Kinetics, Thermodynamics, and Mechanism of Cu(II) Ion Sorption by Biogenic Iron Precipitate: Using the Lens of Wastewater Treatment to Diagnose a Typical Biohydrometallurgical Problem.

The feasibility of improving typical biohydrometallurgical operation to minimize copper losses was investigated by the use of biogenic iron precipitate for the uptake of Cu(II) ions from aqueous solutions. The iron precipitate was obtained from mineral sulfide bioleaching and characterized using SEM/EDS, XRD, FTIR, BET, TGA, and pH analyses. The results show that the precipitate is highly heterogeneous and that Cu(II) ion adsorption can be described by both Freundlich and Langmuir adsorption isotherms, with a maximum adsorption capacity of 7.54 mg/g at 30 °C and 150 mg/L. The sorption followed pseudo-second-order kinetics, while the major presence of -OH and -NH functional groups initiated a chemisorption mechanism through an ion-exchange pathway for the process. Ionic Cu(II) (radius (0.72 Å)) attached easily to the active sites of the precipitate than hydrated Cu(II) (radius (4.19 Å)). With an estimated activation energy of 23.57 kJ/mol, the obtained thermodynamic parameters of Δ° (0.034-0.050 kJ/mol K), Δ° (8.37-10.64 kJ/mol), and Δ° (20.07-23.81 kJ/mol) indicated that the adsorption process was chemically favored, nonspontaneous, and endothermic, respectively. The 43% Cu(II) removal within 60 min equilibrium contact time at pH 5 was indicative of the reduced efficiency of copper extraction observed in a real-life biohydrometallurgical process due to sorption by the iron precipitate. The result of this study might provide an insight into the management of the biohydrometallurgical process to minimize copper losses. It may also help mitigate environmental pollution caused by the disposal of these biogenic iron precipitate residues.