The leaching of chalcopyrite with ferric chloride

A comparative study of electrochemical leaching and chemical leaching of chalcopyrite was done to elucidate the leaching mechanism of chalcopyrite with FeCl₃. The leaching rate of chalcopyrite exhibits a half order dependency on the FeCl₃ concentration, whereas it is independent of the FeCl₂ concentration. The mixed potential of chalcopyrite exhibits a 72 mV · decade⁻¹ dependency upon FeCl₃ concentration; no influence on the mixed potential was observed by the addition of FeCl₂. In FeCl₃ solutions acidified with HC1, the predominant chemical species of Fe(III) was found to be FeCl ₂ ^u+ from equilibrium calculations. The concentration of this species is approximately proportional to the amount of FeCl₃ added to the solutions. Based on these observations, an electrochemical mechanism is proposed which involves the oxidation of chalcopyrite and the reduction of FeCl ₂ ⁺ , the predominant species of Fe(III). By converting the leaching rate to electric current density,i, 140 mV · decade⁻¹ dependency of mixed potential,E, against logi is obtained. This dependency of the chemical leaching of chalcopyrite with FeCl₃ as well as its activation energy agree with those for electrochemical leaching. These findings strongly support the electrochemical mechanism of FeCl₃ leaching of chalcopyrite. Formerly Graduate Student, Kyoto University     

The leaching of galena in ferric sulfate media

The leaching of galena (PbS) in ferric sulfate media was investigated over the temperature range 55 °C to 95 °C and for various Fe(SO₄)_1.5, H₂SO₄, FeSO₄, and MgSO₄ concentrations. Relatively slow kinetics were consistently observed; in most instances, the 1-2/3α-(1−α)^2/3 vs time relationship, indicative of a diffusion-controlled reaction, was closely obeyed. The diffusion-controlled kinetics were attributed to the formation of a tenacious layer of PbSO₄ and S⁰ on the surface of the galena. The generation and morphology of the reaction products were systematically determined by scanning electron microscopy, and complex growth mechanisms were illustrated. The leaching rate increased rapidly with increasing temperature, and the apparent activation energy is 61.2 kJ/mol. The rate increases as the 0.5 power of the ferric ion concentration but is nearly independent of the concentration of the FeSO₄ reaction product. The rate is insensitive to H₂SO₄ concentrations <0.1 M but increases at higher acid levels. The presence of neutral sulfates, such as MgSO₄, decreases the leaching rate to a modest extent.     

The leaching of nickeliferous laterite with ferric chloride

Several experiments were conducted to investigate the extraction of nickel from nickeliferous laterite by ferric chloride solutions as a function of pulp density, solution composition, and temperature. Solubility relationships for goethite and nickel laterite in aqueous solution were reviewed in terms of leaching rates and reaction mechanisms. Generally, the amount of nickel extracted increased with temperature, the amount of “free acid,” and ferric chloride concentration; however, the amount was inhibited by ferrous chloride. In this investigation, as much as 96 pct of the available nickel was extracted by ferric chloride solution. Nickel extraction was found to be more dependent on ferric chloride concentration than on the concentration of hydrochloric acid. Mechanistically, nickel extraction occurred by the formation of an intermediate ferric chloride complex, which was then hydrolyzed to hematite.     

The dissolution of chalcopyrite in ferric sulfate and ferric chloride media

The literature on the ferric ion leaching of chalcopyrite has been surveyed to identify those leaching parameters which are well established and to outline areas requiring additional study. New experimental work was undertaken to resolve points still in dispute. It seems well established that chalcopyrite dissolution in either ferric chloride or ferric sulfate media is independent of stirring speeds above those necessary to suspend the particles and of acid concentrations above those required to keep iron in solution. The rates are faster in the chloride system and the activation energy in that medium is about 42 kJ/mol; the activation energy is about 75 kJ/mol in ferric sulfate solutions. It has been confirmed that the rate is directly proportional to the surface area of the chalcopyrite in both chloride and sulfate media. Sulfate concentrations, especially FeSO₄ concentrations, decrease the leaching rate substantially; furthermore, CuSO₄ does not promote leaching in the sulfate system. Chloride additions to sulfate solutions accelerate slightly the dissolution rates at elevated temperatures. It has been confirmed that leaching in the ferric sulfate system is nearly independent of the concentration of Fe³⁺, ka[Fe³⁺]^0.12. In ferric chloride solutions, the ferric concentration dependence is greater and appears to be independent of temperature over the interval 45 to 100 °C.     

The dissolution of galena in ferric chloride media

The dissolution of galena (PbS) in ferric chloride-hydrochloric acid media has been investigated over the temperature range 28 to 95 °C and for alkali chloride concentrations from 0 to 4.0 M. Rapid parabolic kinetics were observed under all conditions, together with predominantly (>95 pet) elemental sulfur formation. The leaching rate decreased slightly with increasing FeCl₃ concentrations in the range 0.1 to 2.0 M, and was essentially independent of the concentration of the FeCl₂ reaction product. The rate was relatively insensitive to HCl concentrations <3.0 M, but increased systematically with increasing concentrations of alkali or alkaline earth chlorides. Most significantly, the leaching rate decreased sharply and linearly with increasing initial concentrations of PbCl₂ in the ferric chloride leaching media containing either 0.0 or 3.0 M NaCl. Although the apparent activation energy was in the range 40 to 45 kJ/mol (∼10 kcal/mol), this value was reduced to 16 kJ/mol (3.5 kcal/mol) when the influence of the solubility of lead chloride on the reaction rate was taken into consideration. The experimental results are consistent with rate control by the outward diffusion of the PbCl₂ reaction product through the solution trapped in pores in the constantly thickening elemental sulfur layer formed on the surface of the galena.     

The effect of the elemental sulfur reaction product on the leaching of galena in ferric chloride media

The dissolution of galena in 0.3 M FeCl₃-0.3 M HC1 solutions containing 0 to 6 M LiCl was studied at 80 °C, and parabolic kinetics were observed at all LiCl concentrations. The leaching rate increases gradually with increasing LiCl concentrations to ≈4 M LiCl; the presence of >4 M LiCl results in a rapid increase in the leaching rate. The solubility of PbCl₂ in 0.3 M FeCl₃-0.3 M HC1 solutions containing 0 to 6.5 M LiCl was measured over the temperature range of 50 °C to 90 °C. The solubility increases systematically with increasing temperature and LiCl concentration. The parabolic kinetics, coupled with the correlation between the leaching rate and the solubility of PbCl₂, suggest that the dissolution of galena is controlled by the outward diffusion of the PbCl₂ reaction product through the constantly thickening layer of elemental sulfur formed during leaching. This conclusion is also supported by various morphological studies which consistently indicated a thin layer of PbCl₂ between the corroding galena and the porous elemental sulfur reaction product.     

The leaching of galena in cupric chloride media

The kinetics of dissolution of galena (PbS) in CuCl₂-HCl-NaCl media have been investigated using the rotating disk technique. Rapid nonlinear kinetics are observed over the temperature range 45 °C to 90 °C and for NaCl concentrations from 0 to 4.0 M. The leaching rate is in-dependent of CuCl₂ concentrations >0.1 M but increases with increasing concentrations of either HC1 or NaCl. The leaching rate decreases with the accumulation of either the PbCl₂ or CuCl reaction product in the leaching medium but is insensitive to the disk rotation speed. The apparent activation energy for the rate controlling process is 33 kJ/mol, and this value falls to about 15 kJ/mol when interpreted as a dissolution rate for PbCl₂, whose solubility increases with temperature. The above observations are shown to be consistent with rate control by the outward diffusion of the PbCl₂ and CuCl reaction products through the solution trapped in the pores of the constantly thickening elemental sulfur layer which forms on the surface of the galena. CANMET, Energy, Mines, and Resources Canada, 555 Booth Street, Ottawa, ON, K1A 0G1, Canada.     

The effect of chloride ion on the ferric chloride leaching of galena concentrate

Previous investigations of the ferric chloride brine leaching of galena concentrate have shown that additions of chloride ion result in accelerated dissolution rates. The current study has provided the necessary information to extend and modify these previous results by incorporating the important effect of chloride ion on the dissolution kinetics. As part of this study the solubility of lead chloride in ferric chloride-brine solutions has been determined and results indicate that additions of either FeCl₃ or NaCl increase the PbCl₂ solubility. This is attributed to the effect of complexing on the level of free chloride ion. In addition, the dissolution kinetics of elemental lead and lead chloride were also determined and compared with the kinetics of PbS dissolution. It is significant that the rate of dissolution of PbCl₂ decreases as the concentration of Cl⁻ is decreased and as the concentration of dissolved lead increases. These results along with SEM examination of partially reacted Pb shot show that solid PbCl₂ forms on the surface long before the bulk solution is saturated with lead. The PbCl₂ is proposed to form by a direct electrochemical reaction between Cl⁻ and PbS prior to the formation of dissolved lead. The reaction was determined to be first order with respect to Cl⁻ and closely obeys the following kinetic model based on a rate limiting charge transfer reaction at the surface: The model is in excellent agreement with experimental results up to about 95 pct reaction as long as the solubility of PbCl₂ is greater than about 0.051 M. Where these conditions are not met, deviation from the surface reaction model occurs due to the extremely slow dissolution rate of PbCl₂. Therefore the effect of Cl⁻ on the brine leaching of PbS is attributed to two factors, the direct reaction of Cl⁻ with the pbS surface and the effect of Cl⁻ on the dissolution rate of PbCl₂. The overall dissolution process is viewed as occurring in three stages; in the first stage the reaction is controlled by the surface reaction and described by the model above, then as solid PbCl₂ is produced the diffusion of Cl⁻ would be equal in importance with the surface reaction,i.e, the second stage. As the reaction proceeds further, a shift in the rate-limiting step from surface reaction to product layer or pore diffusion occurs, the third stage. Thus the rate-determining step would no longer be just the surface reaction as observed experimentally at longer reaction times. The practical implications of these results for the processing of a complex sulfide concentrate using sequential, selective, or total leach approaches are also discussed.     

Model for the ferric chloride leaching of galena

A shrinking core model for the FeCl₃ leaching of galena (PbS), which accounts for the microstructure previously observed during this process, is presented. The microstructure is characterized by two distinct product layers—PbCl₂ in direct contact with the PbS core and S^o above the PbCl₂ layer. Rate equations for the evolution of the three solid phases and the PbS leaching conversion are derived for the case of flat plate geometry appropriate for the reaction of massive galena fragments. In the case of rate control by diffusion of the lead chloride reaction products through the S^o layer, the system is shown to exhibit parabolic behavior as long as the S^o layer is built up primarily at the PbCl₂-S^o interface. For the mechanism considered in this study, negative deviation from parabolic behavior is observed to increase as the amount of S^o forming at the external S^o-solution interface rises. When the system is controlled by surface reaction kinetics, the model predicts linear rates under all circumstances.     

Morphology of chalcopyrite leaching in acidic ferric sulfate media

Two-dimensional computer simulations based on percolation theory were used to explain the morphology associated with atmospheric chalcopyrite leaching in acidic ferric sulfate solution. The aim of this study was to understand the differences in observed morphology between chalcopyrite residues leached with and without pyrite in the leach environment. The study of chalcopyrite morphology is of interest because there are no records of similar investigations available. Simulations showed high copper extractions from chalcopyrite when surface atoms were mobile leading to agglomeration of like atoms and the formation of highly porous mineral structures. High degrees of surface mobility are associated with active anodic behavior. The simulated morphology was consistent with previously observed residue morphology from chalcopyrite leach experiments in the presence of pyrite. Thus it was found that the enhanced recoveries and peculiar morphology observed during pyrite catalyzed leaching are attributable to active anodic behavior. Conversely, the simulations also showed that the recovery of copper was low when surface atoms were effectively locked in place resulting in mineral passivation. The simulation morphology obtained in this case was also consistent with experimental results of chalcopyrite leached without the presence of pyrite which have shown non-porous film like product layers.     

Reaction mechanism for the ferric chloride leaching of sphalerite

Reaction mechanisms for the ferric chloride leaching of sphalerite are proposed based on data obtained in leaching and dual cell experiments presented in this work and in a previous study. The results from the leaching experiments show that at low concentrations the rate is proportional to [Fe³⁺]_T ^0.5 and [Cl^-]_T ^0.43 but at higher concentrations the reaction order with respect to both [Fe³⁺]_T and [Cl^-]_T decreases. Using dual cell experiments which allow the half cell reactions to be separated, increased rates are observed when NaCl is added to the anolyte and to the catholyte. The increase in rate is attributed to a direct, anodic electrochemical reaction of Cl^- with the mineral. When NaCl is added only to the catholyte, a decrease in the rate is observed due to a decrease in theE ⁰ of the cathode which is attributed to the formation of ferric-chloro complexes. Several possible electrochemical mechanisms and mathematical models based on the Butler-Volmer relation are delineated, and of these, one model is selected which accounts for the experimentally observed changes in reaction order for both Fe³⁺ and Cl^-. This analysis incorporates a charge transfer process for each ion and an adsorption step for ferric and chloride ions. The inhibiting effect of Fe²⁺ noted by previous investigators is also accounted for through a similar model which includes back reaction kinetics for Fe²⁺. The proposed models successfully provide a theoretical basis for describing the role of Cl^-, Fe³⁺, and Fe²⁺ as well as their interrelationship in zinc sulfide leaching reactions. Possible applications of these results to chloride leaching systems involving other sulfides or complex sulfides are considered.     

Lateritic saprolite leaching in concentrated magnesium chloride media

Magnesium chloride brines present a number of potential advantages for the processing of lateritic saprolite ores for nickel production. Concentrated MgCl₂ solutions enhance the activity of acid used, allow atmospheric leaching at elevated temperature, and inhibit magnesium dissolution, which reduces acid consumption and increases metal selectivity. However, with a chloride based leach it is economically requisite to recover hydrochloric acid, conventionally accomplished by pyrohydrolysis. This work was performed in conjunction with a novel flowsheet for the processing on saprolite ores, which recovers HCl by the precipitation and subsequent decomposition of magnesium hydroxychlorides, alleviating some of the issues with pyrohydrolysis. Leaching experiments have been conducted in concentrated MgCl₂ brines, up to 4·5 m, to determine the amenable process conditions and explore the kinetics of the process. It was determined that >95% extraction of metals was possible using both aqueous and gaseous HCl, while suppressing the dissolution of Mg from the ore.

Les saumures de chlorure de magnésium présentent un nombre d’avantages potentiels dans le traitement des minerais de saprolite latéritique pour la production du nickel. Les solutions concentrées de MgCl₂ augmentent l’activité de l’acide utilisé, permettent la lixiviation atmosphérique à haute température, et inhibent la dissolution du magnésium, ce qui réduit la consommation d’acide et augmente la sélectivité du métal. Cependant, avec une lixiviation à base de chlorure, on doit récupérer l’acide hydrochlorique pour raison économique, ce qui est accompli conventionnellement par pyrohydrolyse. On a effectué ce travail en conjonction avec un nouveau schéma de procédé pour le traitement des minerais de saprolite, lequel récupère le HCl par précipitation et par décomposition subséquente des hydroxychlorures de magnésium, ce qui atténue certains des problèmes reliés à la pyrohydrolyse. On a effectué des expériences de lixiviation dans des saumures concentrées de MgCl₂, jusqu’à 4·5 m, afin de déterminer les conditions favorables du procédé et d’explorer la cinétique du procédé. On a déterminé qu’il était possible d’extraire >95% des métaux en utilisant à la fois le HCl aqueux et gazeux, tout en supprimant la dissolution du Mg du minerai.     

The precipitation of hematite from ferric chloride media at atmospheric pressure

The precipitation of hematite from ferric chloride media at temperatures <100 °C and at ambient pressure was studied as part of a program to recover a marketable iron product from metallurgical processing streams or effluents. Hematite (Fe₂O₃) can be formed in preference to ferric oxyhydroxides (e.g., β-FeO·OH) at temperatures as low as 60 °C by controlling the precipitation conditions, especially seeding. The hematite product typically contains >66 pct Fe and <1 pct Cl, and its composition does not change appreciably on repeated recycling. The amount of product formed increases significantly with increasing FeCl₃ concentrations to ∼0.2 M FeCl₃, but nearly constant product yields are obtained thereafter; the precipitates consist only of hematite, provided that an adequate amount of seed is present. The contamination with Zn, Ca, and Na is <0.1 pct, even for high concentrations of dissolved ZnCl₂, CaCl₂, or NaCl. The extent of the precipitation reaction depends principally on the temperature and the free-acid concentration; accordingly, the controlled addition of a base allows the nearly complete elimination of the iron from metallurgical processing streams or effluents, as readily filterable Fe₂O₃.     

The leaching of chalcopyrite with ferric sulfate

The leaching kinetics of natural chalcopyrite crystals with ferric sulfate was studied. The morphology of the leached chalcopyrite and the electrochemical properties of chalcopyrite electrodes also were investigated. The leaching of chalcopyrite showed parabolic-like kinetics initially and then showed linear kinetics. In the initial stage, a dense sulfur layer formed on the chalcopyrite surface. The growth of the layer caused it to peel from the surface, leaving a rough surface. In the linear stage, no thick sulfur layer was observed. In this investigation, chalcopyrite leaching in the linear stage was principally studied. The apparent activation energy for chalcopyrite leaching was found to range from 76.8 to 87.7 kJ mol⁻¹, and this suggests that the leaching of chalcopyrite is chemically controlled. The leaching rate of chalcopyrite increases with an increase in Fe(SO₄)_1.5 concentration up to 0.1 mol dm⁻³, but a further increase of the Fe(SO₄)_1.5 concentration has little effect on the leaching rate. The dependency of the mixed potential upon Fe(SO₄)_1.5 concentration was found to be 79 mV decade⁻¹ from 0.01 mol dm⁻³ to 1 mol dm⁻³ Fe(SO₄)_1.5. Both the leaching rate and the mixed potential decreased with an increased FeSO₄ concentration. The anodic current of Fe(II) oxidation on the chalcopyrite surface in a sulfate medium was larger than that in a chloride medium.     

Influence of solid state properties on ferric chloride leaching of mechanically activated galena

The reaction of mechanically activated galena with ferric chloride solution was investigated in the concentration range [Fe³⁺] =0.01–0.6 M at temperatures between 303 and 338 K. The mechanical activation lasting 5–30 min was carried out in a planetary mill. It has been found that this reaction is sensitive to the microstrains produced in the structure of galena during grinding as well as to the concentration of Fe³⁺ in the solution. The influence of Fe³⁺ concentration is in operation practically only in the region [Fe³⁺] < 0.2 M.     

Reaction kinetics of the ferric chloride leaching of sphalerite—an experimental study

Chloride leaching processes have significant potential for treating complex sulfides. One advantage of chloride leaching is fast dissolution rates for most sulfide minerals. This experimental study is concerned with ferric chloride leaching of sphalerite, a common component of many complex concentrates. The effects of stirring, temperature, ferric ion concentration, and particle size have been examined. In addition, reaction residues at various levels of zinc extraction were examined by SEM, and the products of reaction were identified by energy dispersive X-ray analysis and X-ray diffraction. These observations indicated that the dissolution reaction is topochemical. Moreover, the leaching results fit a surface reaction control model. The activation energy was calculated to be 58.4 kJ/mole which is reasonable for a rate limiting surface reaction. The order of the reaction was 0.5 with respect to Fe³⁺ at low concentrations and zero at high concentrations. The change in reaction order occurred at similar Fe³⁺ concentrations for various particle sizes. This is believed to be indicative of an electrochemical reaction mechanism at low Fe³⁺ and an adsorption mechanism at higher Fe³⁺. A kinetic model for the ferric chloride leaching of sphalerite was also obtained for the lower Fe³⁺ concentrations and is given by: (ie5-01) This model is in excellent agreement with the experimental results for fractions of zinc extracted up to 0.95.     

The kinetics of leaching galena with ferric nitrate

The kinetics of leaching galena with ferric nitrate as oxidant has been studied. Experimental results indicate that the rate of galena dissolution is controlled by surface chemical reaction. Rate is proportional to the square root of the concentration of ferric ion. The addition of more than one mole/liter sodium nitrate decreases reaction rate. With nitrate additions below this concentration, rate either remains constant or is slightly enhanced. An activation energy of 47 kJ/mol was measured, and rate is proportional to the inverse of the initial size of galena particles. These results are explained in terms of mixed electrochemical control. The anodic reaction involves the oxidation of galena to lead ion and elemental sulfur, and the cathodic reaction involves the reduction of ferric ion to ferrous ion.     

The solubility of silver in γ-Fe

The solubility of silver in fcc iron was measured between 1366 and 1561 K by an isopiestic technique in which purified iron and silver alloy were equilibrated in a sealed isothermal capsule. The silver content of fcc iron coexisting in equilibrium with iron-saturated liquid silver can be represented by the relation obtained from the experiments log₁₀ pct Ag=?6027/T+2.289 The standard free energy change for the dissolution \(\underline {Ag} \) is ΔG ^o=+27,580?10.47T cal≠+115,500?43.85T joule in which the standard state of liquid silver is the pure element and that of the dissolved silver is silver in a hypothetical solution in γ-Fe such that πt (a _Ag/pct Ag)→1 as pct Ag→0.