Process for making isooctenes from aqueous isobutanol

• US 9,410,098 B2
• Filed: 08/15/2013
• Issued: 08/09/2016
• Est. Priority Date: 06/16/2006
• Status: Active Grant

• Current Assignee: Gevo Incorporated
• Original Assignee: Bitamax Advanced Biofuels LLC
• Inventors: D'Amore, Michael B, Miller, Edward S Jr., Manzer, Leo Ernest, Knapp, Jeffrey P
• Primary Examiner(s): KEYS, ROSALYND ANN
• Application Number:
  US13/967,696
• Publication Number:
  US 20140005443A1
• Time in Patent Office: 1,090 Days
• Field of Search: None
• US Class Current: 1/1
• CPC Class Codes: C07C 1/20 starting from organic compounds containing only oxygen atoms as heteroatoms
• CPC Class Codes: C07C 1/22 by reduction
• CPC Class Codes: C07C 11/02 Alkenes
• CPC Class Codes: C07C 2521/08 Silica
• CPC Class Codes: C07C 2527/054 Sulfuric acid or other acids with the formula H2Sn03n+1
• CPC Class Codes: C07C 2529/18 of the mordenite type
• CPC Class Codes: C07C 2529/40 of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
• CPC Class Codes: C07C 2531/10 sulfonated
• CPC Class Codes: C07C 29/04 by hydration of carbon-to-carbon double bonds
• CPC Class Codes: C07C 31/12 containing four carbon atoms
• CPC Class Codes: C07C 31/125 containing five to twenty-two carbon atoms
• CPC Class Codes: C07C 41/06 by addition of organic compounds only
• CPC Class Codes: C07C 43/04 Saturated ethers
• CPC Class Codes: C07C 5/03 of non-aromatic carbon-to-carbon double bonds
• CPC Class Codes: C07C 9/21 2, 2, 4-Trimethylpentane
• CPC Class Codes: C10G 2300/4006 Temperature
• CPC Class Codes: C10G 2300/4012 Pressure
• CPC Class Codes: C10G 2300/805 Water
• CPC Class Codes: C10G 2400/22 Higher olefins
• CPC Class Codes: C10L 1/16 Hydrocarbons
• CPC Class Codes: C10L 1/1608 : Well defined compounds, e.g. hexane, benzene
• CPC Class Codes: C10L 1/18 : containing oxygen
• CPC Class Codes: C10L 1/1824 : mono-hydroxy
• CPC Class Codes: C10L 1/1852 : Ethers; Acetals; Ketals; Orthoesters
• CPC Class Codes: C10L 2200/0469 : Renewables or materials of biological origin
• CPC Class Codes: C10L 2270/023 : for gasoline engines
• CPC Class Codes: C10L 2270/026 : for diesel engines, e.g. automobiles, stationary, marine
• 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: C12P 5/026 : Unsaturated compounds, i.e. alkenes, alkynes or allenes

Abstract

The present invention relates to a catalytic process for making isooctenes using a reactant comprising isobutanol and water. The isooctenes so produced are useful for the production of fuel additives.

Claims

1. A process for production of gasoline, diesel fuel, jet fuel, or transportation fuel additive comprising:

producing isobutanol from a feedstock derived from a renewable source by a genetically modified microorganism via a biosynthetic pathway comprising substrate to product conversions that include;

pyruvate to acetolactate;

acetolactate to 2,3-dihydroxyisovalerate;

2,3-dihydroxyisovalerate to α

-ketoisovalerate;

α

-ketoisovalerate to isobutyraldehyde; and

isobutyraldehyde to the isobutanol; and

reacting the isobutanol to produce an intermediate for the production of gasoline, diesel fuel, jet fuel, or transportation fuel additive.

2. The process of claim 1, wherein the genetically modified microorganism is tolerant to isobutanol at levels greater than 1% weight per volume.

3. The process of claim 1, further comprising refining the isobutanol prior to the reacting, wherein the isobutanol that results from the distillation is substantially free of one or more of ethanol or acetone.

4. The process of claim 3, wherein the refining yields an aqueous stream that comprises at least about 5% water by weight of the water and isobutanol.

5. The process of claim 1, wherein reacting comprises contacting the isobutanol with at least one acid catalyst.

6. The process of claim 5, wherein the intermediate comprises isooctene, dibutyl ether, or butene.

7. The process of claim 6, further comprising recovering the isooctene and converting the isooctene to isooctane, isooctanol, or isooctyl alkyl ether.

8. The process of claim 7, wherein converting comprises contacting the isooctene with a hydrogenation catalyst in the presence of hydrogen.

9. The process of claim 7, further comprising:

recovering the isooctane, isooctanol, or isooctyl alkyl ether; and

adding the isooctane, isooctanol, or isooctyl alkyl ether that is recovered to a transportation fuel.

10. The process of claim 6, further comprising contacting the isooctene with an acid catalyst in the presence of at least one straight-chain or branched C1 to C5 alcohol.

11. A process for production of gasoline, diesel fuel, jet fuel, or transportation fuel additive comprising:

obtaining isobutanol that is essentially free of ethanol and is produced by a genetically modified microorganism via a biosynthetic pathway that implements a fermentation broth, the biosynthetic pathway comprising;

pyruvate to acetolactate;

acetolactate to 2,3-dihydroxyisovalerate;

2,3-dihydroxyisovalerate to α

-ketoisovalerate;

α

-ketoisovalerate to isobutyraldehyde; and

isobutyraldehyde to the isobutanol; and

contacting the isobutanol with an acid catalyst to produce an intermediate for the production of gasoline, diesel fuel, jet fuel, or transportation fuel additive.

12. The process of claim 11, wherein contacting comprises contacting the isobutanol with the acid catalyst in an aqueous solution where water is at least about five percent (5%) by weight.

13. The process of claim 11, wherein the intermediate comprises at least one of isooctene, dibutyl ether, or butene.

14. The process of claim 13, further comprising converting the intermediate to isooctane by contacting the intermediate with a hydrogenation catalyst in the presence of hydrogen.

15. The process of claim 13, further comprising contacting the intermediate with water in the presence of at least one acidic catalyst and least one straight-chain or branched C1 to C5 alcohol to produce isooctyl alkyl ether.

16. The process of claim 11, wherein the genetically modified microorganism is tolerant to isobutanol at levels greater than 1% weight per volume.

17. The process of claim 11, wherein the fermentation broth contains at least about fifty percent (50%) isobutanol by weight to water in the fermentation broth.