Biofuels production from bio-derived carboxylic-acid esters

Abstract

A process for producing 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.

1 . A process for producing a biofuel comprising: a) obtaining a fermentation broth containing a at least one free carboxylic acid, or a mixture of a carboxylic acid, or at least one carboxylic acid and associated salts thereof; b) drying said fermentation broth containing said free carboxylic acid into a powder; and c) synthesizing an ester by reacting said carboxylic acid in said powder with an alcohol solvent under a CO 2  atmosphere in substantial absence of any other acid catalyst at either a reaction temperature or pressure or both that is at a supercritical, critical or near critical condition for at least one of the alcohol or CO 2 ; and d) subjecting said ester to either hydrogenolysis or hydrogenation to form a biofuel. 
     
     
         2 . The process according to  claim 1 , further comprising e) recovering said biofuel. 
     
     
         3 . The process according to  claim 1 , wherein said biofuel is an alkane or an alcohol. 
     
     
         4 . The process according to  claim 3 , wherein said biofuel includes at least one of the following: ethane, ethanol, propane, propanol, butane, 1-butanol, octane, and octanol 
     
     
         5 . The process according to  claim 1 , wherein said fermentation broth contains cell mass and insoluble compounds and further comprising filtering said cell mass and insoluble compounds from said fermentation broth either before drying or after ester synthesis. 
     
     
         6 . The process according to  claim 5 , further comprising concentrating said ester before either hydrogenolysis or hydrogenation. 
     
     
         7 . The process according to  claim 5 , further comprising separating said insoluble compounds by filtering before either hydrogenolysis or hydrogenation. 
     
     
         8 . The process according to  claim 5 , wherein said fermentation broth is either (a) part of a continuous fermentation process, and further comprising recycling said insoluble compounds back into said fermentation broth; or (b) part of a batch fermentation process, and further comprising recycling said insoluble compounds into a second fermentation reactor. 
     
     
         9 . (canceled) 
     
     
         10 . The process according to  claim 1 , wherein said alcohol solvent has an R-group of C 1 -C 20 , and is at least one saturated, unsaturated, cyclic, or aromatic species. 
     
     
         11 . The process according to  claim 1 , wherein said carboxylic acid is selected from the group consisting of: formic acid, acetic acid, propionic acid, lactic acid, butyric acid, isobutyric acid, valeric acid, hexanoic acid, heptanoic acid, decanoic acid, lauric acid, myristic acid, and C 15- C 18  fatty acids, fumaric acid, itaconic acid, malic acid, succinic acid, maleic acid, malonic acid, gitaric acid, gkicaric acid, oxalic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, gkitaconic acid, ortho-phthalic acid, isophthalic acid, terephthalic acid, citric acid, isocitric acid, aconitic acid, tricarballylic acid, and trimesic acid. 
     
     
         12 . The process according to  claim 1 , wherein said carboxylic acid is a polycarboxylic acid, in particular a dicarboxylic or a tricarboxylic acid. 
     
     
         13 . (canceled) 
     
     
         14 . The process according to  claim 12 , wherein when said carboxylic acid is a polycarboxlyic acid, said ester is at least a diester. 
     
     
         15 . The process according to  claim 1 , wherein said reaction temperature is between about 150° C. and about 250° C., and said pressure is in a range between about 400 psi and 3,000 psi 
     
     
         16 . The process according to  claim 1 , wherein said free carboxylic acids are not subject to activation with a halide to form an acyl halide. 
     
     
         17 . The process according to  claim 1 , wherein said fermentation broth is at a pH of less than 5. 
     
     
         18 . 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. 
     
     
         19 . The process according to  claim 1 , wherein said drying is by at least one of the following: spray drying, drum drying, or cryodesiccation. 
     
     
         20 . The process according to  claim 1 , wherein said mixture of free carboxylic acids contains at least a diacid, triacid, orpolyacid, and said reaction with alcohol yields a minimum of 50% conversion of said diacid, triacid, or polyacid to a corresponding ester of the free carboxylic acid. 
     
     
         21 . The process according to  claim 1 , further comprises purifying said ester to at least 90% purity. 
     
     
         22 . The process according to  claim 21 , wherein said purifying is by at least one of the following: crystallization, chromatography, or distillation.