Reduction Kinetics of Fe(III) on Chalcopyrite up to 110 °C

"In the present study, electrochemical measurements, especially cathodic potentiodynamic polarization (CPC) and cyclic potentiodynamic polarization (CPP), have been employed to study the kinetics of ferric reduction on chalcopyrite in aqueous Fe(II)Fe( III)H2SO4 solution at 90 °C and 110 °C. Results from the calculation of speciation in the above solution reveal that, at both 90 °C and 110 °C, the real Fe3+/Fe2+ ratio is much lower than the nominal ratio, which leads to smaller VALUES (for the reversible potential of the ferric/ferrous couple. Exchange current densities of the ferric/ferrous couple were obtained and are on the order of 106 10 5 A/cm2 a t 9 0 °C and 1 07 10 6 A/cm2 at 110 °C, respectively. The Tafel slopes from the CPP method are higher than those from the CPC method at both 90 °C and 110 °C. The transfer coefficients were about 0.360.59 at 90 °C and 0.370.65 at 110 °C. Based on the exchange current densities obtained, the rate constant kc was calculated. It was found that kc at 90 °C was slightly larger than at 110 °C, especially for the results obtained by the CPC method. The average rate constants are 862.17 cm/s for CPC and 65.30 cm/s for CPP at 90 °C, and 477.69 cm/s for CPC and 63.53 cm/s for CPP at 110 °C for nominal Fe3+/Fe2+ ratios ranging from 1:1 to 1000:1. INTRODUCTIONChalcopyrite is one of the most abundant copper-bearing minerals, accounting for approximately 70% of the world’s known copper reserves (Wang, 2005). Most of the currently proposed leaching processes are based on sulfuric acid with ferric ions and/or dissolved oxygen as oxidants. Some of these processes have been piloted in attempts to implement these technologies on an industrial scale, such as Activox (U.S. 5,232,491, 1993), Nenatech (U.S. 5,993,635, 1999), Dynatec (U.S. 5,730,776, 1998), AAC/UBC (U.S. 6,503,293, 2003), Total Pressure Oxidation (U.S. 5,698,170, 1997), CESL (U.S. 5,874,055, 1999) and Galvanox (U.S. 7,846,233, 2010).To date, much effort has been devoted to understanding the kinetics and mechanisms of the oxidative processes (Biegler & Horne, 1985; Córdoba, Muñoz, Blázquez, González, & Ballester, 2008, 2009; Ghahremaninezhad, Asselin, & Dixon, 2010; Hirato, Majima, & Awakura, 1987; Hiroyoshi, Kuroiwa, Miki, Tsunekawa, & Hirajima, 2004; Warren, Wadsworth, & El-raghy, 1982) or the cathode reduction reactions of chalcopyrite itself (Arce & González, 2002; Biegler & Swift, 1976; Biegler, 1977; Nava, González, Leinen, & Ramos-Barrado, 2008), by chemical or electrochemical methods. However, as the most important cathodic processes in chalcopyrite leaching systems, the cathodic reductions of ferric ions or dissolved oxygen are worth measuring due to their effects on the overall leaching rate, as predicted by mixed potential theory."