Hydrogenation catalyst, process for preparing and process of using said catalyst

• US 5,155,086 A
• Filed: 04/02/1991
• Issued: 10/13/1992
• Est. Priority Date: 09/12/1989
• Status: Expired due to Term

• Current Assignee: Engelhard Corporation Menlo Park CN
• Original Assignee: Engelhard Corporation (BASF SE)
• Inventors: Sullivan, Thomas J., Roberts, Brian D., Thakur, Deepak S., Vichek, Anita L.
• Primary Examiner(s): MCFARLANE, ANTHONY R
• Application Number:
  US07/680,100
• Time in Patent Office: 560 Days
• Field of Search: 502/341, 502/342, 502/346, 502/343, 502/344
• US Class Current: 502/342
• CPC Class Codes: B01J 23/80 with zinc, cadmium or mercury
• CPC Class Codes: B01J 35/30 characterised by their physical properties
• CPC Class Codes: B01J 35/40 characterised by dimensions, e.g. grain size in a colloidal state B01J35/23; crystallite size B01J35/77
• CPC Class Codes: B01J 35/613 10-100 m2/g
• CPC Class Codes: B01J 35/615 100-500 m2/g
• CPC Class Codes: B01J 35/633 less than 0.5 ml/g
• CPC Class Codes: B01J 35/635 0.5-1.0 ml/g
• CPC Class Codes: B01J 35/647 2-50 nm
• CPC Class Codes: B01J 35/651 50-500 nm
• CPC Class Codes: B01J 35/66 Pore distribution
• CPC Class Codes: B01J 37/031 Precipitation
• CPC Class Codes: C07C 29/141 with hydrogen or hydrogen-containing gases
• CPC Class Codes: C07C 29/145 with hydrogen or hydrogen-containing gases
• CPC Class Codes: C07C 29/149 with hydrogen or hydrogen-containing gases
• CPC Class Codes: C07C 31/02 Monohydroxylic acyclic alcohols

Abstract

In one embodiment, the invention relates to a catalyst in powdered form which comprises a major amount of the oxides of copper and zinc, and a minor amount of aluminum oxide wherein the pore volume of pores of said catalysts having a diameter between about 120 and about 1000 Å is at least about 40% of the total pore volume. In another embodiment, the invention relates to a process for preparing hydrogenation catalysts comprising the oxides of copper, zinc and aluminum which comprises the steps of

(A) preparing a first aqueous solution containing at least one water-soluble copper salt and at least one water-soluble zinc salt;

(B) preparing a second solution containing at least one water-soluble basic aluminum salt and at least one alkaline precipitating agent;

(C) mixing the first and second solutions whereby an insoluble solid is formed;

(D) recovering the insoluble solid.

The invention also relates to a process for hydrogenating aldehydes, ketones, carboxylic acids and carboxylic acid esters with catalysts of the type described. Catalysts of the invention are useful in both fixed bed and slurry phase hydrogenation reactions.

Claims

1. A catalyst in powdered form comprising a major amount of the oxides of copper and zinc, and a minor amount of aluminum oxide wherein the pore volume of the pores in said catalyst having a diameter of between about 120 and about 1000 Å

is at least about 40% of the total pore volume.

2. The catalyst of claim 1 wherein the pore volume of the pores having a diameter of greater than 120 Å

is at least about 70% of the total pore volume.

3. The catalyst of claim 1 wherein the powders have a surface area of at least 50 square meters per gram.

4. The catalyst of claim 1 wherein the powders have an average particle diameter of from about 8 to about 30 microns.

5. The catalyst of claim 1 wherein the atomic ratio of copper to zinc is from about 0.2 to about 5.5.

6. The catalyst of claim 1 wherein the atomic ratio of copper to zinc is from about 0.5 to about 3.0.

7. The catalyst of claim 1 wherein the atomic ratio of copper to zinc is less than 1.

8. The catalyst of claim 1 wherein the copper to zinc atomic ratio is less than about 0.85.

9. The catalyst of claim 1 wherein the atomic ratio of copper to zinc is from about 0.5 to about 0.85.

10. The catalyst of claim 1 containing from about 3 to about 50% by weight of aluminum oxide.

11. The catalyst of claim 1 wherein the atomic ratio of copper and zinc to aluminum is less than about 15.

12. The catalyst of claim 1 which is free of chromium and cobalt.

13. The catalyst of claim 1 wherein, for atomtic ratios of copper to zinc from about 0.5 to 5.5 and an aluminum content greater than about 8 wt. percent, the particle size span from the smallest 10% of the particles to the largest 10% is between 10 and 45 microns.

14. The catalyst of claim 1 wherein, for atomic ratios of copper to zinc from about 0.5 to 5.5 and an aluminum content greater than about 8 wt. percent, the median particle size is between 5 and 20 microns.

15. The catalyst of claim 1 wherein, for atomic ratios of copper to zinc of greater than about 1.5 and an aluminum content greater than about 3 wt. percent, the particle size span is between 22 and 45 microns.

16. The catalyst of claim 1 wherein, for atomic ratios of copper to zinc of greater than about 1.5 and an aluminum content greater than about 3 wt. percent, the median particle size is between 8 and 25 microns.

17. A process for preparing a hydrogenation catalyst comprising the oxides of copper, zinc and aluminum which comprises the steps of

(A) preparing a first aqueous solution containing at least one water-soluble copper salt and at least one water-soluble zinc salt;

(B) preparing a second solution containing at least one water-soluble basic aluminum salt and at least one alkaline precipitating agent;

(C) mixing the first and second solutions whereby an insoluble solid is formed;

(D) recovering the insoluble solid; and

(E) calcining the recovered solid.

18. The process of claim 17 wherein the mixing in step (C) is conducted at a pH above about 7.

19. The process of claim 17 wherein the atomic ratio of copper to zinc in the first aqueous solution is within a range of from about 0.2 to about 5.5.

20. The process of claim 17 wherein the copper to zinc atomic ratio in the first aqueous solution is from about 0.5 to about 3.0.

21. The process of claim 17 wherein the catalyst recovered from the calcination of the removed solid in step (E) contains from about 0.5 to about 50% by weight of aluminum oxide.

22. The process of claim 17 wherein the catalyst recovered from the calcination of the removed solid in step (E) contains from about 18 to about 30% by weight of aluminum oxide.

23. The process of claim 17 wherein the atomic ratio of copper to zinc in the first aqueous solution is less than about 0.85.

24. The process of claim 17 wherein the first and second solutions are simultaneously mixed in step (C).

25. A process for preparing a hydrogenation catalyst comprising the oxides of copper, zinc and aluminum which comprises the steps of

(A) preparing a first aqueous solution containing at least one water-soluble copper salt and at least one water-soluble zinc salt in amounts sufficient to provide an atomic ratio of copper to zinc of less than about 1;

(B) preparing a second solution containing at least one water-soluble basic aluminum salt and at least one alkaline precipitating agent;

(C) simultaneously mixing the first and second solutions at a rate whereby the pH of the resulting mixture is at least about 7, and an insoluble solid is formed;

(D) recovering the insoluble solid; and

(E) calcining the recovered solid.

26. The process of claim 25 wherein the atomic ratio of copper to zinc in the first aqueous solution is less than about 0.85.

27. The process of claim 25 wherein the atomic ratio of copper to zinc in the first aqueous solution is from about 0.25 to about 0.85.

28. The process of claim 25 wherein the amount of aluminum salt in the second solution is sufficient to produce a catalyst wherein the atomic ratio of copper and zinc to aluminum is less than about 15.