Real-scale chlorination at pH4 of BW30 TFC membranes and their physicochemical characterization

Chlorination remains a big hurdle in membrane technology as the most commonly used membranes for water purification consist of a polyamide top-layer, which is not fully resistant towards chlorine-induced oxidation. In this work, DOW FILMTEC™ BW30 membrane elements were systematically chlorinated with NaOCl at pilot-scale under acidic conditions (pH4) at 10 bar for 2.5 h. Variations in membrane performance and their physicochemical properties were determined by ATR-FTIR, XPS, WD-XRF, SEM, AFM and zeta-potential measurements. With increasing bleaching concentration, both membrane roughness and chlorine incorporation via N- and ring-chlorination increased, while surface charge remained quasi unaltered. Both water flux and salt passage decreased proportionally over the whole concentration range. Accordingly, positron annihilation lifetime spectroscopy (PALS) revealed a decrease in the size of the top-layer free-volume elements as chlorine concentration increased, confirming, for the first time in a quantitative manner, the so-called tightening effect. The obtained results also show that thin-film composite (TFC) membranes are altered differently when chlorinated under pressure than via simple immersion, as conventionally performed in literature.