Hydrogenation products from biologically-derived carboxylic-acid esters

Patent metadata

Field	Value
Publication number	US-9914713-B2
Application number	US-201314650468-A
Country	US
Kind code	B2
Filing date	Dec 9, 2013
Priority date	Dec 20, 2012
Publication date	Mar 13, 2018
Grant date	Mar 13, 2018

Abstract

The production of organic acids in low-cost, high-efficiency fermentation system makes available a new route to chemical production from biomass. A process for producing a hydrogenation product involving carboxylic acid esters recovered directly from a fermentation process is described.

First claim

We claim:

1. A process for producing a hydrogenation product comprising: a) obtaining a fermentation broth having at a pH of less than 5, containing at least one free organic acid, or a mixture of organic acids, or at least one free organic acid and an associated alkali or alkaline earth metal salts of the organic acid; b) drying said fermentation broth into a powder; and c) reacting said organic acid in said powder with an alcohol solvent under a CO 2 atmosphere in substantial absence of any other extrinsic acid catalyst at a reaction temperature and pressure that corresponds to supercritical, critical or near critical conditions for at least the alcohol or CO 2 to synthesize an ester; and d) hydrogenating said ester to form a hydrogenation product.

2. The process according to claim 1 , wherein said hydrogenation product includes anyone of the following: 1,4-butanediol (BDO), tetrahydrofuran (THF), γ-butyrolactone (GBL), N-methyl-2-pyrrolidone (NMP), 2-pyrrolidone.

3. The process according to claim 1 , further comprising filtering said fermentation broth to remove cell mass and insoluble compounds either before drying or after ester synthesis.

4. The process according to claim 1 , further comprising filtering said fermentation broth to remove insoluble by-products resultant from ester synthesis, and concentrating said ester.

5. The process according to claim 1 , wherein said fermentation broth is either part of a continuous fermentation process, and further comprising recycling insoluble compounds back into said fermentation broth; or part of a batch fermentation process, and further comprising recycling said insoluble compounds into a second fermentation reactor.

6. The process according to claim 1 , wherein said organic acid is selected from the group consisting of: formic acid, acetic acid, propionic acid, lactic acid, butyric acid, isobutyric acid, valeric acid, hexanoic acid, heptanoic acid, decanoic acid, lauric acid, myristic acid, and C 15 -C 18 fatty acids, fumaric acid, itaconic acid, malic acid, succinic acid, maleic acid, malonic acid, glutaric acid, glucaric acid, oxalic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, glutaconic acid, ortho-phthalic acid, isophthalic acid, terephthalic acid, citric acid, isocitric acid, aconitic acid, tricarballylic acid, and trimesic acid.

7. The process according to claim 1 , wherein said organic acid is a polycarboxylic acid.

8. The process according to claim 7 , wherein said polycarboxylic acid is at least a dicarboxylic or a tricarboxylic acid.

9. The process according to claim 8 , wherein said synthesized ester is predominantly at least a diester.

10. The process according to claim 1 , wherein said reaction temperature and pressure is at a temperature between about 150° C. and about 250° C., at a pressure in a range between about 400 psi and 3,000 psi.

11. The process according to claim 1 , wherein said process does not activate said free organic acid as an acyl halide.

12. The process according to claim 1 , wherein said fermentation broth of step a) is at a pH in a range between about 1.5 and about 4.5.

13. The process according to claim 1 , wherein said organic acid is a diacid and said synthesis of the ester yields a minimum of 50% conversion to a diester of the organic acid.

14. The process according to claim 1 , further comprising purifying said ester to about at least about 90% purity.

15. The process according to claim 1 , wherein said alcohol has an R-group of C 1 -C 20 , and is either a saturated, unsaturated, or aromatic species.

16. The process according to claim 1 , wherein said process further comprises subjecting said hydrogenation product to either further hydrogenation or hydrogenolysis to produce a biofuel compound.

17. The process according to claim 1 , wherein said dried fermentation broth powder is shipped to a location different from where said fermentation broth is sourced.

18. The process according to claim 1 , wherein said ester synthesis is performed at a remote location different from where said fermentation broth is sourced.

19. The process according to claim 1 , wherein said organic acid is at least a C 4 diacid, and said synthesized ester is at least a diester, and said hydrogenation product is a 1,4-butanediol.

Assignees

• Archer Daniels Midland Co

Inventors

• Stensrud Kenneth
• Venkitasubramanian Padmesh

Classifications

• C07D207/267

  with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atom · CPC title

• C12P7/44

  Polycarboxylic acids · CPC title

• C07D307/33 Primary

  in position 2, the oxygen atom being in its keto or unsubstituted enol form · CPC title

• C12P7/46

  Dicarboxylic acids having four or less carbon atoms, e.g. fumaric acid, maleic acid · CPC title

• C07C29/149 Primary

  with hydrogen or hydrogen-containing gases · CPC title