A method of producing a catalyst for hydrogenation of aromatic compounds, for mahanirvana co and co2

 

(57) Abstract:

The invention relates to a method for producing a catalyst for the hydrogenation of aromatic hydrocarbons, gas purification from oxygen and oxides of carbon, for mahanirvana co and CO2and other processes. The described method of preparation of the catalyst for hydrogenation of aromatic hydrocarbons, for mahanirvana co and CO2by processing the dry mixture of the basic Nickel carbonate (window) oxide and/or aluminum hydroxide with a solution of chromic anhydride, followed by drying, calcination and pelletizing. For the preparation of a catalyst mass used oxide and/or aluminum hydroxide containing at least one compound of an element from groups: K, Na, Si, Fe, Ca, Mg in an amount of 0.001-0.5 wt. % in terms of oxide, the resulting catalyst mass is added ammonium hydroxide in a molar ratio of anhydride chromic acid: ammonium hydroxide=1:(0.2 to 1) and obtain a catalyst of the following composition, wt. %: Nickel 20-50, chromium oxide 10-30, alumina - rest. The technical result - the catalyst obtained by this method has a high activity and high stability for a long time. 3 table.

Jsobrev from oxygen and carbon oxides, for mahanirvana co and CO2.

In industry Nickel-almograve catalysts receive two ways: pelletizing and molded by extrusion. The catalysts obtained by pelletizing, have high strength and are widely used in industry, although the method more complicated.

Known Nickel-lomography catalyst for hydrogenation of organic compounds (ed. mon. The USSR 229467, IPC B 01 J 37/02, 1969) containing 15-20% of aluminum oxide, 30-50% of chromium oxide, the rest is Nickel. The catalyst was prepared by co-deposition soda solution of basic Nickel carbonate and hydroxides of chromium and aluminum from their nitrate salts at 50-90oC and a constant pH, followed by filtering the mixture, washing to complete absence of the nitrate ion, drying, calcination, pelletizing and recovery. This method allows to obtain a catalyst with high catalytic activity.

The disadvantage of this method is that the existence of stages of filtering the mixture, washing up to the total absence of nitrate-ion complicates its implementation. This leads to poor reproducibility of the catalytic activity of cities and purification of gases from oxygen and carbon monoxide ( ed. mon. The USSR 409467, IPC B 01 J 23/86, 1977), containing, wt.%: Nickel - 8-33, chromium oxide - 4-12 and alumina - 38-81. The catalyst was prepared by treating pasty or dry mixture of basic Nickel carbonate and oxide or aluminum hydroxide with a solution of chromic anhydride, followed by drying, calcination and pelletizing. Treatment with chromic anhydride is carried out at a weight ratio of basic Nickel carbonate to chromic anhydride equal to (3-5):1.

The disadvantage of this method is the low activity of the known catalyst.

A method of obtaining a Nickel-alimohammadi catalyst (ed. mon. The USSR 417978, B 01 J 23/86, 1982) by treatment with a solution of chromic anhydride paste made from powdered Nickel carbonate and aluminum hydroxide, followed by drying the catalyst mass, calcination, pelletizing and recovery. Original powdered components of the catalyst and/or calcined catalyst mass is subjected disaggregation and get the catalyst with high mechanical strength.

The disadvantage of this method is the low activity of the catalyst.

Closest to the proposed to the technical essence and achieved the technical connection (ed. mon. The USSR 403429, IPC B 01 J 37/04, 1977), which consists in mixing compounds of Nickel, aluminum and chromium, followed by drying, calcination, pelletizing and recovery. Blending take pasty or dry mixture of basic Nickel carbonate and a hydroxide or oxide of aluminum and treated with a solution of chromium trioxide.

The disadvantage of this method is that it failed to obtain a catalyst with high stability and high activity, although the rate of hydrogenation of benzene to cyclohexane is increased by 30-40%.

The task of the invention to provide a catalyst with high stability and high activity.

This object is achieved in that the catalyst for the hydrogenation of aromatic hydrocarbons, for mahanirvana co and CO2composition, wt.%: Nickel - 20-50, chromium oxide - 10-30, aluminum oxide - the rest is produced by processing of a dry mix of basic Nickel carbonate (window) oxide and/or aluminum hydroxide with a solution of chromic anhydride, followed by drying, calcination and pelletizing. For the preparation of a catalyst mass used oxide and/or aluminum hydroxide containing at least one soy is priori weight add ammonium hydroxide in a molar ratio of anhydride chromic acid:ammonium hydroxide= 1:(0,2-1).

In the proposed solution for the preparation of the catalyst using alumina of any phase and/or hydrated compound of aluminium of the formula Al2O3n H2O, where 1,1 n of 2.0, which can be obtained by any known means, such as rehydration product rapid dehydration hydrargillite, bayerite, nordstrandite, boehmite, Diaspora, and contain additional modifier compound K, Na, Si, Fe, Ca, Mg in an amount of 0.001-0.5 wt.%, that may be partially present in the original products, or they are introduced into the original aluminum hydroxide before rapid dehydration by any known means, for example by impregnation, mixing, or coprecipitation. To the basic Nickel carbonate added to the above compound of aluminum, to the resulting dry mixture is added successively a solution of chromic anhydride and then ammonium hydroxide. The ammonium hydroxide is added in a certain relation to chromium to form complex compounds of Nickel, chromium and compounds modifying metals present in the oxide and/or aluminum hydroxide. When the heat treatment proposed catalyst mixture, the formation of the active phase of the catalyst.

Received catalysis is x2">

In the mixer load basic Nickel carbonate and oxide and/or aluminum hydroxide containing additional compounds of elements from groups: K, Na, Si, Fe, Ca, Mg, that may be partially contained in the carrier, the remainder of the additional compounds is introduced into the oxide and/or aluminum hydroxide impregnation of the above elements in the catalyst mixture. With stirring, poured a solution of chromium trioxide. After the termination of allocation of bubbles poured ammonium hydroxide. The resulting mass is dried at 80-90oC, calcined at 350-360o6 h, tabletirujut.

Composition and physico-chemical properties of the obtained catalyst is determined as follows:

- the content of Ni, Cr, K, Na, Si, Fe, Ca, Mg - x-ray fluorescence method;

the crushing strength - on device MP-9S.

Data on the method of preparation of the catalyst and its composition is shown in table. 1.

The proposed catalyst was tested in the reaction of hydrogenation of benzene to cyclohexane. Testing is carried out in the reactor flow-circulation type.

The results of the tests are presented in table. 2.

The catalyst was tested in the reaction of mahanirvana flow-circulation method "ptx2">

For the preparation of the catalyst take the boxes 192 g, Al2ABOUT330,8 g, SGAs368,2, the Ratio of window:CrO3is 2.8:1. The resulting sample contains in the oxide form, wt.%: Nickel 50, CR2ABOUT323,8, aluminum oxide 26,2.

Example 2.

In the Z-shaped mixer load 540 g of basic Nickel carbonate and 50 g of alumina containing 0.01 wt.% Na2O. Dissolve 232 g of chromic anhydride in 168 g of water and with stirring, poured into the mixer. After the termination of allocation of bubbles poured 162 ml of 25% ammonium hydroxide. The resulting mass is dried in the mixer at a temperature of 80-90oC. in a drying Cabinet at 100oC, calcined at 350-360oWith 6 hours tabletirujut with graphite (2-4 wt.%), further, the catalyst restore.

Example 3.

The catalyst is prepared analogously to example 2, only the aluminum hydroxide contains Fe2ABOUT3in the amount of 0.001 wt.%, the molar ratio of chromium trioxide to the ammonium hydroxide is 1:0.8 to, and the catalyst consists of 20 wt.% Nickel and 15 wt.% oxide of chromium.

Example 4.

The catalyst is prepared analogously to example 2, only the aluminum oxide contains MgO in an amount of 0.02 wt.%, the molar ratio of Hromova chrome.

Example 5.

The catalyst is prepared analogously to example 2, only the aluminum hydroxide contains SiO2; in the amount of 0.5 wt.%, and the catalyst consists of a 48 wt.% Nickel and 27 wt.% oxide of chromium.

Example 6.

The catalyst is prepared analogously to example 2, only the aluminum oxide contains Cao in the amount of 0.3 wt.%, the molar ratio of chromium trioxide to the ammonium hydroxide is 1:0.7, and the catalyst consists of 45 wt.% Nickel and 20 wt.% oxide of chromium.

Example 7.

The catalyst is prepared analogously to example 2, only the aluminum oxide contains2About in an amount of 0.01 wt.%, the molar ratio of chromium trioxide to the ammonium hydroxide is 1:0.6 to, and the catalyst consists of a 37 wt.% Nickel and 15 wt.% oxide of chromium.

Example 8.

The catalyst is prepared analogously to example 2, only the aluminum oxide includes the additional SiO2in the amount of 0.3 wt.%, the molar ratio of chromium trioxide to the ammonium hydroxide is 1:1, and the catalyst consists of 35 wt. % Nickel and 10 wt.% oxide of chromium.

Example 9.

The catalyst is prepared analogously to example 2, only the aluminum oxide contains MgO 0.2 wt.%, CaO 0.1 wt.% and Fe2ABOUT30.02 wt.%, molar otnosheniia chrome.

Example 10.

Similar to example 2, only the weight ratio of aluminum oxide to aluminum hydroxide is 50:50, and aluminum oxide contains 0.2 wt.% MgO and 0.1 wt.% The CaO.

As can be seen from the above examples, the proposed catalyst in contrast to the known preformed catalyst has a high activity. All tested catalysts have high stability for a long time.

The catalyst activity in the reaction of hydrogenation of benzene is 7-14 g6H6/g of catalyst per hour.

A method of producing a catalyst for the hydrogenation of aromatic hydrocarbons, for mahanirvana co and CO2composition, wt.%:

Nickel - 20-50

The chromium oxide - 10-30

Alumina - Rest

by processing the dry mixture of the basic Nickel carbonate (window) oxide and/or aluminum hydroxide with a solution of chromic anhydride, followed by drying, calcination and pelletizing, characterized in that for the preparation of a catalyst mass used oxide and/or aluminum hydroxide containing at least one compound of an element from groups: K, Na, Si, Fe, Ca, Mg in an amount of 0.001-0.5 wt.%, in terms of the oxide, the resulting catalyst is= 1 : (0.2 to 1).

 

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FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention relates to catalysts used in isoamylenes-into-isoprene dehydrogenation process and contains, wt %: iron oxide 62-75.4, potassium carbonate 12-21.5, chromium oxide 1-3, potassium hydroxide 0.5-2.5, sulfur 0.1-2.0, ammonium nitrate 0.1-2.0, silicon dioxide 1-5, calcium carbonate 1-5, and cerium nitrate 1-3.

EFFECT: increased mechanical strength, resistance to saturated steam and moisture, and stability during long-time operation.

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