Process for preparing catalyst with copper or zinc and with chromium, molybdenum, tungsten, or vanadium, and product thereof

• US 5,134,108 A
• Filed: 05/22/1991
• Issued: 07/28/1992
• Est. Priority Date: 05/22/1991
• Status: Expired due to Term

• Current Assignee: Engelhard Corporation (BASF SE)
• Original Assignee: Engelhard Corporation (BASF SE)
• Inventors: Sullivan, Thomas J., Roberts, Brian D., Thakur, Deepak S., Nebesh, Eugene, Palka, Eugene
• Primary Examiner(s): Shine, W. J.
• Assistant Examiner(s): McGinty, Douglas J.
• Application Number:
  US07/703,923
• Time in Patent Office: 433 Days
• Field of Search: 502/318, 502/307, 502/343, 502/345, 502/306, 502/315, 502/316, 502/324, 502/329, 502/328, 502/337, 502/338, 502/340, 502/331
• US Class Current: 502/318
• CPC Class Codes: B01J 23/847 Vanadium, niobium or tantalum or polonium
• CPC Class Codes: B01J 23/8472 Vanadium
• CPC Class Codes: B01J 23/85 Chromium, molybdenum or tungsten
• CPC Class Codes: B01J 23/868 copper and chromium
• CPC Class Codes: B01J 23/8892 Manganese
• CPC Class Codes: B01J 35/31 Density
• 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 35/66 Pore distribution
• CPC Class Codes: B01J 37/03 Precipitation; Co-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 31/125 containing five to twenty-two carbon atoms
• CPC Class Codes: C07C 51/36 by hydrogenation of carbon-to-carbon unsaturated bonds

Abstract

This hydrogenation catalyst comprises a major amount of the oxides of a first metal selected from copper or zinc, a second metal selected from chromium, molybdenum, tungsten and vanadium, and optionally, a minor amount of the oxide of a promoter metal selected from the group consisting of manganese, barium, zinc, nickel, cobalt, cadmium, iron and any combination thereof provided that the promotor metal is not zinc if the first metal is zinc. The average particle diameter of the powder is from about 6 to about 20 microns; and the particle surface area is from about 20 to about 70 m² /g. The process for preparing this catalyst comprises the steps of

(A) simultaneously and adding to a first vessel, (1) a first aqueous solution comprising a copper or zinc salt; (2) a second aqueous solution comprising a soluble base, provided that either the copper solution or the soluble base solution also contains a soluble salt of at least one second metal; or (3) a third aqueous solution comprising a soluble salt of at least one seocnd metal is added simultaneously to the first vessel whereby an aqueous slurry of insoluble solid is formed in the first vessel, provided further that the second metal is chromium, molybdenum, tungsten, or vanadium;

(B) advancing at least a portion of the aqueous slurry from the first vessel to a second vessel;

(C) recovering the solids from the aqueous slurry in the second vessel; and

(D) calcining the recovered solids.

Claims

1. A process for preparing a catalyst comprising the oxides of copper or zinc and at least one additional metal which comprises the steps of

(A) simultaneously and separately adding to a first vessel, (1) a first aqueous solution comprising a copper or zinc salt;

and (2) a second aqueous solution comprising a soluble base, provided that either (i) the first or second solutions also contains a soluble salt of at least one second metal selected from chromium, molybdenum, tungsten or vanadium, or (ii) if the first or second solutions do not contain a soluble salt of at least one of the second metals, (3) a third aqueous solution comprising a soluble salt of at least one of said second metal is added simultaneously to the first vessel, whereby an aqueous slurry of an insoluble solid is formed in the first vessel;

(B) advancing at least a portion of the aqueous slurry from the first vessel to a second vessel;

(C) recovering the solids from the aqueous slurry in the second vessel; and

(D) calcining the recovered solids wherein the average particle diameter of the calcined solids is from about 6 to about 20 microns;

the particle surface area is from about 20 to about 70 m² /g;

the pore volume of pores having diameters in the range up to 120 Å

is from about 5 to about 45%, in the range of about 120 to about 350 Å

is from about 40 to about 80%, and in the range of about 350 to about 1000 Å

is from about 10 to about 40% of the total pore volume.

2. The process of claim 1 wherein water also is added simultaneously to the first vessel in step (A).

3. The process of claim 1 wherein a water-soluble salt of at least one promoter metal selected from the group consisting of manganese, barium, zinc, nickel, cobalt, cadmium, iron, calcium, magnesium, and any combination thereof is included in either

(a) the first aqueous solution, or

(b) in the third aqueous solution if utilized, or

(c) is added simultaneously to the first vessel in step (A) as a fourth aqueous solution, provided that the promoter metal is not zinc if the first aqueous solution contains a zinc salt.

4. The process of claim 1 wherein the soluble second metal salt is included in the first aqueous solution.

5. The process of claim 3 wherein the salt of the promoter metal is included in the first aqueous solution.

6. The process of claim 3 wherein the first aqueous solution comprises the soluble salts of copper, chromium and the promoter metal.

7. The process of claim 1 wherein the soluble base in the second aqueous solution is ammonium hydroxide.

8. The process of claim 3 wherein the promoter metal is manganese or barium.

31. A catalyst prepared in accordance with the process of claim 1.

9. A process for preparing a catalyst comprising the oxides of copper and chromium which comprises the steps of

(A) simultaneously and continuously adding to a first vessel:

water;

a first aqueous solution comprising soluble salts of copper, chromium, and a promoter metal selected from the group consisting of manganese, barium, zinc, nickel, cobalt, cadmium, iron and any combination thereof; and

a second aqueous solution comprising a soluble base, to form an aqueous slurry of an insoluble solid in the first vessel;

(B) continuously advancing at least a portion of the aqueous slurry from the first vessel to the second vessel;

(C) recovering at least some of the solid from the slurry in the second vessel; and

(D) calcining the recovered solid wherein the average particle diameter of the calcined solid is from about 6 to about 20 microns;

the particle surface area is from about 20 to about 70 m² /g;

the pore volume of pores having diameters in the range up to 120 Å

is from about 5 to about 45%, in the range of about 120 to about 350 Å

is from about 40 to about 80%, and in the range of about 350 to about 1000 Å

is from about 10 to about 40% of the total pore volume.

10. The process of claim 9 wherein the first aqueous solution contains from about 1 up to about 15% by weight of the promoter metal based on the total weight of metals present in the solution.

11. The process of claim 9 wherein the promoter metal is manganese or barium.

12. The process of claim 9 wherein the atomic ratio of copper:

chromium in the first aqueous solution is about 1;

1.

13. The process of claim 10 wherein the first aqueous solution contains from about 3 to about 10% of manganese based on the total weight of metals present in the solution.

14. The process of claim 9 wherein the soluble base is ammonium hydroxide.

15. The process of claim 9 wherein the aqueous solution of soluble base is added at a rate sufficient to maintain the pH of the aqueous slurry in the first vessel at between about 5 and about 6.5.

16. A process for preparing a catalyst comprising the oxides of copper, chromium and manganese which comprises the steps of

(A) simultaneously and continuously adding a first aqueous solution comprising water-soluble salts of copper, chromium and manganese to a first vessel while separately and continuously adding water and a second aqueous solution comprising a soluble base to form an aqueous slurry of insoluble solids in the first vessel;

(B) continuously advancing at least a portion of the aqueous slurry from the first vessel to a second vessel;

(C) continuously recovering at least some of the solids from the slurry in the second vessel; and

(D) calcining the solids recovered in step (C) wherein the average particle diameter of the calcined solids is from about 6 to about 20 microns;

the particle surface area is from about 20 to about 70 m² /g;

the pore volume of pores having diameters in the range up to 120 Å

is from about 5 to about 45%, in the range of about 120 to about 350 Å

is from about 40 to about 80%, and in the range of about 350 to about 1000 Å

is from about 10 to 40% of the total pore volume.

17. The process of claim 16 wherein the atomic ratio of copper to chromium in the first aqueous solution is about 1:

1.

18. The process of claim 16 wherein the soluble base in the second aqueous solution is ammonium hydroxide.

19. The process of claim 16 wherein the first aqueous solution contains from about 1 to about 15% by weight of manganese based on the total weight of metals present in the first solution.

32. A catalyst prepared in accordance with the process of claim 16.

20. A catalyst in powdered form comprising a major amount of the oxides of a first metal selected from the group of copper or zinc and a second metal selected from chromium, molybdenum, tungsten and vanadium, and, optionally, a minor amount of the oxide of a promoter metal selected from the group consisting of manganese, barium, zinc, nickel, cobalt, cadmium, iron and any combination thereof, provided that promoter metal is not zinc if the first metal is zinc, and wherein the average particle diameter of the powder is from about 6 to about 20 microns;

the particle surface area is from about 20 to about 70 m² /g;

the pore volume of pores having diameters in the range up to 120 Å

is from about 5 to about 45%, in the range of about 120 to about 350 Å

is from about 40 to about 80%, and in the range of about 350 to about 1000 Å

is from about 10 to about 40% of the total pore volume.

21. The catalyst of claim 20 wherein the first metal is copper.

22. The catalyst of claim 20 containing up to about 15% by weight of at least one oxide of at least one promoter metal.

23. The catalyst of claim 20 wherein the promoter metal is manganese.

24. The catalyst of claim 20 wherein the second metal is chromium.

25. The catalyst of claim 24 wherein the packed bulk density is from about 0.8 to about 1.3 g/cc.

26. The catalyst of claim 25 wherein the atomic ratio of copper:

chromium is about 1;

1.

27. The catalyst of claim 23 containing from 1 to about 15% by weight of manganese.

28. The catalyst of claim 20 wherein the surface area of the particles is in the range of from about 25 to about 65 m² /g.

29. The catalyst of claim 20 wherein the average particle diameter of the powder is from about 6 to about 12 microns.

30. The catalyst of claim 20 wherein the particles are all below 25 microns in diameter, at least about 80% are below 15 microns, about 50% are below about 8 microns and about 0% are below 2 microns.