A new kind of composite membrane for the pervaporaLion dehydration of acetic acid was prepared by casting sodium alginate (NaAlg) solution onto a microporous polypropylene membrane (MPPM) which possessed well-controlled porosity and excellent solvent resistance. The MPPM surface was modified by N-2 plasma prior to the fabrication of the corresponding NaAlg-based composite membrane in order to improve its compatibility with the NaAlg active layer. The active layer of the NaAlg/MPPM composite membrane was then cross-linked with multivalent ions. This cross-linking behavior restricted the mobility of the polymer chains in the active layer and accordingly increased their relaxation time Interestingly, the activation energy of the pervaporation process increased linearly with the relaxation Lime. Pervaporation results indicated that the prepared composite membranes exhibited desirable separation properties, and a good compromise between flux and separation factor was observed. For the separation of an 80/20 wt% acetic acid/water mixture at 50 degrees C, the Ca2+ cross-linked composite membrane (Ca-Alg/MPPM) displayed a separation factor of 631 and a flux of 653 g/m(2) h, which surpassed most NaAlg-based homogeneous membranes and other composite membranes reported in the literature. These results suggest that the prepared composite membranes have promising potential for acetic acid dehydration. (C) 2013 Elsevier B.V. All rights reserved.