Renewable compositions

• US 8,193,402 B2
• Filed: 12/03/2008
• Issued: 06/05/2012
• Est. Priority Date: 12/03/2007
• Status: Expired due to Fees

• Current Assignee: Gevo Incorporated
• Original Assignee: Gevo Incorporated
• Inventors: Gruber, Patrick R., Peters, Matthew W., Griffith, Josefa M., Obaidi, Yassin Al, Manzer, Leo E., Taylor, Joshua D., Henton, David E.
• Primary Examiner(s): MCAVOY, ELLEN M
• Application Number:
  US12/327,723
• Publication Number:
  US 20090299109A1
• Time in Patent Office: 1,280 Days
• Field of Search: 585/240, 585/14
• US Class Current: 585/240
• 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) 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;

whereby the product of step (f) itself meets the requirements of at least one of ASTM D4814, ASTM D975, ASTM D910, 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, ASTM D910 or ASTM D1655.

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, alumina, neutral chromium treated alumina, acid treated aluminum oxide, zeolites, solid phosphoric acid, 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 copper, chromium, molybdenum, iridium, palladium, rhodium, nickel, ruthenium, platinum, rhenium;

compounds thereof;

Raney catalysts; 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 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.

13. 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.

14. 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.

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

16. The biofuel or biofuel precursor of claim 15, 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.

17. The biofuel or biofuel precursor of claim 15, wherein the product of step (f) is a transportation fuel meeting the requirements of ASTM D4814, D975, D910, or D1655.

18. The biofuel or biofuel precursor of claim 15, wherein the one or more C₂-C₆ alcohols comprise isobutanol, and the product of step (d) comprises primarily butene dimers and/or butene trimers.

19. The biofuel or biofuel precursor of claim 17, wherein the one or more C₂-C₆ alcohols comprise isobutanol, and the product of step (e) comprises primarily butene dimers and/or butene trimers.

20. A biofuel meeting the requirements of D4814, D975, D910, or D1655, prepared by blending the biofuel or biofuel precursor of claim 15 with a petroleum-derived hydrocarbon.

21. A process of preparing a renewable aviation gasoline comprising the method of claim 1, whereby the product of step (f) itself meets the requirements of ASTM D910, or a blend of at least 10% of the product of step (f) with a mixture of hydrocarbons meets the requirements of ASTM D910.

22. The process of claim 1, wherein dehydrating step (c) is conducted in the gas phase.

23. The process of claim 1, wherein oligomerization step (e) is conducted in the liquid phase.