Exploring the Reductive Pathway for the Hydrometallurgical Production of Copper from Chalcopyrite
Creators: Vardner, Jonathan Thomas
Publisher: name: Columbia University
Year: 2021
Subjects: subject: Chemical engineering
subject: FOS: Chemical engineering
subject: FOS: Chemical engineering
subject: Copper
subject: Chalcopyrite
subject: Hydrometallurgy
subject: Vanadium
subject: Markov processes

description: The high demand for copper is coinciding with a sharp decline in the grade of copper reserves, and as a result, copper scarcities are expected to arise in the coming decades. In this work, a transformative hydrometallurgical process is being developed to lower the costs of copper production and thereby sustain the use of copper throughout the global transition to renewable energy technologies. The focal point of the hydrometallurgical process is the reductive treatment of chalcopyrite, which is in contrast to the oxidative treatment more commonly pursued in the literature. Chalcopyrite may be reduced directly by the cathode of an electrochemical reactor, which is monitored by atomic absorption spectroscopy (AAS), x-ray diffraction (XRD), and x-ray photoelectron spectroscopy (XPS). The efficiency of the electrochemical reaction is optimized by adjusting the electrode materials, applied current density, and reactor design. Chalcopyrite may also be reduced by reaction with the vanadium (II) ion, which circumvents engineering challenges associated with slurry electrodes but requires the separation and electrochemical regeneration of the vanadium (II) ion. A preliminary technoeconomic analysis suggests that both reduction pathways may be competitive with the pyrometallurgical standard for copper production. The performance of vanadium redox flow batteries (VRFBs) is hindered by the diffusion and migration of the vanadium species across the separator, however the migration of vanadium species has not been accurately measured or characterized with values of the transference numbers. In this work, models based on dilute solution theory and concentrated solution theory are developed to introduce the dimensionless ratio of migration to diffusion (M/D) to the literature. It is shown that transference numbers may be measured with high accuracy and precision for experiments conducted in the migration-dominated regime. An experimental procedure is designed to measure vanadium crossover as a function of current density for vanadium-containing electrolytes of various state of charge (SOC), state of discharge (SOD), and sulfuric acid concentration. Model-guided design of experiment is used to estimate the transference number of the vanadium species in Nafion 117 with minimal uncertainty related to unknown or unmeasured physical properties. Markov Chain Monte Carlo simulations are used to quantify the relative uncertainties of the transference number estimates to be less than five percent, consistently. The transference number estimates are related to faradaic efficiency loss and capacity fade of working VRFBs operating in the migration-dominated regime. The technique used in this work may be generalized to measure salt transference numbers in novel electrochemical systems and membrane separators to inform their rational design.