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

 

(57) Abstract:

The inventive method of producing a catalyst for oxidation of carbon monoxide and organic impurities in the gas emissions by mixing the components containing compounds of chromium and copper with aluminum hydroxide, followed by molding, drying and calcination. Used aluminum hydroxide pseudoboehmite patterns, pretreated with acid capable of forming water-soluble basic aluminum salts, acid module 0,05 - 0,12. Mix it with powdered aluminum hydroxide, and the content of kislotoupornogo aluminum hydroxide in the catalyst mass support in the amount of 8 to 25 wt.% in terms of aluminum oxide. The method involves adding to the mixture of hydroxides of aluminum first compounds of chromium, and then copper compounds. As compounds of chromium using chromium oxide as well as copper compounds - basic carbonate of copper. The calcination of the pellets of the catalyst at 550 - 750°C. for 3 h.p. f-crystals, 1 table.

The invention relates to methods for oxide catalysts used in the deep oxidation of carbon monoxide and organic impurities in the gases carbon monoxide, includes treatment of aluminum hydroxide with nitric acid when the acid value of the module Mto6. (Mtoacid module molar ratio of the added acid to pray Al2O3the aluminum hydroxide). Nitric acid is formed at the stage of joint mixing coprecipitation of initial components (nitrate of copper and zinc, oxalic acid and aluminum hydroxide) as a result of a reaction between nitrates of copper and zinc with oxalic acid, taken in the stoichiometric ratio (1).

The main disadvantage of this method is that at the stage of joint displacement-deposition source components nitric acid is produced in large quantities (Mto6) and the conditions of obtaining the catalyst mass is dissolving aluminum hydroxide in aluminum nitrate, more than 50%

The formation of aluminium nitrate is not conducive to obtaining a mechanically durable granules of the catalyst and results in the release of significant quantities of nitrogen oxides at the stage of calcination the catalyst mass is more than 80g NOxper 1 kg of catalyst ).

The closest technical solution is the method of producing a catalyst for purification of exhaust g is of aluminum hydroxide, free of sulfur and containing impurities of iron in a quantity of 0.05-0.1 wt.

The disadvantage of this technical solution is that the resulting catalyst does not have a sufficiently high catalytic activity and mechanical strength.

The goal is to develop a method of producing catalyst for the oxidation of carbon monoxide and organic impurities in the gas emissions with high mechanical strength and catalytic activity.

The problem is solved due to the fact that in the present method of preparation of the catalyst for oxidation of carbon monoxide and organic impurities in the gas emissions by mixing the components containing compounds of chromium and copper with aluminum hydroxide, followed by molding, drying, and calcination, use aluminum hydroxide pseudoboehmite patterns, pre-treated with acid, capable of forming water-soluble basic aluminum salts, acid module 0,05-0,12, mix it with powdered aluminum hydroxide, and the content of kislotoupornogo aluminum hydroxide in the catalyst mass support in the amount of 8-25 wt. (in terms of aluminum oxide).

aboutC.

Powder of aluminum hydroxide introduced into kislotoobrazovanie weight of aluminum hydroxide, can be any structural modification of amorphous, pseudonimity, Amity, gibbosity, baleriny (preferably amorphous and pseudonymity). Perhaps the use of waste products of active aluminum oxide.

When used as a powder of aluminum hydroxide crystalline modifications, for example, gibbsite or bayerite, you must perform the operation of grinding.

Comparative analysis of the prototype shows that the inventive method has the following significant differences.

Use aluminum hydroxide pseudoboehmite patterns, pretreated with acid capable of forming water-soluble basic salts of aluminum, acid module 0,05-0,12;

these aluminum hydroxide is mixed with powdered aluminum hydroxide;

content kislotoupornogo aluminum hydroxide in the catalyst mass support in the amount of 8-25 wt. (in terms of aluminum oxide is the prototype and obtained by the present method was tested in the process of deep oxidation in oxygen excess on model mixtures, containing N-butyl or carbon monoxide.

The tests were conducted in a flow-circulation laboratory setup at atmospheric pressure, the same space velocity of the gas mixture and the same test conditions.

For measure the catalytic activity of the catalyst 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.

For measure the catalytic activity of the catalyst in the oxidation of N-butane adopted by the reaction rate (cm3WITH4H10/g with 10-2) oxidation of N-butane at 400aboutC. the higher the speed of reaction of complete oxidation of butane corresponds to a more active catalyst.

The mechanical strength of the pellet crush strength by forming was determined on the instrument MP-9S. For measure the mechanical strength made the ultimate compressive stress, which results in the destruction of granules allocated to the conditional section.

P R I m e R 1 (the prototype). Sample basic carbonate of copper (CuCO3.Cu(OH)2) of 7.8 g, kromhout 20 min to obtain a homogeneous mass. The resulting mass ekstragiruyut through a Spinneret with the diameter of 6 mm extrudates provalivajut on the air 24 hours and then calcined at 450aboutC for 6 h

The catalyst has the following composition, wt. Cr2O314,5 CuO 12.5 BaO 2,0 Al2O3Else

The resulting catalyst has a catalytic activity: the reaction rate of the full oxidation of butane at 400aboutWith equal 1,44 10-2cm3WITH41010/g and 85% degree of oxidation of carbon monoxide is achieved at 245aboutC. the Mechanical strength of the pellet crush strength along generatrix is 1.5 MPa.

Conditions of preparation of the catalysts and the results of their tests are given in the table.

P R I m m e R 2. 13.6 kg of a suspension of aluminum hydroxide with x-ray amorphous structure containing 25% of the solid phase in terms of aluminum oxide, is treated with nitric acid based receiving acid module (MC), 0.12 (360 cm3acid with a concentration of 700 g/l NGO3) and placed in a reactor, where, subjecting it to hydrothermal treatment at 130aboutC and a pressure of 3 ATM for 4 h with constant stirring.

Received flowable kislotoobrazovanie weight of aluminum hydroxide, PSD aluminum with an amorphous structure and a total moisture content of 25% and stirred for 20 minutes Then in weight enter 2,59 kg chromium trioxide and again stirred for 20 minutes After addition of 1.03 kg of copper oxide and stirring for 20 min the catalyst mass humidity 35% extruded into pellets with a diameter of 4.5 mm

For kislotoupornogo aluminum hydroxide pseudoboehmite patterns in catalyst mass is 15.1% in terms of aluminum oxide.

Molded pellets provalivajut in air at room temperature for 12 h, then dried at 110aboutC for 2 h, and then raise the temperature to 180aboutC and dried at this temperature for another 1 h, then the catalyst was calcined at 750aboutC for 4 h

The resulting catalyst has the following composition (in terms of oxides), wt. Cr2O319,7 CuO 10,3 Al2O370,0

Catalytic activity: the reaction rate of the full oxidation of butane at 400aboutWith equal 3,98 10-2cm3WITH4H10/GS; temperatures reach 85% degree of oxidation of carbon monoxide equal to 208aboutC. Mechanical crushing strength along generatrix is 3.9 MPa.

P R I m e R 3. Conditions of preparation of the catalyst is similar to example 2. The calcination of the catalyst godslove obtain a catalyst similar to example 2. The calcination of the catalyst is carried out at 550aboutC for 6 h (see table).

P R I m e R 5. 10 kg of aluminum hydroxide pseudoboehmite patterns, intermediate in the production of aluminum oxide according to GOST 8136-85 grade a-1 or a-2, are placed in a reactor and treated at room temperature and atmospheric pressure nitric acid based obtain MK 0,05 (132,3 cm3acid with a concentration of 700 g/l NGO3).

Received flowable mass pseudoboehmite aluminum hydroxide with a total moisture content of 70% is placed in a mixer where add 6,47 kg of powder of aluminum hydroxide pseudoboehmite structure with a total moisture content of 25% and stirred for 20 minutes, then add 2,18 kg of ammonium bichromate and again stirred for 20 minutes After addition of 0.96 kg basic carbonate of copper and stirring for 20 min the catalyst mass to a moisture content of 28% ekstragiruyut into pellets. Share kislotoupornogo aluminum hydroxide pseudoboehmite patterns in catalyst weight is 15.2% in terms of aluminum oxide.

The crop has wilted and dried granules carried out analogously to example 2. The calcination is carried out at a temperature of 550aboutC for 6 h

The resulting catalyst has sledujte acid module of 0.05 produces a catalyst with high activity and good strength (see table).

P R I m e R 6. Conditions of preparation of the catalyst is similar to example 5. The calcination of the catalyst is carried out at 650aboutC for 5 h (see table).

P R I m e R 7. Conditions of preparation of the catalyst is similar to example 5. The calcination of the catalyst is carried out at 750aboutC for 4 h (see table).

P R I m e R 8. 10,10 kg of aluminum hydroxide pseudoboehmite structure obtained by aluminate technologies, are placed in a reactor and treated at room temperature and atmospheric pressure nitric acid based obtain Mto= 0,09 (160,0 cm3acid with a concentration of 700 g/l NGO3). Received flowable mass pseudoboehmite aluminum hydroxide with a total humidity of 80% is placed in a mixer where add 3,05 kg pre-crushed in a ball mill, a powder of aluminum hydroxide with the structure of gibbsite and stirred for 20 minutes Then weight enter 4,36 kg of ammonium bichromate and again stirred for 10 min, after which faucet enter 1,37 kg of copper oxide. After stirring for 20 min the catalyst mass ekstragiruyut into pellets. Share kislotoupornogo aluminum hydroxide pseudoboehmite patterns in catalyst mass is the Calcination is carried out at 650aboutC for 5 h

The resulting catalyst has the following composition (in terms of oxides) wt. Cr2O332,9 CuO 17,1 Al2O350,0

As can be seen from the table obtained in this acid module (Mto0,09) the catalyst has good activity and strength).

P R I m e R 9. 5.6 kg of aluminum hydroxide pseudoboehmite structure obtained by aluminate technologies, are placed in a reactor and treated at room temperature and atmospheric pressure of acetic acid from the calculation of receipt Mto0,09 (74 cm3glacial acetic acid). Received flowable kislotoobrazovanie mass pseudoboehmite aluminum hydroxide with a total moisture content of 75% is placed in a mixer where add 5.6 kg of powder of amorphous aluminum hydroxide with a total moisture content of 25% and after stirring for 20 min add 4.3 it chromic anhydride and again stirred for 10 min, then enter the 1,72 kg of copper oxide. After stirring for 20 min the catalyst mass ekstragiruyut into pellets. Share kislotoupornogo aluminum hydroxide pseudoboehmite patterns in catalyst mass is 8% in terms of aluminum oxide.

The crop has wilted and dried Gran The resulting catalyst has the following composition (in terms of oxides), wt. Cr2O330,9 CuO 16,2 Al2O352,9

As can be seen from the table, the catalyst has high activity and good mechanical strength.

P R I m e R 10. 23.3 kg of aluminum hydroxide pseudoboehmite structure is treated at room temperature and atmospheric pressure hydrochloric acid based obtain Mto=0,09 (733 cm3acid with a concentration of 300 g/l Hcl). Received flowable mass pseudoboehmite aluminum hydroxide and the total humidity of 70% is placed in a mixer add much 5,33 kg powder pseudoboehmite aluminum hydroxide with a total moisture content of 25% and after stirring for 20 min add 4,42 kg chromium trioxide and again stirred for 20 min, and then injected 1.7 kg of copper oxide. After stirring for 20 min the catalyst mass ekstragiruyut into pellets. Share kislotoupornogo aluminum hydroxide pseudoboehmite patterns in catalyst weight is 19.6% in terms of aluminum oxide.

The crop has wilted, drying and calcination are analogously to example 9.

The resulting catalyst has the following composition (in terms of oxides), wt. Cr2O320,9 CuO 10,6 Al2O368,5

The properties of the overall structure is treated at room temperature and atmospheric pressure nitric acid based obtain Mto0,09 (557 cm3acid with a concentration of 700 g/l NGO3). Received flowable mass pseudoboehmite aluminum hydroxide with a total moisture content of 70% is placed in a mixer where add 1,31 kg powder belanoha aluminum hydroxide with a total moisture content of 25% and after stirring for 20 min add 1,85 kg chromium trioxide and again stirred for 10 min, then enter the 0,74 kg of copper oxide. After stirring for 20 min the catalyst mass is extruded into pellets. Share kislotoupornogo aluminum hydroxide pseudoboehmite patterns (in terms of aluminum oxide) in the catalyst mass is 25%

The crop has wilted, drying and calcination are analogously to example 9.

The resulting catalyst has the following composition (in terms of oxides), wt. Cr2O313,9 CuO 7,3 Al2O378,8

Properties of the obtained catalyst are shown in table.

P R I m e R 12 (the beyond). Conditions of preparation of the catalyst is similar to example 6, but the processing pseudoboehmite aluminum hydroxide are aqueous solution of nitric acid based obtain Mto=0,04 (105,9 cm3acid with a concentration of 700 g/l NGO3).

Received cotalitasianism strength, the value of which is close to the strength of the granules obtained by the prior art (example 1), and is 1.6 MPa.

P R I m e p 13 (outrageous). Conditions of preparation of the catalyst is similar to example 3, the processing pseudoboehmite aluminum hydroxide are aqueous solution of nitric acid based obtain Mto0,15 (450 cm3acid with a concentration of 700 l/g HN3). The resulting catalyst has a sufficiently high mechanical strength of the granules, but very low catalytic activity, as the monoxide, and Bhutan (see table).

P R I m e R 14 (outrageous). 10,0 kg of aluminum hydroxide pseudoboehmite structure is treated with nitric acid at Mto=0,09 (198,6 cm3acid with a concentration of 700 g/l HNO3). Received flowable mass in the total humidity of 75% is placed in a mixer where add 14.4 kg of powder of amorphous aluminum hydroxide with a total moisture content of 25% and after stirring for 10 min add 7,9 kg chromium trioxide and again stirred for 20 minutes, then add 3.1 kg of copper oxide. After stirring for 30 min the catalyst mass is extruded into pellets. For kislotoupornogo aluminum hydroxide pseudoboehmite strokes the previous example, the resulting catalyst has the following composition, wt. CR2O326,8 CuO 13,8 Al2O359,4

The catalytic activity of this catalyst is sufficiently high, but the mechanical strength of the pellets is very low (see table).

P R I m e R 15 (outrageous). 5 kg of aluminum hydroxide pseudoboehmite structure is treated at room temperature and atmospheric pressure nitric acid based obtain Mto=0,09 (69 cm3nitric acid with a concentration of 700 g/l HNO3). Received kislotoobrazovanie mass of aluminum hydroxide with a total moisture content of 50% is placed in a mixer where add 1,77 kg of powder of aluminum hydroxide bemani patterns, stirred for 10 min, administered 2,42 kg chromium trioxide and after 10 minutes of stirring 0.96 kg of copper oxide. After stirring for 20 min the catalyst mass is extruded into pellets. Share kislotoupornogo aluminum hydroxide pseudoboehmite patterns (in terms of aluminum oxide) in the catalyst mass is 29.5%

After drying and calcination according to example 8, the catalyst has the following composition, wt. Cr2O343,5 CuO 11,3 Al2O345,2

The finished catalyst has a low catalytic activity, although the highest proc example 9, but processing pseudoboehmite aluminum hydroxide are aqueous solution of sulfuric acid at the rate of receipt Mto0,09 (121 cm3acid with a concentration of 800 g/l H2ABOUT4).

The resulting catalyst has a relatively high catalytic activity in oxidation reactions of butane and carbon monoxide, but a very low mechanical strength of granules (see table). Use when processing pseudoboehmite aluminum hydroxide acid, not forming water-soluble salts of aluminum, it is not possible to obtain granules with high mechanical strength.

P R I m e R 17 (outrageous). Conditions of preparation of the catalyst is similar to example 9, but the calcination of the catalyst is carried out at a temperature of 500aboutWith over 8 hours

The catalyst has high catalytic activity in oxidation reactions of carbon monoxide and a sufficiently high mechanical strength, but the speed of reaction of complete oxidation of butane at 400aboutWith is only 266 10-2cm3WITH41010/g, which is one of the lowest values of the rate of oxidation of butane from the examples (see table).

P R I m e R 18 (outrageous). Conditions suburbs is their 4 o'clock

The resulting catalyst has a low catalytic activity for butane and carbon monoxide and low mechanical strength (see table). Therefore, the use of high annealing temperatures (above 750aboutC) leads to a significant phase transformations as alumina, and active component and as a result, a sharp deterioration of the quality of the catalyst.

P R I m e R 19 (outrageous). 5,31 kg of aluminum hydroxide with the structure of gibbsite mixed with 8,29 l of distilled water, treated with nitric acid based obtain Mto0,12 (360 cm3acid with a concentration of 700 g/l HNO3) and placed in a reactor where the mixture is subjected to hydrothermal treatment at a temperature of 130aboutC and a pressure of 3 ATM for 4 h with constant stirring. The resulting mass with the total humidity of 75% is placed in the mixer and is further processed as in example 2.

The resulting catalyst has the lowest mechanical strength (see table).

P R I m e R 20(the beyond). Conditions of preparation of the catalyst is similar to example 9, but flowable kislotoobrazoutei mass pseudoboehmite aluminum hydroxide with the addition of 5.6 kg dry giving 20 min 4.3 kg chromium trioxide.

The resulting catalyst has a high mechanical strength, but a low catalytic activity (see table.), which practically does not differ from the catalytic activity of the catalyst obtained by the prototype.

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 increase the mechanical strength and catalytic activity of the catalyst compared to the prototype, and the absence of one of the distinctive characteristics leads to loss of catalytic activity or strength of the catalyst.

These advantages of the proposed method allows to increase service life of the catalyst and to reduce the amount loaded into the reactor catalyst, resulting in lower operating costs.

1. A METHOD of producing a CATALYST FOR OXIDATION of CARBON MONOXIDE AND ORGANIC IMPURITIES IN the GAS EMISSIONS by mixing the components containing compounds of chromium and copper with aluminum hydroxide, followed by molding, drying, and calcination, characterized in that the use of aluminum hydroxide pseudoboehmite patterns, pre-treated acid is about with powdered aluminum hydroxide, moreover, the contents kislotoobrazovanie aluminum hydroxide in the catalyst mass support in the amount of 8 to 25 wt. in terms of aluminum oxide.

2. The method according to p. 1, characterized in that the mixture of hydroxides of aluminum, first add compounds of chromium, and then copper compounds.

3. The method according to PP.1 and 2, characterized in that as the chromium compounds used chromium oxide, and compounds of copper basic carbonate of copper.

4. The method according to p. 1, characterized in that the calcination of the pellets of the catalyst is carried out at 550 750oC.

 

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