ALTERNATIVE PATHS TO ALCOHOLS AND HYDROCARBONS FROM BIOMASS

• US 20100185021A1
• Filed: 12/02/2009
• Published: 07/22/2010
• Est. Priority Date: 12/02/2008
• Status: Active Grant

• Current Assignee: Terrabon Mix-Alco, LLC, Texas A&M University System
• Original Assignee: Texas A&M University System
• Inventors: Spencer, John, Luce, Gary, Spencer, Rae, Vasquez, Sebastian Taco, Holtzapple, Mark T., Granda, Cesar B., Ross, Michael Kyle
• Granted Patent: US 8,232,440 B2
• Time in Patent Office: Days
• US Class Current: 568/700
• CPC Class Codes: C07C 1/24 by elimination of water
• CPC Class Codes: C07C 2/02 by addition between unsaturated hydrocarbons
• CPC Class Codes: C07C 29/149 with hydrogen or hydrogen-containing gases
• CPC Class Codes: C07C 31/08 Ethanol
• CPC Class Codes: C07C 67/04 by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
• CPC Class Codes: C07C 69/14 of monohydroxylic compounds
• CPC Class Codes: C10G 2300/1011 Biomass
• CPC Class Codes: C10G 2300/4081 Recycling aspects
• CPC Class Codes: C10G 2300/42 Hydrogen of special source or of special composition
• CPC Class Codes: C10G 2400/20 C2-C4 olefins
• CPC Class Codes: C10G 2400/22 Higher olefins
• CPC Class Codes: C10G 3/00 Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids production from non-melting solid oxygen-containing carbonaceous materials C10G1/00
• CPC Class Codes: C10G 50/00 Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
• CPC Class Codes: C12P 7/40 containing a carboxyl group including Peroxycarboxylic acids
• CPC Class Codes: Y02P 30/20 using bio-feedstock

Abstract

A method of producing alcohols, hydrocarbons, or both from biomass by converting biomass into a carboxylic acid, reacting the carboxylic acid with an olefin to produce an ester and hydrogenolyzing the ester to produce alcohol. A method of producing hydrocarbons from biomass by converting at least a portion of the biomass into a carboxylic acid, a ketone, or an ammonium carboxylate salt, reacting at least one of a portion of the carboxylic acid, a portion of the ketone, or a portion of the ammonium carboxylate salt in an oligomerization reactor as at least part of a process that produces an oligomerization product and separating hydrocarbons from the oligomerization product.

Claims

1. A method of producing alcohols, hydrocarbons, or both from biomass, the method comprising:

converting biomass into a carboxylic acid;

reacting the carboxylic acid with an olefin to produce an ester; and

hydrogenolyzing the ester to produce alcohol.

2. The method of claim 1, wherein reacting the carboxylic acid with an olefin to produce an ester and hydrogenolyzing the ester to produce an alcohol are carried out in the same reactor.

3. The method of claim 2, wherein reacting the carboxylic acid with an olefin to produce an ester and hydrogenolyzing the ester to produce an alcohol are carried out with one catalyst.

4. The method of claim 1, further comprising:

dehydrating at least a portion of the alcohol to produce an olefin feed, at least a portion of the olefin feed providing the olefin that reacts with the carboxylic acid to produce the ester.

5. The method of claim 4, wherein reacting the carboxylic acid with an olefin to produce an ester and hydrogenolyzing the ester to produce an alcohol are carried out in the same reactor.

6. The method of claim 5, wherein reacting the carboxylic acid with an olefin to produce an ester and hydrogenolyzing the ester to produce an alcohol are carried out with one catalyst.

7. The method of claim 4, further comprising:

oligomerizing at least another portion of the alcohol to produce hydrocarbons.

8. The method of claim 4, further comprising:

oligomerizing at least another portion of the olefin feed to produce hydrocarbons.

9. The method of claim 1, further comprising:

oligomerizing at least a portion of the alcohol to produce an olefin feed, at least a portion of the olefin feed providing the olefin that reacts with the carboxylic acid to produce the ester.

10. The method of claim 1, further comprising:

oligomerizing at least a portion of the alcohol to produce hydrocarbons.

11. The method of claim 10, wherein reacting the carboxylic acid with an olefin to produce an ester and hydrogenolyzing the ester to produce an alcohol are carried out in the same reactor.

12. The method of claim 11, wherein reacting the carboxylic acid with an olefin to produce an ester and hydrogenolyzing the ester to produce an alcohol are carried out with one catalyst.

13. The method of claim 10, further comprising:

oligomerizing at least another portion of the alcohol to produce an olefin feed, at least a portion of the olefin feed providing the olefin that reacts with the carboxylic acid to produce the ester.

14. The method of claim 1, wherein converting the biomass into a carboxylic acid further comprises:

fermenting the biomass to yield a liquid fermentation broth comprising water and carboxylate salts;

dewatering the liquid fermentation broth to separate the water from the carboxylate salts; and

converting the carboxylate salts into carboxylic acids.

15. The method of claim 1, furthering comprising:

converting the alcohol into a hydrocarbon.

16. The method of claim 15, wherein reacting the carboxylic acid with an olefin to produce an ester and hydrogenolyzing the ester to produce an alcohol are carried out in the same reactor.

17. The method of claim 16, wherein reacting the carboxylic acid with an olefin to produce an ester and hydrogenolyzing the ester to produce an alcohol are carried out with one catalyst.

18. The method of claim 15, wherein converting the alcohol into a hydrocarbon comprises an oligomerization process.

19. The method of claim 18, wherein the converting the alcohol into a hydrocarbon comprises:

oligomerizing at least a portion of the alcohol to produce the hydrocarbon.

20. The method of claim 18, wherein the converting the alcohol into a hydrocarbon comprises:

dehydrating at least a portion of the alcohol to produce an olefin feed; and

oligomerizing at least a portion of the olefin feed to produce the hydrocarbon.

21. A method of producing hydrocarbons from biomass, the method comprising:

converting at least a portion of the biomass into a carboxylic acid, a ketone, or an ammonium carboxylate salt;

reacting at least one of a portion of the carboxylic acid, a portion of the ketone, or a portion of the ammonium carboxylate salt in an oligomerization reactor as at least part of a process that produces an oligomerization product; and

separating hydrocarbons from the oligomerization product.

22. The method of claim 21, further comprising:

converting another portion of the carboxylic acid, another portion of the ketone, or another portion of the ammonium carboxylate salt to alcohol; and

providing at least a portion of the alcohol to the oligomerization reactor for the process that produces the oligomerization product.

23. The method of claim 22, wherein converting the another portion of the carboxylic acid into alcohol comprises:

reacting the another portion of the carboxylic acid with an olefin to produce an ester; and

hydrogenolyzing the ester to produce the alcohol.

24. The method of claim 22, wherein reacting at least one of the portion of the carboxylic acid, the portion of the ketone, or the portion of the ammonium carboxylate salt in the oligomerization reactor as at least part of the process that produces the oligomerization product and converting the another portion of the carboxylic acid, the another portion of the ketone, or the another portion of the ammonium carboxylate salt to alcohol are carried out in the oligomerization reactor.

25. The method of claim 24, wherein reacting at least one of the portion of the carboxylic acid, the portion of the ketone, or the portion of the ammonium carboxylate salt in the oligomerization reactor as at least part of the process that produces the oligomerization product and converting the another portion of the carboxylic acid, the another portion of the ketone, or the another portion of the ammonium carboxylate salt to alcohol are carried out with one catalyst.

26. The method of claim 22, further comprising:

separating a recycle stream from the oligomerization product;

processing the recycle stream in a reformer to produce hydrogen; and

providing a least a portion of the produced hydrogen for the process of converting the another portion of the carboxylic acid, the another portion of the ketone, or the another portion of the ammonium carboxylate salt to alcohol.

27. The method of claim 26, wherein at least a portion of the biomass is converted to the ammonium carboxylate salt, the method further comprising:

separating ammonia from the recycle stream prior to processing the recycle stream in a reformer to produce hydrogen.

28. The method of claim 26, further comprising:

separating olefins from the recycle stream prior to processing the recycle stream in a reformer to produce hydrogen; and

providing the olefins to the oligomerization reactor for the process that produces the oligomerization product.

29. The method of claim 28, wherein at least a portion of the biomass is converted to an ammonium carboxylate salt, the method further comprising:

separating ammonia from the recycle stream prior to processing the recycle stream in a reformer to produce hydrogen.

30. The method of claim 22, further comprising:

separating a recycle stream from the oligomerization product;

separating olefins from the recycle stream; and

providing the olefins to the oligomerization reactor for the process that produces the oligomerization product.

31. The method of claim 21, wherein at least a portion of the biomass is converted into a carboxylic acid.

32. The method of claim 31, wherein converting at least a portion of the biomass into a carboxylic acid comprises:

fermenting the biomass to produce a calcium carboxylate salt or an ammonium carboxylate salt; and

converting the calcium carboxylate salt or the ammonium carboxylate salt to carboxylic acid using an acid recovery process.

33. The method of claim 21, wherein at least a portion of the biomass is converted into a ketone.

34. The method of claim 33, wherein converting at least a portion of the biomass into a ketone comprises:

fermenting the biomass to produce a calcium carboxylate salt; and

thermally converting the calcium carboxylate salt into the ketone.

35. The method of claim 33, wherein converting at least a portion of the biomass into a ketone comprises:

fermenting the biomass to produce a calcium carboxylate salt or an ammonium carboxylate salt;

converting the calcium carboxylate salt or the ammonium carboxylate salt to carboxylic acid using an acid recovery process, and

catalytically converting carboxylic acid into ketone.

36. The method of claim 33, further comprising converting another portion of the ketone into alcohol by hydrogenating the another portion of the ketone.

37. The method of claim 21, wherein converting at least a portion of the biomass into a ketone comprises:

fermenting the biomass to produce a calcium carboxylate salt; and

producing hot ketone vapors and calcium carbonate in a ketone reactor operated with a sweep gas.

38. The method of claim 37 wherein the sweep gas is reactive, condensable or both.

41. The method of claim 21, wherein at least a portion of the biomass is converted into the ammonium carboxylate salt.

42. The method of claim 41, further comprising converting another portion of the ammonium carboxylate salt to alcohol;

and

providing the alcohol to the oligomerization reactor for the process that produces the oligomerization product,

wherein converting the another portion of the ammonium carboxylate salt into alcohol comprises;

converting the another portion of the ammonium carboxylate salt into a second carboxylic acid;

reacting the second carboxylic acid with an olefin to produce an ester; and

hydrogenolyzing the ester to produce the alcohol.

43. The method of claim 41, further comprising:

separating ammonia from the ammonium carboxylate salt prior to reacting the portion of the ammonium carboxylate salt in the oligomerization reactor as at least part of the process that produces the oligomerization product.

44. The method of claim 21, wherein converting at least a portion of the biomass into a carboxylic acid, a ketone, or an ammonium carboxylate salt comprises a fermentation process in a fermenter, the method further comprising:

separating a gaseous recycle stream from the oligomerization product; and

providing at least a portion of the gaseous recycle stream to the fermenter.

45. The method of claim 44, further comprising:

converting another portion of the carboxylic acid, another portion of the ketone, or another portion of the ammonium carboxylate salt to alcohol; and

providing the alcohol to the oligomerization reactor.

46. The method of claim 45, wherein at least a portion of the biomass is converted into a carboxylic acid.

47. The method of claim 45, wherein at least a portion of the biomass is converted into a ketone.

48. The method of claim 45, wherein at least a portion of the biomass is converted into an ammonium carboxylate salt.

49. The method of claim 48, further comprising:

separating ammonia from the gaseous recycle stream prior to providing the at least a portion of the gaseous recycle stream to the fermenter.

50. The method of claim 45, wherein reacting at least one of the portion of the carboxylic acid, the portion of the ketone, or the portion of the ammonium carboxylate salt in the oligomerization reactor as at least part of the process that produces the oligomerization product and converting the another portion of the carboxylic acid, the another portion of the ketone, or the another portion of the ammonium carboxylate salt to alcohol are carried out in the oligomerization reactor.

51. The method of claim 50, wherein reacting at least one of the portion of the carboxylic acid, the portion of the ketone, or the portion of the ammonium carboxylate salt in the oligomerization reactor as at least part of the process that produces the oligomerization product and converting the another portion of the carboxylic acid, the another portion of the ketone, or the another portion of the ammonium carboxylate salt to alcohol are carried out with one catalyst.

52. The method of claim 45, further comprising:

separating fermenter gases exiting the fermenter;

processing the fermenter gases in a reformer to produce hydrogen; and

providing a least a portion of the produced hydrogen for the process of converting the another portion of the carboxylic acid, the another portion of the ketone, or the another portion of the ammonium carboxylate salt to alcohol.

39. The method of claim 39 wherein the sweep gas comprises hydrogen.

40. The method of claim 39 wherein the sweep gas comprises steam.