Bulk cross-linked hydroxyethyl cellulose-silica composite membrane for acid-stable nanofiltration

Abstract

This work focused on the construction of an acid-resistant composite nanofiltration membrane with the selective layer of bulk cross-linked hydroxyethyl cellulose (HEC)-silica and a support of porous polypropylene. Membranes were fabricated through in-situ sol-gel reaction and slot-die coating method employing tetraethyl orthosilicate (TEOS) as the silica precursor and cross-linking agent of HEC. Membrane structure and performance were tuned by controlling the hydrolysis time of TEOS and differentiating TEOS and HEC contents, and systematically characterized in terms of physico-chemical property, permeation attribution and acid stability. It was found that membrane performance was strongly correlated with the relative contents of C–O–Si and Si–O–Si bonds of the formed HEC-silica selective layer. High content of C–O–Si bond formed via condensation reaction of HEC and TEOS endowed the selective layer with denser network structure and good rejection ability. Both insufficient and excessive hydrolysis led to a poor rejection ability of formed membrane. The optimized HEC-silica membrane possessed an average pore size of about 1.43 nm within the scope of nanofiltration membrane, a high pure water permeability coefficient of around 10.5 LMH/bar, and a medium rejection of 85.2% to 500 mg/l Na2SO4 aqueous solution at 5.0 bar. No changes in both chemical structure and separation performance occurred with the HEC-silica composite membrane after being soaked in aqueous H2SO4 solution of 4.9 wt% for 7 days, while evident structure destruction and serious performance degradation occurred with the compared polyamide-based commercial membrane NF270. Long-term soaking test using 15.0 wt% H2SO4 aqueous solution for 30 days also demonstrated that the acid resistance HEC silica membrane was comparable with those reported acid stable nanofiltration membranes. Furthermore, the HEC-silica membrane also maintained its water permeation and solute rejection abilities during a 30-day continuous filtration of aqueous solution of 4.9 wt% H2SO4 and 50 mg/l polyethylene glycol fraction (PEG2000). The good acid resistance of the HEC-silica composite membrane was attributed to its bulk cross-linked network structure composed of C–O–Si, Si–O–Si and C–C bonds.