Electrochemical treatment of wastewaters containing metal-organic complexes: A one-step approach for efficient metal complex decomposition and selective metal recovery

Metal-organic complexes, especially those of ethylenediaminetetraacetic acid (EDTA) with metals such as copper (Cu) and nickel (Ni) (denoted here as Cu-EDTA and Ni-EDTA), are common contaminants in wastewaters from chemical and plating industries. In this study, a multi-electrode (ME) system using a two-chamber reactor and two pairs of electrodes is proposed for simultaneous electrochemical oxidation of a wastewater containing both Cu-EDTA and Ni-EDTA complexes as well as separation and selective recovery of Cu and Ni onto two different cathodes via electrodeposition. Our results demonstrate that the ME system successfully achieved 90% EDTA removal, 99% solid Cu recovery at the Cu recovery cathode and 56% Ni recovery (33.3% on the Ni recovery cathode and 22.6% in the solution) after a four-hour operation. The system further achieved 85.5% Ni recovery after consecutive five cycles of operation for 20 h. While Cu removal was mainly driven by the direct reduction of EDTA-complexed Cu(II) at the cathode, oxidation of EDTA within the Ni-EDTA complex at the anode was a prerequisite for Ni removal. The oxidation of metal-bound EDTA and free EDTA was driven by •OH and direct electron transfer on the PbO2 anode surface and graphite anode, respectively. We further show that ME system performs well for all pH conditions, treatment of real wastewaters as well as wastewaters containing other metals ions (Cr and Zn) along with Cu/Ni. The separation efficiency of Cu and Ni is dependent on applied electrode potential as well as nature and concentration of binding ligand present with comparatively lower separation efficiency achieved in the presence of weaker binding capacity and/or at lower ligand concentration and lower applied electrode potential. As such, some optimization of electrode potential is required depending on the nature/concentration of ligands in the wastewaters. Overall, this study provides new insights into the design and operation of EAOP technology for effective organic abatement and metal recovery from wastewaters containing mixtures of various metal-organic complexes.