The adsorption of quaternary mixtures of ethanol/glycerol/glucose/acetic acid onto a microporous hyper-cross-linked resin HD-01 was studied in fixed beds. A mass transport model based on film solid linear driving force and the competitive Langmuir isotherm equation for the equilibrium relationship was used to develop theoretical fixed bed breakthrough curves. It was observed that the outlet concentration of glucose and glycerol exceeded the inlet concentration (c/c(0) > 1), which is an evidence of competitive adsorption. This phenomenon can be explained by the displacement of glucose and glycerol by ethanol molecules, owing to more intensive interactions with the resin surface. The model proposed was validated using experimental data and can be capable of foresee reasonably the breakthrough curve of specific component under different operating conditions. The results show that HD-01 is a promising adsorbent for recovery of ethanol from the fermentation broth due to its large capacity, high selectivity, and rapid adsorption rate. (C) 2013 Elsevier Ltd. All rights reserved.