Hydrogenation catalyst and process for preparing same

• US 5,418,201 A
• Filed: 06/15/1993
• Issued: 05/23/1995
• Est. Priority Date: 04/24/1992
• Status: Expired due to Term

• Current Assignee: Engelhard Corporation (BASF SE)
• Original Assignee: Engelhard Corporation (BASF SE)
• Inventors: Sullivan, Thomas J., Roberts, Brian D., Plundo, Robert A., Thakur, Deepak S.
• Primary Examiner(s): Lieberman, Paul
• Assistant Examiner(s): McGinty, Douglas J.
• Application Number:
  US08/077,216
• Time in Patent Office: 707 Days
• Field of Search: 502/324, 502/245
• US Class Current: 502/348
• CPC Class Codes: B01J 23/8892 Manganese
• CPC Class Codes: B01J 37/03 Precipitation; Co-precipitation
• CPC Class Codes: C07C 29/149 with hydrogen or hydrogen-containing gases
• CPC Class Codes: C07C 31/125 containing five to twenty-two carbon atoms

Abstract

In one embodiment, the invention relates to a catalyst in powdered form comprising the oxides of copper, iron, aluminum and manganese wherein the atomic ratio of copper to iron is at least 1:1. In another embodiment, the invention relates to a process for preparing such hydrogenation catalysts which comprises the steps of

(A) preparing a first aqueous solution containing at least one water-soluble copper salt, at least one water-soluble iron salt, and at least one water-soluble manganese 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 wherein an insoluble solid is formed;

(D) recovering the soluble solid; and

(E) calcining the recovered solid to form the desired catalyst.

The invention also relates to a process for hydrogenating aldehydes, ketones, carboxylic acids and carboxylic acid esters.

Claims

1. A catalyst in powdered form consisting essentially of the oxides of copper, iron, aluminum and manganese wherein the atomic ratio of copper to iron is at least 1:

1;

wherein said catalyst contains at least about 1% by weight each of manganese and aluminum and the atomic ratio of copper to aluminum is at least about 1;

1.

2. The catalyst of claim 1 wherein the powders have a surface area of at least about 50 m² /g.

3. The catalyst of claim 1 wherein the powders have a surface area of from about 50 to about 175 m² /g.

4. The catalyst of claim 1 wherein the atomic ratio of copper to iron is from about 3:

1 to about 6;

1.

5. The catalyst of claim 1 containing from about 1 to about 15% by weight of manganese.

6. The catalyst of claim 1 wherein the atomic ratio of copper to aluminum is from about 1:

1 to about 3;

1.

7. The catalyst of claim 1 which also contains a minor amount of at least one inorganic carrier material.

8. The catalyst of claim 7 containing up to about 20% of the carrier material.

9. The catalyst of claim 7 wherein the carrier is calcium silicate.

10. The catalyst of claim 1 which is free of chromium.

11. The catalyst of claim 1 wherein the atomic ratio of copper to manganese is from about 2:

1 to about 35;

1.

12. A catalyst in powdered form consisting essentially of the oxides of copper, iron, aluminum and manganese wherein the atomic ratio of copper to iron is from about 4:

1 to about 6;

1, the atomic ratio of copper to aluminum is from about 1;

1 to about 3;

1, and the catalyst contains from about 1 to about 10% by weight of manganese and from about 1 to about 10% by weight aluminum.

13. The catalyst of claim 12 also containing up to about 15% by weight of a porous inorganic carrier material.

14. The catalyst of claim 13 wherein the carrier is present as calcium silicate.

15. The catalyst of claim 12 wherein the powders have a surface area in the range of from about 70 to about 160 m² /g.

16. A process for preparing a hydrogenation catalyst consisting essentially of the oxides of copper, iron, aluminum and manganese which comprises the steps of

(A) preparing a first aqueous solution containing at least one water-soluble copper salt, at least one water-soluble iron salt, and at least one water-soluble manganese salt wherein the atomic ratio of copper to iron in the first aqueous solution is at least 1:

1, the amount of manganese contained in the first aqueous solution is an amount sufficient to provide a final catalyst containing at least about 1% by weight of manganese and the atomic ratio of copper to aluminum is at least about 1;

1;

(B) preparing a second solution containing at least one water-soluble basic aluminum salt and at least one alkaline precipitating agent, the amount of aluminum contained in the second solution is an amount sufficient to provide a catalyst containing at least about 1% aluminum;

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

(D) recovering the insoluble solid; and

(E) calcining the recovered solid to produce said catalyst in oxide form.

17. The process of claim 16 wherein the atomic ratio of copper to iron in the first aqueous solution is within the range of from about 3:

1 to about 6;

1.

18. The process of claim 16 wherein the atomic ratio of copper to manganese in the first aqueous solution is from about 2:

1 to about 35;

1.

19. The process of claim 16 wherein the catalyst recovered from the calcination in step (E) contains from about 1 to about 15% by weight of manganese.

20. The process of claim 16 wherein the first and second solutions are simultaneously mixed in step (C).

21. The process of claim 16 wherein the first and second solutions are simultaneously added with mixing to a vessel containing water and at least one alkaline earth metal silicate.

22. A process for preparing a hydrogenation catalyst consisting essentially of the oxides of copper, iron, aluminum and manganese which comprises the steps of

(A) preparing a first aqueous solution containing at least one water-soluble copper salt, at least one water-soluble iron salt, and at least one water-soluble manganese salt in an amount sufficient to provide an atomic ratio of copper to iron of from about 3:

1 to about 6;

1, and an atomic ratio of copper to manganese of from about 2;

1 to about 20;

1, the amount of manganese contained in the first aqueous solution is an amount sufficient to provide a final catalyst containing at least about 1% by weight of manganese;

(B) preparing a second solution containing at least one water-soluble basic aluminum salt and at least one alkaline precipitating agent, the amount of aluminum contained in the second solution is an amount sufficient to provide a catalyst containing at least about 1% by weight aluminum;

(C) simultaneously mixing the first and second solutions in a vessel containing water and calcium silicate whereby an insoluble solid is formed;

(D) recovering the insoluble solids; and

(E) calcining the recovered solid to produce said catalyst in oxide form.

23. The process of claim 22 wherein the catalyst recovered from the calcination in step (E) contains from about 1 to about 15% by weight of manganese.