Method of preparing catalyst for low-temperature carbon monoxide-water steam conversion process

FIELD: shift reaction processes and catalysts.

SUBSTANCE: invention concerns preparing catalysts for low-temperature conversion of carbon monoxide, which catalysts can be used in industrial nitrogen-hydrogen mixture generation process for ammonia synthesis. Catalyst is prepared by mixing components containing aluminum hydroxide, copper, and zinc followed by mechanical activation, drying, and calcination of granules, wherein copper- and zinc-containing components utilized are metallic copper and zinc powders and mechanical activation of components is accomplished by passing gas mixture containing carbon dioxide, ammonia, oxygen, and water steam at molar ratio 1:(0.22-1.1):(0.12-0.35):(0.13-0.24), respectively. Catalyst activity is thus increased by 6.4 to 12.3%.

EFFECT: increased catalyst activity, eliminated formation of waste water, and reduced number of process operations (by a factor of two and a half).

1 tbl, 3 ex

 

The technical field

The invention relates to a method for preparing catalysts for low-temperature conversion of carbon monoxide, which can be used in industry for preparation of nitric mixture for the synthesis of ammonia.

The level of technology

There is a method of preparation of the catalyst for redox processes, including dry mixing dual core carbonate salts of copper and zinc with calcium aluminates and, if necessary, with a basic Nickel carbonate, compaction, tableting, the crop has wilted or after dry mixing plasticization using as a plasticizer of an aqueous solution containing boric acid, water-soluble nonionic surfactant and ammonium water, extruding, drying or the crop has wilted, hydrothermal and thermal treatment of the granules, and use a double major carbonate salt comprises a mixture of phases gidroksicarbonata zinc and copper with the structure type of aurichalcite (ZnCu)5(CO3)3(OH)6(A) and gidroksicarbonata copper and zinc rosasite (CuZn)2(CO3)(OH)3(P)content in the catalyst, depending on its destination corresponds controlled rentgenograficheski the ratio of integrated intensity of diffraction lines was the index [400] (J A) to the integrated intensity of the diffraction line rosasite with index [020] (JP) and is in the range of 0.2 to 9.5. [Patent Ru 2172210 C1, B01J 23/80, 37/04, publ. BI No. 23, 2001].

The disadvantage of this method is the large number of technological stages of the process, using as raw material a double salt of copper and zinc can lead to contamination of catalyst products, from which he received the double salt. The catalyst prepared according to this technology, has poor activity at t=200°C.

There is a method of preparation of the 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 80-90°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 [Patent Ru 2241540 C2, B01J 37/04, publ. BI No. 33, 2004].

The disadvantages of this method are the complexity and duration of the technological process, a significant amount of wastewater. The catalyst prepared according to this technology, has nedostatochnosty at t=200° C.

Closest to the proposed invention to the technical essence and the achieved result, that is the prototype, is a method for preparing a catalyst for low-temperature conversion of carbon monoxide with water vapor, comprising a mixture of oxide or aluminum hydroxide with zinc oxide and ammonium carbonate complex of copper, followed by drying, calcination catalytic mass and molding. The alumina before the mixture is dispersed in an aqueous ammonia solution before the formation of 10-20 wt.% aluminum hydroxide is mixed with other components and add ammonium molybdate, is dispersed to the complete removal of ammonia. Then 5-15 wt.% the obtained catalytic mass is stirred with an aqueous solution of polyvinyl alcohol powder obtained by annealing the rest of catalytic mass [As. Su # 1524920 A1, B01J 37/04, 23/88, 23/80, publ. BI No. 44, 1989].

The disadvantages of the prototype should include a multi-stage and complexity of the technological process, insufficient activity of the catalyst at low temperatures, the use in the preparation of deficient compounds of molybdenum

The invention

The objective of the invention is to provide a method of producing a catalyst for low-temperature conversion of carbon monoxide with water vapor, which has a higher activity is, with the reduction in the number of technological operations and with the exception of sewage.

The problem is solved in the proposed method of producing a catalyst for low-temperature conversion of carbon monoxide with water vapor, comprising a mixture of components containing aluminum hydroxide, copper and zinc, mechanical activation, molding, drying and calcination of the pellets, in which the copper - and zinc-containing components using metal powders of copper and zinc, and the mechanical activation of components is carried out by passing a gas mixture containing carbon dioxide, ammonia, oxygen and water vapor [CO2:NH3:O2:H2O], when the molar ratio of component - 1:0,22÷1,1:0,12÷0,35:0,13÷0,24, respectively.

Information confirming the possibility of carrying out the invention.

Example 1

To prepare 30 g of the catalyst take metal powders of copper, zinc and powder of aluminum hydroxide in quantity is 10.68; 7,33; 7,72 g, respectively, placed in a tumbler mixer mills, there is loads of copper grinding media. During mechanochemical activation through a fitting located on the cover glass of vibration mills, the reaction volume serves gas mixture: carbon dioxide, ammonia, oxygen, water vapor, at a molar ratio of CO2NH 3:O2:H2O- 1:0,22:0,12:0,13.

The temperature of synthesis is 100°C.

During the course of mechanochemical synthesis is the formation of the double carbonate salts of copper and zinc. The resulting hydrocarbons are subjected to drying at 110°C, for 2 hours. The dried intermediate tabletirujut under the pressure of 0.2 MPa and calcined at 200°C for 2 hours. The resulting catalyst has the following composition, wt.%: CuO - 45%; ZnO - 30%; Al2About3- 25%.

Example 2

The catalyst is prepared analogously to example 1 with the only difference that pass the gas mixture of the following composition (molar ratio): CO2:NH3:O2:H2O - 1:0,51:0,35:0,18. The resulting hydrocarbons are subjected to drying at 100°C for 1.5 hours. The dried intermediate tabletirujut under the pressure of 0.22 MPa and annealed at 210°C for 2.3 hours. The resulting catalyst has the following composition, wt.%: CuO - 45.2%; ZnO - 29.7%; Al2O3- 25.1%.

Example 3

The catalyst is prepared analogously to example 1 with the only difference that pass the gas mixture of the following composition (molar ratio): CO2:NH3:O2:H2O - 1:1,1:0,26:0,24. The resulting hydrocarbons are subjected to drying at 120°C for 2.5 hours. The dried intermediate tabletirujut under pressure of 0.25 MPa and annealed at 240°C for 2.5 hours. who received the catalyst has the following composition, wt.%: CuO - 44.9%; ZnO - 30.2%; Al2About3- 24.9%.

The activity of the catalyst samples was evaluated by the degree of conversion of CO in the reaction of conversion of carbon monoxide with water vapor in the hydrogen. Test conditions: temperature 200°s, steam: gas ratio = 1, the volumetric rate of gas 15000 h-1. The composition of the gas, vol.%: WITH 12,5; CO29,4; N255,0; Not the rest [of Industrial catalysts. Materials coordination center. Issue 5. Novosibirsk, 1976, p.78].

The table shows data on the activity of the catalyst and characteristics of the method of preparation.

Table
Example № p/pThe catalyst activity (degree maturing at t=200°)The number of technological operationsThe amount of waste water per 1 ton of catalyst,

m3/t
Example 196,44-
Example 294,74-
Example 390,54-
The placeholder84,1102-3

The table below shows that the use of the claimed invention increases the activity of the catalyst 6.4-12.3 per cent, in addition, excluding the t wastewater generation, and also reduces the number of technological operations in 2.5 times.

The preparation method of catalyst for low-temperature conversion of carbon monoxide with water vapor, comprising a mixture of components containing aluminum hydroxide, copper and zinc, mechanical activation, molding, drying and calcination of the pellets, characterized in that as the copper - and zinc-containing components using metal powders of copper and zinc, and the mechanical activation of components is carried out by passing a gas mixture containing carbon dioxide, ammonia, oxygen and water vapor, at a molar ratio of components 1:0,22÷1,1:0,12÷0,35:0,13÷0,24 respectively.



 

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1 tbl

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1 tbl

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1 tbl

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

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