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# c12) United States Patent 

# Stensrud et al. 

# (54) BIOFUELS PRODUCTION FROM BIO-DERIVED CARBOXYLIC-ACID ESTERS 

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

(72) Inventors: Kenneth Stensrud, Decatur, IL (US); Padmesh Venkitasubramanian, Forsyth, 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 105 days. This patent is subject to a terminal dis› claimer. 

(21) Appl. No.: 15/297,610 

(22) Filed: Oct. 19, 2016 

## (65) Prior Publication Data 

US 2017/0044086 Al Feb. 16, 2017 

(62) Division of application No. 14/650,475, filed as application No. PCT/US2013/073793 on Dec. 9, 2013, now abandoned. 

(51) Int. Cl. 

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## Related U.S. Application Data 

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# (IO) Patent No.: US 10,118,886 B2 

# (45) Date of Patent: *Nov. 6, 2018 

(52) U.S. Cl. CPC ............ C07C 67108 (2013.01); C07C 291149 (2013.01); C07C 671297 (2013.01); C07D 307108 (2013.01); CJ0G 3/50 (2013.01); Cl0L 1102 (2013.01); Cl0L 11023 (2013.01); Cl0L 1104 (2013.01); Cl0L 1106 (2013.01); C07C 29/147 (2013.01); C07D 307/33 (2013.01); CJOL 2200/0469 (2013.01); CJ0L 2290/26 (2013.01); Cl2P 7/40 (2013.01); Cl2P 7/46 (2013.01); Cl2P 7/48 (2013.01); Y02P 20/544 (2015.11); Y02P 30/20 (2015.11) 

(58) Field of Classification Search CPC ..... C07C 67/08; C07C 67/297; C07C 29/147; C07C 29/149; Cl0G 3/50; Y02P 30/20; COIL 2290/26; C12P 7/46; C12P 7/40; C12P 7/48 See application file for complete search history. 

## (56) References Cited 

CA 2657666 Al * 9/2009 ................ Cl2P 7/62 

* cited by examiner 

Primary Examiner - Yate’ K Cutliff 

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

## (57) ABSTRACT 

A process for producing biofuels compounds directly from carboxylic acid esters recovered from a fermentation system is described. The process involves taking a fermentation broth that has been reduced to a dry powder containing free organic acids; reacting the carboxylic acid in the powder with an alcohol solvent under a CO$_{2}$ -containing atmosphere in substantial absence of any other acid catalyst at a reaction temperature and pressure that corresponds to supercritical, critical or near critical conditions for at least one of the alcohol or CO$_{2 }$ to synthesize an ester, then subjecting the ester to either hydrogenolysis or hydrogenation to form a biofuel. 

US010118886B2 

## FOREIGN PATENT DOCUMENTS 

## 16 Claims, 6 Drawing Sheets 

