Renewable compositions

• US 8,487,149 B2
• Filed: 07/24/2012
• Issued: 07/16/2013
• 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., Al Obaidi, Yassin, Manzer, Leo E., Taylor, Joshua D., Henton, David E.
• Primary Examiner(s): MCAVOY, ELLEN M
• Application Number:
  US13/557,066
• Publication Number:
  US 20120323055A1
• Time in Patent Office: 357 Days
• Field of Search: 585/240
• US Class Current: 585/240
• CPC Class Codes: C07C 1/24 by elimination of water
• CPC Class Codes: C07C 11/02 Alkenes
• CPC Class Codes: C07C 11/09 Isobutene
• CPC Class Codes: C07C 15/00 Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
• CPC Class Codes: C07C 2/08 Catalytic processes
• CPC Class Codes: C07C 2/76 by condensation of hydrocarbons with partial elimination of hydrogen
• CPC Class Codes: C07C 5/03 of non-aromatic carbon-to-carbon double bonds
• CPC Class Codes: C07C 51/265 having alkyl side chains which are oxidised to carboxyl groups
• CPC Class Codes: C07C 63/26 1,4 - Benzenedicarboxylic acid
• CPC Class Codes: C07C 9/14 with five to fifteen carbon atoms
• CPC Class Codes: C07C 9/15 Straight-chain hydrocarbons
• CPC Class Codes: C10G 2300/1011 Biomass
• CPC Class Codes: C10G 2300/42 Hydrogen of special source or of special composition
• 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: 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: C10L 2200/043 : Kerosene, jet fuel
• CPC Class Codes: C10L 2200/0469 : Renewables or materials of biological origin
• CPC Class Codes: C10L 2270/04 : for turbines, planes, power generation
• CPC Class Codes: C10L 2290/26 : Composting, fermenting or anaerobic digestion fuel components or materials from which fuels are prepared
• CPC Class Codes: C10L 2290/543 : Distillation, fractionation or rectification for separating fractions, components or impurities during preparation or upgrading of a fuel
• CPC Class Codes: C12P 5/00 : Preparation of hydrocarbons or halogenated hydrocarbons
• CPC Class Codes: C12P 7/04 : acyclic
• CPC Class Codes: C12P 7/06 : Ethanol, i.e. non-beverage
• CPC Class Codes: C12P 7/16 : Butanols
• CPC Class Codes: Y02E 50/10 : Biofuels, e.g. bio-diesel
• CPC Class Codes: Y02P 30/20 : using bio-feedstock
• CPC Class Codes: Y02T 50/678 : Aviation using fuels of non-fossil origin

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) culturing a microorganism capable of producing one or more C₂-C₆ alcohols in a fermentor, thereby forming a fermentation broth comprising microorganisms and one or more C₂-C₆ alcohols;

(b) removing a portion of the fermentation broth from the fermentor;

(c) distilling the portion, thereby forming an alcohol-depleted liquid phase and an alcohol-enriched vapor phase comprising water and one or more C₂-C₆ alcohols;

(d) condensing the alcohol-enriched vapor phase formed in step (c), thereby forming an alcohol-rich liquid phase and a water-rich liquid phase; and

(e) separating the alcohol-rich phase liquid from the water-rich liquid phase using a liquid-liquid separator;

(f) dehydrating at least a portion of the one or more C₂-C₆ alcohols in the alcohol-rich phase of step (e), thereby forming a product comprising one or more C₂-C₆ olefins;

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

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

(i) hydrogenating at least a portion of the product of step (h) in the presence of hydrogen, thereby forming a product comprising one or more C₆-C₂₄ saturated alkanes;

whereby the product of step (i) 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; and

wherein said steps (b)-(e) are conducted simultaneously with step (a).

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 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.

7. The process of claim 6, 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.

8. 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.

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

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

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

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

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

14. The biofuel or biofuel precursor of claim 13, wherein the one or more C₁-C₆ alcohols comprise an alcohol selected from the group consisting of isobutanol, 2-methyl-1-butanol, and 3-methyl-1-butanol.

15. The biofuel or biofuel precursor of claim 13, wherein the product of step (f) is a transportation fuel meeting the requirements of ASTM D4814, D975, D910, or D1655.

16. The biofuel or biofuel precursor of claim 13, wherein the one or more C₂-C₆ alcohols comprise isobutanol, and the product of step (h) comprises primarily butene dimers and/or butene trimers.

17. A biofuel meeting the requirements of ASTM D4814, D975, D910, or D1655, prepared by blending the biofuel or biofuel precursor of claim 13 with a petroleum-derived hydrocarbon.

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

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