The objective of this work is to develop an appropriate technology for environmentally sound membrane-based purification of a tannery effluent assuring, simultaneously, the recovery of chromium, considered as the most hazardous inorganic water pollutant extensively used in leather tanning. A comparison between the permeate fluxes obtained during treatment of a synthetic tannery effluent through nanofiltration (NF270 and NF90 membranes) and reverse osmosis (BW30 and SW30) membranes was first performed. Then, a dedicated polymeric membrane was prepared by coating chitosan (cs) on a polyethersulfone (PES) microfiltration membrane (cs-PES MFO22) support. The resulting membrane was characterized by Fourier Transforms Infrared Spectroscopy Attenuated Total Reflectance (FTIR-ATR), Emission Scanning Electronic Microscopy (SEM) to confirm the process of surface modification and cross-linking of chitosan with glutaraldehyde. This membrane was found to be highly effective for chromium removal (>99%), which was more than eight times higher in reference to monovalent cations (e.g., Na+ and K+) and more than six times higher in reference to the divalent cations (Mg2+ and Ca2+) studied. The reverse osmosis permeate conforms to local Algerian regulations regarding being discharged directly into the natural environment (in this case, Reghaia Lake) or into urban sewers linked to wastewater biological treatment stations. While the SW30 membrane proved to be the most effective for purification of the tannery effluent, the chitosan modified membrane proved to be appropriate for recovery of chromium from the reverse osmosis concentrate.

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The selective recovery of chromium remaining in tannery effluents after the leather tanning process is highly desirable to potentiate its reuse, simultaneously minimizing the ecotoxicity of these effluents. To the best of our knowledge, this work evaluates for the first time the ability of a chitosan-based membrane for selective recovery of chromium from a tannery wastewater by subsequent diafiltration and selective chromium desorption, envisaging their integration after tannery wastewater treatment by reverse osmosis (RO). A polyethersulfone (PES) microfiltration membrane top-coated with a chitosan layer (cs-PES MF022) was used for selective recovery of Cr(III), from concentrate streams obtained by treatment of synthetic and real tannery effluents through reverse osmosis (RO), through a diafiltration process. The diafiltration of the RO concentrates was conducted by an intermittent addition of water acidified to pH 3.6. The prepared cs-PES MF022 membranes were able to retain 97% of the total mass of Cr(III) present in the RO concentrates, from a real tannery effluent, with a selectivity of 4.2 and 5 in reference to NH4+ and Cl−, respectively, 12.9 and 14.6 in reference to K and Na, and > 45 in reference to Mg, Ca, and S. Such a high selectivity is explained by the preferential adsorption of Cr(III) onto chitosan, and by the relatively high permeability of cs-PES MF022 membranes to the other ionic species. Proof of concept studies were performed to investigate the desorption of Cr(III) at pH 2 and 5.8. A higher Cr(III) desorption degree was obtained at pH 2, leading to a final solution enriched in Cr(III), which may be re-used in tannery operations, thus improving the process economy and reducing the hazardous impact of the effluents discharged by this industry.

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