Process for making isooctenes from aqueous isobutanol

• US 9,410,099 B2
• Filed: 06/24/2015
• Issued: 08/09/2016
• Est. Priority Date: 06/16/2006
• Status: Active Grant

• Current Assignee: Gevo Incorporated
• Original Assignee: Butamax Advanced Biofuels LLC (International Flavors & Fragrances Incorporated)
• Inventors: D'Amore, Michael B., Manzer, Leo Ernest, Miller, Edward S. Jr., Knapp, Jeffrey P.
• Primary Examiner(s): KEYS, ROSALYND ANN
• Application Number:
  US14/749,095
• Publication Number:
  US 20150291900A1
• Time in Patent Office: 412 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 a recovered isooctene from renewable sources comprising:

(a) providing a feedstock derived from a renewable source to a recombinantly engineered microorganism;

(b) fermenting the feedstock with the recombinantly engineered microorganism, thereby forming isobutanol;

(c) recovering at least a portion of the isobutanol;

(d) contacting at least a portion of the recovered isobutanol with an acid catalyst in the presence of water to produce a first reaction product that comprises at least one isooctene,

wherein the recombinantly engineered microorganism is engineered to express 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.

2. The process of claim 1, wherein the acid catalyst can be a homogeneous or heterogeneous catalyst.

3. The process of claim 2, wherein the acid catalyst is a homogeneous catalyst selected from the group consisting of inorganic acids, organic sulfonic acids, heteropolyacids, fluoroalkyl sulfonic acids, metal sulfonates, metal trifluoroacetates, compounds thereof, and combinations thereof.

4. The process of claim 3, wherein the homogeneous catalyst is selected from the group consisting sulfuric acid, fluorosulfonic acid, phosphoric acid, p-toluenesulfonic acid, benzenesulfonic acid, hydrogen fluoride, phosphotungstic acid, phosphomolybdic acid, and trifluoromethanesulfonic acid.

5. The process of claim 2, wherein the acid catalyst is a heterogeneous catalyst selected from the group consisting of heterogeneous heteropolyacids, natural clay minerals, cation exchange resins, metal oxides, mixed metal oxides, metal sulfides, metal sulfates, metal sulfonates, metal nitrates, metal phosphates, metal phosphonates, metal molybdates, metal tungstates, metal borates, zeolites, and combinations thereof.

6. The process of claim 1, further comprising:

(e) contacting the isooctene with at least one hydrogenation catalyst in the presence of hydrogen to produce a second reaction product comprising at least one isooctane; and

(f) recovering the at least one isooctane from the second reaction product to produce a recovered isooctane.

7. The process of claim 6, further comprising:

(g) adding the recovered isooctane to a transportation fuel.

8. The process of claim 6, wherein the hydrogenation catalyst comprises a principal component that is a metal selected from the group consisting of palladium, ruthenium, rhenium, rhodium, iridium, platinum, nickel, cobalt, copper, iron, osmium, compounds thereof, and combinations thereof.

9. The process of claim 1, further comprising:

(e) contacting the isooctene with water in the presence of at least one acid catalyst to produce a second reaction product comprising at least one isooctanol; and

(f) recovering the at least one isooctanol from the second reaction product to produce a recovered isooctanol.

10. The process of claim 9, further comprising:

(g) adding the recovered isooctanol to a transportation fuel.

11. The process of claim 9, wherein the acid catalyst of (e) can be a homogeneous or heterogeneous catalyst.

12. The process of claim 11, wherein the acid catalyst is a homogeneous catalyst selected from the group consisting of inorganic acids, organic sulfonic acids, heteropolyacids, fluoroalkyl sulfonic acids, metal sulfonates, metal trifluoroacetates, compounds thereof, and combinations thereof.

13. The process of claim 12, wherein the homogeneous catalyst is selected from the group consisting sulfuric acid, fluorosulfonic acid, phosphoric acid, p-toluenesulfonic acid, benzenesulfonic acid, hydrogen fluoride, phosphotungstic acid, phosphomolybdic acid, and trifluoromethanesulfonic acid.

14. The process of claim 11, wherein the acid catalyst is a heterogeneous catalyst selected from the group consisting of heterogeneous heteropolyacids, natural clay minerals, cation exchange resins, metal oxides, mixed metal oxides, metal sulfides, metal sulfates, metal sulfonates, metal nitrates, metal phosphates, metal phosphonates, metal molybdates, metal tungstates, metal borates, zeolites, and combinations thereof.

15. The process of claim 1, further comprising:

(e) contacting the isooctene with at least one acid catalyst in the presence of at least one straight-chain or branched C₁ to C₅ alcohol to produce a second reaction product comprising at least one isooctyl alkyl ether; and

(f) recovering the at least one isooctyl alkyl ether from the second reaction product to produce a recovered isooctyl alkyl ether.

16. The process of claim 15, further comprising:

(g) adding the recovered isooctyl alkyl ether to a transportation fuel.

17. The process of claim 15, wherein the acid catalyst of (e) can be a homogeneous or heterogeneous catalyst.

18. The process of claim 17, wherein the acid catalyst is a homogeneous catalyst selected from the group consisting of inorganic acids, organic sulfonic acids, heteropolyacids, fluoroalkyl sulfonic acids, metal sulfonates, metal trifluoroacetates, compounds thereof, and combinations thereof.

19. The process of claim 18, wherein the homogeneous catalyst is selected from the group consisting sulfuric acid, fluorosulfonic acid, phosphoric acid, p-toluenesulfonic acid, benzenesulfonic acid, hydrogen fluoride, phosphotungstic acid, phosphomolybdic acid, and trifluoromethanesulfonic acid.

20. The process of claim 17, wherein the acid catalyst is a heterogeneous catalyst selected from the group consisting of heterogeneous heteropolyacids, natural clay minerals, cation exchange resins, metal oxides, mixed metal oxides, metal sulfides, metal sulfates, metal sulfonates, metal nitrates, metal phosphates, metal phosphonates, metal molybdates, metal tungstates, metal borates, zeolites, and combinations thereof.

21. A process for production of a recovered butene from renewable sources comprising:

(a) providing a feedstock derived from a renewable source to a recombinantly engineered microorganism;

(b) fermenting the feedstock with the recombinantly engineered microorganism, thereby forming isobutanol;

(c) recovering at least a portion of the isobutanol;

(d) contacting at least a portion of the recovered isobutanol with an acid catalyst in the presence of water to produce a reaction product that comprises at least one butene; and

(e) recovering the at least one butene from the reaction product to produce a recovered butene,

wherein the recombinantly engineered microorganism is engineered to express 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.

22. The process of claim 21, wherein the acid catalyst can be a homogeneous or heterogeneous catalyst.

23. The process of claim 22, wherein the acid catalyst is a homogeneous catalyst selected from the group consisting of inorganic acids, organic sulfonic acids, heteropolyacids, fluoroalkyl sulfonic acids, metal sulfonates, metal trifluoroacetates, compounds thereof, and combinations thereof.

24. The process of claim 23, wherein the homogeneous catalyst is selected from the group consisting sulfuric acid, fluorosulfonic acid, phosphoric acid, p-toluenesulfonic acid, benzenesulfonic acid, hydrogen fluoride, phosphotungstic acid, phosphomolybdic acid, and trifluoromethanesulfonic acid.

25. The process of claim 22, wherein the acid catalyst is a heterogeneous catalyst selected from the group consisting of heterogeneous heteropolyacids, natural clay minerals, cation exchange resins, metal oxides, mixed metal oxides, metal sulfides, metal sulfates, metal sulfonates, metal nitrates, metal phosphates, metal phosphonates, metal molybdates, metal tungstates, metal borates, zeolites, and combinations thereof.