Strong impact of exposure to water/solvent mixtures on permeance of nanofiltration membranes

Water/solvent mixtures released from industrial processes, especially in pharma and fine chemical synthesis or in advanced oil production, are an environmental concern, necessitating the development of efficient remediation and recycling techniques. Solvent-tolerant nanofiltration (STNF), situated between aqueous nanofiltration (NF) and solvent-resistant nanofiltration (SRNF), offers a promising solution. This study investigates the potential of using aqueous NF- and SRNF-membranes to treat water/solvent mixtures. Commercial membranes (NF270, DuraMem® 300, DuraMem® 200) and a lab-synthesized polyvinylidene fluoride (XL-PVDF NF) membrane were used to treat dimethyl sulfoxide (DMSO), acetonitrile (ACN), Isopropyl alcohol (IPA), or dimethylformamide (DMF) mixtures with water. The addition of 10% DMSO, ACN, IPA, or DMF to water significantly reduced the permeance of these NF-membranes, and an increase in temperature failed to restore the initial permeance. Changes in both viscosity and surface tension of the water/solvent solutions strongly influence the permeance of the NF-membranes. Flory-Huggins and Zimm-Lundberg theories offered an explanation for the phenomenon where solvent clusters form within the dense polymer matrix of NF-membranes upon exposure to water/solvent mixtures, resulting in decreased water permeabilities. NMR analysis identified of the presence of small amounts of solvents in the STNF-membranes, even still after prolonged exposure to pure water permeation. The results emphasize the current shortcomings of aqueous and solvent-resistant membrane chemistries in handling water/solvent mixtures. Minor solvent additions significantly modify NF membrane permeance, emphasizing the need for innovative material design, especially given the variable solvent content in industrial applications.