1111111111111111 1111111111 1111111111 11111 111111111111111 lll111111111111111  10  REACTOR:  FERMENTATION BROTH  12  Filter  Dey  13  14  FERMENTATION-DERIVED  CARBOXYLICACID  (e.g.,SuccinicAcid)  +  SALTS,BY-PRODUCTS,  BROTHSOUDS,ETC.  22  18  R-OH  (e.g.,MeOH)  MONOESTER/ DIESTER MIX  C02.t.  (e.g.,mono-ordimethyl  succinate)  (SOLUBLE)  +  16  SALTS,BY•PRODUCTS,  BROTH SOLIDS (INSOLUBLE)  Filter  20  24  34 $^{Hydrogenation/Hydrogenolysis }$ Treatment  MONO•/ DIESTER (SOLUBLE)  (e.g.,mono-ordlmethyl  succinate)+R-OH  SALTS,BY•PRODUCTS,  BROTHSOLIDS,ETC.  PRODUCE:  B10FUELS  32  Hydrogenation  __  __,  PRODUCE:  1,4  BUTANE DIOL  (BDO)  THF, GBL, NMP  POLYMERS  DIESTER:  30  Distillation  Recycle  26  SEPARATE:  MONOESTER  DIESTER  R-OH  FERMENTATION BROTH  28  MONOESTER:  SOLVENTS  CHELATING AGENT  US010118886B2  c12)  United States Patent  Stensrud et al.  (54)  BIOFUELS PRODUCTION FROM  BIO-DERIVED CARBOXYLIC-ACID ESTERS  (65)  Prior Publication Data  (22)  Filed:  Oct. 19, 2016  (21)  Appl. No.:  15/297,610  ( *)  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.  (73)  Assignee:  Archer Daniels Midland Company,  Decatur, IL (US)  (72)  Inventors:  Kenneth Stensrud,  Decatur, IL (US);  Padmesh Venkitasubramanian,  Forsyth, IL (US)  (71)  Applicant:  Archer Daniels Midland Company,  Decatur, IL (US)  US 2017/0044086 Al  Feb. 16, 2017  C07C 67108  C07C 671297  C07C 291149  C07D 307108  Cl0L 1102  Cl0L 1104  (2006.01)  (2006.01)  (2006.01)  (2006.01)  (2006.01)  (2006.01)  (51)  Int. Cl.  Related U.S. Application Data  (Continued)  (Continued)  (62)  Division of application No. 14/650,475, filed as  application No. PCT/US2013/073793 on Dec. 9,  2013, now abandoned.  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.  (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  FOREIGN PATENT DOCUMENTS  (57)  ABSTRACT  (74)  Attorney, Agent, or Firm  - William B. Miller  Primary Examiner  - Yate’ K Cutliff  CA  2657666 Al  *  9/2009  ................ Cl2P 7/62  * cited by examiner  16 Claims, 6 Drawing Sheets 