Selective acetylene hydrogenation

• US 5,488,024 A
• Filed: 07/01/1994
• Issued: 01/30/1996
• Est. Priority Date: 07/01/1994
• Status: Expired due to Term

• Current Assignee: Phillips Petroleum Company (ConocoPhillips)
• Original Assignee: Phillips Petroleum Company (ConocoPhillips)
• Inventors: Johnson, Marvin M., Brown, Scott H., Kimble, James B., Zisman, Stan A., Cheung, Tin-Tack P.
• Primary Examiner(s): Cross, E. Rollins
• Assistant Examiner(s): Irzinski, E. D.
• Application Number:
  US08/269,723
• Time in Patent Office: 578 Days
• Field of Search: 585/259, 585/260, 585/261, 585/262, 585/500, 585/601, 502/202, 502/207, 502/300, 502/325, 502/328, 502/329, 502/330, 502/332, 502/333, 502/340, 502/341, 502/342, 502/343, 502/344, 502/347, 502/348
• US Class Current: 178/18.07
• CPC Class Codes: B01J 23/50 Silver
• CPC Class Codes: B01J 23/66 Silver or gold
• CPC Class Codes: B01J 37/16 Reducing
• CPC Class Codes: C07C 11/04 Ethylene
• CPC Class Codes: C07C 2521/04 Alumina
• CPC Class Codes: C07C 2521/06 Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
• CPC Class Codes: C07C 2523/04 Alkali metals
• CPC Class Codes: C07C 2523/44 Palladium
• CPC Class Codes: C07C 2523/50 Silver
• CPC Class Codes: C07C 2523/66 Silver or gold
• CPC Class Codes: C07C 5/09 to carbon-to-carbon double bonds
• CPC Class Codes: C07C 7/167 for removal of compounds containing a triple carbon-to-carbon bond
• CPC Class Codes: Y02P 20/52 using catalysts, e.g. selective catalysts

Abstract

A catalyst composition comprising palladium, silver and a support material (preferably alumina) is contacted at a relatively low temperature (of up to about 60° C.) with a liquid composition comprising an effective reducing agent (preferably an alkali metal borohydride, hydrazine, formaldehyde, formic acid, ascorbic acid, dextrose, aluminum powder). Preferably, at least one alkali metal compound (more preferably KOH, RbOH, CsOH, KF) is also present in the liquid composition. An improved process for selectively hydrogenating acetylene (to ethylene) employs this wet-reduced catalyst composition.

Claims

1. A preparation method which consists essentially of the steps of:

(1) contacting (a) a solid composition comprising palladium, silver and an inorganic support material with (b) a liquid reduction composition comprising (i) at least one reducing agent selected from the group consisting of hydrazine and alkali metal borohydrides and (ii) at least one non-reducing liquid component, at a temperature of up to about 60°

C. for a time period of at least about 1 second, so as to produce a wet-reduced solid composition;

(2) substantially separating said wet-reduced solid composition produced in step (1) from said liquid reduction composition; and

(3) drying the substantially separated, wet-reduced solid composition obtained in step 2.

2. A method in accordance with claim 1, wherein said inorganic support material is selected from the group consisting of alumina, titania, zirconia and mixtures thereof;

said at least one non-reducing liquid component is selected from the group consisting of water, methanol and mixtures thereof;

said temperature is about 10°

-60°

C.; and

said time period is about 10 seconds to about 10 hours.

3. A method in accordance with claim 2, wherein said inorganic support material is alpha-alumina, and said solid composition contains about 0.01-0.2 weight percent palladium and about 0.02-2 weight percent silver.

4. A method in accordance with claim 3, wherein said at least one reducing agent is selected from the group consisting of sodium borohydride and potassium borohydride.

5. A method in accordance with claim 3 wherein said at least one reducing agent is hydrazine.

6. A method in accordance with claim 1, wherein the weight percentage of said at least one reducing agent in said liquid reduction composition is about 0.5-50 weight-%.

7. A method in accordance with claim 1, wherein said liquid reduction composition comprises hydrazine and additionally at least one alkali metal compound selected from the group consisting of halides, hydroxides, carbonates, bicarbonates, nitrates and carboxylates.

38. A method in accordance with claim 2, wherein said temperature is about 20°

-50°

C., said time period is about 0.02-2 hours, and the pressure during said contacting is approximately atmospheric.

8. A preparation method which consists essentially of the steps of:

(1) contacting (a) a solid composition comprising palladium, silver and an inorganic support material with (b) a liquid reduction composition comprising (i) at least one reducing agent selected from the group consisting of hydrazine and alkali metal borohydrides and (ii) at least one non-reducing liquid component, at a temperature of up to about 60°

C. for a time period of at least one second, so as to produce a wet-reduced solid composition;

(2) substantially separating said wet-reduced solid composition produced in step (1) from said liquid reduction composition;

(3) drying the substantially separated, wet-reduced solid composition obtained in step 2; and

(4) heating the dried, wet-reduced solid composition obtained in step (3) in an oxidizing gas atmosphere at a temperature of about 300°

-700 °

C. for a time period of at least about 10 minutes.

9. A method in accordance with claim 8, wherein said inorganic support material is selected from the group consisting of alumina, titania, zirconia and mixtures thereof:

said non-reducing liquid component is selected from the group consisting of water, methanol and mixtures thereof;

said temperature in step (1) is about 10°

-60°

C.; and

said time period in step (1) is about 10 seconds to about 10 hours.

10. A method in accordance with claim 9, wherein said temperature in step (1) is about 20°

-50°

C. said time period in step (1) is about 0.02-2 hours, and the pressure during said contacting is approximately atmospheric.

11. A method in accordance with claim 9, wherein said inorganic support material is alpha-alumina, and said solid composition contains about 0.01-0.2 weight-% palladium and about 0.02-2 weight-% silver.

12. A method in accordance with claim 11, wherein said at least one reducing agent in said reduction composition is hydrazine.

13. A method in accordance with claim 12, wherein said reduction composition further comprises potassium hydroxide.

14. A method in accordance with claim 11, wherein said at least one reducing agent is selected from the group consisting of sodium borohydride and potassium borohydride.

15. A method in accordance with claim 8, wherein the weight percentage of said at least one reducing agent in said liquid reduction composition is about 0.5-50 weight-%.

16. A method in accordance with claim 8, wherein said liquid reduction composition comprises hydrazine and additionally at least one alkali metal compound selected from the group of halides, hydroxides, carbonates, bicarbonates, nitrates and carboxylates.

17. A method in accordance with claim 8, wherein said heating in step (4) is carried out in air at a temperature of about 400°

-600°

C. for a time period of about 0.2-20 hours.

18. A preparation method which consists essentially of the steps of:

(1) contacting (a) a solid composition comprising palladium silver and an inorganic support material with (b) a liquid reduction composition comprising (i) at least one reducing agent selected from the group consisting of aldehydes containing 1-6 carbon atoms per molecule, ketones containing 1-6 carbon atoms per molecule, carboxylic acids containing 1-6 carbon atoms per molecule, aluminum metal and zinc metal, and (ii) at least one non-reducing liquid component, and (iii) at least one dissolved alkali metal compound selected from the group consisting of alkali metal hydroxides and alkali metal fluorides, at a temperature of up to about 60°

C. for a time period of at least about 1 second, so as to produce a wet-reduced solid composition;

(2) substantially separating said wet-reduced solid composition produced in step (1) from said liquid reduction composition; and

(3) drying the substantially separated, wet-reduced solid composition obtained in step (2).

19. A method in accordance with claim 18, wherein said inorganic support material is selected from the group consisting of alumina, titania, zirconia and mixtures thereof;

said at least one reducing agent is selected from the group consisting of formaldehyde, formic acid, ascorbic acid and aluminum metal;

said at least one non-reducing liquid component is selected from the group consisting of water, methanol and mixtures thereof;

said at least one dissolved alkali metal compound is selected from the group consisting of potassium hydroxide, potassium fluoride, rubidium hydroxide, rubidium fluoride, cesium hydroxide and cesium fluoride;

said temperature is about 10°

-60°

C., and said time period is about 10 seconds to about 10 hours.

20. A method in accordance with claim 19, wherein said temperature is about 20°

-50°

C., said time period is about 0.02-2 hours, and the pressure during said contacting is approximately atmospheric.

21. A method in accordance with claim 19 wherein said inorganic support material is alpha-alumina, and said solid composition contains about 0.01-0.2 weight-% palladium and about 0.02-2 weight-% silver.

22. A method in accordance with claim 21, wherein said at least one reducing agent is formaldehyde, and said at least one alkali metal compound is selected from the group consisting of potassium hydroxide and potassium fluoride.

23. A method in accordance with claim 21, wherein said at least one reducing agent is selected from the group consisting of formic acid and ascorbic acid, and said at least one alkali metal compound is selected from the group consisting of potassium hydroxide and potassium fluoride.

24. A method in accordance with claim 21, wherein said at least one reducing agent is aluminum metal powder, and said at least one alkali metal compound is selected from the group consisting of potassium hydroxide and potassium fluoride.

25. A method in accordance with claim 18, wherein the weight percentage of said at least one reducing agent in said liquid reduction composition is about 0.5-50 weight-%.

26. A method in accordance with claim 18, wherein said liquid reduction composition consists essentially of components (i), (ii) and (iii).

27. A preparation method which consists essentially of the steps of:

(1) contacting (a) a solid composition comprising palladium, silver and an inorganic support material with (b) a liquid reduction composition comprising (i) at least one reducing agent selected from the group consisting of aldehydes containing 1-6 carbon atoms per molecule, ketones containing 1-6 carbon atoms per molecule, carboxylic acids containing 1-6 carbon atoms per molecule, sugars containing an aldehyde group, sugars containing an α

-hydroxyketone group, aluminum metal and zinc metal, (ii) at least one non-reducing liquid component, and (iii) at least one dissolved alkali metal compound selected from the group consisting of alkali metal hydroxides and alkali metal fluorides, at a temperature of up to about 60°

C. for a time period of at least about 1 second, so as to produce a wet-reduced, solid composition;

(2) substantially separating the wet-reduced solid composition produced in step (1) from said liquid reduction composition;

(3) drying the substantially separated, wet-reduced solid composition obtained in step (2); and

(4) heating the dried, wet-reduced solid composition obtained in step (3) in an oxidizing gas atmosphere at a temperature of about 300°

-700°

C. for a time period of at least about 10 minutes.

28. A method in accordance with claim 27, wherein said inorganic support material is selected from the group consisting of alumina, titania and zirconia;

said at least one reducing agent is selected from the group consisting of formaldehyde, formic acid, ascorbic acid, dextrose and aluminum metal;

said at least one non-reducing liquid component is selected from the group consisting of water, methanol and mixtures thereof;

said at least one dissolved alkali metal is selected from the group consisting of potassium hydroxide, potassium fluoride, rubidium hydroxide, rubidium fluoride, cesium hydroxide and cesium fluoride;

said temperature in step (1) is about 10°

-60°

C.; and

said time period in step (1) is about 10 seconds to about 10 hours.

29. A method in accordance with claim 28, wherein said temperature in step (1) is about 20°

-50°

C., said time period in step (1) is about 0.02-2 hours, and the pressure during said contacting is about atmospheric.

30. A method in accordance with claim 28, wherein said inorganic support material is alpha-alumina, and said solid composition contains about 0.01-0.2 weight-% palladium and about 0.02-2 weight-% silver.

31. A method in accordance with claim 30, wherein said at least one reducing agent is formaldehyde, and said at least one alkali metal compound is selected from the group consisting of potassium hydroxide and potassium fluoride.

32. A method in accordance with claim 30, wherein said at least one reducing agent is selected from the group consisting of formic acid and ascorbic acid, and said at least one alkali metal compound is selected from the group consisting of potassium hydroxide and potassium fluoride.

33. A method in accordance with claim 30, wherein said at least one reducing agent is dextrose, and said at least one alkali metal compound is selected from the group consisting of potassium hydroxide and potassium fluoride.

34. A method in accordance with claim 30, wherein said at least one reducing agent is aluminum metal powder, and said at least one alkali metal compound is selected from the group consisting of potassium hydroxide and potassium fluoride.

35. A method in accordance with claim 27, wherein the weight percentage of said at least one reducing agent in said liquid reduction composition is about 0.5-50 weight-%.

36. A method in accordance with claim 27, wherein said liquid reduction composition consists essentially of components (i), (ii) and (iii).

37. A method in accordance with claim 27, wherein step (4) is carried out in air at a temperature of about 400°

-600°

C. for a time period of about 0.2-20 hours.