Method of extracting butyric acid from a fermented liquid and chemically converting butyric acid into biofuel
View Patent ↗Disclosed is a method of converting butyric acid contained in a fermentation broth into biofuel. This chemical conversion method includes separating biohydrogen from gases generated in the course of production of butyric acid through fermentation of carbohydrate, extracting butyric acid from the broth using an insoluble solvent, esterifying butyric acid thus producing butylbutyrate, and hydrogenolyzing all or part of butylbutyrate, thus obtaining butanol. Thereby, biobutanol can be efficiently and economically produced, and butylbutyrate, which has oxidation stability superior to that of conventional biodiesel (fatty acid methyl ester) and is thus regarded as novel biofuel, can be produced together.
1. A method of producing a biofuel from fermented butyric acid, comprising:
a) providing a fermentation broth containing butyric acid produced through fermentation of a carbohydrate;
b) subjecting the fermentation broth to extraction in a liquid-liquid extraction column using trialkylamine as an extraction solvent to obtain the butyric acid in the form of trialkylammonium butyrate;
c) supplying the trialkylammonium butyrate to a distillation column to separate the trialkylammonium butyrate into butyric acid and trialkylamine; and
d) converting the butyric acid separated from the distillation column into butylbutyrate through esterification with butanol, and supplying the trialkylamine separated from the distillation column to the liquid-liquid extraction column as the extraction solvent for step b).
2. The method as set forth in claim 1 , wherein the trialkylamine is selected from the group consisting of tripentylamine, trihexylamine, trioctylamine and tridecylamine.
3. The method as set forth in claim 1 , wherein the esterification of the butyric acid is performed under reaction conditions including a reaction temperature of 80˜300° C., a reaction pressure ranging from atmospheric pressure to 20 atm, a space velocity of 0.1˜5.0 h −1 and a molar ratio of butanol to butyric acid of 1˜10, in presence of at least one catalyst having an esterification function.
4. The method as set forth in claim 1 , wherein the esterification of the butyric acid is performed under reaction conditions including a reaction temperature of 90˜200° C., a the reaction pressure ranging from atmospheric pressure to 10 atm, a space velocity of 0.3˜2.0 h −1 and a the molar ratio of butanol to butyric acid of 1.5˜5.
5. The method as set forth in claim 1 , wherein a catalyst used for the esterification of the butyric acid is a homogeneous catalyst or a heterogeneous catalyst, in which the homogeneous catalyst comprises sulfuric acid, hydrochloric acid or nitric acid, and the heterogeneous catalyst is selected from the group consisting of solid acid catalysts having super strong acid properties, including an ion exchange resin, zeolite, silica alumina, alumina, sulfonated carbon and heteropolyacid.
6. The method as set forth in claim 1 , wherein the biofuels are butanol, butylbutyrate or a mixture of butanol and butylbutyrate.
7. The method as set forth in claim 1 , wherein the fermentation is performed by continuously adding an aqueous carbohydrate solution to a fermentation reactor packed with a support on which a strain for producing butyric acid is immobilized so that the carbohydrate in the aqueous carbohydrate solution is fermented into butyric acid.
8. The method as set forth in claim 7 , wherein the strain for producing butyric acid is Clostridium tyrobutylicum, Clostridium butylicum or Clostridium acetobutyricum.
9. The method as set forth in claim 1 , further comprising: e) converting the butylbutyrate into butanol through hydrogenolysis with hydrogen.
10. The method as set forth in claim 9 , wherein a part of the butanol converted in step e) is recycled to step d) for the esterification of the butyric acid.
11. The method as set forth in claim 10 , wherein the other part of the butanol converted in step e) is recovered as a final product.
12. The method as set forth in claim 9 , wherein a biogas discharged through the fermentation is supplied to a pressure swing adsorption unit so that the biogas is separated into hydrogen and carbon dioxide, and the separated hydrogen is used for the hydrogenolysis in step e).
13. The method as set forth in claim 9 , wherein the hydrogenolysis is performed under reaction conditions including a reaction temperature of 120˜300° C., a reaction pressure ranging from atmospheric pressure to 100 atm, a space velocity of 0.1˜5.0 h −1 and a molar ratio of hydrogen to butylbutyrate of 1˜100, in presence of a catalyst having a hydrogenation function in a form in which at least one metal or metal oxide is supported on a support.
14. The method as set forth in claim 13 , wherein the at least one metal or metal oxide is selected from the group consisting of copper, zinc, chromium, nickel, cobalt, molybdenum, tungsten, oxides thereof, platinum, palladium, ruthenium, rubidium and oxides thereof.
15. The method as set forth in claim 9 , wherein the hydrogenolysis is performed under reaction conditions including a reaction temperature of 150˜250° C., a the reaction pressure of 5˜50 atm, a space velocity of 0.3˜2.0 h −1 and a the molar ratio of hydrogen to butylbutyrate of 10˜50.