SU806106A1 - Method of catalyst for carbon oxide conversion or methanol synthesis - Google Patents

Description

one

The invention relates to methods for the regeneration of catalysts for the conversion of carbon monoxide or methanol synthesis, containing compounds of copper, zinc, aluminum, chromium, magnesium, manganese, which have lost catalytic activity as a result of thermal deactivation, regeneration or loss of mechanical strength.

 A known method for the regeneration of a zinc-chromed catalyst for the conversion of carbon monoxide by heating the catalyst lost the actuality of the catalyst to 180-200 0 in a current of a vapor-gas mixture containing nitrogen or carbon dioxide with a steam: gas ratio of 4-7. gas mixture of oxygen or air and increasing the temperature of the catalyst to 280-300 ° C 1.

The closest to the proposed method is the regeneration of a catalyst for the conversion of carbon monoxide based on copper oxides, and zinc with a promoter — alumina and / or oxides of chromium, manganese, and magnesium, according to which the spent catalyst is treated with a solution of oxidizing agents: Hydrogen Peroxide, dilute acids - nitrogen or

chromium, bichromate or potassium permanganate in apparatus with a stirrer or air sparging at 40-60 C. After treatment with oxidizing agents, the solutions are drained and the catalyst mass is dried in a current. air at 120-150 0 then the cooled catalyst mass is washed at 35-40 C with a solution of a 1-micron-complex

copper. Then the regenerated catalyst is dried and calcined at 320450 ° C.

This method of regeneration is used only if the catalyst has lost activity by less than 60-70% and slightly lost mechanical strength (less than by 20-30%) 12.

The disadvantage of this method

the degree of regeneration is not high enough.

The purpose of the invention is to increase the degree of regeneration.

The goal is achieved

The proposed method for the regeneration of a catalyst for the conversion of carbon monoxide .. yes or methanol synthesis is based on copper, zinc oxides and aluminum oxide promoter and / or chromium oxides and

magnesium by processing the waste. catalyst with a liquid oxidizing agent, and then an ammonia-containing solution, which is used as the ammoniac acid of the general formula where R is H, OH, CHj, at 50-80 seconds, followed by evaporation at 90-120 ° C by plasticization and calcination. Distinctive features of the method are the use of acids of the general formula - (where R is H, OH, CHj and the conditions of catalyst treatment with ammonia containing solution, as well as evaporation conditions.) The proposed method allows re-generation of catalysts containing such valuable components like copper, zinc, manganese, chromium and other lost more than 60-70% or completely active and mechanical strength .The treated and mechanically destroyed catalyst is treated in solutions of oxidizing agents for hydrogen peroxide or nitric acid — with air bubbling at 40 ° C for 1–4 h. After stopping the supply of air into the apparatus, ammonium carbonate, ammonium acetate, or ammonium formate solution is poured and the process is creations at BO-BO-C for 3-6 hours, and then at 90-120 C, the pulp is evaporated and plasticized in a mixer for 3-5 hours. The resulting material is dried, calcined at 380-400-s for 4- 5 hours and tableted. Example. Regeneration of thermally deactivated carbon monoxide conversion catalyst NTK-4. 1 weight unit of the reconstituted or thermo-deactivated catalyst NTK-4 is ground and fed into a heated reactor-mixer, where 1.5 weight units are pre-filled. 15% hydrogen peroxide. With vigorous stirring, air is purged (at a rate of 1 kg of mass of 1 nm / h), the temperature in the reactor is raised to 50-60 ° C, and the contact mass is acidified for 2-3 hours. Then stop the flow of air and mixed with 6 wt.ed. ammonium carbonate solution, which was previously prepared in a separate container with an ammonia content of 160 g / l and COg 100 g / l at a pH of 10.511, 0. The temperature in the mixing reactor is raised 70-75 0 and the extraction process is carried out for 4-6 hours; After that, the mass in the reactor is heated to 90-95 ° C and the entire pulp is evaporated and plasticized for an hour. The ammonia released during evaporation and carbon dioxide are directed to the preparation of ammonium carbonate solutions. Next, the contact mass is sent for drying, calcined at 380-400 ° C for 4-5 hours, moistened with 5% distilled water and tableted. EXAMPLE 2. Regeneration of an alumino-copper catalyst for the conversion of carbon monoxide (type C-18-1). 1 pb the previously ground alumina-zinc catalyst, which lost its mechanical strength during the reduction process, is loaded into the mixer-reactor and filled with stirring 2.2 wt. 20% nitric acid. Peptizing the mass is carried out for 3-4 hours using the heat released from the solution, which was previously prepared in a separate container by dissolving formic acid in ammonia water so that the concentration of ammonia was 250 g / l and HCOOH 200 g / l at a pH of 10-10.5. Further heating of the mixture, evaporation, plasticization, drying, calcining, moistening and tableting are carried out analogously to example 1. EXAMPLE 3. Regeneration of the matanol catalyst CBM-1. 1 pb fused during the reduction of the methanol catalyst SNM-1 is crushed and loaded into the reactor-mixer, where pour 3.0 wt. 20% nitric acid. Next, stirring is carried out without preheating, mixed, with 5.0 weight units. ammonium carbonate solution, plasticized, evaporated, dried, calcined and tableted as in example 1. PRI me R 4. Generation of the methanolic catalyst CHM-1. 1 kg of the catalyst of methanol synthesis SNM-1, which was lost in activity, after preliminary grinding, is loaded into a reactor-mixer and 0.7 kg of a 25% solution of hydrogen peroxide is oxidized by passing air for 2-3 hours. Then, 7 tons of ammonia are poured into the reactor. an acetate solution prepared separately by mixing acetic acid and ammonia water with an NH concentration of 220 g / li 180 g / l at a pH of 11.0. The processes of leaching, evaporation, drying, calcination, and tabletting are carried out as in Example 1. EXAMPLE 5. Regeneration of the Incan Catalyst Absorbed GIAP-10.

1 wt. Units, mechanically destroyed catalyst-absorber GIAP-1.0, containing zinc sulfide less than 10 wt.% (Less than 3% in terms of elemental sulfur) is loaded into the reactor-mixer, where pour 3-4 weight. Units. ammonium carbonate solution with an ammonia content of 160 g / l and carbon dioxide 100 g at a pH of 10.5. The temperature in the mixer rises to 70-75 ° C and the extraction process is carried out for 4-6 hours, after which the temperature in the reactor is raised to 90-95 ° C and the pulp is evaporated and plasticized within 4-5 hours. Further drying, calcination and tabletting is carried out according to example 1.

Mechanical strength rises to its original value, and the sulfur absorption capacity of the absorber is restored by 80-85% compared to the original

Example 1 kg of thermally deactivated catalyst NTK-4 is ground and fed into a heated reactor, where 1 liter of 15% hydrogen peroxide solution is pre-filled. With vigorous stirring, the temperature in the reactor is raised to 50-60 0 and the acidification process is carried out for 1.5-2.0 hours. Then 5 l of ammonium carbonate solution with ammonia content 160 g / l and carbon dioxide 100 g are added to the reactor / l. The temperature in the reactor is raised to IB-QO C and the extraction process is carried out for 1.5 hours. Next, the resulting mass is heated to 98100 ° C and the entire slurry is evaporated and plasticized for 3-4 hours. Further operations are carried out as in Example 1.

Example. 1 kg of mechanically destroyed absorber GNAP-10 is loaded into the mixer reactor, where 5 pour 3.5 liters of ammonium carbonate solution with an ammonia content of 16.0 g / l and carbon dioxide 100 g / l. The temperature in the mixer is raised to 55-58 ° C and the extraction process is carried out for 3.5-4.0 hours, after which the resulting mass is heated to 110-115 ° C and the pulp is evaporated and plasticized for 3-4 hours. operations are carried out as in example 1. Comparison of the properties of freshly prepared and regenerated catalysts according to examples 1-4 is given in the table.

NTK-4 freshly prepared75, 0

NTK-4 after re-generation 74.2

a) A1-Zn-Cu freshly prepared 80.6

b). A1-Zn-Cu after regeneration 88.5

a) SNM-1 freshly prepared, nny65,0

b) SNM-1 after regeneration68.5

a) Zn-Cr freshly prepared

b) Zn-Cr after regeneration

CO conversion rate with

0.96 water vapor at 220 s and a pressure of 1 at. 0.94 (share units)

th

0.94 0.93

Performance

f

4.0.10 for condensed methanol at 250 ° C and

-S

4.2.10 pressure of 1.7 atm (ml / g of catalyst, min)

Claims (2)

The degree of decomposition is m085 of tanol at 350 ° C in units of l. 0.84 Claims of Invention A method for regenerating a catalyst for the conversion of carbon monoxide or methanol synthesis based on copper oxide, zinc oxide and a promoter — aluminum oxide and / or chromium oxide, or manganese oxide, or magnesium oxide, which involves treating the spent catalyst with a liquid oxidizer and then an alumina-containing solution, calcination, characterized in that / with the purpose of increasing the degree of regeneration, ammonia acids of total O are used as ammonia-containing solution O as the formula: RH, OH, CH5 and OH / treatment with this solution at 50-80 ° C followed by evaporation at 90-120 ° C, kneading, and calcining. Sources of information taken into account in the examination 1. The author's certificate of the USSR. No. 218835, cl. B 01 3 23/92, 1967. 2. USSR author's certificate for application No. 2183878/04, class B 01 5 23/94, 1975 (prototype).