RESUMO
The nature of tennantite (Cu12As4S13), chalcopyrite (CuFeS2) and sphalerite (ZnS) particles' mixture dissolution in nitric acid (HNO3) media was investigated in this study. The effects of temperature (323−368 K), HNO3 (1−8 mol/L) and Fe3+ (0.009−0.036 mol/L) concentrations, reaction time (0−60 min) and pyrite (FeS2) additive (0.5/1−2/1; FeS2/sulf.conc.) on the conversion of the minerals were evaluated. It has been experimentally shown that the dissolution of the mixture under optimal conditions (>353 K; 6 mol/L HNO3; FeS2/synt. conc = 1/1) allows Cu12As4S13, CuFeS2 and ZnS conversion to exceed 90%. The shrinking core model (SCM) was applied for describing the kinetics of the conversion processes. The values of Ea were calculated as 28.8, 33.7 and 53.7 kJ/mol, respectively, for Cu12As4S13, CuFeS2 and ZnS. Orders of the reactions with respect to each reactant were calculated and the kinetic equations were derived to describe the dissolution rate of the minerals. It was found that the interaction between HNO3 solution and Cu12As4S13, CuFeS2 and ZnS under the conditions investigated in this are of a diffusion-controlled nature. Additionally, the roles of Fe(III) in the initial solution and FeS2 in the initial pulp as catalysts were studied. The results indicated that the increase in Fe3+ concentration significantly accelerates the dissolution of the mixture, while the addition of FeS2 forms a galvanic coupling between FeS2, and Cu12As4S13 and CuFeS2, which also accelerates the reaction rate. The results of the study are considered useful in developing a hydrometallurgical process for polymetallic sulfide raw materials treatment.
RESUMO
The nature of the hydrothermal reaction between arsenopyrite particles (FeAsS) and copper sulfate solution (CuSO4) was investigated in this study. The effects of temperature (443-523 K), CuSO4 (0.08-0.96 mol/L) and H2SO4 (0.05-0.6 mol/L) concentrations, reaction time (1-120 min), stirring speed (40-100 rpm) and particle size (10-100 µm) on the FeAsS conversion were studied. The FeAsS conversion was significant at >503 K, and it is suggested that the reaction is characterized by the formation of a thin layer of metallic copper (Cu0) and elemental sulfur (S0) around the unreacted FeAsS core. The shrinking core model (SCM) was applied for describing the process kinetics, and the rate of the overall reaction was found to be controlled by product layer diffusion, while the overall process was divided into two stages: (Stage 1: mixed chemical reaction/product layer diffusion-controlled) interaction of FeAsS with CuSO4 on the mineral's surface with the formation of Cu1+ and Fe2+ sulfates, arsenous acid, S0, and subsequent diffusion of the reagent (Cu2+) and products (As3+ and Fe2+) through the gradually forming layer of Cu0 and molten S0; (Stage 2: product layer diffusion-controlled) the subsequent interaction of CuSO4 with FeAsS resulted in the formation of a denser and less porous Cu0 and S0 layer, which complicates the countercurrent diffusion of Cu2+, Cu1+, and Fe2+ across the layer to the unreacted FeAsS core. The reaction orders with respect to CuSO4 and H2SO4 were calculated as 0.41 and -0.45 for Stage 1 and 0.35 and -0.5 for Stage 2. The apparent activation energies of 91.67 and 56.69 kJ/mol were obtained for Stages 1 and 2, respectively.
