Thermodynamic behavior and kinetic analysis of carbothermal reduction process of low-grade oxysulfur lead–zinc ore

Abstract

During the exploitation of sphalerite resources, a considerable amount of low-grade oxysulfur Pb–Zn deposits is generated, which poses a significant threat to the environment and soil and water conservation in mining areas. Therefore, low-grade Pb–Zn resources urgently require source emission reduction and appropriate utilization. This study applied a mineral technology and conducted X-ray diffraction and scanning electron microscopy–energy dispersive X-ray spectroscopy to investigate the phase transformation and the mechanism underlying the volatilization of Pb and Zn at different times and temperatures. The Pb–Zn volatilization kinetics of a low-grade oxysulfur Pb–Zn ore by a one-step pyrometallurgical process in an argon atmosphere was studied, and the effects of different temperature conditions on the Zn volatilization process were investigated. The results showed that the Zn-containing phase in the raw material was decomposed to ZnO and ZnS upon heating. Moreover, ZnO was reduced via carbothermal reduction, whereas ZnS was reduced via a CaO-assisted carbothermal reaction and volatilized in the form of gaseous Zn. In the Pb-containing phase, PbSO4 generated PbO, Pb, and PbS in the presence of Fe, FeS, and CaO. PbO was volatilized in the form of gaseous Pb through carbothermal reduction and interactions between PbS and PbO. The Pb–Zn volatilization reaction conformed to the shrinking core model with a constant size, and the volatilization-based removal of Pb and Zn process was controlled by internal diffusion. A macroscopic kinetic model of the reaction was established on the basis of experimental data. The apparent activation energy of Pb and Zn volatilization was 163.90 and 328.19 kJ/mol, respectively. This study promotes the utilization of the low-grade oxysulfur Pb–Zn ore through a pyrometallurgical method to provide theoretical support for large-scale industrial treatments.