Production of ethanol from methanol

• US 8,080,693 B2
• Filed: 02/20/2009
• Issued: 12/20/2011
• Est. Priority Date: 02/28/2008
• Status: Active Grant

• Current Assignee: Enerkem Inc.
• Original Assignee: Enerkem Inc.
• Inventors: Chornet, Esteban, Valsecchi, Boris, Lavoie, Jean-Michel, Avila, Yasmin, Nguyen, Betty
• Primary Examiner(s): WITHERSPOON, SIKARL A
• Application Number:
  US12/378,903
• Publication Number:
  US 20090326080A1
• Time in Patent Office: 1,033 Days
• Field of Search: 568/885, 568/902.2
• US Class Current: 568/885
• CPC Class Codes: C07C 29/149 with hydrogen or hydrogen-containing gases
• CPC Class Codes: C07C 31/08 Ethanol
• CPC Class Codes: C07C 51/12 on an oxygen-containing group in organic compounds, e.g. alcohols
• CPC Class Codes: C07C 53/08 Acetic acid pyroligneous acid C10C; preparation of vinegar C12J
• CPC Class Codes: C07C 67/08 by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
• CPC Class Codes: C07C 67/36 by reaction with carbon monoxide or formates C07C67/02, C07C67/03, C07C67/10 take precedence
• CPC Class Codes: C07C 69/14 of monohydroxylic compounds

Abstract

A process for converting methanol to ethanol which comprises reacting methanol and carbon monoxide in the presence of a catalyst to produce a product comprising at least 25 mole % methyl acetate and, in some instances, acetic acid. The acetic acid then is reacted with at least one alcohol to produce at least one acetate selected from methyl acetate, ethyl acetate, and butyl acetate. The at least one acetate (if produced) and the methyl acetate produced as a result of reacting methanol and carbon monoxide then are hydrogenated to produce ethanol. Syngas may be produced from biomass to produce all or a portion of the methanol, hydrogen, and carbon monoxide requirements for the process.

Claims

1. A process for converting methanol to ethanol, comprising:

(a) reacting methanol and carbon monoxide in the liquid phase, and under conditions to produce a product comprising at least 25 mole % methyl acetate; and

(b) hydrogenating said methyl acetate to produce ethanol.

2. The process of claim 1 wherein said methanol and said carbon monoxide are reacted at a molar ratio of methanol to carbon monoxide of from about 2 to about 10.

3. The process of claim 2 wherein said methanol and said carbon monoxide are reacted at a molar ratio of methanol to carbon monoxide of from about 2 to about 5.

4. The process of claim 1 wherein said methanol and said carbon monoxide are reacted at a temperature of from about 100°

C. to about 350°

C.

5. The process of claim 4 wherein said methanol and said carbon monoxide are reacted at a temperature of from about 120°

C. to about 280°

C.

6. The process of claim 5 wherein said methanol and said carbon monoxide are reacted at a temperature of from about 150°

C. to about 250°

C.

7. The process of claim 6 wherein said methanol and said carbon monoxide are reacted at a temperature of from about 150°

C. to about 200°

C.

8. The process of claim 1 wherein said methanol and said carbon monoxide are reacted at a pressure of from about 15 atm to about 100 atm.

9. The process of claim 8 wherein said methanol and said carbon monoxide are reacted at a pressure of from about 15 atm to about 50 atm.

10. The process of claim 9 wherein said methanol and said carbon monoxide are reacted at a pressure of from about 20 atm to about 50 atm.

11. The process of claim 1 wherein said methanol and said carbon monoxide are reacted in the presence of a catalyst.

12. The process of claim 11 wherein said catalyst comprises rhodium.

13. The process of claim 12 wherein said catalyst comprises rhodium supported on a support selected from the group consisting of carbon and alumina.

14. The process of claim 11 wherein said catalyst is dispersed in an inert liquid medium.

15. The process of claim 14 wherein said inert liquid medium is an inert oil.

16. The process of claim 1 wherein, in step (a), said methanol is reacted with a CO-rich syngas.

17. The process of claim 1 wherein said product in step (a) further comprises acetic acid.

18. The process of claim 17, and further comprising:

prior to step (b), reacting said acetic acid with at least one alcohol to produce at least one acetate, and in step (b), hydrogenating (i) said methyl acetate produced in step (a), and (ii) said at least one acetate produced by reacting said acetic acid with at said least one alcohol, to produce ethanol.

19. The process of claim 18 wherein said acetic acid is reacted with said at least one alcohol at a temperature of from about 80°

C. to about 250°

C.

20. The process of claim 19 wherein said acetic acid is reacted with said at least one alcohol at a temperature of from about 80°

C. to about 150°

C.

21. The process of claim 20 wherein said acetic acid is reacted with said at least one alcohol at a temperature of from about 80°

C. to about 120°

C.

22. The process of claim 18 wherein said acetic acid is reacted with said at least one alcohol at a pressure of from about 1 atm to about 20 atm.

23. The process of claim 22 wherein said acetic acid is reacted with said at least one alcohol at a pressure of from about 1 atm to about 10 atm.

24. The process of claim 18 wherein said at least one alcohol is ethanol.

25. The process of claim 18 wherein said at least one alcohol is methanol.

26. The process of claim 18 wherein said at least one alcohol is butanol.

27. The process of claim 18 wherein said at least one alcohol includes methanol and ethanol.

28. The process of claim 1 wherein said methyl acetate is hydrogenated at a temperature of from about 150°

C. to about 300°

C.

29. The process of claim 28 wherein said methyl acetate is hydrogenated at a temperature of from about 170°

C. to about 275°

C.

30. The process of claim 29 wherein said methyl acetate is hydrogenated at a temperature of from about 225°

C. to about 275°

C.

31. The process of claim 1 wherein said methyl acetate is reacted with said hydrogen at a pressure of from about 10 atm to about 100 atm.

32. The process of claim 31 wherein said methyl acetate is reacted with said hydrogen at a pressure of from about 20 atm to about 60 atm.

33. The process of claim 1, wherein, in step (b), said methyl acetate is hydrogenated by reacting said methyl acetate with a hydrogen-rich syngas.

34. A process for converting methanol to ethanol, comprising:

(a) reacting methanol and carbon monoxide at a molar ratio of methanol to carbon monoxide of from about 2 to about 10, a temperature of from about 175°

C. to about 250°

C., and a pressure of from about 20 atm to about 50 atm, in the presence of a catalyst wherein said catalyst consists essentially of rhodium or consists essentially of rhodium supported on a support selected from the group consisting of carbon and alumina, wherein said catalyst is dispersed in an inert oil, to produce a product comprising at least 25 mole % methyl acetate; and

(b) hydrogenating said methyl acetate at a molar ratio of hydrogen to methyl acetate of from about 5 to about 10, at a temperature of from about 225°

C. to about 275°

C., and at a pressure of from about 10 atm to about 50 atm, in the presence of a catalyst comprising copper, to produce ethanol.

35. A process for producing ethanol from synthesis gas, said synthesis gas comprising carbon monoxide and hydrogen, said process comprising:

(a) reacting a first portion of said carbon monoxide with a first portion of said hydrogen to produce methanol;

(b) reacting said methanol produced in step (a) with a second portion of said carbon monoxide in the liquid phase and under conditions to produce a product comprising at least 25 mole % methyl acetate; and

(c) hydrogenating said methyl acetate with a second portion of said hydrogen to produce ethanol.

36. A process for producing ethanol from synthesis gas, said synthesis gas comprising carbon monoxide and hydrogen, said process comprising:

(a) reacting said carbon monoxide of said synthesis gas with a first portion of said hydrogen of said synthesis gas to produce a product comprising methanol, wherein up to 50 mole % of said carbon monoxide is converted to said methanol;

(b) reacting said methanol produced in step (a) with the unreacted carbon monoxide from step (a) under conditions to produce a product comprising at least 25 mole % methyl acetate; and

(c) hydrogenating said methyl acetate with a second portion of said hydrogen of said synthesis gas to produce ethanol.

37. The process of claim 36 wherein said first portion of said hydrogen is reacted with said carbon monoxide at a H₂:

CO molar ratio of from about 1;

1 to about 3;

1.

38. The process of claim 36 wherein said methanol and said unreacted carbon monoxide from step (a) are reacted at a molar ratio of methanol to carbon monoxide of from about 2 to about 10.

39. The process of claim 38 wherein said methanol and said unreacted carbon monoxide from step (a) are reacted at a molar ratio of methanol to carbon monoxide of from about 2 to about 5.

40. The process of claim 36 wherein said methanol and said unreacted carbon monoxide from step (a) are reacted at a temperature of from about 100°

C. to about 350°

C.

41. The process of claim 40 wherein said methanol and said unreacted carbon monoxide from step (a) are reacted at a temperature of from about 120°

C. to about 280°

C.

42. The process of claim 41 wherein said methanol and said unreacted carbon monoxide from step (a) are reacted at a temperature of from about 150°

C. to about 250°

C.

43. The process of claim 42 wherein said methanol and said unreacted carbon monoxide from step (a) are reacted at a temperature of from about 150°

C. to about 200°

C.

44. The process of claim 36 wherein said methanol and said unreacted carbon monoxide from step (a) are reacted at a pressure of from about 15 atm to about 100 atm.

45. The process of claim 44 wherein said methanol and said unreacted carbon monoxide from step (a) are reacted at a pressure of from about 15 atm to about 50 atm.

46. The process of claim 45 wherein said methanol and said unreacted carbon monoxide from step (a) are reacted at a pressure of from about 20 atm to about 50 atm.

47. The process of claim 36 wherein said methanol and said unreacted carbon monoxide from step (a) are reacted in the presence of a catalyst.

48. The process of claim 47 wherein said catalyst comprises rhodium.

49. The process of claim 48 wherein said catalyst comprises rhodium supported on a support selected from the group consisting of carbon and alumina.

50. The process of claim 47 wherein said catalyst is dispersed in an inert liquid medium.

51. The process of claim 50 wherein said inert liquid medium is an inert oil.

52. The process of claim 36 wherein said product in step (a) further comprises acetic acid.

53. The process of claim 52, and further comprising:

prior to step (b), reacting said acetic acid with at least one alcohol to produce at least one acetate, and in step (b), hydrogenating (i) said methyl acetate produced in step (a), and (ii) said at least one acetate produced by reacting said acetic acid with at least one alcohol, to produce ethanol.

54. The process of claim 53 wherein said acetic acid is reacted with said at least one alcohol at a temperature of from about 80°

C. to about 250°

C.

55. The process of claim 54 wherein said acetic acid is reacted with said at least one alcohol at a temperature of from about 80°

C. to about 150°

C.

56. The process of claim 55 where said acetic acid is reacted with said at least one alcohol at a temperature of from about 80°

C. to about 120°

C.

57. The process of claim 53 wherein said acetic acid is reacted with said at least one alcohol at a pressure of from about 1 atm to about 20 atm.

58. The process of claim 57 wherein said acetic acid is reacted with said at least one alcohol at a pressure of from about 1 atm to about 10 atm.

59. The process of claim 53 where said at least one alcohol is ethanol.

60. The process of claim 53 wherein said at least one alcohols is methanol.

61. The process of claim 53 wherein said at least one alcohol is butanol.

62. The process of claim 53 wherein said at least one alcohol includes methanol and ethanol.

63. The process of claim 36 wherein said methyl acetate is hydrogenated at a temperature of from about 150°

C. to about 300°

C.

64. The process of claim 63 wherein said methyl acetate is hydrogenated at a temperature of from about 170°

C. to about 275°

C.

65. The process of claim 64 wherein said methyl acetate is hydrogenated at a temperature of from about 225°

C. to about 275°

C.

66. The process of claim 36 wherein said methyl acetate is reacted with said hydrogen at a pressure of from about 10 atm to about 100 atm.

67. The process of claim 66 wherein said methyl acetate is reacted with said hydrogen at a pressure of from about 20 atm to about 60 atm.

68. A process for converting methanol to ethanol, comprising:

(a) reacting methanol and carbon monoxide in the presence of a catalyst, wherein said catalyst consists essentially of rhodium or consists essentially of rhodium supported on support selected from the group consisting of carbon and alumina, and under conditions to produce a product comprising at least 25 mole % methyl acetate; and

a. hydrogenating said methyl acetate to produce ethanol.