KR20020041346A - Water and gas treatment for increasing activity and decreasing deactivation of catalyst - Google Patents

Abstract

PURPOSE: Provided is a refractory inorganic oxides catalyst supported by solid powder with enhanced activity and selectivity, exhibiting no inactivation after the use of 200 hours. The catalyst is used in PROX reaction, elimination of volatile organic material and catalytic oxidation. CONSTITUTION: The treatment method comprises the steps of making inorganic organic catalyst such as alumina, titania and silica oxide by slurry washing to the honeycomb, drying, calcining at 300-800deg.C and cooling to 100deg.C; and improving the surface of the above catalyst by heating at more than 100deg.C and flowing on its surface with one or more liquid materials selected from water, alcohols, ammonia water, hydrogen peroxide water and hydrochloride and with one or more gases chosen from hydrogen, oxygen, ozone, carbon monoxide, methane, propane and butane.

Description

WATER AND GAS TREATMENT FOR INCREASING ACTIVITY AND DECREASING DEACTIVATION OF CATALYST}

The present invention relates to a process for preparing a catalyst to increase the activity and selectivity of the catalyst and to inhibit deactivation. Conventional catalyst production methods have been used after washing and coating alumina, titania, silica oxide, etc. in slurry form with an inorganic refractory to honeycomb, and drying and calcining at 300 ° C to 800 ° C. However, these catalysts have the disadvantages of low conversion rate, weak water content, and poor durability.

The present invention is to provide a catalyst that eliminates the disadvantages shown in the prior art, to improve the conversion at low temperatures, to prevent deactivation, to increase the reactant selectivity of the catalyst, to maximize the performance.

In the method used in the present invention, an inorganic refractory to honeycomb is washed with alumina, titania, silica oxide, etc. in slurry form, dried, calcined at 300 ° C. to 800 ° C., and then cooled to 100 ° C., and then the temperature is increased. While flowing one or two or more kinds of solvents such as water or alcohols, ammonia water, acetone, gasoline, hydrogen peroxide water, hydrochloric acid, etc., gaseous components such as hydrogen, oxygen, ozone, carbon monoxide, methane, propane, butane Or by flowing two or more kinds of catalysts to cause a structural change of the catalyst to maintain the fine metal particles of the catalyst to increase the activity of the catalyst, to suppress the deactivation of the catalyst, and to increase the selectivity.

The present invention is explained in more detail by the following examples, which are not intended to limit the present invention.

Examples 1 to 10 were prepared by treating water or hydrogen peroxide, ethanol, etc. with a gas to produce a catalyst, and using this, the catalyst performance was exhibited. It is a (PROX) reaction, and Example 6 to Example 10 are reactions which oxidize methyl ethyl ketone (MEK) and xylene (Xylene) which are volatile organic compounds. Comparative Example 1 and Comparative Example 2 showed the performance of the catalyst for the reactants without water and gas treatment. Comparative Example 1 is a PROX reaction, and Comparative Example 2 is a reaction of oxidizing methyl ethyl ketone (MEK) and xylene (Xylene), which are volatile organic compounds. In the proxy reaction, the carbon monoxide oxidation reaction, the reactants were carbon monoxide (CO) 6.5%, carbon dioxide (CO ₂ ) 20%, oxygen (O ₂ ) 3.25%, and the balance gas was hydrogen.

The reaction materials for oxidizing the volatile organic compound methyl ethyl ketone (MEK) and xylene were 1% methyl ethyl ketone, 1% xylene, and 20.9% oxygen. The remaining balance gas was nitrogen. In the reaction temperature, the proxy reaction was carried out at 20 ° C., and the reaction of oxidizing volatile organic compounds methyl ethyl ketone (MEK) and xylene (Xylene) was carried out while raising the temperature from 150 ° C. to 400 ° C. Meanwhile, the catalyst was charged in a fixed bed continuous flow reactor using a catalyst loaded with 5% by weight of platinum on gamma alumina, and the catalyst amount and the reactant flow rate were determined such that the space velocity was 50,000 / hr. The experimental data shows the values obtained by continuous experiments for 200 hours.

Table 1 shows the constituents of the water and gas treatment methods, and Table 2 shows the carbon monoxide conversion of the prox reaction and the oxidation conversion of methyl ethyl ketone (MEK) and xylene (Xylene).

Example 1

200 g of gamma alumina was wet-pulverized with a ball mill for 20 hours to prepare an aqueous slurry. A 15 cm × 15 cm × 10 cm sized honeycomb having 200 gas flow cells per square inch of cross section was immersed in the slurry and taken out of the cell. Blow the excess slurry into the compressed air, and then dry at 120 ℃ for 12 hours, it was immersed in an aqueous solution of chloroplatinic acid containing 10 g of platinum, impregnated, dried at 120 ℃ for 12 hours and calcined at 400 ℃ for 2 hours to catalyst The treated honeycomb at 150 ° C. (10% water as component (A), 1% hydrogen as component (B)), and the remaining balance gas through nitrogen for 1 hour and dried for 1 hour to complete the water and gas treatment method. With the catalyst by, the proxy reaction was advanced in the reaction (C).

Example 2)

The same water and gas treatment methods as those of Example 1 except that component (A) in Table 1 was 10% hydrogen peroxide solution and component (B) was 1% methane.

Example 3

The same water and gas treatment methods as those of Example 1 except that component (A) of Table 1 was 10% ethanol and component (B) was propane.

Example 4

The same water and gas treatment methods as those of Example 1 except that component (A) of Table 1 was 10% ammonia water and component (B) was butane.

Example 5

The same water and gas treatment methods as those in Example 1 except that component (A) of Table 1 is 10% hydrochloric acid and component (B) is oxygen.

Example 6

The same water and gas treatment methods as those of Example 1 except that the reaction of Table 1 (C) is an oxidation reaction of methyl ethyl ketone and xylene.

Example 7

The same water and gas treatment methods as those of Example 2 except that the reaction of Table 1 (C) is an oxidation reaction of methyl ethyl ketone and xylene.

Example 8

The same method of water and gas treatment as in Example 3, except that the reaction of Table 1 (C) is an oxidation reaction of methyl ethyl ketone and xylene.

Example 9

The same water and gas treatment methods as those in Example 4 except that the reaction of Table 1 (C) is an oxidation reaction of methyl ethyl ketone and xylene.

Example 10)

The same water and gas treatment methods as those in Example 5 except that the reaction of Table 1 (C) is an oxidation reaction of methyl ethyl ketone and xylene.

Comparative Example 1)

200 g of gamma alumina was wet-pulverized with a ball mill for 20 hours to prepare an aqueous slurry. A 15 cm × 15 cm × 10 cm sized honeycomb having 200 gas flow cells per square inch of cross section was immersed in the slurry and taken out of the cell. Blow the excess slurry into the compressed air, and then dry at 120 ℃ for 12 hours, it was immersed in an aqueous solution of chloroplatinic acid containing 10 g of platinum, impregnated, dried at 120 ℃ for 12 hours and calcined at 400 ℃ for 2 hours to catalyst With the treated honeycomb, the proxy reaction was advanced to (C) reaction.

Comparative example 2)

The reaction of Table 1 (C) was the same as in Comparative Example 1 except that the reaction of methyl ethyl ketone and xylene was oxidation.

Table 1. Components of Water and Gas Treatment Methods

Table 2. Proox reaction (carbon monoxide removal reaction) and conversion rate of oxidation reaction of MEK and Xylene

GHSV (space velocity) = 50,000 / hr (unit;%)

As described in detail above, the water and gas treatment methods for improving the performance and reducing the deactivation of the catalyst of the present invention have high oxidation reaction performances such as methyl ethyl ketone and xylene, which are volatile organic compounds of the catalyst at low temperature and fast space velocity. In addition, the performance of the proxy reaction, which is an oxidation reaction of carbon monoxide at room temperature, is also high. And it lasts 200 hours does not occur deactivation provides an effect that can be used to prepare a catalyst used in the oxidation reaction.

Claims (4)

Water and gas treatment method characterized by reforming the surface of the catalyst by flowing a liquid material and gas components to the catalyst at 100 ℃ or more after the production of the catalyst The liquid material of claim 1, wherein one or two or more kinds of solvents such as water or alcohols, ammonia water, acetone, gasoline, hydrogen peroxide, hydrochloric acid, etc. The gas component of claim 1, wherein one or two or more kinds of gases, such as hydrogen, oxygen, ozone, carbon monoxide, methane, propane, butane, and the like are flowed. The method of claim 1, wherein the modified catalyst is used for the proximal reaction, the removal of volatile organic compounds, the catalytic oxidation reaction, etc.