An optimization model for the treatment of perfluorocarboxylic acids considering membrane preconcentration and BDD electrooxidation.

Treatment of persistent perfluorocarboxylic acids in water matrixes requires of strong oxidation conditions, as those achieved by boron doped diamond (BDD) electrooxidation (ELOX). However, large scale implementation of ELOX is still hindered by its high energy consumption and economical investment. In this work, we used process systems engineering tools to define the optimal integration of a membrane pre-concentration stage followed by the BDD electrolysis of the concentrate, to drastically reduce the costs of treatment of perfluorohexanoic acid (PFHxA, 100 mg L-1) in industrial waste streams. A multistage membrane cascade system using nanofiltration (NF90 and NF270 membranes) was considered to achieve more sophisticated PFHxA separations. The aim was to minimize the total costs by determining the optimal sizing of the two integrated processes (membrane area per stage and anode area) and the optimal process variables (pre-concentration operating time, electrolysis time, input and output concentrations). The non-linear programming model (NLP) was implemented in the General Algebraic Modelling System (GAMS). The results showed that for a 2-log PFHxA abatement (99% removal), the optimal two membrane stages using the NF90 membrane obtains a 75.8% (6.4 $ m-3) reduction of the total costs, compared to the ELOX alone scenario (26.5 $ m-3). The optimized anode area and the energy savings, that were 85.3% and 88.2% lower than in ELOX alone, were the major contributions to the costs reduction. Similar results were achieved for a 3-log and 4-log PFHxA abatement, pointing out the promising benefits of integrating electrochemical oxidation with membrane pre-concentration through proper optimization for its large-scale application to waters impacted by perfluorocarboxylic acids.