A method of obtaining a nickel hydrogenation catalyst

 

(57) Abstract:

The invention relates to methods for Nickel catalysts for the hydrogenation of oxides of carbon, oxygen and aromatic hydrocarbons. The inventive method comprises the mixing of the basic Nickel carbonate with alumina carrier in the presence of an aqueous solution of ammonia, followed by drying, calcination, grinding, mixing with graphite and pelletizing. As alumina carrier, a mixture of high and low temperature forms of alumina in a ratio of from 0.05:0.95 to 0.50 to: 0,50 (in terms of Al2O3and as a low-temperature forms of alumina take boehmite, pseudoboehmite, hydro-argillite, -Al2O3or-Al2O3and as a high temperature form - a-Al2O3or-Al2O3. The invention provides for obtaining a Nickel hydrogenation catalyst with high activity. table 1.

The invention relates to the production of Nickel hydrogenation catalysts, in particular to methods of producing catalysts for the hydrogenation of oxides of carbon, oxygen and aromatic hydrocarbons. A method of obtaining Nickel catalystframework anhydride, followed by drying at 100oC for 10 h, annealed in air at 450oC for 10 h, the mixture with graphite and pelletizing [1]

The main disadvantage of this method is the use of chromic anhydride, which, as you know, belongs to a class of highly toxic substances that cause the need for additional measures for compliance with health and safety which, in turn, leads to a rise in the cost of the catalyst.

Closest to the invention to the technical essence is a method of obtaining a Nickel catalyst that does not contain chromium, consisting in mixing the alumina powder with ammonium complex of the basic Nickel carbonate, followed by calcining in air at 350-500oC, chopping, mixing with graphite and pelletizing. However, the Nickel catalyst obtained in this way has not a high activity [2]

The present invention provides an increase in the activity of the Nickel hydrogenation catalysts. This technical effect is achieved by using a mixture of high and low temperature forms of alumina.

The invention consists in obtaining a Nickel catalyst ecoterritory forms of aluminum oxide) in the presence of patinator aqueous solution of ammonia, followed by drying at 100-120oC and calcining at 350-500oC, chopping, mixing with graphite and pelletizing.

Our research ecumenically catalysts (ANC) by the methods of x-ray phase analysis (XRD), derivatographic and temperature-programmed reduction (TPR) indicates the presence of two forms of Nickel, recovering at 300-400oC (I) and 500-650oC (II). Catalytic tests microprotol installed in the reaction of hydrogenation of benzene to cyclohexane showed that the dependence of activity on the ratio of these forms is an extreme character: most activity have samples with a ratio of forms I and II is about 1:1.

Found that the original form (state) of Al2O3affects the total amount of recovered Nickel and the ratio of forms I and II. It is established that the high-temperature form ( and q-Al2O3) contribute to the formation of form I and low temperature (boehmite, pseudoboehmite, hydro-argillite, g -, r-Al2O3) II. Thus, by varying the ratio of high and low temperature forms of alumina can be controlled phase composition of the ANC and thus to optimize kataliticheskaya on the circulation-flow-through unit (CPU) at a temperature of 200oC and a pressure of 0.1 MPa according to standard methods described in the technical specifications "Catalysts mahanirvana (TU 113-03-2003-92, p. 4.12), as well as in the reaction of hydrogenation of benzene to cyclohexane at microprotol installation flow (PU) type at a pressure of 1.0 MPa, the rate of hydrogen supply 15 l/h and flow rate of feed of raw material 3 h-1. Before conducting the experiments, the samples were activated in a stream of hydrogen at 200oC for 6 hours as a criterion of activity took is the conversion of benzene at a temperature of 140oC.

Example 1. To 65 kg of a powder mixture of a-Al2O3and g-Al2O3(at a ratio of 0.50:0.50 and in terms of Al2O3) add a 58.3 kg of basic Nickel carbonate (NiO content 60%) and stirred for 0.5 h until a homogeneous mixture, then poured 100 ml of 25% aqueous ammonia and stirred for 1 h to obtain a homogeneous mass. Then the mass with stirring is heated to 100-120oC and stirred for 4-6 h to obtain a dry powder. The resulting powder was calcined in a stream of air at a temperature of 350oC 4 h Calcined product additionally crush, add water in an amount of 10 l and 4 kg of graphite and stirred for 0.5 h to obtain homogeneous the iO 35 wt. Al2O3the rest of it.

Activity: CPU 2.5 cm3CO/g

Example 2. Analogously to example 1, except that instead of a mixture of a-Al2O3and g-Al2O3took a mixture of a-Al2O3and r-Al2O3(at a ratio of 0.50:0.50 and in terms of Al2O3).

The composition of the catalyst: NiO 35 wt. Al2O3the rest of it.

Activity: CPU 2.4 cm3CO/g

Example 3. Similarly to example 1, except that instead of a mixture of a-Al2O3and g-Al2O3took a mixture of a-Al2O3and boehmite (at a ratio of 0.50:0.50 and in terms of Al2O3).

The composition of the catalyst: NiO 35 wt. Al2O3the rest of it.

Activity: CPU 2.3 cm3CO/g

Example 4. Analogously to example 1, except that instead of a mixture of a-Al2O3and g-Al2O3took a mixture of a-Al2O3and pseudoboehmite (at a ratio of 0.50 to 0.50 in terms of Al2O3).

The composition of the catalyst: NiO 35 wt. Al2O3the rest of it.

Activity: CPU 2.3 cm3CO/g

Example 5. Analogously to example 1, except that instead of a mixture of a-Al2O3and g-Al2O3took a mixture of a-Al2O3and hydrargillite (at a ratio of 0.50:0.50 and in terms of Al2cm3CO/g

Example 6. Analogously to example 1, except that instead of a mixture of a-Al2O3and g-Al2O3took a mixture of q-Al2O3and g-Al2O3(at a ratio of 0.50:0.50 and in terms of Al2O3).

The composition of the catalyst: NiO 35 wt. Al2O3the rest of it.

Activity: CPU 2.6 cm3CO/g

Example 7. Analogously to example 1, except that instead of 65 kg of a mixture of a-Al2O3and g-Al2O3with a ratio of 0.50:0.50 in (in terms of Al2O3) took 50 kg of a mixture of a-Al2O3and g-Al2O3at a ratio of 0.05:0.95 and instead of 58.3 kg basic Nickel carbonate took 83,3 kg

The composition of the catalyst: NiO 50 wt. Al2O3- the rest.

Activity: PU 70%

Example 8 (prototype). In the Z-shaped mixer load 2.5 kg shredded aluminium oxide g-Al2O3) and 2.3 kg of basic Nickel carbonate (NiO content 60%) and under stirring to the mixture is added 2.5 l of a 25% aqueous solution of NH4OH. Stirring is effected at ambient temperature for 1 h, followed by stirring at a temperature of 100-120oC for 4-6 h (to remove ammonia). The resulting mass (in the form of a dry powder), annealed at asmerom 5 x 5 mm

The composition of the catalyst: NiO 35% Al2O3the rest of it.

Activity: CPU 1.9 cm3CO/ g, PU 35%

Comparative data on activity obtained in examples 1-8 and industrial analogues: a catalyst for hydrogenation of carbon oxides (process mahanirvana) NYC-1 (TU 113-03-2003-92) and Nickel-chromium" catalyst for the hydrogenation of aromatic compounds (OST 113-03-4001-90) are summarized in table.

The table shows that the results obtained by the proposed method samples (examples 1-7) are superior in activity industrial analogues synthesized sample prototype (example 8).

Thus, the proposed method allows to obtain a Nickel hydrogenation catalysts with increased activity.

A method of obtaining a Nickel hydrogenation catalyst comprising a mixture of a basic carbonate of Nickel alumina carrier in the presence of an aqueous solution of ammonia, followed by drying, calcination, grinding, mixing with graphite and pelletizing, characterized in that as the alumina carrier, a mixture of high and low temperature forms of alumina in a ratio of from 0.05 to 0.95 to 0.50 0,50 (in terms of Al2O3and in l2O3and as high-temperature form -- Al2O3or-Al2O3.

 

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