Use of carboxylic acids and furanic molecules for esterification

Patent metadata

Field	Value
Publication number	US-2017015643-A1
Application number	US-201615253220-A
Country	US
Kind code	A1
Filing date	Aug 31, 2016
Priority date	Dec 20, 2012
Publication date	Jan 19, 2017
Grant date	—

Abstract

A process for recovering and using an organic/carboxylic acid or furanic molecule by means of making an ester of a free carboxylic acid or furanic molecule with an alcohol in carbon dioxide (CO 2 ) without the presence of any other acid catalyst at a reaction temperature and pressure that corresponds to supercritical, critical or near critical conditions for the alcohol and/or CO 2 is described. The process can constitute part of a general process of refining carboxylic acids derived from a fermentation broth or use in the production of a variety of chemical compounds, such as C 4 platform compounds or polymers.

First claim

We claim:

1 . A process for recovering and converting a carboxylic acid or a furanic molecule comprising: a) converting an aldose sugar to a sugar acid either by a chemical or biological means; b) bio-transforming said sugar acid to a keto-acid intermediate or furanic molecule in a solution; c) adjusting pH value of said solution containing said keto-acid intermediate or furanic molecule to a pH of less than 5 so as to generate free acids; and d) reacting said free acids with an alcohol and CO 2 to generate an ester of said carboxylic acid, keto-acid intermediate or furanic molecule.

2 . The process according to claim 1 , wherein said process further comprises drying said solution containing said keto-acid intermediate or furanic molecule.

3 . The process according to claim 1 , wherein said carboxylic acid is selected from the group consisting of: aldaric acids, aldonic acids, or uronic acids of a hexose or a pentose, and a mixture thereof.

4 . The process according to claim 3 , wherein said aldaric acid is selected from the group consisting of: allaric acid, altraric acid, glucaric acid, galactaric acid, mannaric acid, gularic acid, idaric acid, talaric acid, xylaric acid, lyxaric acid, arabinaric acid, and ribaric acid.

5 . The process according to claim 3 , wherein said aldonic acid is selected from the group consisting of: allonic acid, altronic acid, gluconic acid, galactonic acid, mannonic acid, gulonic acid, idonic acid, talonic acid, xylonic acid, lyxonic acid, arabonic acid, and ribonic acid.

6 . The process according to claim 3 , wherein said uronic acid is selected from the group consisting of: alluronic acid, altruronic acid, glucuronic acid, galacturonic acid, mannuronic acid, guluronic acid, iduronic acid, taluronic acid, xyluronic acid, lyxuronic acid, araburonic acid, and riburonic acid.

7 . The process according to claim 1 , wherein said furanic molecule is an organic molecule having a 5-carbon heterocycle.

8 . The process according to claim 1 , wherein said chemical means of converting said aldose sugar is an oxidative operation with either nitric acid or a noble metallic catalyst.

9 . The process according to claim 1 , wherein said biological means of converting said aldose sugar is a bio-transformation.

10 . The process according to claim 1 , wherein said sugar acid is bio-transformed to a keto-acid intermediate using one or more enzymes selected from an enolase superfamily.

11 . The process according to claim 10 , wherein said enzyme is at least: a glucarate dehydratase, gluconate dehydratase, altronate dehydratase, or a mixture thereof.

12 . The process according to claim 1 , wherein said keto-acid intermediate is a molecule that has a methylene carbon atom adjacent to a ketone functional group.

13 . The process according to claim 1 , wherein said alcohol has an R-group of C 1 -C 20 that is at least a saturated, unsaturated, cyclic, or aromatic species.

14 . The process according to claim 1 , wherein said alcohol is a C 2 -C 6 -diol.

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

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

17 . The process according to claim 1 , wherein said ester is further converted into pharmaceutical, cosmetic, food or feed ingredient, or polymer materials.

18 . A process for making esters comprising: oxidizing an aldose sugar to form a sugar acid, and reacting said sugar acid with an alcohol and CO 2 to form a corresponding ester, according to one of the following reaction pathways;

wherein in pathways a)-d) said sugar acid is biotransformed into a keto-acid intermediate or furanic molecule in a solution, and said solution containing said keto-acid intermediate or furanic molecule has a pH of less than 5 so as to generate free acids.

Assignees

• Archer Daniels Midland Co

Inventors

• Venkitasubramanian Padmesh
• Stensrud Kenneth F

Classifications

• C07D307/68 Primary

  Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen · CPC title

• C12P7/62

  Carboxylic acid esters · CPC title

• Y02P20/54

  using solvents, e.g. supercritical solvents or ionic liquids · CPC title

• C12P17/04

  containing a five-membered hetero ring, e.g. griseofulvin {, vitamin C} · CPC title