Poly(styrene sulfonic acid) (PSSA)/Poly(vinyl alcohol) (PVA) blend membranes prepared by the solution casting were employed as heterogeneous acid catalysts for biodiesel production from acidic oil obtained from waste cooking oil (WCO). The membranes were annealed at different temperature in order to enhance their stability. The structure and properties of the membranes were investigated by means of Fourier transform infrared spectroscopy (FTIR), thermogravimetry (TG), X-ray diffraction (XRD). It is found that the crosslinking structure among PVA and PSSA chains formed when the thermal treatment temperature was higher than 80 C. The retention of PSSA in the blend membranes in the methanol/water solvent was markedly increased from 50% to 85% with the increase of the annealing temperature from
room temperature (for the untreated membrane) to 150 C due to the formation of the crosslinking struc-ture. The results of esteri?cation of acidic oil show that the conversion was slightly improve with the PVA content in the membrane at a ?xed PSSA content. The thickness of the catalytic membrane had no significant effect on the conversion in the end. The membrane annealed at 120 C exhibited the best catalytic performance among the membranes, with a stable conversion of 80% with the runs.