Tsuyoshi Hirajima

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 case of ferrous sulfate addition enhancing chalcopyrite leaching

It is generally accepted that ferric ions as an oxidant are effective for leaching chalcopyrite but ferrous ions contribute to the leaching only as a source of ferric ions. However, this paper found that several chalcopyrite samples were more effectively leached in ferrous sulfate solution than in ferric sulfate solution. Chalcopyrite samples from four different sources were leached in 0.1 mol dm−3 sulfuric acid solution containing 0.1 mol dm−3 ferrous sulfate or ferric sulfate at 303 K in air for 168 h. Three samples were more effectively leached in the ferrous sulfate solution than in the ferric sulfate solution. Especially, with the sample from the Akenobe mines, Hyogo, Japan, the amount of copper extracted with ferrous sulfate was about five times larger than that with ferric sulfate. By using the Akenobe sample, leaching experiments and oxygen consumption measurements were carried out under various conditions. The amount of extracted copper increased markedly with increasing ferrous sulfate addition and decreasing pH. During the leaching experiments, most of the soluble iron was present in the ferrous form. By adding ferrous sulfate, proton consumption increased. The mole ratio of elemental sulfur to extracted copper was about 2. When the leach solution was purged with nitrogen, the amount of copper extracted was negligible even with ferrous sulfate. By adding ferrous sulfate, dissolved oxygen consumption on the sample surface increased. From these results, it was concluded that ferrous ions enhance the following reaction for the Akenobe sample: CuFeS2 + O2 + 4H+ = Cu2+ + Fe2+ + 2S0 + 2H2O. The importance of this effect in the bacterial leaching of chalcopyrite is discussed.

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.

Adhesion of Escherichia coli onto quartz, hematite and corundum: Extended DLVO theory and flotation behavior

The adhesion of Escherichia coli onto quartz, hematite and corundum was experimentally investigated. A strain of E. coli was used that had the genes for expressing protein for silica precipitation. The maximum cell adhesion was observed at pH <4.3 for quartz and at pH 4.5-8.5 for corundum. For hematite, cell adhesion remained low at all pH values. The microbe-mineral adhesion was assessed by the extended DLVO theory approach. The essential parameters for calculation of microbe-mineral interaction energy (Hamaker constants and acid-base components) were experimentally determined. The extended DLVO approach could be used to explain the results of the adhesion experiments. The effect of E. coli on the floatability of three oxide minerals was determined and the results showed that E. coli can act as a selective collector for quartz at acidic pH values, with 90% of the quartz floated at 1.5 x 10(9)cells/ml. However, only 9% hematite and 30% corundum could be floated under similar conditions. By using E. coli and no reagents, it was possible to separate quartz from a hematite-quartz mixture with Newtons efficiency of 0.70. Removal of quartz from the corundum mixture was achieved by E. coli with Newtons efficiency of 0.62.

Inhibitory effect of iron-oxidizing bacteria on ferrous-promoted chalcopyrite leaching

It is generally accepted that iron-oxidizing bacteria, Thiobacillus ferrooxidans, enhance chalcopyrite leaching. However, this article details a case of the bacteria suppressing chalcopyrite leaching. Bacterial leaching experiments were performed with sulfuric acid solutions containing 0 or 0.04 mol/dm3 ferrous sulfate. Without ferrous sulfate, the bacteria enhance copper extraction and oxidation of ferrous ions released from chalcopyrite. However, the bacteria suppressed chalcopyrite leaching when ferrous sulfate was added. This is mainly due to the bacterial consumption of ferrous ions which act as a promoter for chalcopyrite oxidation with dissolved oxygen. Coprecipitation of copper ions with jarosite formed by the bacterial ferrous oxidation also causes the bacterial suppression of copper extraction. Copyright 1999 John Wiley & Sons, Inc.

Sorption characteristics of fluoride on to magnesium oxide-rich phases calcined at different temperatures.

The effect of calcination temperature during production of magnesium oxide-rich phases from MgCO(3) on the sorption of F(-) ions in the aqueous phase has been investigated. Magnesium oxide-rich phases were formed by calcination at over 873 K for 1h. Higher calcination temperatures produced more crystalline MgO with smaller specific surface area and provided larger values of the total basicity per unit surface area. The higher calcination temperatures lead to slower F(-) removal rate, and lower equilibrium F(-) concentrations, when the equilibrium F(-) concentrations are less than 1 mmol dm(-3). Larger total basicity per unit surface area made the reactivity with F(-) ions in aqueous phase more feasible, resulting in a greater degree of F(-) sorption. For equilibrium F(-) concentrations more than 1 mmol dm(-3), lower calcination temperatures favored the co-precipitation of F(-) with Mg(OH)(2), probably leading to the formation of Mg(OH)(2-x)F(x), and the achievement of larger sorption density. This is the first paper which describes the relationship between the solid base characteristics obtained by CO(2)-TPD for MgO with different calcination temperatures as a function of the reactivity of F(-) sorption in the aqueous phase.

Adhesion of Ferroplasma acidiphilum onto pyrite calculated from the extended DLVO theory using the van Oss–Good–Chaudhury approach

The adhesion behavior of Ferroplasma acidiphilum archaeon to pyrite mineral was investigated experimentally and theoretically. F. acidiphilum showed high affinity to adhere to pyrite surface at acidic regions, however low affinity was observed at neutral and alkaline regions. The microbe-mineral adhesion was assessed by the extended DLVO theory. Hamaker constants, electron donors, electron acceptors and surface charges for the microbe and the mineral were experimentally determined. The extended DLVO theory was used to explain the adhesion results. Significant changes to the pyrite surface properties after being treated with the microbial cells were observed. Pyrite lost its hydrophobic nature and became hydrophilic, the contact angle of untreated pyrite was 61 degrees and this decreased to 36 degrees after the treatment. As a consequence, the flotation experiment results showed that F. acidiphilum strain could act as a good depressant for pyrite in xanthat flotation; where in absence of F. acidiphilum cells, over 95% of pyrite can be recovered as a float. However, when the mineral was pretreated with F. acidiphilum cells, less than 20% can be recovered as a float.

Effect of calcination temperature on Mg–Al bimetallic oxides as sorbents for the removal of F− in aqueous solutions

Bimetallic oxides were synthesized from hydrotalcite using increasing calcination temperatures (873, 1073, 1273 K). These bimetallic oxides were fully characterized and the sorption density of F(-) was investigated. X-ray diffraction patterns for the produced bimetallic oxides showed that MgO was the primary phase within the range of investigated calcination temperatures, but MgO crystallinity increased with calcination temperature and an additional MgAl2O4 phase was formed. In the process of F(-) sorption, the bimetallic oxides were primarily transformed into hydrotalcite with intercalation of F(-). The Higher calcination temperature increased the MgAl2O4 phase, which did not contribute to the immobilization of F(-). These findings show that optimizing the calcination temperature can be used to maximize the sorption density of this material for F(-) removal.

Bio-templated synthesis of lithium manganese oxide microtubes and their application in Li+ recovery.

Microbial transformations, a primary pathway for the Mn oxides formation in nature, provide potential for material-oriented researchers to fabricate new materials. Using Mn oxidizing fungus Paraconiothyrium sp. WL-2 as a bio-oxidizer as well as a bio-template, a special lithium ion sieve with microtube morphology was prepared through a solid-state transformation. Varying the calcination temperature from 300 to 700 °C was found to influence sample properties and consequently, the adsorption of Li(+). Lithium manganese oxide microtube (LMO-MTs) calcined at different temperatures as well as their delithiated products (HMO-MTs) were characterized by X-ray diffraction (XRD), X-ray absorption fine structure (XAFS) spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Calcination temperatures affect not only the content but also the crystal structure of LMO spinel, which is important in Li(+) adsorption. The optimized sample was obtained after calcination at 500 °C for 4h, which shows higher Li(+) adsorption capacity than particulate materials.