The catalyst for deep oxidation of organic compounds and carbon monoxide in the gas emissions and the method of its production (options)

 

(57) Abstract:

The invention relates to catalysts and methods of producing oxide catalysts used in the processes of deep oxidation of organic compounds and carbon monoxide in the gas emissions from industrial productions. The described catalysts for deep oxidation of organic compounds and carbon monoxide in the gas emissions, including oxides of chromium, copper, aluminium oxide with an additional connection. As additional connections aluminium oxide contains at least one connection element from the group of alkali and alkaline-earth metals, silicon, iron in an amount of 0.01-2.0 wt.% and the catalyst has the following composition (in terms of oxides), wt.%: the chromium oxide - 5-25, copper oxide - 5-25, aluminium oxide with at least one additional connection element from the group of alkali and alkaline-earth metals, silicon, iron - 0,01-2,0 - rest. Also described ways (options) obtain the above-described catalyst. The first method consists in mixing the components containing compounds of chromium, copper, aluminum hydroxide with an additional connection, followed by molding, drying and calcination. The second way of obtaining Kay in the impregnation of the support, includes aluminum oxide with an additional compound with a solution of chromium compounds, copper, drying, calcination. The inventive catalyst has a higher catalytic activity in the above oxidation reaction and mechanical strength compared with the prototype. 3 s and 5 C.p. f-crystals, 2 tab.

The invention relates to catalysts and methods of producing oxide catalysts used in the processes of deep oxidation of organic compounds and carbon monoxide in the gas emissions from industrial productions.

There is a method of preparation of the catalyst of the oxidation of organic substances (ed. mon. THE USSR 533391, IPC3B 01 J 37/00, 1976), which consists in impregnating aminoarabinose carrier with a solution containing chromium and copper, followed by drying and heat treatment. Carry out the impregnation or modification of aluminum oxide with an excess of a solution of bichromate of copper, soak in the solution for 3 hours, after which excess solution of bichromate of copper sucked off under vacuum, the sample is dried, and heat treatment is conducted at temperatures of 600-800oC.

The disadvantage of this method is the complexity of the technology of preparation of the catalyst, namely the carrier impregnated in excess propion will require additional stage - recycling impregnating solutions containing highly toxic compounds.

A known method of producing a catalyst for oxidation of carbon monoxide and organic impurities in the gas emissions (U.S. Pat. RF 2032467, IPC6B 01 J 37/04, 1995), which includes a mixture of components that contain compounds of chromium and copper with aluminum hydroxide, followed by molding, drying and calcining, where the use of aluminum hydroxide pseudoboehmite patterns, pretreated with acid capable of forming water-soluble basic salts of aluminum in acidic 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.

The disadvantage of this method is the fact that the use of aluminum hydroxide pretreated with acid, which complicates the technology of its preparation.

The closest technical solution is the method of producing a catalyst for purification of exhaust gases from organic compounds (ed. mon. THE USSR 1295570, IPC4B 01 J 37/04, 1993), which includes a mixture of components containing compounds is of luminia, free of sulfur and containing an admixture of iron oxide in a quantity of 0.05-0.1 wt.%.

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

The task of the invention is the development of catalysts for deep oxidation of hydrocarbons and carbon monoxide in the gas emissions with increased activity, mechanical strength and stability, and method of its production (options).

The problem is solved at the expense of catalysts for deep oxidation of organic compounds and carbon monoxide in the gas emissions, including oxides of chromium, copper, aluminium oxide with an additional connection. As additional connections aluminium oxide contains at least one connection element from the group of alkali and alkaline-earth metals, silicon, iron in an amount of 0.01-2.0 wt.%, and the catalyst has the following composition (in terms of oxides), wt.%:

The chromium oxide - 5-25

The copper oxide - 5-25

The aluminum oxide with at least one additional connection element from the group of alkali and alkaline-earth metals, silicon, iron-rotation of trihydroxide aluminum, and having the composition of Al2O3mo2Oh, where n= 0,03-2,0.

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

The chromium oxide - 9-13

The copper oxide - 8-12

The aluminum oxide with at least one additional connection element from the group of alkali and alkaline-earth metals, silicon, iron - 0,01-2,0 - rest.

The problem is solved by the methods (variants) of obtaining the above-described catalysts for deep oxidation of organic compounds and carbon monoxide in the gas emissions.

The first method consists in mixing the components containing compounds of chromium, copper, aluminum hydroxide with an additional connection with the subsequent molding, drying and calcination. As aluminum hydroxide use hydrated compound of aluminum composition of Al2O3mo2Oh, where n= 0,03-2,0 containing at least one additional connection element from the group of alkali and alkaline earth metals, silicon, iron in an amount of 0.01-2.0 wt. % to be able to form basic salts of aluminum. Then add oxygen-containing compounds of chromium and copper, is introduced into the catalyst mixture, plastificator 550-700oWith, and get the catalyst of the following composition (in terms of oxides), wt.%:

The chromium oxide - 5-25

The copper oxide - 5-25

The aluminum oxide with at least one additional connection element from the group of alkali and alkaline-earth metals, silicon, iron - 0,01-2,0 - rest.

As a precursor of aluminum hydroxide is preferably used a product obtained by the rapid dehydration of trihydroxide aluminum, having a composition of Al2ABOUT3mo2O, where n=0,03-2,0.

Plasticization of charge spend acids that can form basic salts of aluminum with Mto=0,08-0,15.

The second way of obtaining catalysts for deep oxidation of organic compounds and carbon monoxide in gas emissions is the impregnation of a carrier comprising alumina with an additional compound with a solution of chromium compounds, copper, drying, calcination. The aluminum oxide containing at least one additional connection element from the group of alkali and alkaline-earth metals, silicon, iron in an amount of 0.01-2.0 wt. %, impregnated with a solution containing compounds of chromium, copper impregnated carrier is dried, calcined at temperatures up to 550-700OID copper - 5-25

The aluminum oxide with at least one additional connection element from the group of alkali and alkaline-earth metals, silicon, iron - 0,01-2,0 - rest.

The precursor of aluminium oxide is preferably a product obtained by the rapid dehydration of trihydroxide aluminum, having a composition of Al2O3mo2Oh, where n=0,03-2,0.

The content in the alumina additional connection element from the group of alkali and alkaline-earth metals, silicon, iron in an amount of 0.01-2.0 wt. % contributes to the formation of the modified surface of the media.

In the proposed solution used for preparation of the catalyst hydrated compound of aluminum composition of Al2O3nH2O, where n=0,03 to 2.0, which can be obtained by any known means, for example by rapid dehydration of the product: gibbsite, hydrargillite, bayerite, nordstrandite, boehmite, Diaspora, containing in its composition optionally modifying compounds: alkali and alkaline-earth metals, silicon, iron in an amount of 0.01-2.0 wt.%, that may be partially contained within the original products, or they are administered before rapid dehydration by any known sposobnogo aluminum compounds is the formation of the catalyst on the modified surface of the carrier, that ensures the formation of a strong connection of the carrier with active component, resulting in a catalyst with higher indicators: activity, stability and durability.

In a joint introduction to the catalyst active component and hydrated aluminum compounds by the method of mixing is considerably simplified the technology of its preparation.

The introduction of the active component by impregnation of moisture content in the alumina containing up to 2 wt.% alkaline and alkaline-earth metals, silicon, iron, results in a catalyst with high activity, and thus there is no waste water and toxic gas emissions.

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

For measure the catalytic activity of the catalyst in the reaction of deep oxidation of n-butane adopted by the reaction rate (cm3C4H10/Gcat.C) oxidation of n-butane at 400oC. the higher the speed of reaction of complete oxidation of n-butane corresponds to a more active catalyst.

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

The following examples illustrate the invention.

Example 1

For the preparation of the catalyst used 550 g of hydrated aluminum compounds composition of Al2ABOUT3mo2Oh, where n=1.5, containing oxides of sodium, potassium, silicon, iron. To connect aluminum added 68 g of oxygen-containing compounds of chromium (chromium oxide) and stirred. Then the mixture is injected 77 g of oxygen-containing compounds of copper (malachite), add 20 g of wood flour and mix. Plasticization of the catalyst mixture is conducted 306 ml of an aqueous solution of nitric acid based 0,1226 mole of nitric acid per mole of alumina (40 ml NGO3the concentration of 760 g/l), is then formed by extrusion of granules with a diameter of 4.5 mm carried out the stage of wilting on air is redlagaemyi the catalyst has the following composition (in terms of oxides), wt.%:

The chromium oxide - of 10.21

The copper oxide - 10,89

Alumina - 78,90

including oxides: of sodium - 0,08, potassium - 0,02, silicon - 1,0, iron - 0,9.

Example 2

960 g of hydrated aluminum compounds (n=2) containing sodium oxide, is mixed with 10 g of polyethylene oxide add 384,9 g of oxygen-containing compounds of chromium (ammonium bichromate), stirred, and then the mixture is injected 50 g of oxygen-containing compounds of copper (copper oxide obtained by thermal decomposition of basic carbonate of copper), mix. As the acidity of a catalyst mixture used 602 ml of an aqueous solution of nitric acid at a rate of 0.15 mol of nitric acid per mole of alumina. When ready catalyst mass is formed into pellets with a diameter of 4.5 mm Pellets provalivajut in air, dried and calcined at 550oC.

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

The chromium oxide - 25

The copper oxide - 5

Alumina - 70

Including sodium oxide - 0,01

Example 3

The catalyst is prepared analogously to example 2, but the catalyst mixture contains 958,9 g of hydrated aluminum compounds containing oxides: barium, potassium, iron, calcium, 25 g of wood sotoi acid from the calculation of 0.08 mol of nitric acid per mole of alumina.

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

The chromium oxide - 5,0

The copper oxide - 25,0

Alumina - 70,0

including oxides: barium - 0,6; potassium - 0,1; iron - 0,7; calcium - 0,6.

Examples 4-5

The catalysts are prepared analogously to example 2, but they differ in the composition and content of additional elements.

Example 6

Prepare 802 g refractory porous media using hydrated compound of aluminum (n=0,03), containing oxides: of sodium, potassium, silicon, iron. The medium (diameter of 4.5 ml, specific surface area: 180 m2/g, a water capacity of 1 ml/g) soaked in water holding capacity water solution with concentration of elements (mg/ml: chromium - 110,9; copper - 67,7. To prepare an impregnating solution using acetic acid salt of chromium and copper. The impregnation of the support is carried out in propitiate rotary drum at room temperature, dried impregnated carrier in a stream of hot air at 120oC. the Calcined catalyst at a temperature of up to 700oC.

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

The chromium oxide is 13.0

The copper oxide - 6,8

Aluminium oxide is an 80.2

including oxides: natraemia catalyst contains crystalsound copper-chromium spinel.

Example 7

The catalyst is prepared analogously to example 6, but it differs by the structure and content of additional elements.

Example 8 (prototype)

7,8 g basic carbonate of copper, 6.4 g of chromic anhydride, 0.33 g of barium oxide and 35.5 g of aluminum hydroxide pour 40 ml of water and stirred to obtain a homogeneous mass. The resulting mass ekstragiruyut through a Spinneret with a diameter of 6-7 mm extrudates provalivajut on the air 24 hours, dried and calcined at 400-450oWith 6 hours.

The catalyst has the following composition, wt.%:

CR2ABOUT3- 14,5

CuO - 12,5

HLW - 2

Al2O3- Rest

Data on the composition of the catalysts according to the given examples are presented in table 1.

Table 2 presents data on the catalytic activity in the reaction of deep oxidation of n-butane and carbon monoxide and the mechanical strength of the inventive catalyst and the prototype. As can be seen from the table, the inventive catalyst has a higher catalytic activity in the above oxidation reaction and mechanical strength compared with the prototype.

1. The catalyst for deep oxidation of organic compounds and carbon monoxide in Gasco aluminum oxide contains at least one additional connection element from the group of alkali and alkaline earth metals, silicon, iron in an amount of 0.01-2.0 wt. % and the catalyst has the following composition (in terms of oxides), wt. %:

The chromium oxide - 5-25

The copper oxide - 5-25

The aluminum oxide with at least one additional connection element from the group of alkali and alkaline earth metals, silicon, iron - 0,01-2,0 - Rest

2. The catalyst p. 1, characterized in that the precursor of aluminium oxide is the product obtained by the rapid dehydration of trihydroxide aluminum and having a composition of Al2O3nH2O, where n= 0,03-2,0.

3. The catalyst PP. 1 and 2, characterized in that it has the following composition (in terms of oxides), wt. %:

The chromium oxide - 9-13

The copper oxide - 8-12

The aluminum oxide with at least one additional connection element from the group of alkali and alkaline earth metals, silicon, iron - 0,01-2,0 - Rest

4. A method of producing a catalyst for deep oxidation of organic compounds and carbon monoxide in the gas emissions by mixing the components containing compounds of chromium, copper, aluminum hydroxide with an additional connection, followed by molding, drying, and calcination, wherein as aluminum hydroxide ispolzuyte one additional connection element from the group of alkali and alkaline earth metals, silicon, iron in an amount of 0.01-2.0 wt. % to be able to form basic salts of aluminum, add oxygen-containing compounds of chromium, copper, then in catalyst charge is injected plasticizer to obtain a plastic mass is formed into subsequent crop has wilted granules, dried, calcined at 550-700oWith and obtain a catalyst of the following composition (in terms of oxides), wt. %:

The chromium oxide - 5-25

The copper oxide - 5-25

The aluminum oxide with at least one additional connection element from the group of alkali and alkaline earth metals, silicon, iron - 0,01-2,0 - Rest

5. The method according to p. 4, characterized in that as the precursor of aluminum hydroxide is used a product obtained by the rapid dehydration of trihydroxide aluminum, having a composition of Al2O3nH2O, where n= 0,03-2,0.

6. The method according to p. 4, characterized in that the plasticization of the catalyst mixture is conducted acids that can form basic salts of aluminum with Mto= 0,08-0,15.

7. A method of producing a catalyst for deep oxidation of organic compounds and carbon monoxide in the gas emissions, by impregnation of a carrier comprising alumina with an additional connection, RA is she least one additional connection element from the group of alkali and alkaline earth metals, silicon, iron in an amount of 0.01-2.0 wt. %, impregnated with a solution containing compounds of chromium, copper impregnated carrier is dried, calcined at temperatures up to 550-700oWith and obtain a catalyst of the following composition (in terms of oxides), wt. %:

The chromium oxide - 5-25

The copper oxide - 5-25

The aluminum oxide with at least one additional connection element from the group of alkali and alkaline earth metals, silicon, iron - 0,01-2,0 - Rest

8. The method according to p. 6, characterized in that the precursor of aluminium oxide is the product obtained by the rapid dehydration of trihydroxide aluminum, having a composition of Al2O3nH2O, where n= 0,03-2,0.

 

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