Oxidation Of Chalcopyrite Research Articles

CRISPR/dCas12a knock-down of Acidithiobacillus ferrooxidans electron transport chain bc1 complexes enables enhanced metal sulfide bioleaching

Acidithiobacillus ferrooxidans is an acidophilic chemolithoautotroph that plays an important role in biogeochemical iron and sulfur cycling and is a member of the consortia used in industrial hydrometallurgical processing of copper. Metal sulfide bioleaching is catalyzed by the regeneration of ferric iron, however, bioleaching of chalcopyrite, the dominant unmined form of copper on Earth, is inhibited by surface passivation. Here, we report the implementation of CRISPR interference (CRISPRi) using the catalytically inactive Cas12a (dCas12a) in A. ferrooxidans to knockdown the expression of genes in the petI and petII operons. These operons encode bc1 complex proteins and knockdown of these genes enabled the manipulation (enhancement or repression) of iron oxidation. The petB2 gene knockdown strain enhanced iron oxidation, leading to enhanced pyrite and chalcopyrite oxidation, which correlated with reduced biofilm formation and decreased surface passivation of the minerals. These findings highlight the utility of CRISPRi/dCas12a technology for engineering A. ferrooxidans while unveiling a new strategy to manipulate and improve bioleaching efficiency.

Sulfuric Acid Baking and Fe(III)-Cl--H2SO4 Leaching Behavior of Ni- and Cu-Containing Sulfide and Silicate Rich Suhanko Concentrate.

Ni- and Cu-rich concentrate from a new site in Suhanko, Finland, was investigated. Mineral phases identified included talc, chalcopyrite, kaolinite, and pyrrhotite with 3.2% Cu and 1.5% Ni, and the latter is associated with pyrrhotite. In addition, the concentrate contained the precious elements Pd (14.9 g/t), Ag (17.1 g/t), Pt (2.1 g/t), and Au (1.1 g/t). This concentrate was baked and leached using a Fe(III)-Cl--H2SO4 system. The results showed that the leaching efficiencies of Ni, Cu, and Si from raw concentrate were 60%, 40%, and 5%; however, those from baked concentrate were 96%, 60%, and below 0.1%, indicating that the baking process enhanced Ni and Cu extraction while simultaneously inhibiting the dissolution of Si, which was due to the baking process liberating the associated Ni and Cu by the oxidation of chalcopyrite and pyrrhotite and converting the acid-soluble silicate into an insoluble form. Sulfuric acid leaching solution with Fe(III) as oxidant and Cl- as lixiviant was shown to be effective at leaching Ni (97%), Cu (62%), and Ag (89%), while simultaneously enriching the PMs Pd, Pt, and Au in the residue.

Reactive transport modelling of tailings hydrogeochemistry under a composite cover

Quantitative forecasts of acid mine drainage (AMD) production are important for remediation planning. Reactive transport simulations corresponding to a detailed sampling location at a covered legacy tailings impoundment in northern Ontario, Canada, were conducted to quantitatively assess the predominant hydrogeochemical reactions. The simulations span the period from the end of tailings deposition (circa 1970) to early 2020, 12 years after remediation by a five-layer composite cover. The conceptual model of uncovered tailings weathering and subsequent geochemistry of the covered tailings system was implemented in 1D using the multi-component reactive transport code MIN3P. Transient monthly infiltration, post-cover boundary condition changes, and a dynamic temperature regime were incorporated. The shrinking core model, including parallel O2(aq) and Fe3+ oxidation reactions for the waste rock in the cover and the underlying tailings, was implemented to simulate the oxidation of As-bearing pyrite, chalcopyrite, and sphalerite. Primary carbonate and aluminosilicate host minerals promoted acid-neutralization reactions. Precipitation of secondary phases and sorption/desorption of Cu, Zn, and arsenite were incorporated into the model. The overall agreement between key simulated and field-measured post-cover aqueous geochemical parameters suggests that the conceptual model captured the primary hydrogeochemical processes in the covered tailings. A lack of reliable data on initial tailings mineralogy and pre-cover hydrogeochemistry increased simulation uncertainty. Simulated reaction rates indicate that where intact, the cover decreased sulfide oxidation rates by both O2(aq) and Fe3+ and improved pore-water quality over time. Simulation results indicate that elevated concentrations of Zn and As are likely to persist in the tailings regardless of cover performance, whereas concentrations of Cu and Al are the parameters most sensitive to cover effectiveness.

Evaluate the Depression of High-Concentration Pyrite in Copper Flotation by High-Chromium Grinding Media

ABSTRACT The copper (Cu) concentrators have to process high-pyrite-content ores due to rapid depletion of high-grade ores and a high demand for Cu by clean energy technologies. However, depressing high-concentration pyrite in copper flotation is challenging presently. For the first time, this study evaluated 30 wt% Cr steel, a type of high-chromium (HiCr) steel grinding media, which can effectively produce a high Cu concentrate grade in processing low-concentration pyrite ores, in treating 25% pyrite in a Cu feed at 1.7% Cu in comparison with treating 5% pyrite in a Cu feed at the same Cu grade. Flotation tests showed decreased Cu grade and Cu recovery as pyrite feed grade increased from 5% to 25%, which was attributed to the changed galvanic interaction between grinding media and sulfide minerals, supported by ethylene diamine-tetra acetic acid disodium extraction, pulp chemistry measurements, and electrochemical studies. As pyrite feed grade increased from 5% to 25%, the anodic role of 30 wt% Cr steel did not change, but the anodic role of chalcopyrite and the cathodic role of pyrite were enhanced, promoting chalcopyrite oxidation while retarding pyrite oxidation, both of which facilitated copper activation on pyrite and subsequent pyrite flotation. This study also compared 30 wt% Cr steel and traditional forged steel in depressing 25% pyrite in the feed, and forged steel poorly depressed pyrite due to a strong anodic role of forged steel and a strong cathodic role of pyrite during the galvanic interaction leading to strong copper activation on pyrite. This study points to a direction how to depress high-concentration pyrite in copper flotation.

The Effects of Chloride on the High Temperature Pressure Oxidation of Chalcopyrite: Some Insights from Batch Tests—Part 2: Leach Residue Mineralogy

The complete reaction of chalcopyrite at ≥220 °C under pressure oxidation conditions (10 or 20% w/w pulp density, PO2 700 kPa) is a clean process producing a residue consisting of hematite and un-reacted gangue minerals. However, when the process water contains chloride ions, covellite intermediate formation is significant and subsequently generates elemental sulphur that can persist for up to 60 min. Increasing the temperature to 230 °C reduces this time, although the dissolution of copper and the oxidation of sulphur still follows non-parallel reaction pathways. At 245 °C, the production of elemental sulphur in the presence of moderate chloride levels, 15 g/L, is no longer significant. The effects of other chemical additions (including enhancement of aluminium content) are also examined. Particular emphasis is given to the mineralogy of the leach residues and the deportment of iron in these residues to various phases that include hematite, basic ferric sulphate and natrojarosite. The residues are found to also contain a number of other intermediate phases in addition to covellite and sulphur, such as antlerite and clinoatacamite, depending upon the leach conditions employed.

The Effects of Chloride on the High-Temperature Pressure Oxidation of Chalcopyrite: Some Insights from Batch Tests—Part 1: Leach Chemistry

The complete reaction of chalcopyrite at ≥220 °C under pressure oxidation conditions (10 or 20% w/w pulp density, PO2 700 kPa) is a clean, near complete process, yielding high copper extractions (~99%) in an acidic leach liquor composed of dissolved metal sulphates, when high-quality process water is employed. However, when the process water contains chloride ions, here 3–100 g/L, although the copper extraction rate is enhanced, complete oxidation of sulphur under batch processing conditions is delayed. Chloride addition, therefore, appears to favour an oxidation mechanism that liberates cupric ions and preferentially forms elemental sulphur over sulphate. This provides evidence for the decoupling of the copper extraction and sulphate formation reactions. Increasing the reaction temperature, here to 245 °C, increases the rate of sulphuric acid formation and decreases the iron concentration in the leach liquor. The study also examines the effects of various upfront acid and other salt additions upon copper extraction. Added sulphuric acid was shown to slow the reaction, whereas salts such a cupric chloride and sodium sulphate had small effects on the rate and extent of copper extraction.

Effect of sodium hypochlorite as a depressant for copper species in Cu-Mo flotation separation

One alternative to replace conventional depressants in Cu-Mo separation is using oxidizing agents to promote the formation of products on chalcopyrite that render its surface hydrophilic and thus favor its depression. This work provides a study to understand how sodium hypochlorite can act as a depressor for chalcopyrite in Cu-Mo flotation separation. The effect of NaClO in flotation tests was evaluated by means of electrochemical techniques, scanning electron microscopy (SEM), Fourier transform infrared analysis and contact angle measurements. The flotation results showed a selective depressant effect at a dosage of 1,020 g/t NaClO, conditioning time of 5 min, and pH 7. The mixed potential showed that the oxidation of chalcopyrite and molybdenite is possible through the addition of NaClO. The SEM observations showed changes in oxidized chalcopyrite morphology, which is supported by the decreasing contact angle change; no morphological changes were observed on molybdenite. FTIR analyses showed the characteristic peaks of the OH group after chalcopyrite was treated with NaClO; when molybdenite was treated with NaClO, the FTIR spectrum did not show changes. A scheme is proposed for the formation of oxidation species.

Electrochemical Kinetics Study of Ultrasound-Assisted Chalcopyrite Oxidation

Ultrasound-assisted chalcopyrite leaching has been reported previously, showing a noticeable improvement in leaching kinetics. However, the effect of ultrasound on the chalcopyrite oxidation kinetics from an electrochemical perspective has not been addressed. This study examines the ultrasonic enhancement of chalcopyrite oxidation kinetics in sulfuric acid solution from both conventional leaching and electrochemistry aspects. Electrochemical techniques, including linear sweep voltammetry (LSV) and chronoamperometry (CA), were used to illustrate the kinetics of chalcopyrite ultrasound-assisted leaching. Tafel analysis by LSV showed that 20% amplitude ultrasound power had increased the chalcopyrite electrochemical dissolution rate by about 20% in both Fe3+-free and 10 mM Fe3+-containing 0.5 M sulfuric acid solution. The CA tests indicated a drastic increase in the Fe3+ reduction reaction when ultrasound was applied (20% amplitude). At 0.5 V, the Fe3+ to Fe2+ reduction current density at 30 min drastically increased from − 65.54 without ultrasound to − 1165.84 µA cm−2 with ultrasound.Graphical

Chalcopyrite leaching by amino acid solutions in the presence of hydrogen peroxide

It is demonstrated that amino acids such as glycine, betaine, and lysine may be applied as selective copper leaching agents in the process of hydrochemical oxidation of chalcopyrite at atmospheric pressure and in the temperature range 25÷65°C. The advantage of the proposed method is its relative environmental friendliness. Solid samples of the initial mineral and leached chalcopyrite residues were analyzed by X-ray diffraction analysis, and Mössbauer and Raman spectroscopy. The results of the atomic absorption analysis showed that copper's extraction efficiency increased when the experiment's duration was raised and when the process temperature was higher. The leaching ability of amino acids was evaluated by the specific leaching rate of chalcopyrite in these reagents. Amino acid leaching was thought to be mainly due to the complexation of copper (II) glycinates, copper (II) betainates and copper (II) lysinates. This reaction can be enhanced by adding hydrogen peroxide to the system as an oxidant. It was determined that glycine was more effective as a leaching agent than betaine and lysine. Based on experimental data, it was assumed that the most possible mechanism is selective copper leaching due to the formation of chalcopyrite-based solid solution Cu<sub>1-x</sub>FeS<sub>2</sub>.

In-situ electrochemical study of chalcopyrite pressure oxidation leaching from 110 °C to 150 °C under saturated vapor pressure

Pressure oxidation leaching behavior of chalcopyrite in sulfuric acid solution from 110 °C to 150 °C were investigated by in-situ electrochemical methods. Leaching experiments under saturated vapor pressure conditions were used to simulate the anoxic environment that may be encountered in industrial applications. Scanning electron microscope and X-ray photoelectron spectroscopy were used to characterize the morphology and the chemical status of chalcopyrite surface. Results show that the copper extraction was increased with the increase of leaching temperature. Under the optimal leaching conditions under saturated vapor pressure, the copper and iron extraction are 8.3% and 29.8%, respectively. When the temperature increased from 110 °C to 150 °C, the self-corrosion potential and electrochemical reaction resistance firstly increased and then decreased. In contrast, the resistance of the passive film was always increased with the increase of temperature. The electrochemical study results indicated that the increase in temperature affected the oxidation of chalcopyrite by altering the kinetics of the cathodic reaction and the anodic passivation. Both the self-corrosion current density ( i corr ) and rate constant were affected by the reduction of Fe(III). The XPS results show that elemental sulfur and H 3 O(Fe 3 (SO 4 ) 2 (OH) 6 ) were the main leaching solid products. The formation of H 3 O(Fe 3 (SO 4 ) 2 (OH) 6 ) not only caused a decrease in cathodic reaction kinetics, but also increased the resistance of mass transfer process. Due to the faster release of iron, copper-rich sulphides were formed, which mixed with the elemental sulfur and/or H 3 O(Fe 3 (SO 4 ) 2 (OH) 6 ) led to coverage of the chalcopyrite surface.

Catalytic Activity of Carbon Materials in the Oxidation of Minerals

This study aims to advance the knowledge of using carbon materials as catalysts in the oxidation of chalcopyrite. For this, two different materials (a commercial activated carbon (CC) and commercial biochar (BC)) were added to chalcopyrite ore (CPY) at three weight ratios (1:1, 1:0.5, and 1:0.25). Mixtures were treated with sulfuric/ferric solution for 96 h at 90 °C. Experimental results showed that extraction of copper from CPY was around 36%, increasing to higher than 90% with the addition of CC or BC at the proper ratio. The best result (99.1% Cu extraction) was obtained using a 1:1 ratio of CPY:CC. Analysis of solid residues shows that CC, with a high surface area, adsorbs sulfur onto its surface, limiting elemental sulfur formation. Additionally, the treatment of CPY in the CC’s presence transforms the chalcopyrite into CuS. Sulfur adsorption or CuS formation was not observed after the leaching of chalcopyrite with BC. However, the addition of BC to CPY at a ratio of 1:0.25 also increased the extraction of copper to 91.1%. Two carbon materials were oxidized after treatment with a sulfuric/ferric solution, and BC probably displayed catalytic properties in the leaching medium.

A DFT study of the adsorption of O2 and [Fe(H2O)2(OH)3] on the (001) and (112) surfaces of chalcopyrite.

The oxidation of chalcopyrite, CuFeS2, is still not well understood and relevant in the context of the hydrometallurgical extraction of copper. Herein, we used DFT calculations within the periodic boundary conditions formalism to study the adsorption of O2 and [Fe(H2O)2(OH)3] molecules on the (001) and (112) surfaces of CuFeS2. The O2 molecule adsorbs strongly by a dissociative pathway at sulfur atoms on the (001) surface with an adsorption energy of - 76.5kcalmol-1. The surface is chemically modified forming SO2 groups, in which the S-O bond length is calculated to be 1.47 and 1.54Å. PDOS and Löwdin charges analyses indicate the oxidation of the sulfur atoms on the surface. We tested different adsorption modes of [Fe(H2O)2(OH)3], and a bidantade coordination with the Oads-Fesur and Feads-Ssur bond lengths of 2.02 and 2.47Å is the most favorable with an adsorption energy of - 18.8kcalmol-1 on the (001) surface. Adsorptions of each species are also observed on the (112) surface, but they are weaker than those observed on the (001) surface.

A Quantitative Relationship between Oxidation Index and Chalcopyrite Flotation Recovery

The surface oxidation of chalcopyrite is one of the most important factors affecting its flotation performance. In this study, a critical oxidation degree is proposed to define “slight” and “significant” oxidation in terms of surface species and chalcopyrite flotation recovery. Slight oxidation enhanced chalcopyrite hydrophobicity, but significant oxidation reduced its recovery apparently. Microthermokinetic measurements indicated that the apparent activation energy (Ea) of chalcopyrite oxidation was reduced from around 173 kJ·mol−1 to 163 kJ·mol−1 when the reaction changed from slight oxidation to significant oxidation when applying H2O2. The surface oxidation degree was defined as the ratio of hydrophilic species to hydrophobic species. The highest recovery (94.8%) and contact angle (93°) were achieved at a concentration of 0.1 vol.% H2O2, with the lowest oxidation degree of 0.388 being observed. The oxidation degree was correlated to the flotation recovery, with a quantitative relationship (y = −298.81x + 213.05, y and x represent flotation recovery and oxidation degree, respectively, 0.388 ≤ x ≤ 0.618) being established, thereby giving a guideline to better manage chalcopyrite flotation by controlling its surface oxidation and SBX adsorption on chalcopyrite surfaces.

Effect of deep oxidation of chalcopyrite on surface properties and flotation performance

In this study, chalcopyrite was oxidized in hydrogen peroxide (H 2 O 2 ) solutions of different concentrations to simulate different degrees of oxidation in real ores, and the effects of H 2 O 2 treatment on chalcopyrite surface properties and flotation performance were investigated by surface analysis techniques and floatation experiments, which implied the reason for the poor grade and recovery of oxidized chalcopyrite concentrate in the production process of the ore. Flotation results showed that when the concentration of H 2 O 2 increased from 0% (by weight) to 5%, the flotation recovery of chalcopyrite decreased sharply. However, with increasing H 2 O 2 concentration from 5% to 30%, chalcopyrite recovery improved relatively to different degrees with different collector concentrations. Analyses of X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma-atomic optical emission spectrophotometry (ICP-OES) results indicated that the pretreatment with H 2 O 2 caused that hydrophilic substance formed on chalcopyrite surface with the dissolution of copper ions, and the dissolution amount of copper increased with the increase of H 2 O 2 concentration. UV–visible spectrophotometer and Fourier Transform Infrared spectrum (FTIR) studies indicated that the pretreatment of chalcopyrite with H 2 O 2 had little effect on the adsorption amount of potassium butyl xanthate (PBX) on chalcopyrite surface. However, due to the dissolution of copper ions, PBX interacted with chalcopyrite mainly as buthyl dixanthogen (BX) 2 .

Electrochemical and leaching studies to better understand the role of ethylene glycol in the oxidative acid dissolution of chalcopyrite

It has been demonstrated that the combined use of organic compounds and acidic peroxide solutions greatly improves the dissolution kinetics of chalcopyrite. Among the additives employed, ethylene glycol (EG) is one of the most attractive for operating at moderate temperatures (20–50 °C). However, the role of EG in the leaching process is still not clearly understood, which limits optimization and industrial scale-up. For this reason, in this investigation, an electrochemical study was undertaken, using both a solid chalcopyrite (SE-Cp) electrode coupled to a rotating disk, as well as a chalcopyrite concentrate carbon paste electrode (CPE-CCp). Leaching experiments were also performed with EG and several other organic compounds, comparing the copper dissolved in each case. The results, in the mixed potential range of 0.55–0.75 V, showed that the presence of EG did not increase chalcopyrite oxidation. However, EG adsorption on the surface of the sulfide is sufficient to hinder hydrogen peroxide dismutation, the main cause of H2O2 decomposition in EG-free acidic solutions; at the same time, decreasing the interfacial tension favors chalcopyrite contact with the solution. Finally, the formation of similar products on the chalcopyrite surface, suggest that the organics additives do not alter the dissolution mechanism.

Flotation performance of chalcopyrite in the presence of an elevated pyrite proportion

• Chalcopyrite became more anodic after being contacted with pyrite. • A larger surface pyrite/chalcopyrite ratio led to a stronger galvanic interaction. • Chalcopyrite flotation was compromised by 5% pyrite but restored by 25% pyrite. • Pyrite flotation was enhanced with an increase in pyrite proportion. • Chalcopyrite or pyrite flotation was controlled by the galvanic interaction. Recently, the copper industry is facing a challenge in dealing with low-grade copper ores and the flotation performance deteriorates when a copper ore with an elevated pyrite proportion is processed. This study investigated the effect of pyrite proportion on chalcopyrite and pyrite flotation via a tri-mineral system (chalcopyrite-pyrite-quartz) with a fixed Cu head grade while varying the pyrite proportion. Electrochemical studies revealed that the overall corrosion current of chalcopyrite-pyrite galvanic interaction increased with the increase of pyrite surface area, boosting the anodic role of chalcopyrite. Flotation results showed that both Cu grade and Cu recovery decreased by the introduction of 5% pyrite, but Cu recovery was restored by the introduction of 25% pyrite. Collectorless flotation, EDTA extraction and pulp chemistry measurement indicated that chalcopyrite and pyrite flotation behaviours at different pyrite proportions were governed by the galvanic interaction between chalcopyrite and pyrite which controlled chalcopyrite oxidation and copper activation on pyrite.

Does galvanic coupling with pyrite increase the rate of dissolution of chalcopyrite under ambient conditions? An electrochemical study

The role of galvanic coupling of chalcopyrite and pyrite in the enhanced rate of dissolution of chalcopyrite in acidic sulfate and chloride solutions at 30 °C has been defined in a detailed electrochemical study. The results indicate that, under ambient conditions, the effect of galvanic contact with pyrite only marginally increases the rate of dissolution of chalcopyrite in both sulfate and chloride solutions containing iron(III) despite significant increases in the mixed potential of chalcopyrite. This has been shown to be due to the fact that the effect of potential on the rate of anodic oxidation of chalcopyrite is small in the relevant potential under these conditions. This is confirmed by the observation that the mixed potential and, therefore, the galvanic current is largely unaffected by a 4-fold decrease in pyrite surface area. The galvanic current transients compared well with potentiostatic current/time transients for chalcopyrite at the mixed potential observed during coupling. In the case of copper(II) as the oxidant in chloride solutions, the galvanic currents are small due largely to the fact that the increase in chalcopyrite potential and decrease in pyrite potential are small as a result of the lower reduction potential of the copper(II)/copper(I) couple than the iron(III)/iron(II) couple. The galvanic currents with dissolved oxygen as the oxidant are significantly lower than with iron(III) as the oxidant and confirm the well-known fact that oxygen is less effective than iron(III) as an oxidant for chalcopyrite even when galvanic coupled to pyrite. The electrochemical data obtained in this study indicate that the small galvanic currents observed do likely not account for the relatively large increases in rate previously observed in agitated leaching of chalcopyrite/pyrite slurries at elevated temperatures. • The effect of galvanic contact with pyrite on the rate of dissolution of chalcopyrite was studied. • The mixed potential of chalcopyrite increased significantly on contact with pyrite. • Small galvanic currents due to the small effect of potential on the rate of anodic oxidation of chalcopyrite. • The mixed potential and the galvanic current is largely unaffected by a 4-fold decrease in pyrite surface area. • The galvanic current transients compared well with potentiostatic current/time transients.

Effect of microwave pretreatment on chalcopyrite dissolution in acid solution

Microwave-roasting as an efficient method for extracting copper form chalcopyrite has attracted increasing attention. In this work, the microwave roasted chalcopyrite was pressure leached in 1.0 mol/L sulfuric acid solution at the temperature range of 110–150 °C, and the reasons why microwave-roasting improved the leaching kinetics were further studied by the electrochemical characterizations. Results show that microwave-roasting had a positive effect on better mineral leachability. Under the optimal conditions, the final copper extraction was 90.1% and the iron extraction was 87.5%. The leaching process of the microwave roasted chalcopyrite was controlled by chemical reaction, and the calculated activation energy was 41.7 kJ/mol. The electrochemical study results indicated that microwave-roasting had a significant effect on both the anodic dissolution kinetics and the cathodic reactions kinetics, and the charge transfer resistance of chalcopyrite oxidation and the resistance of the passive film were both lower than that of the un-roasted sample. X-ray diffraction (XRD), and scanning electron microscope (SEM) results suggested that microwave-roasting effectively activate chalcopyrite through modifying the surface structure. Besides the enlargement of the effective reaction surface, the differential scanning calorimetry-thermogravimetric analysis (DSC-TGA) results revealed that the increasing of active sites and/or the internal stress can increase the strain energy and instability of chalcopyrite, which plays an important role in improving chalcopyrite leaching kinetics. The main product of pressure leaching was elemental sulfur that mixed with the copper-rich sulfide, causing the passivation of chalcopyrite.

Influence of galvanic interaction between chalcopyrite and galena on electrochemical and flotation behaviour of chalcopyrite

Chalcopyrite is often associated with galena in nature, which brings great difficulties to the flotation recovery of chalcopyrite. One of the main reasons for these difficulties is that galvanic interaction between chalcopyrite and galena has a significant effect on the oxidation and flotation behavior of chalcopyrite. In this paper, density functional theory and cyclic voltammetry measurement were used to study galvanic interaction between chalcopyrite and galena and its effect on the adsorption of oxygen and xanthate molecules on chalcopyrite (001) surface. The results show that the galvanic interaction inhibits the dissociation of oxygen molecules on the surface of chalcopyrite (001), and it also weakens the bonding DOS of O-Fe bonds, S-Cu bonds and S-Fe bonds, which may be detrimental to the adsorption of xanthate and oxygen molecules on the surface of chalcopyrite (001). The cyclic voltammetry measurements results show that compared with pure chalcopyrite and pure galena electrode, the oxidation peak intensity of the electrode with a mass ratio of chalcopyrite and galena of 1:1 near 0.4 V is weaker at pH 9.18 and a butyl xanthate concentration of 0.001 mol/L, which is consistent with the results of DFT studies.

Chalcopyrite leaching in ammonium chloride solutions under ambient conditions: Insight into the dissolution mechanism by XANES, Raman spectroscopy and electrochemical studies

Ammoniacal leaching solutions have been considered as an effective lixiviant for the oxidative dissolution of chalcopyrite. However, compared with the extensive studies of acidic chalcopyrite dissolution, the dissolution mechanism of chalcopyrite in ammoniacal solutions needs further understanding. In this study, the oxidative dissolution of chalcopyrite in ammonium chloride solutions under room temperature and pH 8.5 was studied by X-ray absorption near-edge spectroscopy (XANES), Raman spectroscopy and electrochemical impedance spectroscopy (EIS). Both batch leaching experiments and electrochemical studies showed that Cu(II) ions were more efficient than dissolved oxygen for chalcopyrite oxidation in ammonium chloride solutions. Leaching kinetics analysis showed that without the initial addition of Cu(II), chalcopyrite dissolution rate was controlled by two different stoichiometric chemical reactions: the initial and slow leaching stage controlled by dissolved oxygen; then predominated by Cu(II) rather than dissolved oxygen with a fast leaching rate when copper concentration exceeded a certain level (>0.12 g/L). Thiosulfate (S2O32−) rather than sulfate (SO42−) was confirmed as the primary soluble sulfur species produced during chalcopyrite dissolution. Decomposition of S2O32− in the presence of both O2 and Cu(II) resulted in the final stable product SO42− accompanied by the formation of other sulfur intermediate species, including S4O62− and SO32−. No evidence was found for the formation of elemental sulfur. Amorphous hematite (Fe2O3) and six-line ferrihydrite (5Fe2O3·9H2O) were the major components residing on the chalcopyrite surface, which were responsible for the slow dissolution rate at late stage. According to the present work, a model for the chalcopyrite dissolution mechanism in alkaline ammonium chloride solutions under ambient conditions is provided.