PROCESS FOR PRODUCING LOW MOLECULAR WEIGHT HYDROCARBONS FROM RENEWABLE RESOURCES

• US 20100170826A1
• Filed: 03/14/2008
• Published: 07/08/2010
• Est. Priority Date: 03/14/2007
• Status: Active Grant

• Current Assignee: Genomatica Incorporated
• Original Assignee: LS9, Inc.
• Inventors: Rude, Mathew, Friedman, Lisa
• Granted Patent: US 8,110,093 B2
• Time in Patent Office: Days
• US Class Current: 208/16
• CPC Class Codes: C10G 11/00 Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils cracking in direct contact with molten metals or salts C10G9/34
• CPC Class Codes: C10G 11/05 Crystalline alumino-silicates, e.g. molecular sieves
• CPC Class Codes: C10G 11/18 according to the "fluidised-bed" technique
• CPC Class Codes: C10G 2300/1011 Biomass
• CPC Class Codes: C10G 2300/301 Boiling range
• CPC Class Codes: C10G 2400/02 Gasoline
• CPC Class Codes: C10G 2400/04 Diesel oil
• CPC Class Codes: C10G 2400/08 Jet fuel
• CPC Class Codes: C10L 1/00 Liquid carbonaceous fuels
• CPC Class Codes: C10L 1/023 for spark ignition
• CPC Class Codes: C10L 1/026 for compression ignition
• CPC Class Codes: C10L 1/06 for spark ignition
• CPC Class Codes: C10L 1/08 for compression ignition
• CPC Class Codes: C12N 9/1025 Acyltransferases (2.3)
• CPC Class Codes: C12N 9/1029 transferring groups other than amino-acyl groups (2.3.1)
• CPC Class Codes: C12P 7/649 Biodiesel, i.e. fatty acid alkyl esters
• CPC Class Codes: Y02E 50/10 Biofuels, e.g. bio-diesel
• CPC Class Codes: Y02E 50/30 Fuel from waste, e.g. synthetic alcohol or diesel
• CPC Class Codes: Y02P 30/20 using bio-feedstock

Abstract

Described herein are methods for cracking a biocrude, particularly catalytically cracking a biocrude that primarily includes olefmic hydrocarbons. Also described herein are compositions and methods of producing such compositions that are useful as fuels or fuel production feedstock.

Claims

1. A method for cracking a biocrude, the method comprising:

obtaining a biocrude from a recombinant microorganism wherein the recombinant microorganism produces the biocrude from a substrate containing a fatty acyl chain; and

cracking the biocrude resulting in a cracked product.

6. The method of any one of claims 1 to 2, wherein the substrate containing a fatty acyl chain is selected from acyl-ACP, free fatty acid, acyl-CoA, a fatty aldehyde, a hydrocarbon intermediate, such as an aliphatic ketone, a fatty alcohol, such as a short or long chain fatty alcohol, a fatty acid ester, including a wax, a phospholipid, a lipid A, and combinations thereof.

7. The method of any one of claims 1 to 4, wherein the recombinant microorganism over expresses one or more peptides selected acyl-CoA synthetase (EC 6.2.1.3, 2.3.1.86), thioesterase (EC 3.1.2.-, 3.1.1.15, 3.1.2.14), acetyl-CoA carboxylase (EC 6.4.1.2, 6.3.4.14), an acyl-carrier protein, pyruvate dehydrogenase (EC 1.2.4.1), aldehyde decarbonylase (EC 4.1.99.5), beta-hydroxydecanoyl thioester dehydrase (EC 4.2.1.60), 3-oxoacyl-[acyl-carrier-protein] synthase I (EC 2.3.1.41), [acyl-carrier-protein] S-malonyltransferase (EC 2.3.1.39), 3-oxoacyl-[acyl-carrier protein] reductase (EC 1.1.1.100), 3-oxoacyl-[acyl-carrier-protein] synthase III (EC 2.3.1.180), enoyl-[acyl-carrier-protein] reductase (EC 1.3.1.9), (3R)-hydroxymyristol acyl carrier protein dehydratase (EC 4.2.1.-), lipase (EC 3.1.1.3), malonyl-CoA decarboxylase (EC 4.1.1.9, 4.1.1.41), aspartate 1-decarboxylase (EC 4.1.1.11), pantothenate kinase (EC 2.7.1.33), pyruvate dehydrogenase (EC 1.2.4.1), pyridine nucleotide transhydrogenase (EC 1.6.1.1) and hydrocarbon synthase.

8. The method of any one of claims 1 to 4 or 6 to 7, wherein the cracking comprises catalytic cracking.

9. The method of any one of claims 1 to 8, wherein the cracking does not include hydrocracking or steam cracking.

10. The method of claim 8, wherein the cracking comprises contacting the biocrude with a catalyst selected from zeolite, aluminum hydrosilicate, treated bentonite clay, fuller'"'"'s earth, bauxite, amorphous silica-alumina and mixtures or combinations thereof.

11. The method of claim 10, wherein the catalyst is an amorphous silica-alumina.

12. The method of any one of claims 1 to 4, and 6 to 11, wherein the cracking is performed at a temperature of 350°

C. or lower.

13. The method of any one of claims 1 to 11, wherein the cracking is performed at a temperature of 300°

C. or lower.

14. The method of any one of claims 1 to 13, wherein the cracking converts C₁₉ to C₃₁ hydrocarbons in the biocrude to C₁ to C₁₈ hydrocarbons.

15. The method of any one of claims 1 to 14, wherein the cracking converts about 65 to about 75 wt. % of hydrocarbons in the biocrude to lower molecular weight hydrocarbons.

16. The method of any one of claims 1 to 15, wherein the recombinant microorganism over expresses an ester synthase (EC 2.3.1.-).

17. The method of any one of claims 1 to 16, wherein the cracked product includes a C₅ to C₁₀ fraction having a boiling point range of about 30 to about 180°

C. at 1 atm.

18. The method of any one of claims 1 to 17, wherein the cracked product includes a C₈ to C₁₄ fraction having a boiling point range of about 120 to about 260°

C. at 1 atm.

19. The method of any one of claims 1 to 18, wherein the cracked product 1includes a C₁₄ to C,₈ fraction having a boiling point range of about 230 to about 320°

C. at 1 atm.

20. The method of any of claims 1 to 19, wherein the cracked product is characterized by multiple fractions that are each distillable at a different temperature range.

21. The method of any one of claims 1 to 20, wherein the cracked product includes a gasoline fraction having a distillation range of about 20 to about 210°

C. at 1 atm.

22. The method of any one of claims 1 to 21, further comprising refining the cracked product into at least one transportation fuel.

23. The method of any one of claims 1 to 22, further comprising mixing the biocrude with petroleum crude prior to cracking, and then cracking the resulting biocrude/petroleum crude mixture.

24. The method of any one of claim 1, 2, 4 or 5, wherein the biocrude is substantially free of any compounds that include oxygen.

25. The method of any one of claims 1 to 24, wherein the cracked product includes at least about 50 wt % C₅ and greater hydrocarbons, based on the total hydrocarbon amount in the cracked product.

26. The method of any one of claim 1, 2, or 5, wherein the biocrude includes greater than about 90 wt % alkene compounds, based on the total weight of the biocrude.

27. The method of any one of claims 1 to 26, wherein the biocrude includes at least about 99 wt % alkene compounds, based on the total weight of the biocrude.

31. The method of any one of claims 1 to 4, wherein the recombinant microorganism over expresses a fatty acyl chain containing product forming enzyme.

32. The method of any one of claims 1 to 4, further comprising culturing the recombinant microorganism under conditions sufficient to produce hydrocarbons.

33. The method according to claim 32, further comprising separating the hydrocarbons.

34. The method of claim 33, wherein culturing and separating is continuous.

35. The method of claim 33, wherein separating comprises contacting the fermentation media with an organic composition and allowing the hydrocarbon to separate into the organic composition.

36. The method of any one of claims 1 to 4, wherein the recombinant microorganism is selected from E. coli, S. maltophilia, K. radiotolerans, Rhodococcus, Saccharomyces cerevisiae, Aspergillus, Trichoderma, Neurospora, Fusarium or Chrysosporiutn.

50. A mixture comprising:

(a) the cracked product of any one of claims 1 to 40; and

(b) at least one other fuel component.

51. The mixture of claim 50, wherein the other fuel component is a petroleum-based fuel.

52. The mixture of claim 51, wherein the petroleum-based fuel is gasoline, diesel, jet fuel, or a mixture thereof.

57. The method of any one of claims 1 to 20, wherein the cracked product includes a jet fuel fraction having a distillation range of about 170 to about 290°

C. at 1 atm.

58. The method of any one of claims 1 to 20, wherein the cracked product includes a diesel fraction having a distillation range of about 180 to about 320°

C. at 1 atm.

59. The method of any of claims 1 to 20, wherein the cracked product includes at least about 15 wt. % of a gasoline fraction based upon the total weight of the recovered cracked product.

60. The method of any of claims 1 to 20, wherein the cracked product includes at least about 30 wt. % of a diesel fraction based upon the total weight of the recovered cracked product.

2. A method for cracking a biocrude, the method comprising:

obtaining a biocrude from a recombinant microorganism wherein the recombinant microorganism over expresses a peptide that converts a substrate containing a fatty acyl chain to a hydrocarbon intermediate, a hydrocarbon or a biocrude; and

cracking the biocrude resulting in a cracked product.

3. A method for cracking a biocrude, the method comprising:

obtaining a biocrude from a recombinant microorganism, wherein the biocrude is substantially free of any compounds that include oxygen; and

cracking the biocrude resulting in a cracked product.

4. A method for cracking biocrude, the method comprising:

obtaining a biocrude from a recombinant microorganism, wherein the biocrude includes greater than about 90 wt % alkene compounds, based on the total weight of the biocrude; and

cracking the biocrude resulting in a cracked product.

5. A method for cracking a biocrudc, comprising catalytically cracking the biocrude at a temperature of 350°

C. or lower.

28. The method of claim 5, wherein the biocrude is produced by a microorganism.

29. The method of claim 28, wherein the biocrude is produced by a recombinant microorganism.

30. The method of claim 5, wherein the biocrude is produced by:

contacting a recombinant microorganism with a carbon source under conditions sufficient for producing the biocrude.

37. A method for cracking a hydrocarbon feedstock produced by a microorganism, the method comprising:

obtaining a hydrocarbon feedstock from a microorganism, wherein the hydrocarbon feedstock includes greater than about 50 wt % C₁₉-C₃₁ compounds , based on the total weight of the biocrude; and

catalytically cracking the hydrocarbon feedstock resulting in a cracked product.

38. The method of claim 37, wherein the hydrocarbon feedstock includes greater than about 80 wt % C₁₉-C₃₁ compounds.

39. A method for cracking a hydrocarbon feedstock produced by a microorganism, the method comprising:

obtaining a hydrocarbon feedstock from a microorganism, wherein the hydrocarbon feedstock includes C₁₉ to C₃₁ hydrocarbons having at least one alkene moiety; and

cracking the hydrocarbon feedstock resulting in a cracked product.

40. The method of claim 39, wherein the hydrocarbon feedstock includes C₂₂ to C₃₁ hydrocarbons having at least one alkene moiety.

41. A method for making a biofuel comprising:

culturing a recombinant microorganism engineered to produce biocrude under conditions sufficient to produce biocrude; and

catalytically cracking the biocrude to produce a biofuel.

42. The method of claim 41, wherein the catalytic cracking is performed at a temperature of about 350°

C. or lower.

43. The method of claim 41 or 42, wherein the catalytic cracking comprises contacting the biocrude with a catalyst selected from zeolite, aluminum hydrosilicate, treated bentonite clay, fuller'"'"'s earth, bauxite, amorphous silica-alumina and mixtures or combinations thereof.

44. The method of claim 43, wherein the catalyst is an amorphous silica-alumina.

45. The method of any one of claims 41 to 44, wherein the biofuel includes a C₅ to C₁₀ fraction having a boiling point range of about 30 to about 180°

C. at 1 atm.

46. The method of any one of claims 41 to 45, wherein the cracked product includes a C₈ to C₁₄ fraction having a boiling point range of about 120 to about 260°

C. at 1 atm.

47. The method of any one of claims 41 to 46, wherein the cracked product includes a C₁₄ to C₁₈ fraction having a boiling point range of about 230 to about 320°

C. at 1 atm.

48. A method comprising:

obtaining a biocrude produced by a recombinant microorganism; and

cracking the biocrude resulting in a cracked product.

49. A method comprising:

obtaining a hydrocarbon feedstock produced by a recombinant microorganism; and

cracking the hydrocarbon feedstock resulting in a cracked product.

53. A biofuel mixture produced from a biocrude, wherein the biofuel includes a gasoline fraction that distills (at 1 atm) at about 20 to about 210°

C.

54. A biofuel mixture produced from a biocrude, wherein the biofuel includes a jet fuel fraction that distills (at 1 atm) at about 170 to about 290°

C.

54-1. A biofuel mixture produced from a biocrude, wherein the biofuel includes a C₅-C₁₀ fraction having a boiling point range (at 1 atm) of about 30 to about 180°

C.

55. A biofuel mixture produced from a biocrude, wherein the biofuel includes a diesel fraction that distills (at 1 atm) at about 180 to about 320°

C.

55-2. A biofuel mixture produced from a biocrude, wherein the biofuel includes a C₈-C₁₄ fraction having a boiling point range (at 1 atm) of about 120 to about 260°

C.

56. A biofuel mixture produced from a biocrude, wherein the biofuel includes and a C₁₄-C₁₈ fraction having a boiling point range (at 1 atm) of about 230 to about 320°

C.