RU1732537C - Process for preparing copper-zinc-manganese catalyst - Google Patents

Abstract

FIELD: catalytic chemistry. SUBSTANCE: the catalysts is prepared by mixing in an ammonia-carbonate solution of oxides or basic carbonate or metallic copper and zinc followed by adjustment of the moisture content to 1-30% addition of a manganese compound such as manganese carbonate and activated carbon to said mixture, cooling to 20-30 C, addition of Al₂O₃ of calcium aluminate. The weight ratio calculated as oxides) Cu, Zn, Mn, carbon and Al is 1: (0.4-1.2): (0.001-0.6):(0.01-0.04):(0.1-2). The catalyst mixture which is then dried in the air at 15-25 C for 50-72 hours or dried at 70-130 C for 2-6 hours, and granules are passivated at 100-200 C in an air current. If a catalyst is obtained for synthesizing methanol, after the drying operation, the granules are impregnated with aqueous nitric acid (the water and HNO₃= 1:(0,01-0,2) ratio is 1:(0.01-0.2) and best treated at 100-320 C in an air current or a mixture thereof with nitrogen oxides [the ratio is 1: (0.1-1)] for 1-6 hours. There conditions improve catalyst activity by 1.1-1.3 times and thermostability by 28-46% EFFECT: improved catalyst activity and thermostability. 2 cl, 3 tbl

Description

 The invention relates to methods for producing catalysts based on compounds of copper, zinc, aluminum for chemical processes: conversion of carbon monoxide with water vapor, methanol synthesis, oxygen conversion of carbon monoxide, purification of waste gases from carbon monoxide and organic impurities.

 The purpose of the invention is the preparation of a catalyst with increased activity and thermal stability due to a certain sequence of stages of preparation and modes of their implementation.

Example 1. 0.382 kg of basic copper carbonate and 0.088 kg of metal zinc powder are loaded into a mixing apparatus, ammonia-carbonate solution is added in an amount of 1 dm ³ with a concentration of ammonia 0.12 kg / dm ³ and carbon dioxide 0.11 kg / dm ³ , mixed at 80 ^about C, evaporated to a moisture content of 5 wt. was added 0.073 kg of manganese carbonate, 0.0054 kg of activated carbon, kneaded, cooled ^to 25 ° C, mixed with 0.55 kg of aluminum oxide at weight ratios of components (calculated as oxides) of copper oxide: zinc oxide: manganese oxide: activated charcoal : alumina 1: 0.4: 0.2: 0.023-2.0. The mass was formed into pellets, dried at ¹⁰⁰ ° C for 3 hours, moistened with water, dried at ¹⁰⁰ ° C for 3 hours to obtain a catalyst having a bulk density of 0.97 kg / dm ³ of composition, by weight. CuO 27.6, ZnO 11.2, MnO ₂ 5.57, activated carbon 0.63, Al ₂ O ₃ 55; porosity 66%
Measure 0.4 dm ³ catalyst and charged to a carbon oxide conversion apparatus reduced at 200-240 ^{° C} the converted gas composition, by weight. CO 3.0 ± 1.5; CO2 ₂ 18 ± 1.5; H ₂ 59.0 ± 1.5; N ₂ 19.0 ± 1.5; (Ar + CH ₄ ) 1.0.

The catalyst was tested in the conversion of carbon monoxide at temperatures of 220-230 ^{° C,} a ratio of steam: gas 0.6 volume ckorocti 6000 hr ^-1, a pressure of 2.8 MPa for 72 hours with a consistent reduction in temperature to 180-200 ^{° C} and test for 24 hours with overheating at 370-400 ^C for 8 hours, return to the previous test mode (steam: gas is 0.6, temperature 220-230 ° ^C).

The residual content of carbon monoxide, vol. 0,12-0,14 at start, after 72 hours of 0.13-0.15 at a temperature of 180-200 ^{° C} 0,16-0,17 at a ratio steam: gas 0,16-0 0.4 18, after overheating at 370-400 ^{° C} for 8 hours and return to the previous test mode 0.13-0.15.

The catalyst is passivated, unloaded from the apparatus and the volume of the catalyst is measured, after testing it is 0.4 dm ³ , porosity 68%
The catalyst is tested in the production of caprolactam, in the purification of waste gases at a space velocity of 12000-20000 nm ³ / h of composition, vol. oxygen 0.5-3, carbon monoxide 0.7-2.5, organic compounds per cyclohexane 0.05-0.1, nitrogen and carbon dioxide the rest. At 360-380 ^о С the degree of gas purification from carbon monoxide 98%; the degree of gas purification from organic compounds 70%
Here and in the following examples, to evaluate the performance of the catalyst, the concept of thermostability of the catalyst is introduced, which characterizes the change in activity as a result of tests from beginning to end with intermediate changes in the test mode and is expressed as the ratio of the average residual percentage of carbon monoxide at the beginning of the test to the average residual percentage of carbon monoxide at the end of the test (0.13-0.14) x 100 92.8%
PRI me R 2. Prepare the catalyst, restore and test, as in example 1, but take the ratio of the components (in terms of oxides) copper oxide: zinc oxide: manganese oxide: activated carbon: aluminum oxide 1: 1,2: 0.02: 0.018: 0.07. As zinc and copper components, metallic copper and zinc oxide are used, which are mixed in reactors with intense heat and mass transfer in the presence of 1.0 dm ^{3 of an} ammonia-carbonate solution with an ammonia content of 0.13 kg / dm ³ , carbon dioxide 0.12 kg / dm ^3, feed air suspension with a temperature of 70-73 ^{° C} and a flow rate of 0.4-0.5 dm ³ / h for 3.5 hours, the precipitate is separated, is adjusted to a moisture content of 2.0% was mixed with carbon and manganese activated charcoal, cooled ^to 30 ° C, admixed with calcium aluminate, and molded into granules, dried at ²⁰ ° C, humidif nyayut provyalivayut water and at ²⁰ ° C for 72 hours. A catalyst having a bulk density of 1.32 kg / dm ^3, a composition by weight. CuO 42.43, ZnO 51.34, MnO 0.94, activated carbon 0.79, Al ₂ O ₃ 3.0, CaO 1.5. The porosity of the catalyst 69%
The residual content of carbon monoxide, vol. 0.11-0.13 early testing, after 72 hours of testing 0.12-0.15 at a temperature of 180-200 ^{° C} 0,12-0,15, at low steam ratios: 0,13-0 gas, 15, after overheating at 370-400 ^о С 0.12-0.14; thermal stability of 92.3% of the volume of the catalyst after unloading of 0.4 DM ³ . Porosity 70%
When tested in the treatment of waste gases in the production of caprolactam, the degree of purification of gas from carbon monoxide is 99%; The degree of purification from organic compounds is 72%
The catalyst tested in the methanol synthesis process in a model apparatus at conditions: Catalyst volume of 2 cm ^3, fraction 2-3 mm, pressure 250 bar, temperature 240, 260 ^{° C,} feed gas composition, vol. 6.5 CO _2, CO, 25,0, N ₂ 12,5, H ₂ 55,0, (Ar + CH ₄₎ to 1. Draining is methanol, ml: at ²²⁰ ° C 0.5 at 240 12 0, at 260 ^{° C} 10.2.

The catalyst sample was impregnated with an aqueous solution of nitric acid at a ratio of water to nitric acid is 1: 0.2, and heat treated at 320 ^{° C} for 1 h and tested in the same conditions. Draining crude methanol amounts ml: at ²²⁰ ° C 1.0 at 240 ^{° C} of 13.4, at 260 ^{° C.} 11.7.

The catalyst sample was impregnated with an aqueous solution of nitric acid at a ratio of water to nitric acid is 1: 0.01, and heat treated at 100 ° ^C. Draining crude methanol amounts ml: at ²²⁰ ° C 0.8 at 240 ^{° C} of 12.9, with 260 ^about C 11.0.

PRI me R 3. The catalyst is prepared, restored and tested, as in example 1, but the components are taken (in terms of oxides) at a ratio of copper oxide: zinc oxide: manganese oxide: activated carbon: calcium aluminate 1: 0.89 : 0.6: 0.04: 0.73, the mass adjusted to a moisture content of 30 wt. The granules are dried at ⁷⁰ ° C for 6 hours. The catalyst was obtained with a bulk density of 0.98 kg / dm ^3, a composition by weight. CuO 28.2, ZnO 25.2, MnO ₂ 16.9, activated carbon 1.13, Al ₂ O ₃ 22.62, CaO 5.48, porosity 70%
The residual content of carbon monoxide, vol. at the beginning of the test 0.13-0.15, 0,14-0,16 after 72 hours, at a temperature of 180-200 ^{° C} 0,16-0,18 under reduced ratio steam: gas 0,18-0,21 , after overheating at 370-400 ^о С 0.15-0.17. Thermostability is 87.5%. The volume of the catalyst after unloading is 0.4 dm ³ , porosity 70%
When tested on waste gas purification in the production of caprolactam, the degree of gas purification from carbon monoxide is 98.2%. The degree of gas purification from organic compounds is 69%
Example 4. The catalyst is prepared by reduction and tested for the conversion of CO, as in example 1, for the synthesis of methanol, it is activated and tested as in example 2, but metal copper is used as the copper component in the ratio of the components copper oxide: zinc oxide : manganese oxide: activated carbon: aluminum oxide 1: 0.7: 0.4: 0.024: 0.3.

The precipitate was adjusted to a moisture content of 15 wt. The granules are dried at 130 ^C. A catalyst having a bulk density of 0.84 kg / dm ^3, a composition by weight. CuO 39.62, ZnO 27.72, MnO ₂ 15.84, activated carbon 0.98, alumina 11.1, CaO 4.74. Porosity 70% Surface 82 m ² / g.

The residual content of carbon monoxide, vol. 0,12-0,14 at start, after 72 hours of testing 0.13-0.15 at 180-200 ^C. 0,14-0,18 under reduced ratio steam: gas 0,17-0,19 , after overheating at 370-400 ^о С 0.14-0.16. Thermostability of 86.6%. The volume of catalyst after unloading is 0.4 dm ³ , the porosity of 70%, the surface is 80 m ² / g.

When cleaning the waste gases from the CO purification rate 98.7% Degree of purification from organic impurities of 69% methanol is Draining ml: at ²²⁰ ° C 1.2 at 240 ^{° C} of 8.2, at 260 ^C. 10.3.

Activate the catalyst in a stream of nitrogen oxides in a ratio of air: NO _x of 1: 1 and temperature of 200 ° ^C. During tests of methanol is drained, ml: at 220 ^o C of 1.4, at 240 ° ^C of 9.6, at 260 ^C. 11 , 2.

Activate the catalyst in a stream of nitrogen oxides in a ratio of air: NO _x of 1: 0.1 and at a temperature of 320 ° ^C. During tests of methanol is drained, ml: at ²²⁰ ° C 1.3 at 240 ^{° C} of 10.0, at 260 ^o C 11.8.

PRI me R 5. The catalyst is prepared, restored and tested, as in example 2, but the ratio of the components is copper oxide: zinc oxide: manganese oxide: activated carbon: aluminum oxide 1: 0.67: 0.001: 0.023: 0, 58, calcium aluminates are used as the aluminum component (VTs-70 according to TU-20-25-26, containing up to 7% Cr ₂ O ₃ ).

Get the catalyst with a bulk density of 0.87 kg / DM ³ composition, wt. CuO 40, ZnO 27.2, MnO ₂ 0.04, activated carbon 0.92, Al ₂ O ₃ 23.4, CaO 6.44, Cr ₂ O ₃ 2. Porosity 65%
The residual content of carbon monoxide, vol. 0.11-0.13 early testing, after 72 hours of testing 0,13-0,14 at 180-200 ^{° C} of 0.14-0.15 at a ratio steam: gas 0,14-0 0.4 15 after overheating at 370-400 ^о С 0.12-0.14. Thermostability is 92.3. The volume of the catalyst after unloading 0.4 DM ^{3 the} porosity of 65%
When cleaning of waste gases in the production of caprolactam purification rate of CO is 99% degree of purification from organic impurities of 69.4% methanol is Draining ml: at ²²⁰ ° C 0.8 at 240 ^{° C} 7.0 at 260 ^C. 9 , 0.

The catalyst sample was impregnated with a solution of nitric acid at a ratio of water to nitric acid is 1: 0.1, heat treated at 200 ° ^C. Draining is methanol, ml: at ²²⁰ ° C 0.9 at 240 ^{° C} of 8.5, at 260 ^C. 10.4.

PRI me R 6. The catalyst is prepared, restored and tested in the conversion of carbon monoxide and purification of waste gases, as in example 1, in the synthesis of methanol, as in example 2, with the difference that the ratio of the components is copper oxide: zinc oxide : manganese oxide: activated carbon: aluminum oxide 1: 0.55: 0.001: 0.015: 0.81, but basic zinc carbonate is used as the zinc component, calcium aluminates are used as the aluminum component. Get the catalyst with a bulk density of 1.0 kg / DM ^{3 the} composition of the mass. CuO 60.38, ZnO 33.65, MnO ₂ 0.06, activated carbon 0.9, Al ₂ O ₃ 4.2, CaO 1.3. Porosity 63%. The residual content of carbon monoxide at the beginning of the test is about. 0.11-0.13, after 72 hours of testing 0,13-0,14, at temperatures of 180-200 ^{° C} 0,12-0,14 at a ratio steam: gas 0.13-0.15 0.4 , after overheating at 370-400 ^о С 0.11-0.14. Thermostability of 96% of the volume of the catalyst after unloading is 0.4 DM ³ . Porosity 64%
When cleaning of waste gases in the production of caprolactam purification rate of CO is 0.9% Degree of purification from organic impurities 71% methanol Draining constitutes ml: at ²²⁰ ° C 2.8 at 240 ^{° C} of 11.4, at 260 ^{° C} 12 ,1. Activate the catalyst in a stream of nitrogen oxides in a ratio of air: NO _x of 1: 0.4, temperature: 150 ^C. Draining is methanol, ml: at ²²⁰ ° C 2.0 at 240 ^{° C} of 13.1, at 260 ^{° C} 12 , 7.

The catalyst was impregnated with a solution of nitric acid in the ratio H ₂ O: HNO ₃ 1: The 0.06 and heat treated at 310 ° ^C. Draining is methanol, ml: at ²²⁰ ° C 1.9 at 240 ^{° C} of 12.8, at ^about 260 C 12.0.

PRI me R 7. The catalyst is prepared, restored and tested, as in example 2, but take the ratio of components (in terms of oxides) copper oxide: zinc oxide: manganese oxide: activated carbon: aluminum oxide 1: 0.54: 0.001: 0.01: 0.08, copper and zinc components are used as basic carbonates. Granules provyalivayut at ²⁵ ° C for 30 hours. A catalyst having a bulk density of 1.2, the composition by weight. CuO 60.34, ZnO 33.0, MnO ₂ 0.06, activated carbon 0.6 Al ₂ O ₃ 4.8, CaO 1.2. The porosity of the catalyst 67%
The residual content of carbon monoxide, vol. 0.10-0.12 early testing, after 72 hours of testing 0.13-0.15 at a temperature of 180-200 ^{° C} 0,14-0,16 at a ratio steam: gas 0.4 0,14- 0.16, after overheating 0.13-0.15. Thermostability of 79.6% of the volume of the catalyst after unloading of 0.4 DM ³ . Porosity 67%
When tested in the treatment of waste gases in the production of caprolactam, the degree of purification of gas from carbon monoxide is 99%; The degree of purification from organic impurities is 73%
In testing the sample in the methanol synthesis process is drained, ml: at ²²⁰ ° C 2.3 at 240 ^{° C} of 13.0, at 260 ^{° C.} 11.0.

After activation, the catalyst in the flowing mixture of air and nitrogen oxides in a ratio of 1: 0.6 at a temperature of 210 ^{° C} and subsequently tested in the methanol synthesis process plums methanol, ml: at ²²⁰ ° C of 3.4, at 240 ^C. 13.4 , at 260 ^{° C} 11.0.

The catalyst was impregnated with an aqueous solution of nitric acid at a ratio of water to nitric acid is 1: 0.07, heat treated at ¹²⁰ ° C, pouring methanol, ml: at ²²⁰ ° C 3.3 at 240 ^{° C} of 13.5, at 260 ^{° C} 11 , 2.

PRI me R 8. The catalyst is prepared, restored and tested, as in example 7, but the granules of the catalyst are heat treated at 450 ^about C. Activated carbon completely burns out at this temperature. Get the catalyst with a bulk density of 0.79 kg / DM ^{3 the} composition, wt. CuO 60.7, ZnO 34.11, MnO ₂ 0.06, Al ₂ O ₃ 3.83, CaO 1.3. The catalyst loading volume is 0.4 dm ³ . Porosity 68%
The residual content of carbon monoxide, vol. 0.22-0.24 early testing, after 72 hours of testing 0,24-0,26, at temperatures of 180-200 ^{° C} 0,25-0,29 at a ratio steam: gas 0.4 0,31- 0.33, after overheating at 370-400 ^о С 0.36--0.38. Thermostability is 59.4. The volume of catalyst after unloading 0.38 DM ³ . Porosity 67%
When testing the catalyst on waste gases of caprolactam production, the degree of purification from carbon monoxide is 96%. The degree of purification from organic compounds is 64%.
In the test sample in the production of methanol is drained, ml: at ²²⁰ ° C 0.1 at 240 ^{° C} 5.0 at 260 ^C. 6.2.

After activation, the catalyst in the flowing mixture of air and nitrogen oxides in a ratio of 1: 1 and temperature of 400 ^{° C} methanol is drained, ml: at ²²⁰ ° C 0.0 at 240 ^{° C} of 3.0, at 260 ^C. 6.8.

PRI me R 9. The catalyst is prepared, restored and tested, as in example 2, but as the copper component take the main carbon dioxide copper "malachite". A complexing solution is prepared by dissolving malachite in an ammonia solution with an ammonia concentration of 0.12 kg / dm ³ . The catalyst is dried at 250 ^about C.

Get the catalyst with a bulk density of 1.2 kg / DM ^{3 the} porosity of the catalyst 67%
The residual content of carbon monoxide, vol. 0,11-0,14 at start, after 72 hours of testing 0.14-0.15 at 180-200 ^{° C} of 0.14-0.15 at low steam ratios: gas 0,15-0,16 , after overheating at 370-400 ^о С 0.15-0.17. Thermostability of the catalyst 78% The volume of catalyst after unloading of 0.39 DM ³ . Porosity 69%
When testing the catalyst for purification from waste gases of caprolactam production, the degree of purification from carbon monoxide is 98%. The degree of purification from organic compounds is 68%.
When the catalyst tested in the methanol synthesis process methanol is drained, ml: at ²²⁰ ° C 0.3 at 240 ^{° C} of 8.6, at 260 ^C. 10.3.

After activation, the catalyst in the flowing mixture of air and nitrogen oxides in a ratio of air: NO _x of 1: 0.17 and a temperature of 180 ^{° C} methanol is drained, ml: at ²²⁰ ° C 0.6 at 240 ^{° C} of 12.6, at 260 ^o C 11.0.

 PRI me R 10. The catalyst is prepared, restored and tested in the conversion of carbon monoxide and purification of waste gases, as in example 1, but the ratio of the components is copper oxide: zinc oxide: manganese oxide: activated carbon: aluminum oxide 1: 0, 5: 0.6: 0.04: 0.1.

Get the catalyst with a bulk density of 1.03 kg / DM ^{3 the} composition, wt. CuO 44.64, ZnO 22.32, MnO2 26.8, activated carbon 1.78, Al ₂ O ₃ 4.46. Porosity 62% Residual carbon monoxide, vol. 0,09-0,1 at start, after 72 hours of testing 0.11-0.12 at temperatures of 180-200 ^{° C} 0.11-0.12 at a ratio steam: gas 0.4 0,12- 0,13, after overheating at 370-400 ^о С 0,11-0,13. Thermostability 97%
When cleaning waste gases in the production of caprolactam, the degree of purification from CO is 99%; the degree of purification from organic impurities is 79%
PRI me R 11 (known). In a known manner, 0.101 kg of copper oxide is loaded into the mixing apparatus, 0.5 l of an aqueous solution of ammonia with a concentration of 15% is poured, and ammonium oxalates with a concentration of 7% are then added 0.26 kg of zinc-aluminum-manganese alloy (Zn: Cu: Al: Mn1: 0.93 : 0.02: 0.02) with a ratio of copper oxide to its 1: 0.4, are added 0.05 kg of chromium oxide was stirred for 0.5 hours until a temperature of 80 ° ^C.

The catalyst mass is molded and passivated at 140 ^about C. Get the catalyst with a bulk density of 1.11 kg / DM ³ , composition, wt. CuO 53.5, ZnO 34.3, Al ₂ O ₃ 1.0, Cr ₂ O ₃ 10.5, MnO ₂ 0.7.

The catalyst was stored for 5 months before testing. The residual content of carbon monoxide, vol. 0.11-0.13 early testing, after 72 hours of testing 0,14-0,16, at a temperature of 180-200 ^C. 0,18-0,2 at a ratio steam: gas 0.4 0.22 0.24, after overheating at 370-400 ^о С 0.22-0.26.

The volume of catalyst after loading 0.36 dm ³ . Porosity 70% Thermal stability 50.0% The catalyst granules are coated with soot deposits.

When testing the catalyst on waste gases of caprolactam production, the degree of purification from carbon monoxide is 89%; the degree of purification from organic compounds is 65%
In testing the sample in the methanol synthesis process is drained, ml: at ²²⁰ ° C 0.0 at 240 ^{° C} of 3.0, at 260 ^C. 5.0.

After activation, the catalyst in the flow of air and a mixture of nitrogen oxides in a ratio of 1: 1 and temperature of 160 ^{° C} methanol is drained, ml: at ²²⁰ ° C 0.6 at 240 ^{° C} 4.0 at 260 ^C. 6.0.

 Physico-chemical characteristics, technological process norms, catalyst activity in the process of steam conversion of carbon monoxide, oxygen conversion of carbon monoxide and methanol synthesis are given in Tables 1-3.

As follows from the presented data, the proposed method allows to increase the activity of the catalyst (especially at 180-200 ^about C) 1.1-1.3 times, with a reduced ratio of steam: gas (0.4) of 1.37-1.57 times, increase the thermal stability by 28-46% in the production of caprolactam, increase the degree of purification of waste gases from carbon monoxide by 8-10% from organic impurities by 4-5%, increase the productivity of the catalyst in the process of methanol synthesis by 1.8-2 times, and after modifying the granules with nitric acid or nitrogen oxides followed by heat treatment of the granules Inteza at 220 ° ^C.

 In addition, the proposed method allows to simplify the process of forming granules, to form the structural characteristics of the catalyst, to restore and maintain the copper component in the active phase for a long time, at least 1 year.

Claims (2)

1. A METHOD FOR PREPARING A MEDICAL ZINC MANGANese CATALYST, including mixing at an elevated temperature in an ammonia-carbonate solution of oxides or basic carbonates, or metallic copper and zinc, adding a compound of manganese and aluminum oxide or calcium aluminate, forming a catalyst mass and passivation of 200 granules in an air stream ^o C, characterized in that, in order to obtain a catalyst with increased activity and thermal stability, the mixture obtained after mixing copper and zinc compounds is brought to a moisture content of 1 30 wt. add to it a manganese compound in the form of manganese carbonate and additionally activated carbon, the mixture is cooled to 20-30 ^o C and aluminum oxide or calcium aluminate is added in a weight ratio (in terms of oxides) copper oxide zinc oxide manganese activated carbon aluminum oxide 1 (0 , 4 1.2) (0.001 0.6) (0.01 0.04) (0.1 2.0), after molding, the granules are dried in air at 15 25 ^o C for 50 72 hours or dried at 70 130 ^o C for 2 to 6 hours 2. The method according to p. 1, characterized in that, in order to obtain a catalyst with increased activity in the process of methanol synthesis, the granules after drying are impregnated with an aqueous solution of nitric acid with a ratio of water nitric acid 1 (0.01 0.2) and heat treated at 100 320 ^o C in a stream of air or a mixture of air and nitrogen oxides in the ratio of air nitrogen oxides 1 (0.1 to 1.0) for 1 to 6 hours

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