Highly active spherical metal support catalysts
View Patent ↗The invention relates to highly active spherical metal support catalysts with a metal content of 10 to 70% by mass, and a process for their production with the use of a mixture of polysaccharides and at least one metal compound which is dropped into a metal salt solution.
1. A spherical metal support catalyst having a metal content of 10 to 70% by mass formed by a process comprising:
selecting a mixture of at least one polysaccharide and at least one metal compound chosen from the group consisting of: a) metal oxides, b) metal hydroxides, c) basic metal carbonates, d) metal hydrogen carbonates, e) metal silicates, f) metal zirconates, g) metal aluminates, h) metal titanates, i) metal chromites and j) metal aluminosilicate, of iron, cobalt, nickel, copper, or zinc, dissolved or suspended in a liquid medium,
dropping said mixture into a metal salt solution so as to form spheres from the mixture, and
forming catalyst spheres by separating the spheres from the metal salt solution after a standing time of 1 to 180 minutes, drying the spheres at temperatures of 80 to 150° C., and reducing the spheres at temperatures of 150 to 600° C.
2. The catalyst according to claim 1 , wherein the metal salt solution comprises at least one metal ion of the at least one selected metal compound.
3. The catalyst according to claim 1 , wherein the metal salt solution comprises at least one polyvalent metal ion chosen from the group consisting of Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Mn 2+ , Al 3+ , and Cr 3+ .
4. The catalyst according to claim 1 , wherein the concentration of metal ions in the metal salt solution is 0.3 to 5% by mass.
5. The catalyst according to claim 1 , wherein the concentration of metal ions in the metal salt solution is 1 to 2% by mass.
6. The catalyst according to claim 1 , wherein dropping said mixture into the metal salt solution is performed from about 10 cm.
7. The catalyst according to claim 1 , wherein the metal salt solution contains nitrate and/or acetate as anions.
8. The catalyst according to claim 1 , wherein in the mixture at least one aggregate material is added which functions as a binder.
9. The catalyst according to claim 8 , wherein the aggregate material is chosen from the group consisting of tylose, bentonite, boehmite, kaolin, silica gel, silica sol, methyl cellulose and sodium silicate.
10. The catalyst according to claim 9 , wherein the at least one metal compound has an ignition residue, and wherein the solid ratio of the ignition residue of the at least one metal compound in the mixture to the at least one aggregate material is 4 to 15.
11. The catalyst according to claim 1 , wherein the at least one metal compound has an ignition residue, and wherein the solid ratio of the ignition residue of the at least one metal compound in the mixture to the at least one polysaccharide is 4 to 15.
12. The catalyst according to claim 1 , wherein alginate is used as the polysaccharide.
13. The catalyst according to claim 1 , wherein one or more doping elements of 0.1 to 5% by mass is added to the mixture.
14. The catalyst according to claim 13 , wherein the doping elements are Mg, Ca, Mn, Mo, Cr, Fe, or Zn.
15. The catalyst according to claim 1 , wherein the catalyst spheres obtained are calcined at temperatures from 150 to 600° C. after the drying and before the reduction.
16. The catalyst according to claim 1 , wherein the catalyst spheres obtained are reduced in hydrogen gas.
17. A process for the hydrogenation of hydrocarbons comprising reacting said hydrocarbons with hydrogen in the presence of a spherical metal support catalyst having a metal content of 10 to 70% by mass, the catalyst being formed by a process comprising:
selecting a mixture of at least one polysaccharide and at least one metal compound chosen from the group consisting of: a) metal oxides, b) metal hydroxides, c) basic metal carbonates, d) metal hydrogen carbonates, e) metal silicates, f) metal zirconates, g) metal aluminates, h) metal titanates, i) metal chromites and j) metal aluminosilicate, of iron, cobalt, nickel, copper, or zinc, dissolved or suspended in a liquid medium,
dropping said mixture into a metal salt solution so as to form spheres from the mixture, and
forming catalyst spheres by separating the spheres from the metal salt solution after a standing time of 1 to 180 minutes, drying the spheres at temperatures of 80 to 150° C. , and reducing the spheres at temperatures of 150 to 600° C.
18. The process of claim 17 , wherein said hydrocarbons and hydrogen are reacted at a temperature of about 100° C.
19. The process of claim 17 , wherein said hydrocarbons and hydrogen are reacted at a temperature of about 220° C.
20. The process of claim 17 , wherein said hydrocarbons and hydrogen are reacted at a pressure of about 30 bar.
21. The process of claim 17 , wherein said hydrocarbons and hydrogen are reacted at a pressure of about 70 bar.
22. The process of claim 17 , wherein said hydrocarbons are aromatic hydrocarbons.