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The catalytic mechanism of activated carbon-assisted bioleaching of enargite concentrate (enargite 37.4%; pyrite 47.3%) was investigated by employing microbiological, electrochemical and kinetic studies. By using moderately thermophilic microorganisms at 45ºC, the final Cu dissolution was improved from 36% to 53% at 0.2% (w/v) activated carbon. An excess activated carbon addition showed an adverse effect. The enargite mineral itself favored higher solution redox potential (Eh) for solubilization. However, the dissolution of co-existing pyrite, which also favors high Eh, immediately hindered enargite dissolution through the passivation effect. The surface of activated carbon functioned as an electron mediator to couple RISCs oxidation and Fe<3+>+ reduction, so that elevation of the Eh level was controlled by offsetting microbial Fe<3+>+ regeneration. As long as the Eh level was suppressed at <700 mV, the dissolution of pyrite was largely avoided, enabling a steady and continuous dissolution of the enargite mineral through the surface chemical reaction model. When the Eh-control by activated carbon becomes no longer sustainable and the Eh hits 700 mV, rapid pyrite dissolution was initiated and the surface chemical reaction of enargite dissolution came to an end. Arsenic species dissolved from enargite was constantly immobilized with an efficiency of 75-90% as amorphous ferric arsenate. However, the sudden initiation of pyrite dissolution also triggered the re-solubilization of ferric arsenate. Therefore, the sustainable Eh-controlling effect was shown to be critical to enable longer Cu dissolution from enargite as well as stabilization of As precipitates.

type:Article, Overcoming the slow-leaching kinetics of refractory primary copper sulfides is crucial to secure future copper sources. Here, the effect of carbon was investigated as a catalyst for a bioleaching reaction. First, the mechanism of carbon-assisted bioleaching was elucidated using the model chalcopyrite mineral, under specified low-redox potentials, by considering the concept of E_normal. The carbon catalyst effectively controlled the Eh level in bioleaching liquors, which would otherwise exceed its optimal range (0 ≤ E_normal ≤ 1) due to active regeneration of Fe^3+ by microbes. Additionally, E_normal of ~0.3 was shown to maximize the carbon-assisted bioleaching of the model chalcopyrite mineral. Secondly, carbon-assisted bioleaching was tested for three types of chalcopyrite/enargite-bearing complex concentrates. A trend was found that the optimal E_h level for a maximum Cu solubilization increases in response to the decreasing chalcopyrite/enargite ratio in the concentrate: When chalcopyrite dominates over enargite, the optimal E_h was found to satisfy 0 ≤ E_normal ≤ 1. As enargite becomes more abundant than chalcopyrite, the optimal E_h for the greatest Cu dissolution was shifted to higher values. Overall, modifying the E_h level by adjusting AC doses to maximize Cu solubilization from the concentrate of complex mineralogy was shown to be useful.

Effect of silver (Ag) catalyst in bioleaching of enargite (Cu_3AsS_4) concentrate was studied using mixed cultures of moderately thermophilic acidophilic microorganisms at 45ºC. Addition of Ag_2S enabled selective Cu dissolution from enargite while suppressing pyrite oxidation: At the highest Ag_2S concentration of 0.04%, Cu recovery reached 96% while Fe dissolution was suppressed to reach only 29% by day 72. Overall results from thermodynamic calculation, liquid/solid analyses and kinetic study suggested that Ag-catalyzed bioleaching of enargite concentrate proceeds via formation of at least two types of secondary products (chalcocite, Cu_2S; trisilver arsenic sulfide, Ag_3AsS_4): Addition of Ag_2S as Ag catalyst thermodynamically and microbiologically contributed to lowering solution redox potentials during bioleaching, consequently satisfying Eox (Cu_2S) < E_h < E_c (Ag+) to enhance enargite dissolution via formation of chalcocite intermediate. Formation of trisilver arsenic sulfide and its intermediate layer (Cu,Ag)_3AsS_4 indicated that Cu ion in the enargite lattice is gradually substituted with Ag. Such secondary products did not impose a rate-limiting step, since the Ag-catalyzed bioleaching was shown to be controlled by a chemical surface reaction, rather than diffusion through product film which was the case in the absence of Ag_2S.