Production of Cu/Zn/A1 catalysts via the formate route
View Patent ↗The invention relates to a process for preparing Cu/Zn/Al catalysts. In this process, the metals are used in the form of their formates and are precipitated in a suitable form. Suitable precipitants are, for example, alkali metal carbonates. The invention further relates to a catalyst as can be obtained by the process according to the invention and to its use.
1. A process for preparing Cu/Zn/Al catalysts, comprising
preparing a first aqueous solution which comprises copper formate and zinc formate,
preparing a second solution which comprises a precipitation reagent,
wherein the first solution and/or the second solution further comprises an aluminum hydroxide sol/gel mixture,
combining the first solution and the second solution to obtain a precipitate,
removing the precipitate from the combination of solutions thereby producing wastewater,
washing the precipitate until an alkali metal content, based on the precipitate after being formed as a catalyst is calcined at 600° C., of less than 500 ppm is attained, and
drying the precipitate.
2. The process as claimed in claim 1 , characterized in that the first solution is prepared by
preparing an aqueous copper formate solution by dissolving a copper salt without residue by use of formic acid,
preparing an aqueous dispersion or solution of a zinc salt,
preparing an aqueous aluminum salt solution, and
combining the copper formate solution, the dispersion or solution of the zinc salt and the aluminum salt solution.
3. The process as claimed in claim 2 , wherein the copper formate solution has a pH of less than 3.
4. The process as claimed in claim 2 , wherein the solution or dispersion of the zinc salt is combined with the copper formate solution to give a copper/zinc solution, wherein the resulting copper/zinc solution has a pH in the range from 3.0 to 4.0, and wherein the aluminum salt solution is added to the copper/zinc solution.
5. The process as claimed in claim 4 , wherein the aluminum salt solution is added in several part-solutions, at least a first portion of the aluminum salt solution being prepared by dissolving at least a first part of the aluminum salt in water with an addition of formic acid.
6. The process as claimed in claim 5 , wherein a second portion of the aluminum salt solution is prepared by dissolving a second portion of the aluminum salt in water and adding a first portion of the aluminum salt solution and the second portion of the aluminum salt solution, to the copper/zinc solution.
7. The process as claimed in claim 6 , characterized in that the aqueous aluminum salt solution, the first portion of the aluminum salt solution and/or the second portion of the aluminum salt solution, before precipitation, is/are heated to temperatures of not more than 40° C.
8. The process as claimed in claim 1 , wherein, during the precipitation step, a pH in the range from 3.5 to 7.5, is maintained.
9. The process as claimed in claim 2 , characterized in that the copper salt is selected from the group consisting of CuO, Cu(OH) 2 , Cu(OH) 2 .CuCO 3 and mixtures thereof.
10. The process as claimed in claim 2 , characterized in that the zinc salt comprises ZnO.
11. The process as claimed in claim 1 further comprising a precipitation reagent comprising an alkali metal base.
12. The process as claimed in claim 1 further comprising a precipitation reagent comprising hydrogen peroxide.
13. The process as claimed in claim 1 , characterized in that the precipitate is aged after the precipitation.
14. The process as claimed in claim 13 , characterized in that the aging is performed over a period of from 10 minutes to 10 hours.
15. The process as claimed in claim 13 , characterized in that the aging is effected at a temperature of more than 60° C.
16. The process as claimed in claim 1 , characterized in that the precipitation step is performed as a continuous precipitation.
17. The process as claimed in claim 1 , characterized in that the first solution comprises copper and zinc in a ratio which is selected between 1:99 and 99:1.
18. The process as claimed in claim 1 , characterized in that the precipitate is calcined after drying.
19. The process as claimed in claim 18 , wherein the precipitate is calcined at temperatures in the range of 140-1000° C., for a period of at least 0.1 second.
20. The process as claimed in claim 1 , characterized in that the wastewater comprises formate ions and the wastewater is subjected to an oxidative treatment which oxidizes the formate ions essentially to carbonate, hydrogencarbonate, carbon dioxide and water.
21. The process as claimed in claim 20 , characterized in that hydrogen peroxide is added to the wastewater for the oxidative treatment.
22. The process as claimed in claim 20 , characterized in that the oxidative treatment of the wastewater occurs before the removal of the precipitate.
23. The process as claimed in claim 20 , characterized in that the oxidative treatment comprises a biological treatment of the wastewater.
24. A Cu/Zn/Al catalyst which has been obtained by the process as claimed in claim 1 and which has a formate content, based on the oxidic catalyst, of less than 5%.
25. The catalyst as claimed in claim 24 , characterized in that the proportion of mesopores of the catalyst having a radius from 3.75 to 7.0 nm in the total pore volume is more than 30%.
26. The catalyst as claimed in claim 24 , characterized in that the proportion of copper, calculated as copper oxide and based on the weight of the oxidic catalyst, is between 55 and 69% by weight.
27. The catalyst as claimed in claim 24 , characterized in that the proportion of zinc, calculated as zinc oxide and based on the weight of the oxidic catalyst, is between 20 and 33% by weight.
28. The catalyst as claimed in claim 24 , characterized in that the proportion of aluminum, calculated as aluminum oxide and based on the weight of the oxidic catalyst, is between 5 and 20% by weight.
29. The catalyst as claimed in claim 24 , characterized in that the oxidic catalyst has a content of alkali metal ions of less than 500 ppm.
30. A methanol synthesis reaction comprising converting CO, CO 2 and H 2 to methanol utilizing the catalyst as claimed in claim 24 .
31. A reformation of methanol reaction utilizing the catalyst as claimed in claim 24 .
32. A low-temperature conversion of carbon monoxide to carbon dioxide comprising reacting carbon monoxide and water over the catalyst of claim 24 to produce carbon dioxide at a temperature from 175 to 250° C.