JP2969343B2 - Manufacturing method of exhaust gas purifying catalyst - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a catalyst for purifying exhaust gas discharged from various internal combustion engines, and more particularly to a catalyst for purifying exhaust gas having excellent durability. The method relates to a method for producing the same.

[0002]

2. Description of the Related Art Heretofore, catalysts for purifying unburned carbon monoxide, hydrocarbons, and nitrogen oxides from exhaust gas from various internal combustion engines have been studied.

In recent years, nitrogen oxides can be selectively reduced by reducing components such as unburned carbon monoxide and hydrocarbons even in an excess of oxygen for purifying exhaust gas of lean-burn engines in order to reduce fuel consumption of internal combustion engines. A catalyst in which a base metal is contained in zeolite or the like has been proposed as a catalyst (Japanese Patent Application Laid-Open No. 63-10 / 1988).
No. 0919).

[0004]

However, the catalysts proposed in these studies have a high activity, but have a problem in durability, and the deterioration of the activity cannot be suppressed. In particular, when these catalysts were exposed to an atmosphere containing water vapor at a high temperature for a long period of time, the activity of the catalyst was remarkably deteriorated.

[0005] Further, many attempts have been made to improve the durability of the catalyst by adding another metal to the catalyst containing copper.
The suppression of the deterioration of the catalyst is not sufficient.

An object of the present invention is to provide a method for producing an exhaust gas purifying catalyst which purifies an oxygen-excessive exhaust gas discharged from an internal combustion engine or the like and has excellent durability in an atmosphere containing steam at a high temperature. To provide.

[0007]

Means for Solving the Problems The inventor of the present invention has made intensive studies on the above-mentioned problems, and has completed the present invention. That is, the present invention can solve the above-described problem by providing the following configuration.

(1) Copper and zeolite are contained in a zeolite in the presence of a reducing agent, ammonia and an inert gas, dried under a reduced pressure or an inert gas atmosphere, and then further made to contain Ag . preparation of <br/> catalyst for exhaust gas purification, characterized in that.

(2) After adding Ag to zeolite, copper and zeolite can be obtained by adding copper to zeolite in the presence of a reducing agent, ammonia and an inert gas, and drying under reduced pressure or an inert gas atmosphere. It is characterized by
Of manufacturing exhaust gas purifying catalyst .

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described based on the following examples.

[0011]

EXAMPLES Example 1 (Preparation of Catalyst 1) ZSM5 zeolite (SiO ₂ / Al ₂ O ₃ = 23.
8) 10 g of an aqueous Cu ammine complex solution containing Cu in the same mole as Al contained in the zeolite (pH = 10.
In addition to 5), hydrazine monohydrate was added to a molar equivalent of Cu while bubbling He gas into the solution. The slurry was stirred at 30 ° C. for 20 hours while bubbling He gas.

After the slurry was filtered off, the obtained cake was again added to another solution and stirred in the same manner.

After filtration, the obtained cake is -100 kPa
While gradually increasing the temperature in a vacuum dryer at 250 ° C., 12
After drying for an hour, Cu zeolite was obtained. The composition of the obtained catalyst was analyzed using fluorescent X-rays. As a result, the copper content was Cu / Al ₂ = 1.92.

Further, the Cu zeolite thus obtained was replaced with 0.5 times mole of Ag contained in the zeolite.
Was added to an aqueous solution of AgNO ₃ containing and stirred at 30 ° C. for 20 hours.

After filtering the slurry, the obtained cake is gradually heated in a vacuum drier of -100 kPa.
After drying at 250 ° C. for 12 hours, catalyst 1 was obtained. When the composition analysis of the obtained catalyst was measured using fluorescent X-rays, Cu
Is Cu / Al ₂ = 1.86 and Ag / Al = 0.86.
It was 50.

[0016] In Example 2 (Preparation of Catalyst 2) Example 1, a catalyst 2 performs the same operation except for changing the aqueous AgNO ₃ solution to AgNO ₃ aqueous solution containing 0.1 moles of Al contained in the zeolite Obtained. When the composition analysis of the obtained catalyst was measured using fluorescent X-ray, C
The content of u is Cu / Al ₂ = 1.90, Ag / Al =
0.08.

[0017] Example 3 (Preparation of Catalyst 3) oxygen 6% nitrogen Cu zeolite before the AgNO ₃ solution with AgNO ₃ aqueous solution containing 0.5 moles of Al contained in the zeolite to ion exchange in Example 1 Catalyst 3 was obtained in the same manner except that pretreatment was performed at 500 ° C. for 1 hour at a balance GHSV of 10,000 hr ⁻¹ . When the composition analysis of the obtained catalyst was measured using fluorescent X-ray, C
The content of u is Cu / Al ₂ = 1.68, Ag / Al =
0.24.

[0018] Example 4 (Preparation of Catalyst 4) oxygen 6% water Cu zeolite before the AgNO ₃ solution with AgNO ₃ aqueous solution containing 0.5 moles of Al contained in the zeolite to ion exchange in Example 1 10% nitrogen balance GHSV = 600 ° C. at 10,000 hr ⁻¹
Catalyst 4 was obtained by performing the same operation except that the pretreatment was carried out with hr.

When the composition analysis of the obtained catalyst was measured using X-ray fluorescence, the content of Cu was Cu / Al ₂ =
1.61, Ag / Al = 0.28.

Example 5 (Preparation of catalyst 5) ZSM5 zeolite (SiO ₂ / Al ₂ O ₃ = 23.
8) 10 g was added to an AgNO ₃ aqueous solution containing Ag in an amount equal to the mole of Al contained in the zeolite, and the mixture was stirred at 30 ° C. for 20 hours.

After the slurry was filtered off, the obtained cake was dried in a dryer at 110 ° C. for 20 hours to obtain Ag-zeolite. Take 5 g of this and remove the Al contained in the zeolite.
Aqueous solution of Cu ammine complex containing 1 mole of Cu
= 10.5), and hydrazine monohydrate was added in the same molar amount as Cu while bubbling He gas into the solution. While bubbling He gas into the slurry, the slurry was heated at 30 ° C for 2 hours.
Stirred for 0 hours. After the slurry was separated by filtration, the obtained cake was again added to the above another solution and stirred in the same manner.

After filtration, the obtained cake is -100 kPa
While gradually increasing the temperature in a vacuum dryer at 250 ° C., 12
After drying for an hour, catalyst 5 was obtained. The composition of the obtained catalyst was analyzed using fluorescent X-rays. As a result, the copper content is Cu
/ Al ₂ = 3.52, Ag content is Ag / Al = 0.
49.

Next, a comparative example will be described with respect to the above embodiment.

Comparative Example 1 (Preparation of Comparative Example Catalyst 1) ZSM5 zeolite (SiO ₂ / Al ₂ O ₃ = 23.
8) 10 g of an aqueous Cu ammine complex solution containing Cu in the same mole as Al contained in the zeolite (pH = 10.
In addition to 5), hydrazine monohydrate was added in the same molar amount as Cu while bubbling He gas into the solution. The slurry was stirred at 30 ° C. for 20 hours while bubbling He gas. After the slurry was filtered off, the obtained cake was again added to another aqueous solution and stirred in the same manner.

After filtration, the obtained cake is -100 kPa
While gradually increasing the temperature in a vacuum dryer at 250 ° C., 12
After drying for an hour, Comparative Catalyst 1 was obtained. The composition of the obtained catalyst was analyzed using fluorescent X-rays. As a result, the copper content was Cu / Al ₂ = 1.92.

Comparative Example 2 (Preparation of Comparative Catalyst 2) ZSM5 zeolite (SiO ₂ / Al ₂ O ₃ = 23.
8) 10 g was added to an AgNO ₃ aqueous solution containing Ag in a molar amount equal to that of Al contained in the zeolite, followed by stirring at 30 ° C. for 20 hours.

After filtering the slurry, the obtained cake was gradually heated in a vacuum drier of -100 kPa.
After drying at 250 ° C. for 12 hours, Comparative Catalyst 2 was obtained. When the composition analysis of the obtained catalyst was measured using fluorescent X-ray,
The Ag content was Ag / Al = 0.61.

The following Comparative Tests 1 and 2 were conducted to examine the catalytic effects of Examples 1 to 5 and Comparative Examples 1 and 2.

Comparative Test 1 (Evaluation of Catalyst) The obtained catalysts 1 to 5 and comparative catalysts 1 and 2 were molded by a tableting machine, pulverized, and sized to 500 μm to 1 mm to obtain a catalyst for evaluation. Before performing the performance evaluation, the catalyst for evaluation was supplied with a gas of O ₂ 6% N ₂ balance in a fixed bed under normal pressure circulation, and SV = 10,0.
The mixture was circulated at 00 hr ^-1 and kept at 500 ° C. for 1 hour to perform pretreatment. For the subsequent performance evaluation, 0.75 ml of the pretreated evaluation catalyst was taken, and a gas having a composition shown in Table 1 (hereinafter, referred to as a reaction gas) was SV = 20 on a fixed bed under normal pressure flow.
It was distributed at 000 hr ^-1 . The NOx concentration at the catalyst bed inlet and the catalyst bed outlet was measured using a chemiluminescence NOx meter, when the NOx concentration reached a steady state from 600 ° C to 200 ° C every 50 ° C. I asked. Table 2 shows the results.

[0030]

[0031]

[Table 1]

[0032]

[Table 2]

Comparative Test 2 (Evaluation of Durability Performance) The obtained catalysts 1 to 5 and comparative catalysts 1 and 2 were molded by a tableting machine, pulverized and sized to 500 μm to 1 mm to obtain a catalyst for evaluation. Before performing the performance evaluation, the catalyst for evaluation was supplied with a gas of O ₂ 6% N ₂ balance in a fixed bed under normal pressure circulation, and SV = 10,0.
The mixture was circulated at 00 hr ^-1 and kept at 500 ° C. for 1 hour to perform pretreatment.

In the subsequent durable treatment, 2 ml of the pretreated catalyst for evaluation was taken, and a gas having a composition shown in Table 3 (hereinafter referred to as a durable gas) was applied at 600.degree. , SV = 10,000 hr ⁻¹ , and a durable treatment was performed.

[0035]

[Table 3]

0.75 ml of the catalyst subjected to the durability treatment was taken, and the catalyst was evaluated in the same manner as in Comparative Test 1 to evaluate the durability. Table 4 shows the results.

[0037]

[Table 4]

As is clear from Tables 2 and 4, the catalyst of the present invention has excellent durability under durability conditions including steam.
In particular, a catalyst having excellent durability in a temperature range of 400 ° C. to 600 ° C. could be prepared.

Although the present invention has been described with reference to a number of examples, the zeolite used in the present invention is not particularly limited. However, unless the SiO ₂ / Al ₂ O _{3 is} 10 or more, the heat resistance of the carrier is sufficient. And the performance cannot be fully exhibited.

The catalyst used in the present invention contains copper. The compound of copper used for adding copper is not particularly limited as long as it is soluble in a solvent. Acetates, nitrates and other complex salts such as ammine complex salts can be used.

The content of copper is preferably 3 to 20% by weight including zeolite.

The reducing agent used in the present invention is not particularly limited as long as it can reduce copper and can be added to a solvent. Further, the gas used for causing the reducing agent to act is not particularly limited as long as it is an inert gas.

Further, the catalyst used in the present invention contains silver. The silver compound used when silver is incorporated is not particularly limited as long as it is soluble in a solvent. Etc. can be used.

Furthermore, when drying the catalyst obtained in the present invention under reduced pressure, the degree of vacuum should be -50 kPa.
It is desirable to be above. The drying temperature is desirably 150 ° C. or more. Further, the inert gas used for drying is not particularly limited, but may be nitrogen, H
e, Ar and the like can be used.

Then, if necessary, it may be used after firing or the like before use.

The exhaust gas purifying catalyst of the present invention can be used after being mixed with a binder such as clay mineral or the like and molded.
It is also possible to contain u. In addition, the binder used for molding the zeolite is not particularly limited, but clay minerals, SiO ₂ , Al ₂ O _{3 and the} like can be used, and these can be used as a wash coat on a refractory carrier.

[0047]

According to the present invention, when copper is contained in zeolite, Cu ions are dispersed in a solution, mixed with zeolite in the presence of an inert gas and a reducing agent, and then dried under reduced pressure or an inert gas atmosphere. In addition, since the catalyst is further characterized by containing Ag in the catalyst, it is possible to provide an exhaust gas purifying catalyst having excellent durability in an atmosphere containing steam at a higher temperature.

Claims (2)

(57) [Claims] Claims 1. A copper and zeolite mixture containing copper in a zeolite in the presence of a reducing agent, ammonia and an inert gas, and drying under reduced pressure or an inert gas atmosphere.
Concrete methods manufactured exhaust gas purifying catalyst, characterized in that the way may contain a g. After which contains the Ag to 2. A zeolite, copper zeolite reducing agent, ammonia and copper is contained into inert gas presence in the zeolite, as obtained was dried under reduced pressure or an inert gas atmosphere A method for producing an exhaust gas purifying catalyst , comprising: