Micropollutants removal from secondary-treated municipal wastewater using weak polyelectrolyte multilayer based nanofiltration membranes

Nanofiltration (NF) is seen as a very promising technology to remove micropollutants (MPs) from wastewater. Unfortunately this process tends to produce a highly saline concentrate stream, as commercial NF membranes retain both the MPs and most of the ions. The high salinity makes subsequent degradation of the MPs in a bio-reactor very difficult. The main goal of this study is to prepare and study a NF membrane that combines a low salt rejection with a high MPs rejection for the treatment of secondary-treated municipal wastewater. This membrane was prepared using layer by layer (LbL) deposition of the weak polycation poly(allylamine hydrochloride) (PAH), and the weak polyanion poly(acrylic acid) (PAA), on the surface of a hollow fiber dense ultrafiltration (UF) membrane. The ionic strength of the coating solutions was varied and properties of the formed polyelectrolyte multilayers (PEMs), such as hydration, hydrophilicity, hydraulic resistance and ions retention were studied. Subsequently we tested the apparent and steady state rejection of MPs from synthetic wastewater under cross-flow conditions. The synthetic wastewater contained the MPs Diclofenac, Naproxen, Ibuprofen and 4n-Nonylphenol, all under relevant concentrations (0.5-40. μg/L, depending on the MP). PEMs prepared at lower ionic strength showed a lower hydration and consequently a better retention of MPs than PEMs prepared at higher ionic strengths. A strong relationship between the apparent rejection of MPs and their hydrophobicity was observed, likely due to adsorption of the more hydrophobic MPs to the membrane surface. Once saturated (steady state), the molecular size of the MPs showed the best correlation with their rejection, indicating rejection on the basis of size exclusion. In contrast to available commercial NF membranes with both high salt and MP rejection, we have prepared an unique membrane with a very low NaCl retention (around 17%) combined with a very promising removal of MPs, with Diclofenac, Naproxen, Ibuprofen and 4n-Nonylphenol being removed up to 77%, 56%, 44% and 70% respectively. This membrane would allow the treatment of secondary treated municipal wastewater, strongly reducing the load of MPs, without producing a highly saline concentrate stream.