Roasting Of High Arsenic Copper Concentrates: Kinetics and Mechanisms of Calcine Formation

Proceedings, Vol. Proceedings of the 58th Conference of Metallurgists Hosting Copper 2019, 2019

Wilkomirsky, I.

A thermodynamic and kinetic model is proposed to explain the formation of bornite, chalcopyrite and magnetite during partial roasting of enargite-containing copper concentrates. The proposed mechanism involves solid-solid-gas and solid-gas reactions between chalcocite, pyrrhotite, gaseous sulfur and oxygen. The formation of bornite could be explained by a two-step reaction: the first one involving the formation of chalcopyrite by a reaction between Cu2S, FeS and gaseous sulfur, followed by a second step in which the newly formed chalcopyrite reacts with additional chalcocite to form bornite. Although thermodynamically the direct formation of bornite is more favorable than that of chalcopyrite, the lower diffusion kinetics of bornite formation could explain the preferential formation of chalcopyrite. If the reaction occurs with stoichiometric chalcocite and pyrrhotite in the presence of gaseous sulfur to form chalcopyrite, no bornite is formed, while for the stoichiometric reaction between chalcopyrite and chalcocite in the absence of sulfur, only bornite is formed. For the formation of magnetite and chalcopyrite the mechanism could involve the partial reaction of chalcocite and pyrrhotite in the presence of oxygen. The proposed model is thermodynamically consistent with the experimental results obtained in laboratory and pilot plant. INTRODUCTION The processing of high-arsenic copper concentrates with over 0.7 wt.-% arsenic by conventional smelting-converting normally require an additional arsenic removal step to reduce arsenic content to levels below 0.2–0.3%. One of these high-arsenic copper concentrates is the one produced by the Ministro Hales Division (DMH) of CODELCO, which has the typical chemical composition shown in Table 1. Enargite (Cu3AsS4), chalcocite (Cu2S) and pyrite (FeS2) are the main mineralogical species present in these concentrates, with over 75 wt.-%, as shown in Table 2. Partial or “neutral” roasting of these concentrates under controlled temperature and partial oxygen pressure conditions at 923–993K (650–720ºC) can remove up to 95% of the arsenic as As2S3 (As4S6), which has a high vapor pressure under these conditions, leaving a calcine with low residual arsenic. In copper concentrates, arsenic is present generally as enargite and arsenopyrite. This compounds as well as others such as pyrite and covelite, decompose readily above 770 K (500ºC), releasing, in addition to gaseous arsenic trisulfide, gaseous sulfur which by oxidizing to SO2 generates most of the heat required by the process.

Mots Clés: Copper 2019, COM2019