A method of producing a catalyst for oxidation of impurities of organic compounds and carbon monoxide in the gas emissions

 

(57) Abstract:

The invention relates to methods for oxide catalysts used in the deep oxidation of impurities of organic compounds and carbon monoxide in the gas emissions of industrial plants, and may be used in the chemical, petrochemical and other industries where such emissions in the exhaust gases. How is that prepared metrogroove powder mixture of chromium compounds and copper, then the received metrogroove powder is mixed with aluminum hydroxide, followed by molding, drying, and calcination at a temperature of 470 - 750oC with further processing of the catalyst, the reducing gas mixture at a temperature of 150 - 300oC. the Task of the proposed technical solution is to develop a method of producing catalyst for the oxidation of impurities of organic compounds and carbon monoxide in the gas emissions that do not contain compounds of Cr+6and with high activity. 8 C.p. f-crystals, 1 table.

The invention relates to methods for oxide catalysts used in the deep oxidation of organic impurities soedineniyami and other industries, where such emissions in the exhaust gas.

Recently imposed more stringent requirements for the catalysts used for the protection of the environment, in particular chromium catalysts. In many countries it is forbidden to use catalysts containing compounds of Cr+6.

Consequently, it is important to develop methods of preparation of catalysts with high activity and, at the same time, does not contain toxic components.

Known methods of preparing catalysts, which use the recovery phase catalysts containing copper-chromium composition.

Depending on the catalyst composition, method of its preparation, operating conditions in a particular process stage of recovery can be very different.

Known methods of preparation of catalysts based on copper chromite, which is primarily used for hydrogenation of unsaturated compounds [1, 2]

The method of preparation of the catalyst is in the recovery of copper-chromite compositions [2] by processing the last stream of nitrogen followed by the addition in the gas phase iterature recovery for regulated recovery options.

However, the catalyst does not have sufficient activity in the oxidation of impurities of organic compounds and carbon monoxide.

A known method of producing a catalyst for the oxidation of the impurities carbon monoxide and organic compounds [3] by mixing the components containing compounds of chromium and copper, aluminum hydroxide, followed by molding, drying, and calcination, and as aluminum hydroxide use aluminum hydroxide pseudoboehmite patterns, pre-treated with acid, which is then mixed with powdered aluminum hydroxide. The catalyst has high mechanical strength and catalytic activity.

The disadvantage of the catalyst is that the catalyst contains Cr+6whose connections are very toxic even in small quantities.

The closest technical solution chosen for the prototype is a method of producing a catalyst for purification of exhaust gases from organic components by mixing compounds of copper, chromium, barium hydroxide of aluminum, followed by molding and drying [4]

This method eliminates the formation of waste water, the catalyst has a high AK is which is highly toxic.

The task of the proposed technical solution is to develop a method of producing catalyst for the oxidation of impurities of organic compounds and carbon monoxide in the gas emissions that do not contain compounds of Cr+6and is highly active.

The problem is solved due to the fact that the method of preparation of the catalyst for oxidation of impurities of organic compounds and carbon monoxide in the gas emissions, namely, that compounds of copper and chromium in the desired proportions are mixed among themselves until a homogeneous powder. Preferably, the copper compounds used malachite - basic carbonate of copper (II), and chromium compounds chromium anhydride CrO3. Metrogroove powder is mixed with aluminum hydroxide, and then the resulting mixture was molded, dried, calcined at a temperature of 470 750oC, cooled in a current of inert gas to a temperature recovery, and processed the reducing gas mixture at a temperature of 150 300oC.

The reducing gas phase contains from 2 to about 25. hydrogen, and the rest inert gas.

The resulting implementation of this method to the
Al2O3Else

Salient features of the proposed solution are the following:

metrogroove powder is prepared by mixing the compounds chromium and copper;

as copper compounds preferably used basic carbonate of copper (II), and compounds chromography anhydride - CrO3;

received metrogroove powder mixed with aluminum hydroxide;

the catalyst mass is molded, dried and calcined at a temperature of 470 - 750oC;

the catalyst is treated with the reducing gas mixture at a temperature of 150 300oC.

In addition, the difference is that:

the reducing gas mixture contains from 2 to about 25. hydrogen, and the rest inert gas;

the processing time of the catalyst recovery mixture comprises 15 to 60 min;

the catalyst after calcination is cooled in a stream of inert gas to a temperature recovery with subsequent introduction of an inert gas, a reducing agent;

the resulting catalyst has the following composition ( in terms of oxides), wt.

CuO 6 25

Cr2O310 35

Al2O3Else

The reducing gas mixture which contains the products of the catalytic decomposition of ammonia.

The essential distinguishing characteristics leads to the achievement of the task.

The proposed method for the preparation of the catalyst allows to obtain a catalyst which does not contain Cr+6that contributes to a more widespread use of catalyst containing metrogroove composition.

In this way the proposed optimal conditions for preparation of the catalyst that is highly active in the oxidation of impurities of organic compounds and carbon monoxide, the catalyst is practically absent Cr+6.

The catalyst is prepared as follows:

Compounds of copper and chromium, in the required proportions, mix among themselves until a homogeneous metrogroove powder; received metrogroove powder is mixed with aluminum hydroxide, followed by molding, drying, and calcination at a temperature of 470 750oC. Then the catalyst is cooled to a temperature recovery of the catalyst 150 - 300oC and start to supply gas-reducing agent.

Cooling of the catalyst is preferably in a stream of inert gas.

When cooking metrogroove poorestwe chromium compounds used preferably chromic anhydride (CrO3) thus obtained catalyst has the following composition ( in terms of oxides), wt.

CuO 6 25

Cr2O310 35

Al2O3Else

The catalyst activity was determined on a flow-circulation installed in the process of deep oxidation in oxygen excess on model mixtures containing n-butane or carbon monoxide.

For measure the catalytic activity of the catalyst in the oxidation of organic substances adopted by the reaction rate (cm3C4H10/the hydrographic 10-2) oxidation of n-butane at a temperature of 400oC. the higher the speed of reaction of complete oxidation of n-butane, corresponds to a more active catalyst.

For measure of catalytic activity in the oxidation of carbon monoxide adopted the temperature at which achieved 85% degree of oxidation of carbon monoxide. The lower the temperature reach 85% degree of oxidation of carbon monoxide, the higher the catalyst activity.

Example 1 (the prototype). A portion of the basic carbonate of copper CuCO3Cu(OH)27,8 g, chromic anhydride CrO36.4g, barium oxide BaO 0.33 g and 35.5 g of aluminum hydroxide Al(OH)3for the career diameter 6 mm, the extrudates provalivajut on the air 24 hours, and then calcined at 450oC for 6 h

The catalyst has the following composition, wt.

Cr2O314,5

CuO 12,5

BaO 2,0

Al2O3Else

The resulting catalyst has the following catalytic activity:

the reaction rate of the full oxidation of butane at 400oC is equal to 1,3110-2cm3C4H10/, C. and 85% degree of oxidation of carbon monoxide is achieved with 256oC. the Content of Cr+6in the finished catalyst is 5,10 wt.

Example 2. Take 0,26 kg chromic anhydride (VI), mix them with 0,36 kg basic carbonate salt of copper (II). Then to the resulting metrogroove powder add 2,35 kg of aluminum hydroxide, stirred for 30 min, adding water to obtain a catalyst mass with a humidity of 35% After mixing the catalyst mass is extruded into pellets, which are then provalivajut in air at room temperature for 12 h, then dried at a temperature of 110oC 2 h, after which the temperature was raised to 180oC and dried for another 1 h, then the catalyst was calcined at 600oC for 4 h cooling the catalyst in a stream of inert gas (nitrogen) to a temperature bostanabad catalyst recovery mixture contains about 16. hydrogen, and the remainder of nitrogen.

The catalyst has the following composition (in terms of oxides), wt.

CuO 13

Cr2O310,0

Al2O3Else

The resulting catalyst has the following catalytic activity:

The reaction rate of the oxidation of n-butane at 400oC is equal to 5,2810-2cm3C4H10/the hydrographic

Temperatures reach 85% degree of oxidation of carbon monoxide equal to 175oC.

Compounds of Cr+6in the finished catalyst is not detected (see table).

Example 3. Conditions of preparation of the catalyst is similar to example 2, the temperature of calcination of the catalyst is 470oC. cooling the catalyst in a stream of inert gas (argon), 300oC and served in the gas phase is about 25. hydrogen for 15 minutes

The catalyst has high activity and contains almost no Cr+6(see table).

Example 4. Conditions of preparation of the catalyst is similar to example 2, the temperature of calcination of the catalyst is 750oC. cooling the catalyst in a stream of inert gas (helium) up to 150oC and served in the gas phase of about 2. hydrogen within 60 minutes of the Characteristics of the measure 2, only cool the catalyst after calcination temperatures of recovery in air flow.

Characteristics of the catalyst, see table.

Example 6. Conditions of preparation of the catalyst is similar to example 2, only in the gas phase serves hydrogen, obtained by thermal decomposition of butylene (see table).

Example 7. Conditions of preparation of the catalyst is similar to example 2, only the reducing gas mixture contains products of the catalytic decomposition of ammonia (see table).

Example 8. 0,92 kg chromium trioxide is mixed with 0.16 kg basic carbonate salt of copper (II). To cooked metrogroove powder add 1.57 kg of aluminum hydroxide and stirred catalyst powder for 40 min, wetting it with water to a moisture content of 33 wt.5. As the preparation of a catalyst mass ekstragiruyut into pellets, which are then provalivajut in air at room temperature for 10 to 12 hours Drying of the pellets of step: first at a temperature of 110oC for 2 h, and then raise the temperature to 180oC and kept at this temperature the granules another 2 hours Calcined catalyst at a temperature of 750oC for 4 h, then cool cat is. hydrogen, the rest is helium for 30 minutes

The resulting catalyst has the following composition (in terms of oxides), wt.

CuO 6,0

Cr2O335,0

Al2O3Else

The catalyst has high activity and contains almost no Cr+6(see table).

Example 9. 0.26 kg chromium trioxide is mixed with 0,69 kg basic carbonate salt of copper (II). To the obtained powder add 1,73 kg of aluminum hydroxide. Mix the catalyst powder for 30 min, then moistened to a moisture content of 35 wt. and formed into extrudates. Last provalivajut in air at room temperature for 10 to 12 hours, dried for 4 hours at a temperature of 110oC and for 1 h at a temperature of 190oC. Calcined extrudates at a temperature of 600oC, cooled in a stream of air to a temperature of 300oC and serves on the catalyst gas mixture containing about 15. hydrogen, the rest of the nitrogen within 30 minutes

The prepared catalyst has the following composition (in terms of oxides), wt.

CuO 25,0

Cr2O310,0

Al2O3Else

The catalyst has high catalytic activity and does not contain Cr+6(see table).

oC.

Characteristics of the catalyst show that the temperature increases above the optimum does not lead to a significant positive effect (see table).

Example 11 (the beyond). Conditions of preparation of the catalyst is similar to example 2, the temperature recovery of the catalyst is equal to 300oC, the hydrogen content in the mixture is about 1. the duration of treatment of the catalyst 60 minutes

As evidenced by the characteristics of the catalyst it has a high activity, however, the residual content of Cr+6in the catalyst significantly (see table).

Example 12 (the beyond). Conditions of preparation of the catalyst is similar to example 2, the temperature recovery of the catalyst is equal to 300oC, the hydrogen content in the mixture is about 27. The duration of the recovery phase 15 minutes

As evidenced by the characteristics of the catalyst, the high content of hydrogen in the reducing mixture (relative to optimal) does not lead to a significant positive effect (see table).

Example 13 (the beyond). Conditions of preparation of the catalyst is similar to example 2, only the stage of restoration ka is">

The catalyst obtained under specified conditions, has a high activity, but contains significant amounts of Cr+6.

Example 14 (the beyond). Conditions of preparation of the catalyst is similar to example 2, only the stage of recovery of the catalyst is carried out at a temperature of 300oC and the content of hydrogen in the mixture is about 25. within 80 minutes

As can be judged by the characteristics of the catalyst (see table) increase the processing time of the catalyst recovery mixture does not lead to a significant positive effect (see table).

Example 15 (the beyond). Conditions of preparation of the catalyst is similar to example 2, the temperature of calcination of the catalyst is equal to 750oC. cooling the catalyst in a stream of inert gas (nitrogen) to a temperature of 100oC and then into the gas phase serves gas reductant (hydrogen) in an amount of about 25. within 60 minutes

The catalyst has high activity, but contains significant amounts of Cr+6(see table).

Example 16 (the beyond). Conditions of preparation of the catalyst is similar to example 9, only the calcined catalyst at a temperature of 450oC, cooled in the air flow EXT. hydrogen, the rest is nitrogen for 30 minutes

The catalyst has a low catalytic activity and contains compounds Cr+6(see table).

Example 17 (the beyond). Conditions of preparation of the catalyst is similar to example 8, the temperature of calcination of the catalyst is equal to 800oC. the Stage of restoration is carried out at a temperature of 150oC, and the content in the gas mixture 2. hydrogen, nitrogen rest for 15 minutes

The resulting catalyst contains minor amounts of Cr+6however , its catalytic activity is low (see table).

Example 18 (the beyond). 0.21 kg chromium trioxide is mixed for 10 minutes with 0.75 kg basic carbonate salt of copper (II). To metrogroove powder add 1,73 kg of aluminum hydroxide and continue mixing for 20 minutes Then the catalyst powder moistened with water to a moisture content of 35 wt. and formed into granules, which are dried first in air at room temperature for 12 h and then at a temperature of 110oC 4 h and at a temperature of 180oC 2 h Calcined catalyst at a temperature of 600oC for 4 h, cooled in a stream of argon to a temperature of 200oC and then fed into a stream of argon hydrogen CLASS="ptx2">

CuO 27

Cr2O38,0

Al2O3Else

The catalyst contains small amounts of Cr+6and its high activity, but a significant positive effect is not observed (see examples 2 and 18 in the table).

Example 19 (the beyond). A portion of 0.94 kg chromium trioxide is mixed with 0,13 kg basic carbonate salt of copper (II) within 7 minutes Into the prepared powder add 1.57 kg of aluminum hydroxide and stirred catalyst powder for 35 min, wetting it to a moisture content of 31 wt. Catalyst mass ekstragiruyut in granules, provalivajut them on the air for 10 hours, dried at a temperature of 110oC for 6 h and calcined at 470oC 5 o'clock cooling the catalyst in a stream of air. The stage of recovery of the catalyst is carried out at a temperature of 200oC, recovery processing a mixture containing about 25. hydrogen, the rest of the nitrogen within 15 minutes

The catalyst has the following composition (in terms of oxides),

CuO 5,0

Cr2O336,0

Al2O3Else

The prepared catalyst has a low catalytic activity (see table).

Example 20 (the beyond). Conditions of preparation of the catalyst a similar example is RA high, however, the content of Cr+6it is high (see table).

As can be seen from the presented examples, for clarity, are summarized in the table, only the set of distinctive features of the proposed method to achieve this goal. The absence of at least one of the distinguishing characteristics leads to a decrease in catalyst activity or the content of large quantities of compounds of Cr+6.

1. A method of producing a catalyst for oxidation of impurities of organic compounds and carbon monoxide in the gas emissions by mixing the components containing compounds of chromium and copper, aluminum hydroxide, followed by molding, drying, and calcination, wherein the copper-chromium powder is prepared by mixing the compounds of chromium and copper, then the copper-chromium powder is mixed with aluminum hydroxide, followed by molding, drying, and annealing at 470 750oWith further processing of the catalyst, the reducing gas mixture at 150 300oC.

2. The method according to p. 1, characterized in that as the copper compounds used basic carbonate of copper (II), and chromium compounds chromium anhydride CrO3.

4. The method according to PP. 1 to 3, characterized in that the processing time of the catalyst recovery mixture comprises 15 to 60 minutes

5. The method according to PP. 1 to 4, characterized in that the catalyst after calcination is cooled in a stream of inert gas to a temperature recovery with subsequent introduction of the inert gas is a reducing agent.

6. The method according to PP. 1 to 5, characterized in that the catalyst has the following composition in terms of oxides, wt.

CuO 6 25

Cr2O310 35

Al2O3Else

7. The method according to PP. 1 to 6, characterized in that the reducing gas mixture contains hydrogen produced during thermal decomposition of hydrocarbons.

8. The method according to PP. 1 to 6, characterized in that the reducing gas mixture contains hydrogen produced during thermal decomposition of hydrocarbons.

8. The method according to PP. 1 to 6, characterized in that the reduction mixture contains the products of the catalytic decomposition of ammonia.

 

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4 dwg, 1 tbl, 2 ex

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