Flat PVDF Membrane with Enhanced Hydrophobicity through Alkali Activation and Organofluorosilanisation for Dissolved Methane Recovery

A three-step surface modification consisting of activation with NaOH, functionalisation with a silica precursor and organofluorosilane mixture (FSiT), and curing was applied to a poly(vinylidene fluoride) (PVDF) membrane for the recovery of dissolved methane (D-CH4) from aqueous streams. Based on the results of a statistical experimental design, the main variables affecting the water contact angle (WCA) were the NaOH concentration and the FSiT ratio and concentration used. The maximum WCA of the modified PVDF (mPVDFmax) was >140° at a NaOH concentration of 5%, an FSiT ratio of 0.55 and an FSiT concentration of 7.2%. The presence of clusters and a lower surface porosity of mPVDF was detected by FESEM analysis. In long-term stability tests with deionised water at 21 L h−1, the WCA of the mPVDF decreased rapidly to around 105°, similar to that of pristine nmPVDF. In contrast, the WCA of the mPVDF was always higher than that of nmPVDF in long-term operation with an anaerobic effluent at 3.5 L h−1 and showed greater mechanical stability, since water breakthrough was detected only with the nmPVDF membrane. D-CH4 degassing tests showed that the increase in hydrophobicity induced by the modification procedure increased the D-CH4 removal efficiency but seemed to promote fouling.