Mathematical modeling of thermophilic bioleaching of chalcopyrite

Previous studies have shown that the different preferences of thermophiles to oxidize S⁰ or Fe²⁺ is reflected by different [Fe³⁺]/[Fe²⁺] levels in solution. In those studies it was concluded that [Fe³⁺]/[Fe²⁺] governs the thermophilic bioleaching of chalcopyrite rather than temperature or pH. Therefore, the proposed model is mainly based on the finding that thermophilic bioleaching of chalcopyrite is governed by [Fe³⁺]/[Fe²⁺] that result from the activity of thermophiles. A direct interaction between chalcopyrite and thermophiles is neglected because it has been reported that this is not a general behavior for all thermophiles. The case of constant temperature, initial pH 1.5–2.5, and chalcopyrite concentrates is considered. The main assumption is that chalcopyrite can be anodically oxidized or cathodically reduced depending on [Fe³⁺]/[Fe²⁺] in solution. When chalcopyrite is oxidized at high [Fe³⁺]/[Fe²⁺] levels, Cu²⁺ is formed directly at low rates: CuFeS₂ + 4Fe³⁺ → Cu²⁺ + 5Fe²⁺ + S⁰. Whereas, when chalcopyrite is reduced at low [Fe³⁺]/[Fe²⁺] levels, an intermediate (Cu₂S) is formed at higher rates: CuFeS₂ + Fe²⁺ + Cu²⁺ + 2H⁺ → Cu₂S + 2Fe³⁺ + H₂S. Because the oxidation of Cu₂S is relatively fast: Cu₂S + 4Fe³⁺ → 2Cu²⁺ + S⁰ + 4Fe²⁺, its accumulation is assumed to be negligible. To take into account the possibility of chalcopyrite being oxidized or reduced depending on [Fe³⁺]/[Fe²⁺] in solution, the principle of mixed potentials is used. The model is validated by comparing the calculated and measured values of copper extraction, total iron in solution, and pH.     

Single and binary component sorption of the fission products Sr2+, Cs+ and Co2+ from aqueous solutions onto sulphate reducing bacteria

This study investigates the removal of the fission products Sr²⁺, Cs⁺ and Co²⁺ in single and binary metal solutions by a sulphate reducing bacteria (SRB) biomass. The effect of initial concentration and pH on the sorption kinetics of each metal was evaluated in single metal solutions. Binary component equilibrium sorption studies were performed to investigate the competitive binding behaviour of each metal in the presence of a secondary metal ion. Results obtained from single metal equilibrium sorption studies indicated that SRB have a higher binding capacity for Sr²⁺ (q_max = 416.7 mg g^?1), followed by Cs⁺ (q_max = 238.1 mg g^?1), and lastly Co²⁺ (q_max = 204.1 mg g^?1). Among the binary systems investigated, Co²⁺ uptake was the most sensitive, resulting in a 76% reduction of the sorption capacity (q_max) in the presence of Cs⁺. These findings are significant for future development of effective biological processes for radioactive waste management under realistic conditions.     

The effect of particle size on acid mine drainage generation: Kinetic column tests

The rate of acid mine drainage (AMD) generation is directly proportional to the surface area and so to the particle size distribution of acid-forming minerals exposed to oxidation. Materials in various particle sizes are subject to weathering processes at field condition; however, the particle size dependent oxidation rate has not been investigated for understanding entire geochemical behavior at a mining site. Therefore, a comprehensive research program was aimed to investigate the effect of particle size on pH variation and acid mine drainage generation using kinetic column tests, and then to find convenient methodologies for upscaling laboratory-based results to the field condition. For this purpose, ore samples collected from Murgul Damar open-pit mining were grinded in three different particle size distributions that are coarse (minus 22.5 mm), medium (minus 3.35 mm) and fine (minus 0.625 mm) sizes, 34 columns were designed in different dimensions for kinetic column tests. It was found that the cumulative concentration of the many constituents measured from medium particles (minus 3.35 mm) are higher than coarser samples due to decreasing specific surface area with increasing particle size. Similarly, because of decreasing of hydraulic conductivity with increasing the fine content, the cumulative concentration of constituents measured from medium particles (minus 3.35 mm) are also higher than finer particles (minus 0.625 mm). Based on statistical and analytical analyses of the results of kinetic column tests, the time required to initiate acid formation at field condition varied between 489 and 1002 days depending on particle size distribution. In addition, considering the effect of particle size and the results of related statistical analysis, main oxidation (SO₄²⁻) and neutralization (Ca²⁺, Mg²⁺, Mn²⁺ etc.) products were also successfully upscaled to the field condition.     

Solvent extraction and separation of palladium(II) and platinum(IV) from hydrochloric acid medium with dibutyl sulfoxide

The solvent extraction and separation performances of Pd(II) and Pt(IV) from hydrochloric acid solutions were investigated using dibutyl sulfoxide (DBSO) diluted in kerosene. Pd(II) was strongly extracted by a lower concentration DBSO in a lower concentration hydrochloric acid solution while the reverse was obtained for Pt(IV) extraction. Based on independent extraction and separation experiments of Pd(II) and Pt(IV), the separation parameters of Pd(II) and Pt(IV), including dibutyl sulfoxide concentration, contact time of aqueous and organic phases, organic/aqueous (O/A) phase ratio and H⁺ concentration of aqueous phase, were studied in detail, and the optimal separation parameters were obtained and summarized as the following: dibutyl sulfoxide concentration 0.6–1.2 mol dm^?3, organic/aqueous (O/A) phase ratio 0.6–1.0, H⁺ concentration of aqueous phase 1.0–1.5 mol dm^?3 and contact time of two phases 5 min. The as-prepared separation parameters were corroborated by the extraction and separation from a synthetic stock solution containing Pd(II), Pt(IV) as well as several common impurities like Fe(II), Cu(II) and Ni(II). The results revealed that Pd(II) could be separated efficiently from Pt(IV) with a high separation coefficient of Pd(II) an Pt(IV) (2.7 × 10⁴) by predominantly controlling dibutyl sulfoxide and hydrochloric acid concentrations. The extraction saturation capacity of Pd(II) was determined from 1.0 mol dm^?3 HCl solution with 3 mol dm^?3 dibutyl sulfoxide and its experimental value exceeded 14 g dm^?3 under the experimental conditions.Stripping of Pd(II) from loaded organic phase was performed using a mixed aqueous solution containing NH₄Cl and ammonia solutes. Pd(II) (99.2%) was stripped using the stripping solution containing 3% (m/v) NH₄Cl and 5 mol dm^?3 ammonia, respectively.     

Uranium recovery from strong acidic solutions by solvent extraction with Cyanex 923 and a modifier

Uranium stripping with strong acid solution is always highly desired due to its simple operation and less pollution. However, intensive acid neutralisation for uranium precipitation in the subsequent step limited its application. A new solvent extraction process has been developed to transfer uranium from strong to weak sulphuric acid solutions suitable for uranium precipitation without intensive neutralisation. An organic system consisting of 10% Cyanex 923 and 10% isodecanol as the modifier in ShellSol D70 was optimised for the process. It was found that uranium was extracted efficiently from 4 to 6 M H₂SO₄ solutions with the organic system, and it could be efficiently stripped with 0.2–0.5 M H₂SO₄ solutions. Both extraction and stripping kinetics of uranium were very fast, reaching the equilibrium within 0.5 min. Temperature between 30 and 60 °C has slight effect on uranium extraction and stripping. Four theoretical stages could effectively extract more than 98% uranium from a solution containing 17.5 g/L U and 6.0 M H₂SO₄ at an A/O ratio of 1:1.5, and it could generate a loaded organic solution containing about 12 g/L U. More than 99% U could be stripped from the loaded organic solution containing 14.6 g/L U with 0.5 M H₂SO₄ using five stages at an A/O ratio of 1:3. As a result, the loaded strip liquor containing more than 40 g/L U would be obtained which is suitable for uranium recovery by precipitation using hydrogen peroxide. A conceptual process has been proposed for uranium transfer from strong to weak sulphuric acid solutions for its recovery.     

The effect of seawater based media on copper dissolution from low-grade copper ore

Due to the scarcity of water in the north of Chile, there is interest in small-scale mining using seawater to leach the minerals. This situation has led to this research aimed to determine the effect of different process variables on the extraction of copper based on the ore type of these small-scale mining activities. The extraction of copper from finely ground (<150 μm) low-grade mixed ore (0.36% Cu) was studied in different acidic media (H₂SO₄ and HCl). The effects of water quality (tap water, seawater and synthetic process water) and lixiviants on copper leaching were investigated at three temperatures (25 °C, 35 °C and 45 °C). Synthetic process water was prepared by adding Na⁺, Cl⁻, Cu²⁺ and SO₄²⁻ to seawater. Copper extractions between 70% and 80% were achieved in 48 h using seawater, similar to the extractions obtained using tap water. Rapid copper dissolution occurred when synthetic process water was used, from 90% to 97%. This marked increase was related to the addition of Cu²⁺, which promoted the formation of CuCl⁺. Seawater was comparable to freshwater in terms of leaching kinetics and yield potential by raising the chloride concentration and increasing the formation of copper chloride ions. The findings of this study also expanded our understanding of the consequences of substituting seawater for freshwater at industrial leaching operations.     

Recycling of waste pickle acid by precipitation of metal fluoride hydrates

Stainless steel is pickled in mixed acid solutions (1–3 M HNO₃ and 0.5–4 M HF). The spent solution is usually neutralized with lime, and in Sweden about 18,000 tons/yr of metal hydroxide sludge is disposed as landfill waste. We are developing a cost-saving and environmentally friendly process, involving crystallization of β-FeF₃ · 3H₂O, where the metal content is recovered and the acid is recycled.Iron has been successfully separated from spent pickle bath solutions by precipitation of β-FeF₃ · 3H₂O in a continuous crystallizer (10 L scale) where the solution is concentrated by nanofiltration. The crystal growth rate of β-FeF₃ · 3H₂O has been determined in industrial pickle bath solutions at 50 °C and the results have been compared to previous measurements in pure HF/HNO₃ solutions prepared in the laboratory. The growth rate of β-FeF₃ · 3H₂O crystals at 50 °C is in the order of 10⁻¹¹ m/s in both industrial and pure acid mixtures.     

Solvent extraction of tetravalent hafnium from acidic chloride solutions using 2-ethyl hexyl phosphonic acid mono-2-ethyl hexyl ester (PC-88A)

Solvent extraction of Hf(IV) from acidic chloride solutions has been carried out with PC-88A as an extractant. Increase of acid concentration decreases the percentage extraction of metal indicating the ion exchange type mechanism. The plot of logD vs log[extractant], M is linear with slope 1.8 indicating the association of two moles of extractant with the extracted metal species. Plot of logD vs log[H⁺] gave a straight line with a negative slope of ∼2 indicating the exchange of two moles of hydrogen ions for every mole of Hf(IV). The effect of Cl⁻ ion concentration at constant concentration of [H⁺] did not show any change in D values. Addition of sodium salts enhanced the percentage extraction of metal and follows the order NaSCN > NaCl > NaNO₃ ∼ Na₂SO₄. Stripping of metal from the loaded organic (LO) with different acids indicated sulphuric acid as the best stripping agent. Regeneration and recycling capacity of PC-88A, temperature, extraction behavior of associated elements was studied.     

Bioleaching of djurleite using Acidithiobacillus ferrooxidans

The bioleaching of djurleite using Acidithiobacillus ferrooxidans (LD-1) was investigated in this paper. Experiments were carried out in shake flasks at pH 2.0, 160 r/min and 30 °C. The leaching residues were analyzed using X-ray diffraction (XRD), Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The total copper extraction of djurleite under optimal condition reached 95.12%. The XRD analysis indicated the residues mainly consisted of ammoniojarosites and S₈. It was observed by the SEM image that the djurleite was heavily etched. The XPS results confirmed the intermediate product formed during djurleite leaching was CuS. The result indicates the reaction pathway is: Cu₃₁S₁₆ → CuS → tCu²⁺ and S⁰.     

Modification of ilmenite surface properties by superficial dissolution method

Acid surface dissolution as a pretreatment method converts Fe²⁺ ions on the ilmenite surface to Fe³⁺ ions. XPS analysis showed that the content of Fe³⁺ increases from 48.5% to 59.8% after surface dissolution for 15 min in a solution of sulfuric acid with a concentration of 10%. This conversion, without any phase transformation, decreases the zeta potential of ilmenite in a wide pH range, resulting in a shift in IEP (Iso-Electric Point) from a pH of 5.4 to 2.3. FTIR spectra and zeta potential measurements showed that the increase of oleate ions adsorption on the ilmenite surface, resulting from the surface dissolution process, is insignificant. After surface dissolution, the formation of more ferric iron oleate species (Ksp = 10^−29.7) being more stable than ferrous iron oleate (Ksp = 10^−15.5) compounds yields an increase of ilmenite hydrophobicity and floatability in a wide pH range. Using 3.65 × 10⁻⁴ M sodium oleate at a pH of 6.3, the maximum flotation recoveries are obtained as 73.5% and 92% for non-treated and acid pretreated ilmenite, respectively.     

Process development for the recovery of europium and yttrium from computer monitor screens

This work describes the development of a process for the recovery of Eu and Y from cathode ray tubes (CRTs) of discarded computer monitors with the proposition of a flow sheet for the metals dissolution. Amongst other elements, europium and yttrium are presented in the CRTs in quantities – 0.73 w/w% of Eu and 13.4 w/w% of Y – that make their recovery worthwhile. The process developed is comprised of the sample acid digestion with concentrated sulphuric acid followed by water dynamic leaching at room temperature. In the CRTs, yttrium is present as oxysulphide (Y₂O₂S) and europium is an associated element – Y₂O₂S:Eu³⁺ (red phosphor compound). During the sulphuric acid digestion, oxysulphide is converted into a trivalent Eu and Y sulphate, in solid form, with the liberation of H₂S. In the second step, metals are leached from the solid produced in the acid digestion step by dynamic leaching with water. This study indicates that a proportion of 1250 g of acid per kg of the sample is enough to convert Eu and Y oxysulphide into sulphate. After 15 min of acid digestion and 1.0 h of water leaching, a pregnant sulphuric liquor containing 17 g L⁻¹ Y and 0.71 g L⁻¹ Eu was obtained indicating yield recovery of Eu and Y of 96% and 98%, respectively. Both steps (acid digestion and water leaching) may be performed at room temperature.     

Stability of As(V)-sorbed schwertmannite under porphyry copper mine conditions

Arsenic (As), a very poisonous inorganic pollutant is a major toxicant in tailings of porphyry copper deposits. Retention of As by Schwertmannite (a ferric-oxyhydroxysulfate mineral) has attracted much attention in recent years due to its strong binding affinity to toxic As species. The stability of As(V)-sorbed schwertmannite under copper mine waste conditions is not fully understood. The present study investigates the effect of Cu²⁺, Fe²⁺, pH, and ageing time on the stability of As(V)-sorbed schwertmannite (Sch-As). The results indicate that Cu²⁺ has no significant effect on the stability of Sch-As and that the As(V) incorporated in schwertmannite can retard or significantly inhibit Fe²⁺-catalyzed transformation of schwertmannite to goethite under acidic conditions (pH 3–4). The Sch-As aged at different pHs from 3 to 11 at 25 °C exhibits no mineralogical phase changes even after ageing for 120-days; however the concentration of As released from the solid phase appears to be strongly pH-dependent even after ageing for only 24 h. The release of As was negligible at pHs from 2 to 7, and there was considerable release of As at extremely acidic and alkaline conditions. This indicates that the release of As from Sch-As was controlled by environmental factors such as pH, Cu²⁺, and Fe²⁺ rather than time.     

Density functional theory study of α-Bromolauric acid adsorption on the α-quartz (1 0 1) surface

Adsorption mechanism of collector α-Bromolauric acid (CH₃(CH₂)₉CHBrCOOH, α-BLA) on α-quartz (1 0 1) surface has been investigated by first-principles calculations based on density functional theory (DFT). The interaction energies of H₂O molecule, calcium ions (Ca²⁺), hydroxyl ions (OH⁻), calcium hydroxyl ions (Ca(OH)⁺), and α-BLA⁻ ions with α-quartz (1 0 1) surface were in the order of Ca(OH)⁺ < Ca²⁺ < OH⁻ < H₂O < α-BLA⁻. The results revealed that the collector α-BLA cannot adsorb on α-quartz (1 0 1) surface due to the hindrance of hydration shell of quartz surface, while Ca(OH)⁺ could repulse the hydration shell and consequently adsorb on quartz surface, which further leads to the adsorption of the collector α-BLA⁻ anions on Ca(OH)⁺-activated quartz surface. Mulliken populations analysis of the external oxygen atom (O2) of quartz surface, calcium atom (Ca) of Ca(OH)⁺, and oxygen atom (O1) of collector α-BLA⁻ (–OH group) shows that the electron transfer between the Ca–O1 and Ca–O2 atoms. The overlap area of electron density between Ca–O1 and Ca–O2 atoms indicates strong interactions among the three atoms of Ca, O1, and O2, suggesting that Ca(OH)⁺ ions act as a bridge between the α-quartz (1 0 1) surface and the α-BLA collector.     

The reduction of chromite in the presence of silica flux

The mechanism and kinetics of the carbothermic reduction of a natural chromite was studied at 1300–1500 °C in the presence of silica. Thermogravimetry, X-ray diffraction (XRD) analysis, energy dispersive X-ray analysis (EDAX) and metallography were the experimental techniques used. Silica affected the reduction at and above 1400 °C. A two stage reduction mechanism was established. The first stage, up to about 40% reduction, is primarily limited to iron metallization and zoning is observed in partially reduced chromites. In this stage silica does not interfere with the reduction. The second stage is mainly confined to chromium metallization and formation of a silicate slag alters the reduction mechanism. Ion-exchange reactions between the reducible cations (Cr³⁺ and Fe²⁺) in the spinel and the dissolved cations (A1³⁺ and Mg²⁺) in the slag allow further reduction. Due to the very high driving force for the diffusion, the overall process is shifted toward a more chemical reaction controlled mechanism. A generalized rate equation was then applied to the individual metallization curves of iron and chromium from which respective rate constants and diffusion coefficients were derived. The rate constants were in the range 6.74 × 10⁻⁴–9.01 × 10⁻⁴ s⁻¹ for iron and 7.20 × 10⁻⁴–8.50 × 10⁻⁴ s⁻¹ for chromium reduction at 1500 °C in the presence of silica. At 1500 °C, the corresponding diffusion coefficients were in the range 3.14 × 10⁻⁸–4.78 × 10⁻⁸ m²/s for Fe²⁺ diffusion in the spinel and in the range 1.70 × 10⁻⁸–2.03 × 10⁻⁸ m²/s for the respective diffusion of Cr³⁺. Finally using Arrhenius plots activation energies were derived.     

Electrocoagulation as a remediation tool for wastewaters containing arsenic

This work shows results of electrocoagulation of solutions containing arsenic. The continuous flow treatment consisted of an electrocoagulation reactor with two parallel iron plates and a sedimentation basin.The results showed that the electrocoagulation process of a 100 mg/L As(V) solution could decrease the arsenic concentration to less than 2 mg/L in the effluent with a current density of 1.2 A/dm² and a residence time of around 9 min. Liquid flow was 3 L/h, and the DC current was reversed each 2 min.Increasing the current density from 0.8 to 1.2 A/dm², the Fe³⁺ and OH⁻ dosages increase too, and thereby favouring the As removal. On the other hand, it seems that increasing the current density beyond a maximum value, the electrocoagulation process would not improve further. This could probably be explained by passivation of the anode.     

Dissolution and passivation mechanisms of chalcopyrite during bioleaching: DFT calculation,XPS and electrochemistry analysis

In this work, density functional theory (DFT) calculation, X-ray photoelectron spectroscopy (XPS) and electrochemistry analysis were carried out to investigate the dissolution process and passivation mechanisms of chalcopyrite in the presence of sulfur and iron oxidizing microorganisms. Both DFT calculation and XPS analysis indicated that the formula of chalcopyrite should be Cu + Fe³ + (S²⁻)₂. Disulfide (S₂²⁻) and polysulfide (S_n²⁻) can be easily formed on the surface of chalcopyrite due to the surface reconstruction. The dissolution process of chalcopyrite in bioleaching was mainly dependent on redox potential. Chalcopyrite was predominantly directly oxidized to polysulfide when redox potential was lower than about 350 mV vs. Ag/AgCl and resulted in low dissolution rate. When redox potential was in the range of about 350–480 mV vs. Ag/AgCl, chalcopyrite was mainly transformed to intermediate species of Cu₂S rather than polysulfide, thus resulting in high dissolution rate. When redox potential was higher than about 480 mV vs. Ag/AgCl, chalcopyrite was principally directly oxidized to polysulfide which caused the passivation of chalcopyrite. Finally, a model of dissolution and passivation mechanisms of chalcopyrite in the presence of sulfur and iron oxidizing microorganisms was provided.     

Simultaneous determination of iron and copper in pregnant liquid solutions

A new method for the determination of Fe_Total and Cu is proposed. The method is based on the formation of the iron and copper complexes with 5-sulfosalicylic acid (SSA), the optimal conditions were found, using SSA 5.1 g L⁻¹ in the presence of ammonia 7.5 g L⁻¹ (pH = 10). Under these conditions the selected analytical wavelengths were 488.5 and 423.5 nm for the determination of iron and copper, respectively, by using the zero crossing approach. The detection and quantification limits were 0.02 mg L⁻¹ and 0.07 mg L⁻¹ for iron and 1.14 mg L⁻¹ and 3.80 mg L⁻¹ for copper. The proposed method was applied to the determination of both analytes in pregnant liquid solutions and the recovery was between 98% and 100% and in all cases the relative standard deviation was minor to 2%.     

Extraction of titanium (IV) from acidic media by tri-n-butyl phosphate in kerosene

The extraction of titanium (IV) from sulfate, and nitrate solutions has been studied using tri-n-butyl phosphate (TBP) in kerosene. Extraction of titanium was affected by acid concentration over the range of 0.5–4 mol L^?1. The titanium distribution coefficient reached a minimum between 1 and 2 mol L^?1 acid for both sulfate and nitrate solutions. Third phase formation was observed in the extraction of titanium from acidic media at all condition tested. At the next stage, the stripping of titanium was studied using H₂SO₄, H₂SO₄ + H₂O₂ and Na₂CO₃. The kinetics of the stripping were very slow for H₂SO₄. The use of complex forming stripping agents (H₂SO₄ + H₂O₂) and Na₂CO₃ significantly improved the kinetics of stripping. About 98% recovery was achieved by extracting titanium from an aqueous nitrate solution using TBP and stripping with sodium carbonate.