mr _0.02 Cu _0.1 C
It was _0.2 Al _2.0 .

Example 23 Example 1 was repeated except that 0.54 part of iron nitrate was added. The composition of components other than oxygen of the obtained catalyst was Fe.
_{It was 0.02} Cu _0.1 Co _0.2 Al _2.0 .

Example 24 Chromium nitrate 0.53 parts, manganese nitrate 0.38 parts, ammonium molybdate 0.12 parts, silica sol 0.2
Parts, Example 1 except that 0.29 parts of cerium nitrate was added
It carried out similarly to. The composition of components other than oxygen of the obtained catalyst was Cr _0.02 Mn _0.02 Mo _0.01 Si _0.01 Ce _0.01 Cu.
_{It was 0.1} Co _0.2 Al _2.0 .

Example 25 The same procedure as in Example 1 was carried out except that 0.54 part of iron nitrate, 0.24 part of indium nitrate, 0.13 part of titanium chloride and 0.29 part of neodymium nitrate were added. The composition of components other than oxygen of the obtained catalyst was Fe _0.02 In _0.01 Ti _0.01 Nd.
_{It was 0.01} Cu _0.1 Co _0.2 Al _2.0 .

Example 26 Using potassium nitrate, converted to potassium oxide, 0.01
% Equivalent amount was impregnated into the catalyst of Example 22.

Example 27 Using magnesium nitrate, the catalyst of Example 23 was impregnated with an amount of 0.01% equivalent to magnesium oxide.

Example 28 Using potassium nitrate, converted to potassium oxide, 0.01
% Equivalent amount was impregnated into the catalyst of Example 24.

Example 29 The catalyst of Example 25 was impregnated with magnesium nitrate in an amount of 0.01% equivalent to magnesium oxide.

Comparative Example 1 50 parts of aluminum nitrate and 400 parts of pure water were added and stirred.
Dissolved. Next, while stirring this solution, 5% ammonia water was gradually added dropwise so that the pH of the solution was between 7.0 and 9.0. The precipitate formed was filtered off, dried at 150 ° C for 12 hours and then at 800 ° C.
And baked in air for 2 hours. Powder 5 thus obtained
After mixing 00 parts and pure 1000 parts by a ball mill, it was pulverized, and the obtained slurry was attached to a monolith carrier substrate and calcined at 400 ° C. for 1 hour. The adhesion amount at this time is 20
It was set to 0 g / L. The composition of components other than oxygen of the obtained catalyst was A _12.0 .

Comparative Example 2 The procedure of Example 1 was repeated except that copper nitrate was not used.
The composition of the components other than oxygen of the obtained catalyst was Co _0.2 Al
It was _2.0 .

Comparative Example 3 The procedure of Example 1 was repeated except that 5% aqueous ammonia was not used. The composition of the components other than oxygen of the obtained catalyst,
It was Cu _0.1 Co _0.2 Al _2.0 .

Comparative Example 4 The procedure of Example 1 was repeated, except that cobalt nitrate was changed to 15.6 parts. The composition of components other than oxygen of the obtained catalyst was Cu _0.1 Co _0.8 Al _2.0 .

Comparative Example 5 The procedure of Example 1 was repeated except that cobalt nitrate was not used. The composition of the components other than oxygen of the obtained catalyst was Cu.
It was _0.1 Al _2.0 .

Test Example 1 Regarding the catalysts of Examples 1 to 29 and Comparative Examples 1 to 5,
The catalyst activity was evaluated under the following conditions. For the activity evaluation, an automatic evaluation device using a model gas imitating automobile exhaust gas was used. The L value used here represents the stoichiometric ratio of the oxidizing gas (NO, O ₂ ) and the reducing gas (CO, C ₃ H ₆ ) and is defined by the following formula.

[0065]

[Equation 1] Evaluation conditions (L = 5.3) Catalyst Monolith type multi-component catalyst Total gas flow rate 20 L / min Catalyst inlet gas temperature 100 to 600 ° C Temperature rising temperature 30 ° C / min Space velocity Approximately 10,000 H ^-1 Inlet gas composition Average air-fuel ratio A model gas composition corresponding to 18.0 CO 0.2% C ₃ H ₆ 5000ppm C NO 500ppm O ₂ 4.50% CO ₂ 10.0% H ₂ O 10.0% N ₂ balance A / F amplitude None The obtained catalytic activity evaluation results are shown in Tables 1 and 2. The catalytic activity of the example was higher than that of the comparative example, and the effect of the present invention described later could be confirmed.

[0066]

[Table 1]

[Table 2]

[0067]

The exhaust gas purifying catalyst of the present invention uses a multi-component catalyst containing copper, cobalt and aluminum as the main components, so that the conventional catalyst has no NOx purifying performance in an oxygen excess atmosphere. Can be improved, and high performance can be maintained with respect to NOx in the exhaust gas in a wide temperature range from low temperature to high temperature.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location B01J 23/78 ZAB A 23/835 ZAB 23/847 23/85 ZAB A 23/86 ZAB A 23 / 88 ZAB A 27/185 ZAB A B01J 23/82 ZAB A 23/84 301 A

Claims (9)

[Claims] 1. The following general formula: Cu _a Co _b Al _d O _g (where a, b and d represent the atomic ratio of each element, and d =
When 2.0, a = 0.01 to 0.3, b = 0.05 to
0.4, and g is the number of oxygen atoms required to satisfy the valences of the above components.), A multi-component complex oxide containing copper, cobalt and aluminum. Exhaust gas purification catalyst. 2. The following general formula: Cu _a Co _b Al _d X _e O _g (wherein X is at least one element selected from the group consisting of chromium, manganese and iron, and a, b, d And e
Indicates the atomic ratio of each element, and when d = 2.0, a =
0.01-0.3, b = 0.05-0.4, e ≦ 0.2
And g is the number of oxygen atoms required to satisfy the valences of the above components). Exhaust gas comprising a multi-component complex oxide containing copper, cobalt and aluminum represented by Purification catalyst. 3. The following general formula: Cu _a Co _b Al _d Y _f O _g (wherein Y is boron, silicon, phosphorus, titanium, vanadium, gallium, yttrium, zirconium, molybdenum, silver, indium, tin, At least one element selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, and tungsten, where a, b, d, and f represent the atomic ratio of each element, and when d = 2.0, a =
0.01-0.3, b = 0.05-0.4, f ≦ 0.2
And g is the number of oxygen atoms required to satisfy the valences of the above components). Exhaust gas comprising a multi-component complex oxide containing copper, cobalt and aluminum represented by Purification catalyst. 4. The following general formula: Cu _a Co _b Al _d X _e Y _f O _g (wherein X is at least one element selected from the group consisting of chromium, manganese and iron, and Y is boron). , Silicon, phosphorus, titanium, vanadium, gallium, yttrium, zirconium, molybdenum, silver, indium, tin,
It is at least one element selected from the group consisting of lanthanum, cerium, praseodymium, neodymium and tungsten, and a, b, d, e and f represent the atomic ratio of each element, and when d = 2.0, a = 0.01-0.3, b
= 0.05-0.4, e ≦ 0.2, f ≦ 0.2,
g is the number of oxygen atoms required to satisfy the valences of the above components) and is composed of a multi-component composite oxide containing copper, cobalt and aluminum, and the exhaust gas purifying catalyst is characterized in that . 5. The multi-component complex oxide containing copper, cobalt and aluminum according to claim 1, and at least one element selected from the group consisting of alkali metals and alkaline earth metals. Is added in an amount of 3.0% by weight or less. 6. The exhaust gas purifying catalyst according to claim 5, wherein the alkali metals are potassium and cesium, and the alkaline earth metals are magnesium, strontium, calcium, and barium. 7. An exhaust gas purifying catalyst, characterized in that the catalyst carrier is provided with a multi-component complex oxide containing copper, cobalt and aluminum according to any one of claims 1 to 6 as a coat layer. . 8. The exhaust gas purifying catalyst according to claim 7, wherein the catalyst carrier is a honeycomb-shaped monolith carrier substrate. 9. Aqueous solution, ammonium carbonate, ammonium hydrogencarbonate is added to an aqueous solution or dispersion containing a multi-component composite oxide containing copper, cobalt and aluminum and containing each metal compound constituting the composite oxide. PH of the solution by adding at least one kind of aqueous solution selected from the group consisting of ammonium sulfate, ammonium sulfate and ammonium hydrogensulfate.
Is adjusted to fall within the range of 7.0 to 9.0, water is removed, and the residue is heat-treated.