RUTHENIUM-COPPER CHROMITE HYDROGENATION CATALYSTS

• US 20080194398A1
• Filed: 02/14/2007
• Published: 08/14/2008
• Est. Priority Date: 02/14/2007
• Status: Abandoned Application

• Current Assignee: Eastman Chemical Company
• Original Assignee: Eastman Chemical Company
• Inventors: BARNICKI, SCOTT DONALD, WORSHAM, PAUL RANDOLPH, PERRI, STEVEN THOMAS, LIU, ZHUFANG, GUSTAFSON, BRUCE LEROY
• Application Number:
  US11/674,808
• Publication Number:
  US 20080194398A1
• Time in Patent Office: Days
• US Class Current: 502/103
• CPC Class Codes: B01J 23/868 copper and chromium
• CPC Class Codes: B01J 23/8993 with chromium, molybdenum or tungsten
• CPC Class Codes: B01J 37/0205 in several steps
• CPC Class Codes: C07C 2601/14 The ring being saturated
• CPC Class Codes: C07C 29/149 with hydrogen or hydrogen-containing gases
• CPC Class Codes: C07C 29/157 containing platinum group metals or compounds thereof
• CPC Class Codes: C07C 31/04 Methanol
• CPC Class Codes: C07C 31/08 Ethanol
• CPC Class Codes: C07C 31/10 containing three carbon atoms
• CPC Class Codes: C07C 31/12 containing four carbon atoms
• CPC Class Codes: C07C 31/125 containing five to twenty-two carbon atoms
• CPC Class Codes: C07C 31/1355 with a six-membered ring
• CPC Class Codes: C07C 31/20 Dihydroxylic alcohols
• CPC Class Codes: C07C 31/202 Ethylene glycol
• CPC Class Codes: C07C 31/205 1,3-Propanediol; 1,2-Propanediol
• CPC Class Codes: C07C 31/207 1,4-Butanediol; 1,3-Butanediol; 1,2-Butanediol; 2,3-Butanediol
• CPC Class Codes: C07C 31/22 Trihydroxylic alcohols, e.g. glycerol
• CPC Class Codes: C07C 31/225 Glycerol
• CPC Class Codes: C07C 31/276 with a six-membered ring
• CPC Class Codes: C07C 35/08 containing a six-membered rings
• CPC Class Codes: Y02P 20/52 : using catalysts, e.g. selective catalysts

Abstract

Disclosed are catalysts comprising copper chromite, ruthenium and at least one promoter selected from alkali metals, alkaline earth metals, rare earth elements having hydrogenation activity. The combination of copper chromite with ruthenium and the alkali, alkaline earth, and/or rare earth elements enhances catalyst activity more than the addition of either type of promoter alone. The catalysts are useful for the preparation of methanol from carbon monoxide and hydrogen and for the hydrogenation of carbonyl compounds such as, for example, aldehydes, ketones, and esters, to their corresponding alcohols. The catalysts may be used for the preparation of cyclohexanedimethanols from dialkyl cyclohexanedicarboxylates or of ethylene glycol from alkyl glycolates.

Claims

1. A catalyst, comprising:

copper chromite, ruthenium, and at least one promoter selected from alkali metals, alkaline earth metals, rare earth metals, and manganese, wherein said ruthenium and said at least one promoter are deposited on said copper chromite.

2. The catalyst according to claim 1 which comprises about 0.1 to about 10 weight percent ruthenium, based on the total weight of said catalyst.

3. The catalyst according to claim 2 which comprises about 0.5 to about 5 weight percent ruthenium.

4. The catalyst according to claim 3 which comprises about 0.5 to about 2 weight percent ruthenium.

5. The catalyst according to claim 1 which comprises about 100 to about 5000 parts per million of said at least one promoter, based on the total weight of said catalyst.

6. The catalyst according to claim 5 which comprises about 1000 to about 3000 parts per million of said at least one promoter.

7. The catalyst according to claim 6 which comprises about 1000 to about 2000 part per million of said at least one promoter.

8. The catalyst according to claim 1 wherein said at least one promoter is selected from sodium, potassium, calcium, barium, magnesium, manganese, and lanthanum.

9. The catalyst according to claim 8 wherein said at least one promoter is selected from lanthanum, calcium, barium, and potassium.

10. The catalyst according to claim 1 which comprises at least 60 weight percent weight percent of said copper chromite, based on the total weight of the catalyst.

11. The catalyst according to claim 1 wherein said copper chromite comprises about 15 to 60 weight percent copper and about 15 to 60 weight percent chromium, based on the total weight of said copper chromite.

12. The catalyst according to claim 1 wherein said copper chromite comprises a gram-atom ratio of copper to chromium of about 1:

10 to about 10;

1.

13. The catalyst according to claim 12 wherein said copper chromite comprises a gram-atom ratio of copper to chromium of about 1:

5 to about 5;

1.

14. The catalyst according to claim 13 wherein said copper chromite comprises a gram-atom ratio of copper to chromium of about 1:

2 to about 2;

1.

15. A catalyst, comprising:

copper chromite having a gram-atom ratio of copper to chromium of about 1;

2 to 2;

1, about 0.5 to about 5 weight percent ruthenium and about 100 to about 5000 parts per million of at least one promoter selected from lanthanum, sodium, magnesium, potassium, manganese, calcium and barium, wherein said ruthenium and said at least one promoter are deposited on said copper chromite and said weight percent and parts per million are based on the total weight of said catalyst.

16. The catalyst according to claim 15 which comprises about 1 weight percent ruthenium.

17. The catalyst according to claim 15 which comprises about 1000 parts per million of said at least one promoter.

18. The catalyst according to claim 17 wherein said at least one promoter is selected from lanthanum, sodium, calcium, barium, and manganese.

19. The catalyst according to claim 15 wherein said copper chromite has a gram-atom ratio of copper to chromium of about 1:

1.

20. A catalyst, consisting essentially of:

copper chromite having a gram-atom ratio of copper to chromium of about 1;

2 to 2;

1, about 0.5 to about 5 weight percent ruthenium and about 100 to about 5000 parts per million of at least one promoter selected from lanthanum, sodium, magnesium, potassium, manganese, calcium and barium, wherein said ruthenium and said at least one promoter are deposited on said copper chromite and said weight percent and parts per million are based on the total weight of said catalyst.

21. The catalyst according to claim 20 which comprises about 1 weight percent ruthenium.

22. The catalyst according to claim 20 which comprises about 1000 part per million of said at least one promoter.

23. The catalyst according to claim 22 wherein said at least one promoter is selected from lanthanum, sodium, calcium, barium, and manganese.

24. The catalyst according to claim 20 wherein said copper chromite has a gram-atom ratio of copper to chromium of about 1:

1.

25. A catalyst, comprising:

copper chromite having a gram-atom ratio of copper to chromium of about 1;

1, about 1 weight percent ruthenium and about 1000 parts per million of at least one promoter selected from lanthanum, manganese, sodium, potassium, calcium, magnesium, and barium;

wherein said ruthenium and said at least one promoter are deposited on said copper chromite and said weight percent and parts per million are based on the total weight of said catalyst.

26. A process for the preparation of a catalyst, comprising:

contacting copper chromite with a solution of a ruthenium compound and a solution of at least one promoter selected from compounds of lanthanum, sodium, potassium, magnesium, calcium and barium;

drying said copper chromite, and calcining said dried copper chromite.

27. The process according to claim 26 wherein said catalyst comprises about 0.1 to about 10 weight percent ruthenium and about 100 to about 5000 parts per million of at least one promoter selected from lanthanum, sodium, manganese, potassium, magnesium, calcium, and barium deposited on said copper chromite, wherein said weight percentage and parts per million are based on the total weight of said catalyst.

28. The process according to claim 27 further comprising, (i) contacting copper chromite with a solution of a ruthenium compound;

(ii) drying said copper chromite;

(iii) calcining said dried copper chromite from step (ii);

(iv) contacting said calcined copper chromite from step (iii) with a solution of at least one compound selected from lanthanum, sodium, magnesium, potassium, calcium, manganese, and barium;

(v) drying said copper chromite from step (iv); and

(vi) calcining said dried copper chromite from step (v).

29. The process according to claim 28 wherein said drying steps (ii) and (v) independently are carried out at a temperature of about 40 to about 150°

C. and said calcination steps (iii) and (vi) independently are carried out at a temperature of about 400 to about 600°

C.

30. The process according to claim 28 wherein said catalyst comprises about 0.5 to about 2 weight percent ruthenium and about 1000 to about 2000 parts per million of at least one promoter selected from lanthanum, sodium, calcium, barium, and manganese.

31. A process for the preparation of methanol, comprising:

contacting a gaseous feed comprising hydrogen, carbon monoxide, and optionally carbon dioxide, with a catalyst comprising copper chromite, ruthenium and at least one promoter selected from alkali metals, alkaline earth metals, rare earth metals, and manganese;

wherein said ruthenium and said at least one promoter are deposited on said copper chromite.

32. The process according to claim 31 wherein said catalyst comprises about 0.1 to about 10 weight percent ruthenium, based on the total weight of said catalyst.

33. The process according to claim 32 wherein said catalyst comprises about 0.5 to about 5 weight percent ruthenium.

34. The process according to claim 33 wherein said catalyst comprises about 0.5 to about 2 weight percent ruthenium.

35. The process according to claim 31 wherein said catalyst comprises about 100 to about 5000 part per million of said at least one promoter, based on the total weight of said catalyst.

36. The process according to claim 35 wherein said catalyst comprises about 1000 to about 3000 parts per million of said at least one promoter.

37. The process according to claim 36 wherein said catalyst comprises about 1000 to about 2000 part per million of said at least one promoter.

38. The process according to claim 31 wherein said at least one promoter is selected from sodium, potassium, calcium, barium, manganese, lanthanum, and combinations thereof.

39. The process according to claim 38 wherein said at least one promoter is selected from lanthanum, calcium, barium, potassium and combinations thereof.

40. The process according to claim 31 wherein said catalyst comprises about 85 to about 99.89 weight percent said copper chromite.

41. The process according to claim 31 wherein said copper chromite comprises about 15 to about 60 weight percent copper and about 15 to 60 weight percent chromium, based on the weight of said copper chromite.

42. The process according to claim 41 wherein said copper chromite comprises a gram-atom ratio of copper to chromium of about 1:

10 to about 10;

1.

43. The process according to claim 42 wherein said copper chromite comprises a gram-atom ratio of copper to chromium of about 1:

5 to about 5;

1.

44. The process according to claim 43 wherein said copper chromite comprises a gram-atom ratio of copper to chromium of about 1:

2 to about 2;

1.

45. The process according to claim 31 wherein said contacting is at a temperature of about 150 to about 350°

C. and at a pressure of about 10 to about 100 bara.

46. The process according to claim 45 wherein said contacting is at a temperature of about 180 to about 250°

C. and at a pressure of about 30 to about 70 bara.

47. The process according to claim 46 wherein said catalyst comprises copper chromite having a gram-atom ratio of copper to chromium of about 1:

2 to 2;

1, about 0.5 to about 5 weight percent ruthenium and about 100 to about 5000 parts per million of at least one promoter selected from lanthanum, sodium, potassium, manganese, calcium, magnesium, and barium, said weight percent and parts per million being based on the total weight of said catalyst.

48. The process according to claim 31 wherein said gaseous feed comprises about 1 to about 25 weight % carbon dioxide, based on the total volume of said gaseous feed.

49. The process according to claim 48 wherein said gaseous feed comprises about 1 to about 5 weight percent carbon dioxide.

50. The process according to claim 48 wherein said gaseous feed comprises about 10 to about 20 weight percent carbon dioxide.

51. The process according to claim 31 which comprises contacting said gaseous feed and said catalyst in a fixed bed or a liquid slurry phase reactor.

52. A process for hydrogenating an carbonyl compound to an alcohol, comprising contacting at least one carbonyl compound with hydrogen in the presence of a catalyst comprising copper chromite, ruthenium and at least one promoter selected from alkali metals, alkaline earth metals, rare earth metals, and manganese;

wherein said ruthenium and said at least one promoter are deposited on said copper chromite.

53. The process according to claim 52 wherein said carbonyl compound comprises an aldehyde, ketone, carboxylic acid ester, or combinations thereof.

54. The process according to claim 53 wherein said carboxylic acid ester comprises an alkyl carboxylate comprising the residue of at least one hydroxy compound containing from 1 to about 40 carbon atoms.

55. The process according to claim 54 wherein said hydroxy compound is selected from methanol, ethanol, propanol, 1-butanol, 2-butanol, 2-ethylhexanol, 2,2-dimethyl-1,3-propanediol, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, cyclohexanol, 4-methylcyclohexanemethanol, diethylene glycol, glycerin, trimethylolpropane, and combinations thereof.

56. The process according to claim 54 wherein said alkyl carboxylate comprises the residue of at least one aliphatic, cycloaliphatic, aryl, or aralkyl carboxylic acid having from 1 to 40 carbon atoms.

57. The process according to claim 56 wherein said alkyl carboxylate comprises an alkyl glycolate.

58. The process according to claim 57 wherein said alkyl glycolate comprises methyl glycolate.

59. The process according to claim 56 wherein said cycloaliphatic carboxylic acid is selected from 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and combinations thereof.

60. A process for the preparation of a cyclohexanedimethanol comprising contacting at least one dialkyl cyclohexanedicarboxylate with hydrogen in the presence of a catalyst comprising copper chromite, ruthenium and at least one promoter selected from alkali metals, alkaline earth metals, rare earth metals, and manganese;

wherein said ruthenium and said at least one promoter are deposited on said copper chromite.

61. The process according to claim 60 wherein said dialkyl cyclohexanedicarboxylate is at least one dialkyl 1,4-cyclohexane dicarboxylate comprising the residue of at least one hydroxy compound containing from 1 to about 20 carbon atoms.

62. The process according to claim 61 wherein said dialkyl 1,4-cyclohexanedicarboxylate has a cis:

trans molar ratio of about 1;

1 to about 2;

1 and said 1,4-cyclohexanedimethanol has a cis;

trans molar ratio of 0.7;

1 to about 2;

1.

63. The process according to claim 61 wherein said hydroxy compound is selected from methanol, ethanol, propanol, 1-butanol, 2-butanol, 2-ethylhexanol, 2,2-dimethyl-1,3-propanediol, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, cyclohexanol, 4-methylcyclohexanemethanol, diethylene glycol, glycerin, trimethylolpropane, and combinations thereof.

64. The process according to claim 60 which is a continuous process.

65. The process according to claim 64 which is conducted in the liquid phase, vapor phase, or a combination of liquid and vapor phase.

66. The process according to claim 65 which is at a temperature of about 150°

C. to about 350°

C. and at a pressure is about 40 to about 450 bara.

67. The process according to claim 66 wherein said dialkyl cyclohexanedicarboxylate comprises dimethyl 1,4-cyclohexanedicarboxylate.

68. The process according to claim 67 wherein said contacting is at a temperature of about 180 to about 250°

C. and at a pressure of about 200 to about 350 bara.

69. The process according to claim 68 which comprises contacting said hydrogen said catalyst in a fixed bed or a liquid slurry phase reactor.