IP Library Granted Patent US 8,487,149
Granted Patent B2
US 8,487,149 · App. 13/557,066 · Granted Jul 16, 2013

Renewable compositions

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Quick Facts
Patent No.
US 8,487,149
App. No.
13/557,066
Granted
Jul 16, 2013
Kind
B2
Abstract

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

Claims (30)

1. A process for preparing renewable hydrocarbons comprising:

(a) culturing a microorganism capable of producing one or more C 2 -C 6 alcohols in a fermentor, thereby forming a fermentation broth comprising microorganisms and one or more C 2 -C 6 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 C 2 -C 6 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 C 2 -C 6 alcohols in the alcohol-rich phase of step (e), thereby forming a product comprising one or more C 2 -C 6 olefins;

(g) isolating the one or more C 2 -C 6 olefins;

(h) oligomerizing at least a portion of the one or more C 2 -C 6 olefins isolated in step (g), thereby forming a product comprising one or more C 6 -C 24 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 C 6 -C 24 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 C 1 -C 6 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 C 2 -C 6 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.

Assignments (10)
RELEASE OF SECURITY INTEREST Recorded Jan 13, 2020
From: WILMINGTON SAVINGS FUND SOCIETY, FSB, AS COLLATERAL TRUSTEE
To: GEVO, INC.; AGRI-ENERGY, LLC; GEVO DEVELOPMENT, LLC
Reel/Frame 051497/0560 →
RELEASE OF SECURITY INTEREST Recorded Jun 21, 2017
From: WILMINGTON SAVINGS FUND SOCIETY, FSB, AS COLLATERAL TRUSTEE
To: GEVO, INC.; GEVO DEVELOPMENT, LLC; AGRI-ENERGY, LLC
Reel/Frame 042940/0081 →
PATENT SECURITY AGREEMENT Recorded Jun 21, 2017
From: GEVO, INC.; GEVO DEVELOPMENT, LLC; AGRI-ENERGY, LLC
To: WILMINGTON SAVINGS FUND SOCIETY, FSB, AS COLLATERAL TRUSTEE
Reel/Frame 042940/0103 →
RELEASE OF SECURITY INTEREST Recorded Oct 4, 2016
From: TRIPLEPOINT CAPITAL LLC
To: GEVO, INC.
Reel/Frame 040219/0177 →
RELEASE OF SECURITY INTEREST Recorded Jan 23, 2015
From: WB GEVO, LTD., AS SUCCESSOR IN INTEREST TO WHITEBOX ADVISORS LLC, AS ADMINISTRATIVE AGENT
To: GEVO, INC.; GEVO DEVELOPMENT, LLC; AGRI-ENERGY, LLC
Reel/Frame 034806/0926 →
PATENT SECURITY AGREEMENT Recorded Jun 10, 2014
From: GEVO, INC.; GEVO DEVELOPMENT, LLC; AGRI-ENERGY, LLC
To: WILMINGTON SAVINGS FUND SOCIETY, FSB, AS COLLATERAL TRUSTEE
Reel/Frame 033120/0453 →
AMENDED AND RESTATED PATENT SECURITY AGREEMENT Recorded Jun 6, 2014
From: GEVO, INC.; GEVO DEVELOPMENT, LLC; AGRI-ENERGY, LLC
To: WB GEVO, LTD., AS ADMINISTRATIVE AGENT
Reel/Frame 033101/0302 →
PATENT SECURITY AGREEMENT Recorded May 13, 2014
From: GEVO, INC.; GEVO DEVELOPMENT, LLC; AGRI-ENERGY, LLC
To: WHITEBOX ADVISORS LLC, AS ADMINISTRATIVE AGENT
Reel/Frame 032891/0881 →
SECURITY AGREEMENT Recorded Dec 18, 2013
From: GEVO, INC. (AS GRANTOR)
To: TRIPLEPOINT CAPITAL LLC (AS GRANTEE)
Reel/Frame 031847/0342 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 26, 2012
From: GRUBER, PATRICK R.; PETERS, MATTHEW W.; GRIFFITH, JOSEFA M.; OBAIDI, YASSIN AL; MANZER, LEO E.; TAYLOR, JOSHUA D.; HENTON, DAVID E.
To: GEVO, INC.
Reel/Frame 029196/0427 →