Deep purification of copper from Cu(II)-EDTA acidic wastewater by Fe(III) replacement/diethyldithiocarbamate precipitation

Abstract

Cu(II)-EDTA is a highly stable typical metal-organic complex in a wide pH range (3.0–12.0) and it is difficult to deeply purify Cu(II) by conventional precipitation methods. In this study, Fe(III) replacement/diethyldithiocarbamate (DDTC) precipitation combined process is proposed as a promising strategy to achieve the deep purification of Cu(II) from Cu(II)-EDTA acidic wastewater. The underlying mechanism has also been systematically elucidated by chemical equilibriums, experiments, and density functional theory (DFT) calculations, laying a foundation for the development and application. Chemical equilibriums show that Fe(III) replacement favors the stoichiometric release of Cu(II) from Cu(II)-EDTA and the formation of Fe(III)-EDTA complex under acidic conditions. Experimentally, Cu(II) is removed (over 99.99%) and deeply purified (under 0.008 mg/L) under the optimal conditions, which is lower than the most stringent discharge standards of copper ions in electroplating effluent (<0.5 mg/L, China). DFT calculations reveal that DDTC could further precipitate the released free copper ions via the carbon disulfide (–C(=S)–S) chelating group while exhibiting a slight effect on the Fe(III) in Fe(III)-EDTA. Considering these results, the electronic structures of Cu(II) and Fe(III), as well as their interaction with EDTA and DDTC ligands, are discussed to understand the mechanism of Fe(III)/DDTC process. By introducing a low dosage of Fe(III), the DDTC could efficiently purify Cu(II) from the Cu(II)-EDTA acid wastewater and realize the near-zero discharge of metal pollutants in metal-organic complex wastewater. It is believed that the main findings may benefit the water pollution reduction and comprehensive recycling of metal resources.