The present study was aimed at the development of a strategy for removing and degrading perfluorohexanoic acid (PFHxA) from industrial process waters at concentrations in the range 60-200 mg L. The treatment train consisted of nanofiltration (NF) separation followed by electrochemical degradation of the NF concentrate. Using a laboratory-scale system and working in the total recirculation mode, the DowFilm NF270 membrane provided PFHxA rejections that varied in the range 96.6-99.4% as the operating pressure was increased from 2.5 to 20 bar. The NF operation in concentration mode enabled a volume reduction factor of 5 and increased the PFHxA concentration in the retentate to 870 mg L. Results showed that the increase in PFHxA concentration and the presence of calcium sulfate salts did not induce irreversible membrane fouling. The NF retentate was treated in a commercial undivided electrochemical cell provided with two parallel flow-by compartments separated by bipolar boron doped diamond (BDD) electrode, BDD counter anode, and counter cathode. Current densities ranging from 20 to 100 A m were examined. The electrochemical degradation rate of PFHxA reached 98% and was accompanied by its efficient mineralization, as the reduction of total organic carbon was higher than 95%. Energy consumption, which was 15.2 kWh m of treated NF concentrate, was minimized by selecting operation at 50 A m. While most of the previous research on the treatment of perfluoroalkyl substances (PFASs) focused on the removal of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), these compounds have been phased out by chemical manufacturers. Our findings are relevant for the treatment of PFHxA, which appears to be one of the present alternatives to long-chain PFASs thanks to its lower bioaccumulative potential than PFOA and PFOS. However, PFHxA also behaves as a persistent pollutant. Moreover, our results highlight the potential of combining membrane separation and electrochemical oxidation for the efficient treatment of PFAS-impacted waters.
Designed room temperature ionic liquids (RTILs) containing silver salt are presented as reactive media in separating propylene/propane gas mixtures. Solubilities of propylene and propane in the reactive media, silver tetrafluoroborate (AgBF 4 ) dissolved in 1-butyl-3-methylimidazolium tetrafluoroborate (BmimBF 4 ) and N-butyl-4-methylpyridinium tetrafluoroborate (BmpyBF 4 ), were investigated as a function of silver ion concentration, temperature, and pressure. Equilibrium data were obtained working in a temperature range between 278 and 318 K and at pressures up to 6 bar. Propylene absorption was chemically enhanced in the silver-based RTILs and was considerably higher than that in the standard RTILs. Absorption of propane in the silver-based RTILs is based on physical interactions only. A simple mathematical model based on the formation of complex species with different stoichiometry has been developed in order to describe the total propylene absorption, and the model was validated with experimental data obtained working with different concentrations of silver salt (between 0.1 and 1 M). The model parameters, equilibrium constants (K Eq,1 f(T) and K Eq,2 f(T)), and enthalpies of complexation (∆H r,1 , ∆H r,2 ) were obtained. Thermal stability of the silver ions was analyzed and to be found dependent on the silver salt concentration. Complete regeneration of the reaction media was possible at a temperature of 313 K and 20 mbar of pressure.
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