Renewable Compositions

• US 20090299109A1
• Filed: 12/03/2008
• Published: 12/03/2009
• Est. Priority Date: 12/03/2007
• Status: Active Grant

• Current Assignee: Gevo Incorporated
• Original Assignee: Gevo Incorporated
• Inventors: Griffith, Josefa M., Obaidi, Yassin Al, Taylor, Joshua D., Manzer, Leo E., Peters, Matthew W., Gruber, Patrick R.
• Granted Patent: US 8,193,402 B2
• Time in Patent Office: Days
• US Class Current: 585/14
• CPC Class Codes: C10G 2300/1011 Biomass
• CPC Class Codes: C10G 2400/08 Jet fuel
• CPC Class Codes: C10G 2400/22 Higher olefins
• CPC Class Codes: C10G 2400/30 Aromatics
• 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: C10G 69/126 polymerisation, e.g. oligomerisation
• CPC Class Codes: C10L 1/04 essentially based on blends of hydrocarbons
• CPC Class Codes: C10L 1/06 for spark ignition
• CPC Class Codes: C10L 1/08 for compression ignition
• CPC Class Codes: Y02E 50/10 Biofuels, e.g. bio-diesel
• CPC Class Codes: Y02P 30/20 using bio-feedstock

Abstract

The present invention is directed to renewable compositions derived from fermentation of biomass, and integrated methods of preparing such compositions.

Claims

1. A process for preparing renewable hydrocarbons comprising:

(a) treating biomass to form a feedstock;

(b) fermenting the feedstock with one or more species of microorganism, thereby forming one or more C₂-C₆ alcohols;

(c) dehydrating at least a portion of the one or more C₂-C₆ alcohols obtained in step (b), thereby forming a product comprising one or more C₂-C₆ olefins;

(d) isolating the one or more C₂-C₆ olefins;

(e) oligomerizing at least a portion of the one or more C₂-C₆ olefins isolated in step (d), thereby forming a product comprising one or more C₆-C₂₄ unsaturated oligomers; and

(f) optionally hydrogenating at least a portion of the product of step (e) in the presence of hydrogen, thereby forming a product comprising one or more C₆-C₂₄ saturated alkanes.

2. The process of claim 1, wherein said dehydrating, oligomerizing, and hydrogenating are each carried out in the presence of a dehydration catalyst, oligomerization catalyst, and a hydrogenation catalyst, respectively.

3. The process of claim 2, wherein each of said dehydrating, oligomerizing, and hydrogenating are carried out in a different reaction zone.

4. The process of claim 2, wherein two or more of said dehydrating, oligomerizing, and hydrogenating are carried out in the same reaction zone.

5. The process of claim 2, wherein one or more of the dehydration catalyst, oligomerization catalyst, or hydrogenation catalyst are heterogeneous catalysts.

6. The process of claim 2, wherein one or more of the dehydration catalyst, oligomerization catalyst, or hydrogenation catalyst are homogeneous catalysts.

7. The process of claim 1, wherein said dehydrating and/or said oligomerizing are carried out in the presence of an acidic catalyst, wherein the acidic catalyst for dehydrating and the acidic catalyst for oligomerizing is the same or different.

8. The process of claim 7, wherein said acidic catalyst for dehydrating and said acidic catalyst for oligomerizing are each independently selected from the group consisting of inorganic acids, organic sulfonic acids, heteropolyacids, perfluoroalkyl sulfonic acids, metal salts thereof, mixtures of metal salts, and combinations thereof.

9. The process of claim 1, wherein said hydrogenating is carried out in the presence of a hydrogenation catalyst selected from the group consisting of iridium, palladium, rhodium, nickel, ruthenium, platinum, rhenium;

compounds thereof; and

combinations thereof.

10. The process of claim 1, further comprising removing said C₂-C₆ alcohols from the feedstock before said dehydrating.

11. The process of claim 10, wherein said removing comprises carrying out said fermenting in step (b) below atmospheric pressure, whereby aqueous C₂-C₆ alcohol vapor is removed.

12. A process for preparing a biofuel or biofuel precursor, comprising the method of claim 1, whereby the product of step (f) itself meets the requirements of at least one of ASTM D4814, ASTM D975, or ASTM D1655, or a blend of at least 10% of the product of step (f) with a mixture of hydrocarbons meets the requirements of at least one of ASTM D4814, ASTM D975, or ASTM D1655.

13. A process of preparing a renewable gasoline comprising the method of claim 1, whereby the product of step (f) itself meets the requirements of ASTM D4814, or a blend of at least 10% of the product of step (f) with a mixture of hydrocarbons meets the requirements of ASTM D4814.

14. A process of preparing a renewable diesel fuel comprising the method of claim 1, whereby the product of step (f) itself meets the requirements of ASTM D975, or a blend of at least 10% of the product of step (f) with a mixture of hydrocarbons meets the requirements of ASTM D975.

15. A process of preparing a renewable jet fuel comprising the method of claim 1, whereby the product of step (f) itself meets the requirements of ASTM D1655, or a blend of at least 10% of the product of step (f) with a mixture of hydrocarbons meets the requirements of ASTM D1655.

16. The process of claim 1, further comprising:

(g) combining the product of step (f) with one or more C₁₀-C₁₄ aromatic hydrocarbons, thereby forming a jet fuel.

17. The process of claim 16, wherein said C₁₀-C₁₄ aromatic hydrocarbons are prepared by:

(1) aromatizing one or more C₂-C₆ olefins, one or more dimers of C₂-C₆ olefins, and/or one or more trimers of C₂-C₆ olefins; and

optionally

(2) oligomerizing the product of step (1).

18. The process of claim 17, wherein the one or more C₂-C₆ olefins are obtained from step (d) and the dimers and trimers of C₂-C₆ olefins are obtained from step (e).

19. The process of claim 17, wherein at least a portion of the hydrogen used in step (f) is provided by the hydrogen formed as a byproduct of step (1).

26. A biofuel or biofuel precursor, prepared by the process of claim 1.

27. The biofuel or biofuel precursor of claim 26, wherein the one or more C₂-C₆ alcohols comprise an alcohol selected from the group consisting of isobutanol, 2-methyl-1-butanol, and 3-methyl-1-butanol.

28. The biofuel or biofuel precursor of claim 26, wherein the product of step (f) is a transportation fuel meeting the requirements of ASTM D4814, D975, or D1655.

29. The biofuel or biofuel precursor of claim 26, wherein the one or more C₂-C₆ alcohols comprise isobutanol, and the product of step (d) comprises primarily butene dimers and/or butene trimers.

30. The biofuel or biofuel precursor of claim 28, wherein the one or more C₂-C₆ alcohols comprise isobutanol, and the product of step (e) comprises primarily butene dimers and/or butene trimers.

31. A biofuel meeting the requirements of D4814, D975, or D1655, prepared by blending the transportation fuel or transportation fuel precursor of claim 26 with a petroleum-derived hydrocarbon.

35. A renewable jet fuel prepared by the process of claim 16.

36. A renewable jet fuel prepared by the process of claim 17.

37. A renewable jet fuel prepared by the process of claim 19.

20. A process for preparing a renewable aromatic compound, comprising:

(i) treating biomass to form a feedstock;

(ii) fermenting the feedstock with one or more species of microorganism, thereby forming one or more C₂-C₆ alcohols;

(iii) dehydrating at least a portion of the one or more C₂-C₆ alcohols obtained in step (ii), thereby forming a product comprising one or more C₂-C₆ olefins;

(iv) isolating the one or more C₂-C₆ olefins;

(v) optionally oligomerizing the one or more C₂-C₆ olefins to one or more dimers and/or one or more trimers of the C₂-C₆ olefins;

(vi) aromatizing one or more C₂-C₆ olefins from step (iv) or one or more dimers and/or one or more trimers of the C₂-C₆ olefins of step (v), thereby forming a product comprising C₆-C₁₄ aromatic hydrocarbons, and hydrogen; and

(vii) optionally oligomerizing the product of step (vi) in the presence of the one or more C₂-C₆ olefins of step (v) to form a product comprising one or more C₈-C₁₆ aromatic hydrocarbons.

21. A process of preparing renewable terephthalates, comprising preparing renewable p-xylene by the method of claim 20, wherein the product of step (vi) comprises at least 50% p-xylene, and further comprising:

(vii) optionally isolating and purifying the p-xylene of step (v); and

(viii) oxidizing the p-xylene, optionally in the presence of one or more alcohols, thereby forming renewable terephthalates.

22. A process for preparing renewable oxidized hydrocarbons comprising:

(A) treating biomass to form a feedstock;

(B) fermenting the feedstock with one or more species of microorganism, thereby forming one or more C₂-C₆ alcohols;

(C) dehydrating at least a portion of the one or more C₂-C₆ alcohols obtained in step (b), thereby forming a product comprising one or more C₂-C₆ olefins;

(D) isolating the one or more C₂-C₆ olefins; and

(E) oxidizing the one or more C₂-C₆ olefins of step (c) to form at least one oxidized hydrocarbon.

23. The process of claim 22, wherein the at least one oxidized hydrocarbon formed in step

(E) comprises one or more unsaturated aldehydes.

24. The process of claim 22, further comprising:

(F) further oxidizing the at least one oxidized hydrocarbon of step (E) to form at least one further oxidized hydrocarbon.

25. The process of claim 24, wherein the at least one further oxidized hydrocarbon comprises one or more unsaturated carboxylic acids and/or one or more unsaturated carboxylic acid esters.

32. A biofuel or biofuel precursor comprising at least about 1% renewable C₈-C₂₄ branched aliphatic hydrocarbons.

33. The biofuel or biofuel precursor of claim 32, wherein said renewable C₈-C₂₄ branched aliphatic hydrocarbons comprise 2,2,4-trimethylpentane, 2,2,4,4,6-pentamethylheptane, 2,2,4,4,6,6,8-heptamethylnonane, 2,2,4,4,6,6,8,8,10-nonamethylundecane, and 2,2,4,4,6,6,8,8,10,10,12-undecamethyltridecane.

34. The biofuel or biofuel precursor of claim 32, wherein said renewable transportation fuel or transportation fuel precursor is a transportation fuel which meets the requirements of D4814, D975, or D1655.

38. A renewable gasoline or gasoline precursor comprising:

about 50% to about 80% isooctane;

about 0% to about 10% isooctene;

about 1% to about 3% isobutylene; and

about 10% to about 20% BTEX.

39. A renewable diesel fuel or diesel fuel precursor comprising:

about 50% to about 100% of one or more C₁₂-C₂₀ aliphatic hydrocarbons;

wherein at least a portion of said C₁₂-C₂₀ aliphatic hydrocarbons comprise monomethyl alkanes.

40. A renewable jet fuel or jet fuel precursor comprising a mixture of aromatic hydrocarbons and C₁₁-C₁₄ aliphatic hydrocarbons.

41. The renewable jet fuel of claim 40, comprising:

about 65 vol. % to about 85 vol. % of one or more C₁₁-C₁₄ aliphatic hydrocarbons; and

about 10 vol. % to about 20 vol. % of aromatic hydrocarbons.

42. The renewable jet fuel of claim 40, wherein the one or more C₁₁-C₁₄ aliphatic hydrocarbons comprise one or more pentamethylheptane isomers.

43. The renewable jet fuel of claim 40, wherein the one or more C₁₁-C₁₄ aliphatic hydrocarbons comprise one or more hydrocarbons selected from the group consisting of trimethylpentanes. pentamethylheptanes, tetramethyloctanes, heptamethylnonanes, trimethylnonanes, and combinations thereof;

and the alkylated aromatic hydrocarbons comprise one or more mono- or dialkyl benzenes.