content_image/926676.jpg content_image/926643.jpg content_image/926675.jpg
# c12) United States Patent Venkitasubramanian et al. 

# (54) USE OF CARBOXYLIC ACIDS AND FURANIC MOLECULES FOR ESTERIFICATION 

(71) Applicant: Archer Daniels Midland Company, Decatur, IL (US) 

(72) Inventors: Padmesh Venkitasubramanian, Forsyth, IL (US); Kenneth F. Stensrud, Decatur, IL (US) 

(73) Assignee: Archer Daniels Midland Company, Decatur, IL (US) 

( *) Notice: Subject to any disclaimer, the term ofthis patent is extended or adjusted under 35 U.S.C. 154(b) by O days. 

(21) Appl. No.: 15/253,220 

(22) Filed: Aug. 31, 2016 

## (65) Prior Publication Data 

US 2017/0015643 Al Jan. 19, 2017 

(63) Continuation-in-part of application No. 14/650,453, filed as application No. PCT/US2013/073783 on Dec. 9, 2013, now Pat. No. 9,464,026. 

(60) Provisional application No. 61/739,769, filed on Dec. 20, 2012. 

(51) Int. Cl. 

<img src='content_image/926676.jpg'>

(52) U.S. Cl. CPC .............. C07D 307168 (2013.01); C12P 7162 (2013.01); Y02P 20/544 (2015.11) 

## Related U.S. Application Data 

<img src='content_image/926643.jpg'>

# (IO) Patent No.: US 9,834,531 B2 

# (45) Date of Patent: Dec. 5, 2017 

(58) Field of Classification Search CPC ..... C07C 67/08; C07C 29/149; C07C 31/207; C07C 69/40; C07C 69/675; C07C 69/704; C07D 307/68; C12P 7/62; C12P 7/40; C12P 7/42; C12P 7/44; C12P 7/46; C12P 7/48; Y02P 20/544; Y02E 50/343 

## (56) References Cited 

<img src='content_image/926675.jpg'>

CA 2657666 * 9/2009 

* cited by examiner 

Primary Examiner - Yevgeny Valenrod 

Assistant Examiner - Blaine G Doletski 

(74) Attorney, Agent, or Firm - William B. Miller 

## (57) 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 corre› sponds to supercritical, critical or near critical conditions for the alcohol and/or CO$_{2 }$ is described. The process can con› stitute 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. 

See application file for complete search history. 

US009834531B2 

## U.S. PATENT DOCUMENTS 

## FOREIGN PATENT DOCUMENTS 

## 17 Claims, 8 Drawing Sheets 

