Hajime Miki

Enhancement of chalcopyrite leaching by ferrous ions in acidic ferric sulfate solutions

The effects of ferrous ions on chalcopyrite oxidation with ferric ions in 0.1 mol dm−3 sulfuric acid solutions were investigated by leaching experiments at 303 K in nitrogen. With high cupric ion concentrations, the chalcopyrite oxidation was enhanced by high concentrations of ferrous ions and copper extraction was mainly controlled by the concentration ratio of ferrous to ferric ions or the redox potential of solutions. Ferrous ions, however, suppressed the chalcopyrite oxidation when cupric ion concentrations were low. A reaction model, which involves chalcopyrite reduction to intermediate Cu2S by ferrous ions and oxidation of the Cu2S by ferric ions, was proposed to interpret the results.

A model for ferrous-promoted chalcopyrite leaching

Oxidative leaching of chalcopyrite with dissolved oxygen and/or with ferric ions is promoted by high concentrations of ferrous ions in sulfuric acid solutions containing cupric ions. This paper proposes a reaction model to interpret this phenomenon and the thermodynamics of the leaching is discussed. The model considers the leaching to take place in two steps: (1) reduction of chalcopyrite to Cu2S by ferrous ions in the presence of cupric ions and (2) oxidation of the Cu2S to cupric ions and elemental sulfur by dissolved oxygen and/or by ferric ions. The intermediate Cu2S is more amenable to oxidation than chalcopyrite, causing enhanced copper extraction. The model predicts that the formation of intermediate Cu2S and ferrous-promoted chalcopyrite leaching occur when the redox potential of the solution is below a critical potential that is a function of the ferrous and cupric ion concentrations. To confirm this, flask-shaking leaching experiments were carried out with 0.1 mol dm−3 sulfuric acid solutions containing known concentrations of ferrous, ferric, and cupric ions at 303 K in air. The results agreed well with the predictions, i.e. copper extraction was enhanced at solution potentials below the critical potential predicted with the model.

A new reaction model for the catalytic effect of silver ions on chalcopyrite leaching in sulfuric acid solutions

Abstract Chalcopyrite leaching in sulfuric acid solutions depends on the redox potential determined by the concentration ratio of ferric to ferrous ions, and the leaching rate is higher at redox potentials below a critical value. Previously, the authors have proposed a reaction model to interpret this phenomenon. The present study applied the model to interpret the catalytic effect of silver ions on chalcopyrite leaching. The model assumes that at lower potentials, chalcopyrite leaching proceeds in two steps: first, chalcopyrite is reduced by ferrous ions to form Cu 2 S that is more rapidly leached; next, the intermediate Cu 2 S is oxidized by ferric and/or dissolved oxygen to release cupric ions. During the chalcopyrite reduction, hydrogen sulfide is released to the liquid phase. Silver ions react with the hydrogen sulfide to form silver sulfide precipitate and decrease the concentration of hydrogen sulfide in the liquid phase, causing a rise in the critical potential of Cu 2 S formation and broadening of the potential range where rapid copper extraction takes place. To confirm the model, the redox potential dependence of chalcopyrite leaching was investigated in the presence of various concentrations of silver ions with 0.1 kmol m −3 sulfuric acid containing known concentrations of ferrous and ferric ions at 298 K in air. The critical potential increased with increasing concentrations of silver ions. This agrees with the model proposed here but cannot be explained by the conventional model proposed by Miller et al.

Microbiological Redox Potential Control to Improve the Efficiency of Chalcopyrite Bioleaching

ABSTRACT The effect of controlling the redox potential (Eh) on chalcopyrite bioleaching kinetics was studied as a new aspect of redox control during chalcopyrite bioleaching, and its mechanism was investigated by employing the “normalized” solution redox potential (Enormal) and the reaction kinetics model. Different Eh ranges were established by use of different acidophiles (Sulfobacillus acidophilus YTF1; Sulfobacillus sibiricus N1; Acidimicrobium ferrooxidans ICP; Acidiplasma sp. Fv-AP). Cu dissolution was very susceptible to real-time change in Eh during the reaction. It was found that efficiency of bioleaching of chalcopyrite can be effectively evaluated on the basis of Enormal, since it is normalized for real-time fluctuations of concentrations of major metal solutes during bioleaching. For steady Cu solubilization during bioleaching at a maximum rate, it was important to maintain a redox potential range of 0 ≤ Enormal ≤ 1 (−0.35 mV optimal) at the mineral surface by employing a “weak” ion-oxidizer. This led to a copper recovery of > 75%. At higher Enormal levels (Enormal > 1 by “strong” microbial Fe2+ oxidation), Cu solubilization was slowed by diffusion through the product film at the mineral surface (< 50% Cu recovery) caused by low reactivity of the chalcopyrite and by secondary passivation of the chalcopyrite surface, mainly by jarosite.

Mechanism of Silver-Catalyzed Bioleaching of Enargite Concentrate

Silver-catalyzed bioleaching of enargite concentrate with three bacteria (Acidimicrobium ferrooxidans ICP, Sulfobacillus sibiricus N1, Acidithiobacillus caldus KU) and one archaeon (Ferroplasma acidiphilum Y) was conducted in order to elucidate the catalytic mechanism of silver sulfide in enargite bioleaching. Whereas Cu recovery remained relatively low (43%) and Fe dissolved completely without silver sulfide, Cu recovery was greatly enhanced (96%) and Fe dissolution was suppressed (29%) in the presence of 0.04% silver sulfide. In the latter case, 52% of the solubilized As was re-immobilized, in contrast to only 14% As re-immobilization in the former. The silver-catalyzed bioleaching (at 0.04% silver sulfide) proceeded at low redox potentials within the optimal range, which likely promoted enargite dissolution via formation of intermediate Cu2S. XAFS analysis revealed that As was mainly immobilized as As (V), which was in agreement with the EPMA results detecting ferric arsenate passivation on some enargite grains. Furthermore, formation of trisilver arsenic sulfide (Ag3AsS4) was detected by XRD and EPMA, covering the surface of enargite particles. An intermediate layer, consisting of (Cu,Ag)3AsS4, was also observed between the enargite grain and trisilver arsenic sulfide layer, implying that Cu in enargite may be gradually substituted by solubilized Ag. The overall mechanism of silver-catalyzed bioleaching of enargite concentrate will be proposed.