The preparation method of the catalyst for carbon monoxide conversion

 

(57) Abstract:

The preparation method of catalyst for low-temperature conversion of carbon monoxide with water vapor. The catalyst was prepared by mixing solutions of ammonium carbonate complexes of copper and zinc at a temperature of 80 to 90°C in a weight ratio of copper oxide: zinc oxide is from 1:1 to 7:1, the introduction of the obtained copper-zinc-ammonia-carbonate solution of aluminate of calcium and/or barium in a weight ratio of (CuO+ZnO) of from 1:19 to 1:2, with a ratio of aluminate of calcium to barium aluminate 1:1, followed by drying and pelletizing the catalyst mass. The catalyst has high activity and thermal stability. table 2.

The invention relates to a process for the preparation of catalysts based on copper compounds and zinc for low-temperature conversion of carbon monoxide with water vapor and can be used in the chemical and petrochemical industry, for example, in the production of ammonia and hydrogen, the synthesis of methanol and other industries.

There is a method of preparation of the catalyst based on copper compounds and zinc for low-temperature conversion of carbon monoxide by dry mixing dual core carbonate salt MCA granules [1].

Using this method, the preparation of the catalyst does not allow to reach the maximum activity because of the low content of the active component is copper, because the calcium aluminates are used to obtain a catalyst of high mechanical strength and their content is over 30%, which reduces the concentration of copper. This method is characterized by a large number of stages.

The closest in technical essence and the achieved result is a method for preparing a catalyst for carbon monoxide conversion by mixing a solution of ammonium carbonate complex of copper with magnesium oxide or zinc oxide with aluminum oxide or aluminum hydroxide at a weight ratio of copper ammonium carbonate complex of magnesium oxide or the amount of the compounds of zinc and aluminum is 1:0.25 to 0,9, and mixing is carried out at 55-110°C, pH 13-7 with subsequent drying of the catalyst mass at 110 to 120°C, annealing at 300 to 500°With and pelletizing [2].

The disadvantages of this method of preparation is that the use of aluminium-containing components of an oxide or hydroxide of aluminum does not allow to achieve their full chemical interaction with seinemaritime is to develop a method of producing catalyst based on copper compounds and zinc, to ensure its high activity and stability, and hence the service life.

This object is achieved in that the catalyst is obtained by mixing while heating to 80 to 90°With ammonium carbonate solutions of copper and zinc in a weight ratio of copper oxide: zinc oxide is from 1:1 to 7:1, the introduction of the obtained copper-zinc-ammonia-carbonate solution of aluminate of calcium and/or barium in a weight ratio of (CuO+ZnO) of from 1:19 to 1:2, with a ratio of aluminate of calcium to barium aluminate 1:1, followed by drying and pelletizing the catalyst mass.

The essence of this method of preparation of the catalyst is that during thermal decomposition of a solution of ammonium carbonate complexes of copper and zinc in suspension with the aluminates of calcium and/or barium is obtained ternary copper-zinc-alumosilicate or copper-zinc-Alymbaeva system with atomic distribution of all components.

Ammonium carbonate technology of preparation of the catalyst combines the positive aspects of the methods of mixing and coprecipitation. It allows to achieve a high degree of interaction between components, with formation of compounds of the precursors of the active state of the catalyst, and drop the limited solubility, can interact formed by the decomposition of a solution of ammonium carbonate complexes of copper and zinc hydroxocobalamin copper and zinc aluminates of metals during the whole decomposition process. This leads to the achievement of a high degree of interaction and atomic distribution of components in the resulting mass, which is a prerequisite for obtaining high-performance catalyst.

The proposed method consists in the following. Prepare ammonium carbonate solution of copper dissolution at 50-60°With metallic copper in ammonium carbonate solution with concentrations of ammonia - 120 g/l and carbon dioxide - 80 g/L. Next, prepare ammonium carbonate solution of zinc dissolution at 30-40°With metallic zinc in ammonium carbonate solution with concentrations of ammonia - 120 g/l and carbon dioxide - 80 g/L. Then mix the resulting solution and get an ammonium carbonate solution of copper and zinc concentrations of ammonia - 120 g/l, carbon dioxide - 80 g/l, si2+- 100 g/l and Zn2+- 50 g/l To the obtained copper-zinc-ammonia-carbonate solution (MCUCR), with the weight ratio of copper : zinc = 1:7-1:1, heated to 50°C under vigorous stirring, debate calcium in a weight ratio to the copper-zinc-ammonia-carbonate solution, equal to 1:2-1:19, when the ratio of calcium aluminate and barium aluminate, equal to 1:1.

The resulting suspensio heated to 90°C and stirred for 10 hours of continuing the Stripping gas mixture containing water vapor, ammonia and carbon dioxide.

The resulting mass is dried at a temperature of 90 to 120°C. the Mass is ground and pressed into tablets. The essence of the method is illustrated by the following examples.

Example 1. To 1000 ml of an ammonium carbonate solution with concentrations of NH3120 g/l and CO2- 80 g/l sprinkled 200 g finely powdered metallic copper, stir the solution to dissolve copper at 50-60°C. To 1000 ml of an ammonium carbonate solution with concentrations of NH3120 g/l and CO2- 80 g/l sprinkled 100 g finely powdered metallic zinc, heat the solution up to 30-40°C and stirred until complete dissolution of zinc. Mix the obtained solutions and get 2000 ml of a solution of ammonium carbonate complexes of copper and zinc at concentrations of NH3120 g/l2- 80 g/l, si2+- 100 g/l and Zn2+- 50 g/l To 500 ml of the obtained copper-zinc-ammonia-carbonate solution (MCUCR), heated to 50°C under vigorous stirring, carefully add p is 90°C and stirred for 10 hours, continuing the Stripping gas mixture (containing water vapor, ammonia and carbon dioxide). The resulting mass is dried at a temperature of 90 to 100°C. the Mass is ground and pressed tablets. Get catalyst the weight of the composition (in terms of metal oxide): CuO - 60%, ZnO - 30%, A12ABOUT3- 4%, BaO - 6%.

The Ratio Of CuO/ZnO=2:1.

The ratio of (CuO+ZnO)/metal aluminate =9:1.

Example 2. The catalyst prepared as in example 1, but in ammonium carbonate solution dissolve 160 g of copper and 180 g of zinc. And to the obtained solution MCUCR, with concentrations of 80 g/l si2+and 90 g/l Zn2+add to 18.7 g of barium aluminate. Get catalyst mass composition: CuO - 40%, ZnO - 45%, Al2ABOUT3- 6%, BaO - 9%.

The Ratio Of CuO/ZnO=1:1,125.

The ratio of (CuO+ZnO)/metal aluminate = 5,67:1.

Example 3. The catalyst prepared as in example 1, but in ammonium carbonate solution dissolve 200 g of copper and 28.6 g of zinc. And to the obtained solution MCUCR, with concentrations of 100 g/l si2+and 14.3 g/l Zn2+add 18 g of barium aluminate. Get catalyst mass composition: CuO - 70%, ZnO - 10%, Al2ABOUT3- 8%, BaO - 12%.

The Ratio Of CuO/ZnO=7:1.

The ratio of (CuO+ZnO)/aluminate met the thief dissolve 200 g of copper and to 71.5 g of zinc. And to the obtained solution MCUCR, with concentrations of 100 g/l si2+and 35,525 g/l Zn2+add 4.6 g of barium aluminate. Get catalyst mass composition: SIO - 70%, ZnO - 25%, Al2ABOUT3- 2%, BaO - 3%.

The Ratio Of CuO/ZnO = 2,8:1.

The ratio (IAR+Zn0)/metal aluminate = 19:1.

Example 5. The catalyst prepared as in example 1, but the solution MCUCR (with concentrations C2+- 100 g/l and Zn2+- 50 g/l) add a 5.25 g of calcium aluminate and 5.25 g of barium aluminate. Get catalyst mass composition: SIO - 60%, ZnO - 30%, Al2ABOUT3- 5.25%, and BaO - 3%, and Cao is 1.75%.

The Ratio Of CuO/ZnO = 2:1.

The ratio of (CuO+ZnO)/metal aluminate = 7:1

Example 6. The catalyst prepared as in example 1, but in ammonium carbonate solution dissolve 160 g of copper and 180 g of zinc. And to the obtained solution MCUCR, with concentrations of 80 g/l si2+and 90 g/l Zn2+add 9.5 g of barium aluminate and 9.5 g of calcium aluminate. Get catalyst mass composition: SIO - 40%, ZnO - 45%, Al2ABOUT3at 7.9%, BaO - 4.5% and Cao - 2,6%.

The Ratio Of CuO/ZnO = 1:1,125.

The ratio of (CuO+ZnO)/metal aluminate = 5,67:1.

Example 7. The catalyst prepared as in example 1, but in the ammonia-Carr>2+and 14.3 g/l Zn2+add 9 g of barium aluminate and 9 g of calcium aluminate. Get catalyst mass composition: SIO - 70%, ZnO - 10%, Al2O3- 10,5%, BaO - 6%, and Cao is 3.5%.

The Ratio Of CuO/ZnO = 7:1.

The ratio of (CuO+ZnO)/metal aluminate =4:1.

Example 8. The catalyst prepared as in example 1, but in ammonium carbonate solution dissolve 200 g of copper and to 71.5 g of zinc. And to the obtained solution MCUCR, with concentrations of 100 g/l si2+and 31,525 g/l Zn2+add 2.3 g of barium aluminate and 2.3 g of calcium aluminate. Get catalyst mass composition: SIO - 70%, ZnO - 25%, Al2ABOUT3of 2.6%, BaO - 1.5% and Cao - 0,9%.

The Ratio Of CuO/ZnO = 2,8:1.

The ratio of (CuO+ZnO)/metal aluminate = 19:1.

Example 9. The catalyst prepared as in example 1, but the solution MCUCR with concentrations of 100 g/l CuO and 50 g/l ZnO added to 10.5 g of a powder of calcium aluminate. Get catalyst mass composition: SIO - 60%, ZnO - 30%, Al2ABOUT3- 6,5%, CaO - 3,5%.

The Ratio Of CuO/ZnO =2:1.

The ratio of (CuO+ZnO)/metal aluminate = 7:1.

Example 10. The catalyst prepared as in example 1, but in ammonium carbonate solution dissolve 160 g of copper and 180 g of zinc. And to the resulting process is Torno weight of the composition: SIO - 40%, ZnO - 45%, Al2ABOUT3- 9.75% and CaO - of 5.25%.

The Ratio Of CuO/ZnO = 1:1,125.

The ratio (Si+Zn0)/metal aluminate = 5,67:1.

Example 11. The catalyst prepared as in example 1, but in ammonium carbonate solution dissolve 200 g of copper and 28.6 g of zinc. And to the obtained solution MCUCR with concentrations of 100 g/l si2+and 14.3 g/l Zn2+add 18 g of calcium aluminate. Get catalyst mass composition: SIO - 70%, ZnO - 10%, Al2ABOUT3- 13% and CaO - 7%.

The Ratio Of CuO/ZnO = 7:1.

The ratio of (CuO+ZnO)/metal aluminate = 4:1.

Example 12. The catalyst prepared as in example 1, but in ammonium carbonate solution dissolve 200 g of copper and to 71.5 g of zinc. And to the obtained solution MCUCR with concentrations of 100 g/l si2+and 35.5 g/l Zn2+added 4.6 g of calcium aluminate. Get catalyst mass composition: SIO - 70%, ZnO - 25%, Al2ABOUT3- 3,25%, and CaO is 1.75%.

The Ratio Of CuO/ZnO = 2,8:1.

The ratio of (CuO+ZnO)/metal aluminate = 19:1.

Example 13. The catalyst prepared as in example 1, but in ammonium carbonate solution dissolve 150 g of copper and 150 g of zinc. And to the obtained solution MCUCR with a concentration of 75 g/l si2+and 75 g/l Zn2+ASS="ptx2">The Ratio Of CuO/ZnO = 1:1.

The ratio of (CuO+ZnO)/metal aluminate = 2,33:1.

The composition of the catalyst in terms of wt.% and the results are given in tables 1 and 2.

Testing of catalysts on the activity in the process of conversion of carbon monoxide with water vapor was conducted in a laboratory setup flow type when the gas composition, vol.%: WITH 10,9; Not 89,1; flow rate 15000 h-1; steam : gas ratio is 0.2:0,25.

From the test results it is seen that the activity of the catalysts tested at 200°C, prepared according to the proposed technology, in all cases higher than that of the prototype, to control 6-64%, depending on the composition, activity after overheating higher than that of the prototype, 10-46%, that is, this method provides a higher resistance to overheating.

Here is the example 14 (comparative) of the samples prepared according to example 3 of the description to the author's certificate No. 596278, which was the prototype for the above application.

Example 14 (comparative). In a reactor equipped with a mixer, pour 5 liters of water, heat it up to 75-80°C and add to 2.3 l of a solution of ammonium carbonate complex of copper containing, g/l: 120 copper (156 in terms of nrate of aluminum oxide and 325 g of zinc oxide. When mixing keep the temperature in the reactor 75-110°C.

About the end of the reaction is judged by the absence of copper ions and ammonia in the filtrate and the pH of the solution is equal to 7.6-7,0. The obtained catalyst mass is dried at 110-120°C and calcined at 330-350°C.

Receive 1.0 kg of a catalyst mass, containing, wt.%: 35,0 copper oxide; 32.5 zinc oxide; 32.5 aluminum oxide. The Ratio Of CuO/ZnO = 1,07:1. The ratio of (CuO/ZnO)/luminet metal = 2,08:1.

The composition of the catalyst in terms of wt.% and the results of tests similar to the methods applied to the test examples 1-13 are given in tables 1 and 2.

Sources of information

1. RF patent №1511909, MKI401 J 37/04, prior. 26.10.87,

2. Auth. mon. THE USSR №596278, MKI201 J 37/04, prior. 03.05.76, (prototype).

The preparation method of the catalyst for carbon monoxide conversion, comprising mixing a solution of ammonium carbonate complex copper compounds based on zinc and aluminium, with subsequent drying and pelletizing the catalyst mass, characterized in that a solution of ammonium carbonate complex of copper mixed with a solution of ammonium carbonate complex of zinc when heated to 80-90°C in the weight and barium in a weight ratio to the sum of (CuO+ZnO) of from 1:19 to 1:2 when the ratio of aluminate of calcium to barium aluminate 1:1.



 

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