Scalable nanofiltration membranes with sharpened pore distribution and enhanced negativity for mono/divalent anion separation

The petrochemical industry is an important producer of high salinity wastewater, necessitating the efficient separation of salts in zero discharge processes. This study reports the development of an industrially scalable thin film composite nanofiltration membranes that facilitate the effective separation of NaCl/Na2SO4. Employing a one-step functionalization process, the membrane pore distribution is sharpened, and the surface negativity is intensified. Branched polyethyleneimine with abundant reactive amine groups is employed as an aqueous co-monomer, leading to the generation of high density grafting active sites. Nucleophilic substitution reaction is employed to functionalize the membrane surface with negatively charged sulfonic acid groups. Simultaneously, large voids within the free volume are filled and the pore size distribution is effectively narrowed. The resultant membranes demonstrate an impressive rejection of 99.5 % for Na2SO4, a selectivity of 163.4 for NaCl/Na2SO4 and a selectivity of 488 for Cl−/SO42−, with a water flux of 45 LMH under 0.5 MPa. The corresponding 8″ × 40″ sized spiral wound membrane modules exhibit a NaCl/Na2SO4 selectivity of 100.4 and a Cl−/SO42− selectivity of 258.3, demonstrating high practical applicability. A pilot trial is planned to integrate these novel membrane products into zero discharge processes within the internal chemical enterprises of Sinopec.