Recovery of Acetic Acid from An Ethanol Fermentation Broth by Liquid-Liquid Extraction (LLE) Using Various Solvents

  • Pham, Thi Thu Huong (Department of Environmental Engineering, Kongju National University) ;
  • Kim, Tae Hyun (Department of Environmental Engineering, Kongju National University) ;
  • Um, Byung-Hwan (Department of Chemical Engineering and Research Center Chemical Technology Hankyong National University)
  • Received : 2015.03.09
  • Accepted : 2015.05.04
  • Published : 2015.12.01


Liquid-liquid extraction (LLE) using various solvents was studied for recovery of acetic acid from a synthetic ethanol fermentation broth. The microbial fermentation of sugars presented in hydrolyzate gives rise to acetic acid as a byproduct. In order to obtain pure ethanol for use as a biofuel, fermentation broth should be subjected to acetic acid removal step and the recovered acetic acid can be put to industrial use. Herein, batch LLE experiments were carried out at $25^{\circ}C$ using a synthetic fermentation broth comprising $20.0g\;l^{-1}$ acetic acid and $5.0g\;l^{-1}$ ethanol. Ethyl acetate (EtOAc), tri-n-octylphosphine oxide (TOPO), tri-n-octylamine (TOA), and tri-n-alkylphosphine oxide (TAPO) were utilized as solvents, and the extraction potential of each solvent was evaluated by varying the organic phase-to-aqueous phase ratios as 0.2, 0.5, 1.0, 2.0, and 4.0. The highest acetic acid extraction yield was achieved with TAPO; however, the lowest ethanol-to-acetic acid extraction ratio was obtained using TOPO. In a single-stage batch extraction, 97.0 % and 92.4 % of acetic acid could be extracted using TAPO and TOPO when the ratio of organic-to-aqueous phases is 4:1 respectively. A higher solvent-to-feed ratio resulted in an increase in the ethanol-to-acetic acid ratio, which decreased both acetic acid purity and acetic acid extraction yield.


Supported by : Korea Institute of Energy Technology Evaluation and Planning (KETEP)


  1. van Heiningen, A., "Converting a Kraft Pulp Mill Into an Integrated Forest Biorefinery," Pulp Paper Canada, 107(6), 38-43 (2006).
  2. Cogan, T. M., "Co-metabolism of Citrate and Glucose by Leuconostoc spp.: Effects on Growth, Substrate, and Products," J. Appl. Bacteriol., 63, 551-558(1987).
  3. Oliva-Neto, P. and Yokoya, F., "Effect of 3,4,4'-trichlorocarbanilide on Growth of Lactic Acid Bacteria Contaminants in Alcoholic Fermentation," Biores Technol., 63, 17-21(1998).
  4. Rodriguez-Lopez, J., Romani, A., Gonzalez-Munoz, M. J., Garrote, G. and Parajo, J. C., "Extracting Value-added Products Before Pulping: Hemicellulosic Ethanol from Eucalyptus Globulus Wood," Holzforschung, 66, 591-599(2012).
  5. Um, B. H. and Hanley, T. R., "A CFD Model for Predicting the Flow Patterns of Viscous Fluids in a Bioreactor Under Various Operating Conditions," Korean J. Chem. Eng., 25(5), 1094-1102(2008).
  6. Drysdale, G. S. and Fleet, G. H., "Acetic Acid Bacteria in Winemaking: A Review," Am. J. Enol. Vitic., 39(2), 143-153(1988).
  7. Shimazu, Y. and Watanabe, M., "Effects of Yeast Strains and Environmental Conditions on Formation of Organic Acid in Must During Fermentation," J. Ferment. Technol., 59(1), 27-32(1981).
  8. Galanakis, C. M., Kordulis, C., Kanellaki, M., Athanasios, A. K., Bekatorou, A. and Lycoirghiotis, A., "Effect of Pressure and Temperature on Alcoholic Fermentation by Saccharomyces Cerevisiae Immobilized on $\gamma$-alumina Pellets," Biores Technol., 114, 492-498 (2012).
  9. Delfini, C. and Costa, A., "Effects of the Grape Must Lees and Insoluble Materials on the Alcoholic Fermentation Rate and on the Production of Acetic Acid, Pyruvic Acid, and Acetaldehyde," Am. J. Enol. Vitic., 44(1), 86-92(1993).
  10. Radler, F., Yeast-metabolism of organic acids, in: Fleet, G. H. (Eds.), Wine microbiology and biotechnology, Harwood Academic Publishers, Philadelphia, USA(1983).
  11. Klosowski, G., Mikulski, D., Grajewski, J. and Blajet-Kosicka, A., "The influence of Raw Material Contamination with Mycotoxins on Alcoholic Fermentation Indicators," Biores Technol., 101, 3147-3152(2010).
  12. Pawelzik, P., Carus, M., Hotchkiss, J., Narayan, R., Selke, S., Wellisch, M., Weiss, M., Wicke, B. and Parel, M. K., "Critical Aspects in the Life Cycle Assessment (LCA) of Bio-based Materials - Reviewing Methodologies and Deriving Recommendations," Resour. Conserv. Recycl., 73, 211-228(2013).
  13. Um, B. H., "A Comparative Study on Green Liquor Pre-pulping Extraction of Mixed Hardwood Chips," Korean Chem. Eng. Res., 51(5), 561-567(2013).
  14. Xu, Z. P., Afacan, A. and Chuang, D. T., "Removal of Acetic Acid from Water by Catalytic Distillation. Part 1. Experimental Studies," Canadian. J. Chem. Eng., 77, 676-681(1999).
  15. Anasthas, H. M. and Gaikar, V. G., "Removal of Acetic Acid Impurities from Ethyl Acetate by Adsorption on ion Exchange Resins," Sep. Sci. Technol., 36, 2623-2646(2001).
  16. Wiencek, J. M. and Qutubuddin, S., "Microemulsion Liquid Membranes. 1 Application to Acetic Acid Removal from Water," Sep. Sci. Technol., 27, 1211-1228(1992).
  17. Um, B. H., Friedman, B. and van Walsum, G.P., "Conditioning Hardwood-derived Pre-pulping Extracts for Use in Fermentation Through Removal and Recovery of Acetic Acid Using Trioctylphosphine Oxide (TOPO)," Holzforschung, 65, 51-58(2011).
  18. Ricker, N. L., Michaels, J. N. and King, C. J., "Solvent Properties of Organic Bases for Extraction of Acetic Acid from Water," J. Sep. Proc. Technol., 1, 36-41(1979).
  19. King, C. J., "Amine-based System for Carboxylic Acid Recovery," Chem. Tech., 5, 285-291(1992).
  20. Senol, A., "Extraction Equilibria of Formic, Levulinic, and Acetic Acids Using (alamine 336/diluent) and Conversional Solvent Systems: Modeling Consideration," J. Chem. Eng. Jpn., 32, 717-731(1999).
  21. Sabolova, E., Schlosser, S. and Martak, J., "Liquid-liquid Equilibria of Butyric Acid in Water+solvent Systems with Trioctylamine as Extractant," J. Chem. Eng. Data, 46, 735-745(2001).
  22. Helsel, R. W., "Removing Carboxylic Acids from Aqueous Wastes," Chem. Eng. Prog., 73(5), 55-59(1977).
  23. Niitsu, M. and Sekine, T., "Solvent Extraction Equilibria of acids. VI. The extraction of Several Mono-and Dicarboxylic Acids with Trioctylphosphine Oxide in Hexane", Bull. Chem. Soc. Jpn., 51, 705-709(1978).
  24. Wardell, J. M. and King, C. J., "Solvent Equilibriums for Extraction of Carboxylic Acids from Water," J. Chem. Eng. Data., 23, 144-148(1978).
  25. Hano, T., Matsumoto, M., Ohtake, T., Sasaki, K. and Kawano, Y., "Extraction Equilibria of Organic Acids with tri-n-octylphosphineoxide," J. Chem. Eng. Jpn., 23, 260-264(1990).
  26. Reisinger, H. and King, C. J., "Extraction and Sorption of Acetic Acid at pH Above pKa to form Calcium Magnesium Acetate," Ind. Eng. Chem. Res., 34, 845-852(1995).
  27. Juang, R. S. and Wu, R. T., "Extraction of Acetate from Simulated Waste Solutions in Chloromycetin Production," Sep. Purif. Technol., 17, 225-233(1999).
  28. Al-Mudhaf, H. F., Hegazi, M. F. and Abu-Shady, A. I., "Partition Data of Acetic Acid Between Aqueous NaCl Solutions and Trioctylphosphine Oxide in Cyclohexane Diluents," Sep. Purif. Technol., 27, 41-50(2002).
  29. Wisniewski, M. and Pierzchalska, M., "Recovery of Carboxylic Acids C1-C3 with Organophosphine Oxide Solvating Extractant," J. Chem. Technol. Biotechnol., 80, 1425-1430(2005).
  30. Walton, S., van Heiningen, A. and van Walsum, P., "Inhibition Effects on Fermentation of Hardwood Extracted Hemicelluloses by Acetic Acid and Sodium," Biores. Technol., 101, 1935-1940 (2010).