US009834531B2  c12)  United States Patent  Venkitasubramanian et al.  (IO)  Patent No.:  US 9,834,531 B2  (45)  Date of Patent:  Dec. 5, 2017  (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  (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.  (52)  U.S. Cl.  CPC ..............  C07D  307168  (2013.01);  C12P  7162  (2013.01);  Y02P 20/544  (2015.11)  (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  See application file for complete search history.  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.  Primary Examiner  - Yevgeny Valenrod  * cited by examiner  Assistant Examiner  - Blaine G Doletski  (74)  Attorney, Agent, or Firm  - William B. Miller  (57)  ABSTRACT  17 Claims, 8 Drawing Sheets  Related U.S. Application Data  (65)  Prior Publication Data  FOREIGN PATENT DOCUMENTS  (56)  References Cited  U.S. PATENT DOCUMENTS  US 2017/0015643 Al  Jan. 19, 2017  CA  2657666  *  9/2009  5,599,977 A *  2/1997 Kiely .................... C07C 51/316  562/523  2014/0206047 Al*  7/2014 Kambourakis  Cl2N 15/52  435/126  C07C 69/00  C07D  307168  C12P  7162  (2006.01)  (2006.01)  (2006.01) 