The preparation method of catalyst for hydrogenation of ketones and aldehydes

 

(57) Abstract:

Usage: in catalytic chemistry, in particular in the preparation method of catalyst for hydrogenation of ketones and aldehydes. The inventive method for preparation of the catalyst for hydrogenation of ketones and aldehydes provides a mixture of chromic acid with a carbonate or oxide of copper, and further mixing the resulting paste with ammonia water with the introduction of the reaction mixture, and insoluble compounds of metals of the second group and/or manganese in an amount of 0.1 to 10 mol. in the calculation of the oxide. Then conduct a heat treatment of the mixture, its formation and recovery of hydrogen. 2 C. p. F.-ly, 1 table.

The invention relates to processes for the preparation of catalysts for the hydrogenation of ketones and aldehydes used in the chemical industry.

A known method of producing a catalyst for chemical processes, including the production of ammonium chromates metals by deposition of ammonia from nitrate salts of copper and chromate [1]

The disadvantage of this method is the formation of large quantities of wastewater ( 30 m3/t) of a catalyst containing compounds of chromium (VI), copper (II), require specially the solution of ammonium complex copper and chromate copper. This forms ammonium chromate metal General formula Cu(OH)(NH4)CrO4[2] Method is a waste. Its main drawback is the instability properties of the return of the filtrate, the multistage and greater complexity.

Closest to the present invention is a method of obtaining multi-component catalysts, including the formation of ammonium chromates metal mixing basic carbonates or oxides of copper, Nickel or zinc with chrome acid at 20 to 100aboutC, followed by mixing the resulting paste with ammonia water, heat treatment and recovery of hydrogen [3]

A way to almost completely eliminate harmful discharges and emissions into the atmosphere.

However, in this way it is impossible for the preparation of catalysts, requiring the introduction of metals not forming compounds of the type MOHNH4CrO4and thereby stabilizing the catalyst surface. The disadvantages of the method include low productivity, low life, insufficient mechanical strength of the resulting catalysts.

The task of the invention to develop the method of preparation of the catalysts, providing a high act of the cottage is solved by the method of preparation of the catalyst for hydrogenation of ketones, comprising a mixture of chromic acid with a carbonate or oxide of copper, and further mixing the resulting paste with ammonia water and the heat treatment of the mixture formation and reduction with hydrogen, in which the heat treatment in the reaction mixture is further added insoluble metal compounds of group II and/or manganese in an amount of 0.1 to 10 mol. At the same time as insoluble compounds of metals of group II and use manganese oxides and/or hydroxides and/or carbonates and/or chromates of these metals. In addition, the heat treatment of the reaction mixture is carried out at 280 350aboutC.

The essence of the proposed method lies in the fact that the result of the interaction of carbonates and/or oxides of copper with chromium acid at 20 to 100aboutAnd further mixing the resulting paste with ammonia water to form ammonium chromates copper General formula: Cu(OH)(NH4)CrO4. The presence of ammonium chromate copper in the reaction mixture provides the system the presence of solid-phase reducing agent (complex associated with ammonia). Then, the resulting ammonium chromate copper mixed with insoluble compounds of metals of group II and/or manganese, such as oxides and/or hydroxides and/or carbonates, which stabilizes monovalent copper, consequently, increases its activity in the process of hydrogenation of ketones. In addition, the introduction of these promoters prevents sintering of the catalyst surface and thereby significantly increases the service life of the catalyst. After drying are intermediate heat treatment at 280 350aboutWith and forming catalyst, and then restore it with hydrogen by a gradual increase in temperature and curing in a stream of hydrogen. Supplementation of insoluble compounds of metals of group II or manganese is carried out in an amount of 0.1 to 10.0 mol. from the copper content in the catalyst. The specified amount of demand is optimal to give the required properties of the catalyst.

Obtaining catalyst according to the proposed method completely eliminates the formation of harmful effluents and emissions into the atmosphere as the heat treatment of ammonium chromate copper is recovered ammonia Cr (VI) to Cr (III) emitting harmless gases-nitrogen and water vapor, and excess ammonia released during the drying of the catalyst, is captured by the water and returns to the step of mixing the starting materials.

P R I m e R 1. 0.800 to kg chromium trioxide, kg 0.800 to the basic carbonate of copper PE is try stirring for 1 h After that, the paste make 646 ml of ammonia water (with a density of 0,904 g/ml) and stirred for 0.5 hours Then the mixture was added 0,125 kg barium oxide, which is 10 mol. from the copper content and continue stirring for 0.5 hours the Paste discharged from the mixer and dried in a drying Cabinet at 100 10aboutC. the Powder is subjected to heat treatment at 280 290aboutAnd tabletirujut tablet with a diameter of 4.5 mm and a height of 4.5 mm, the result is a catalyst corresponding to the formula 9(SIO CuCr2O4)2 BaCrO4and containing, by weight. CuO 45,4; Cr2O342,8; BaO 11.8% of the bulk density of catalyst 1.5 kg/l, specific surface 56 m2/g, the mechanical strength of 45 kg/table. Before use the catalyst restores nitric mixture with an initial hydrogen content of 0.5 to about 10. with increasing temperature with a speed of 15 of the 20aboutWith up to 250aboutC. the Catalyst was then aged at finite temperature in pure hydrogen for 10 h

P R I m m e R 2. 0.800 to kg Chromium trioxide, 0.800 to kg malachite is stirred in the presence of 800 ml of water at 70 to 80aboutC for 1 h in a paddle mixer. Then add 646 ml of ammonia water (with a density of 0,904 g/ml) and stirred for 0.5 hours then into the mixer contribute 0, the Oia weight unloaded and dried in a drying Cabinet at 100 10aboutC. the Heat treatment of the powder is carried out at 290 300aboutC for 8 h, tabletirujut on a rotary press. Get the catalyst corresponding to the formula 9(CuO CuCr2O4) 2CaO. The bulk density of the catalyst 1.4 kg/l, specific surface 62 m2/g, the mechanical strength of 40 kg/table. Before use the catalyst restore in hydrogen at 250aboutC for 10 h

P R I m e R 3. determined as 0.720 kg chromium trioxide, 0.800 to kg malachite mixed in a paddle mixer in the presence of water at 70 to 80aboutC for 1 h Then add 646 ml of ammonia water (with a density of 0,904 g/ml). Stirred for 0.5 hours Then in the same mixer to prepare the barium chromate by adding a paste of) 0.157 kg carbonate of barium and 0.080 kg chromium trioxide. Mix pasta for 0.5 hours and Then the paste is dried in a drying Cabinet at 100 10aboutAnd thermoablative at 290 300aboutC for 10 h, tabletirujut into tablets with a diameter of 4.5 mm, a height of 4.5 mm, the result is a catalyst corresponding to the formula: 9(CuO CuCr2O4)2 BaCrO4and containing, by weight. CuO 45,4; Cr2O342,8; BaO 11,8. The bulk density of catalyst 1.5 kg/l, a specific surface area of 64 m2/g, the mechanical strength of 45 kg/table. Before using to the military in example 1, used for the hydrogenation of furfural in a stream of hydrogen in furfuryl alcohol 120aboutWith atmospheric pressure, the contact load of 0.2 kg of furfural per 1 kg of catalyst, the conversion of furfural on furfuryl alcohol 98% of the service life of the catalyst 1500 hours

P R I m e R 5. The catalyst prepared according to example 2, carry out the hydrogenation of furfural in a stream of hydrogen in furfuryl alcohol at a temperature of 120aboutC, atmospheric pressure, the contact load of 0.2 kg of furfural per 1 kg of catalyst per hour. Conversion of furfural is 99.9% selectivity for furfuryl alcohol 98.3% of the service life of the catalyst 1250 h

P R I m e R 6. The catalyst prepared according to example 3, carry out the hydrogenation of acetone in a stream of hydrogen in isopropyl alcohol at 80aboutC, atmospheric pressure, the contact load 1.0 kg of acetone per 1 kg of catalyst per hour. The conversion of acetone to 79.8% selectivity for isopropyl alcohol 99.5% longer catalyst life 2 years.

P R I m e R 7 (prototype). 1.0 kg chromium trioxide, 1,136 kg basic carbonate of copper mixed in the mixer, add water and 810 ml of ammonia water. The resulting paste is dried and thermoablative at 300aboutC. Molded tablets 4.5 x 4.5 mm is 2/g, the mechanical strength of 30 kg/table. Before use the catalyst restore at 250aboutWith nitric mixture containing 0.5 to 10 rpm. of hydrogen. Received the prototype of the catalyst was tested in the process of gas-phase hydrogenation of acetone to isopropyl alcohol at a flow installation with contact load of 10 kg acetone/kg catalyst including Temperature 80aboutWith the flow rate of hydrogen of 50 l/h for the passage. The conversion was 35%

Physico-chemical properties and performance characteristics of the catalysts prepared according to the methods of examples 1 to 3 shown in the table.

As follows from the presented data, the catalysts prepared according to the proposed technology, offer the following advantages:

high mechanical strength;

long life;

high activity and selectivity;

the technology of their preparation has environmental cleanliness.

These benefits provide an effective industrial use of catalysts.

1. The PREPARATION METHOD of CATALYST FOR hydrogenation of KETONES AND ALDEHYDES, including a mixture of chromic acid with a carbonate or oxide of copper and then the tives such as those before heat treatment in the reaction mixture is further added insoluble metal compounds of group II and/or manganese in an amount of 0.1 to 10 mol. in terms of the oxide.

2. The method according to p. 1, characterized in that as insoluble compounds of metals of group II and use manganese oxides and/or carbonates and/or chromates of these metals.

3. The method according to PP. 1 and 2, characterized in that the heat treatment of the reaction mixture is carried out at 280 350oC.

 

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