Process for making isooctenes from aqueous isobutanol

Patent metadata

Field	Value
Publication number	US-9410099-B2
Application number	US-201514749095-A
Country	US
Kind code	B2
Filing date	Jun 24, 2015
Priority date	Jun 16, 2006
Publication date	Aug 9, 2016
Grant date	Aug 9, 2016

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.

First claim

The invention claimed is:

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 C 1 to C 5 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

Assignees

• Butamax Advanced Biofuels Llc

Inventors

• D'Amore Michael B
• Manzer Leo Ernest
• Miller Jr Edward S
• Knapp Jeffrey P

Classifications

• C07C9/21

  2, 2, 4-Trimethylpentane · CPC title

• C10L1/1608

  Well defined compounds, e.g. hexane, benzene · CPC title

• C07C2527/054

  Sulfuric acid or other acids with the formula H2Sn03n+1 · CPC title

• C10G2300/4012

  Pressure · CPC title

• C07C29/04

  by hydration of carbon-to-carbon double bonds · CPC title