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By Juergen Antrekowitsch, Stephan R. Steinacker

The main aim of the electric furnace treatment in the primary copper industry is the reduction of valuable metals such as zinc, lead or copper itself. On the one hand legal restrictions for the further use of the treated slag are constantly getting stricter while on the other every type of loss in the oxidic phase leads to economic disadvantages. In order to fully understand and to improve the process, kinetics during the reduction play an essential role. In the first part, this paper highlights the theoretical background of the reduction process, while the following chapters present experimental aspects and results from laboratory scale trials at the Montanuniversitaet Leoben. In addition, the comparison between the chemical reaction and the diffusion model plays a continuously important role. By investigating the reducibility of electric furnace slag, process adaptions and ameliorations are developed.

Jan 1, 2016

By K. Anand Rao

Extensive exploration for uranium metal by the Department of Atomic Energy in India led to the discovery of new carbonate host rock uranium deposits Tummalapalle and Gogi, which are located in southern part of India. Alkaline leaching at elevated temperature and pressure using autoclave is the central unit process in the overall strategy for extraction of uranium from these new ore deposits. Autoclave leaching is affected largely by intrinsic nature of the ore and by the process variables and the equipment settings. In order to understand such a complex process and also to be able to predict the process performance under randomly (ore grade, uranium mineralogy, gangue mineralogy etc.) and consciously perturbed variable settings (partial pressure of oxygen, temperature, concentration of leachant, stirring speed and time), sound and robust mathematical models are needed with analytical and/or numerical solutions. Present investigation attempts to develop a variant of kinetic correlation based on shrinking core model for batch alkaline leaching process in an autoclave. The leaching model incorporates particle size distribution according to popular Gates-Gaudin-Schuhmann equation, rather than assuming a single mean size for all the particles participating in the leaching reaction. Kinetic experimental data generated in autoclave leaching of Gogi uranium ore was used to evaluate various constants of the model developed. The ore sample used for experiments assayed 0.21 per cent U3O8. The partial pressure of oxygen was varied between 0.15 to 6.5 atm, temperature from 343 K to 438 K, concentration of sodium carbonate leachant in the range 0.47 g mol/L to 0.94 g mol/L, and the stirring speed from 573 rev/min to 900 rev/min in the experiments. The goodness of fit of the leaching process model is found to be >0.95. Morphological studies carried out on leached and unleached particulate matter using Scanning Electron Microscopy with Energy Dispersive X ray analyses are included in the present study.

Sep 1, 2012

By James S. Hanson

Existing models proposed for the bacterial leaching of metal sulfides generally fail to predict solubilization rates at times greater than a few tens of hours. The reasons for this may be that these models are empirically based and use first order bacterial and chemical oxidation rates. This type of model is satisfactory for short time predictions (on the order of 20 hours) when the bacterially catalyzed dissolution is relatively minor. However, when bacterial action becomes more pronounced, these models consistently predict higher dissolution rates than those commonly observed in laboratory experiments. The present model uses several fundamental chemically and biologically based assumptions to predict the dissolution rate of a chalcopyrite concentrate for extended leach times up to the precipitation of jarosite. The main assumptions made are that Monod growth kinetics prevail, T. ferrooxidans adsorb onto the surface of the mineral (not necessarily mineral specific), and that during periods of high growth oxygen transport may become rate limiting. The model also relies on the energy efficiency of the bacteria in fixing carbon (growth yield) and correlates this value with available surface area of the mineral particles and the bacterial growth rate.

Jan 1, 1989

By Zengjie Wang

Kinetic study of hydrochloric acid leaching of Panzhihua ilmenite from China is presented. Both temperature and concentration of hydrochloric acid have significant effects on the rate process of Fe dissolution from ilmenite ore, while the ratio of liquid to solid has little effect on the Fe dissolution. The Fe dissolution is found to follow the spherical model f (??) =1-(1- ??)1/3 and the apparent activation energy is calculated as 47.21 KJ/mol, suggesting a chemical reaction controlled mechanism. The dissolving behaviors vary at different kinetic stages. At the beginning the amount of the dissolved Fe and Ti increased monotonically with leaching time, while about 15 minutes later the dissolved Ti in the form of TiOCl2 began hydrolyzed into TiO2 fines reunited on the ilmenite ore surface, as observed by SEM and EDS technique. For the unreacted ilmenite particles covered by a layer of hydrolyzed TiO2, the leaching seemed to be as a selective leaching of iron and because Ti dissolved from and hydrolyzed rapidly again into the unreacted ilmenite particles. The leaching process can be ended 4 hour later when almost of Fe has dissolved into the solution and TiO2 remains as solid residues. The effects of acid concentration and leaching temperature were also investigated.

Jan 1, 2009

By G. A. Irons, D. Guo, D. Angheiina

To produce low-carbon (<30 ppm) steel in the tank degassing process, a ladle of steel with an oxidizing slag is placed in a vacuum tank equipped with bottom bubbling. The kinetics of this process are slow compared to the more prevalent RH degassing process, providing the impetus for the present work. There are several aspects to this work: water models of the fluid flow in the ladle; simulation of the decarburization (CO evolution) with C02 desorption in water; pilot-plant (60 kg) studies of the decarburization kinetics; mathematical modelling of the fluid flow in the ladle; mathematical models for each of the kinetic sites (plume, top slag and auto-nucleation); and full-scale trials. The results show that during the refining cycle the contribution from each reaction site changes, suggesting avenues for reducing cycling time and final carbon contents.

Jan 1, 2000

By J. A. Bustnes

The present work deals with kinetic studies of the reduction of molybdenum- and tungsten oxides by hydrogen. The experimental method used was therrnogravimetry under isothermal as well as non-isothermal conditions. The non-isothermal kinetics in the case of the reduction of MOO, to Moo2 has been modeled considering surface reaction as rate- controlling. In the case of the reduction of W02 to W a model was developed on the basis of the movement of the reaction front. The activation energies calculated on the basis of the models were in good agreement with those derived from isothermal experiments.

Jan 1, 1994

By Filippos Patsiogiannis

Laboratory size (4.5 kg) low carbon steel melts were deoxidized using Al and FeAl (33% Al), with and without synthetic fluxes, in alumina and zirconia crucibles. The dissolved oxygen, total oxygen, soluble aluminum, insoluble aluminum, silicon and carbon contents in the melt were determined as a function of refining time and temperature. It was observed that the reaction between aluminum and oxygen in solution closely follows thermodynamic equilibrium. Silica present in the alumina crucibles was found to be a source of oxygen for the melt, while this was not the case for zirconia crucibles. Reoxidation of the melt occurred through oxygen pick-up from the atmosphere. The extent of this reoxidation was found to be a function of oxygen content of the bath and the slag cover on the surface of the melt. The effectiveness of calcium-aluminate based fluxes in protecting the melt from the reoxidation and in increasing the rate of removal of inclusions was evaluated.

Jan 1, 1992

By Filippos Patsiogiannis

Laboratory size (5 kg) aluminum killed low carbon steel melts were desulfurized with synthetic fluxes in zirconia crucibles. The sulfur, oxygen, aluminum, silicon, and manganese contents in the melt were determined as a function of refining time and temperature. With a good argon shield and synthetic flux cover, melt reoxidation was not observed. Sulfur removal followed first order reaction kinetics. The effectiveness of calcia saturated calcium-aluminate (12CaO.7Al2O3) based fluxes in desulfurizing the steel melts was evaluated. The effects of initial sulfur level of the melt, weight of the flux (slag), and additions of tellurium, fluorspar, and barium oxide to the melt on the kinetics of desulfurization were also studied.

Jan 1, 1993

By José Roberto de Oliveira

Based on literature review one can see that the main objectives of MnO reduction is the comprehension of slag interactions and reactions with other elements beyond carbon. That&apos;s because it is worthwhile to study pure MnO reduction, where there will be not oxides interaction and just carbon will be the reduction agent. By a thermodynamic analysis we know that Si can react with MnO, then it&apos;s important to study this influence, so as Mn content. Our work aims to develop kinetics parameters for the MnO reduction, varying Mn and Si contents in bath. This has been given by pressure measure of CO in a Fe-C bath. The CO is generated by the oxide reduction with carbon. It has been proved that: - Mn content decreases the MnO reduction; - the MnO reduction is mainly influenced by Si content in a bath containing Iron, Carbon and Manganese so as Silicium

Jan 1, 1997

By Jorge Alberto Soares Tenório, Viviane Tavares de Moraes, Denise Crocce Romano Espinosa, Franco Alves Lavacchini Ramunno

"The traditional process for recovery of metals from waste electric and electronic equipment (WEEE) usually involves pyrometallurgical processing. However, the application of this technology to processing waste printed circuit boards (WPCBs) might lead to the formation of dioxins and furans, due to thermal degradation of flame-retardants and polymeric resins present in the board substrate. Therefore, this paper proposes a hydrometallurgical route for the recovery of copper. The acid leaching behavior of copper has been investigated at three different temperatures (25°C, 50°C and 75°C) with and without the addition of an oxidizing agent (hydrogen peroxide - H202). The dissolution kinetics for acid copper leaching was calculated based on chemical analysis by ICP-OES (Inductively Coupled Plasma - Optical Emission Spectroscopy). At 50°C with 1 mol/L H2S04 added 10 mL H202 (30%) each half hour under pulp density of 1 g I 10 mL, 100% of copper was extracted after 3 hours. The dissolution kinetics of copper with H2SO4-H2O 2 followed 1 - (1 - X)113 =Ket, i.e. chemically controlled reaction model.IntroductionThe information regarding the generation of waste electric and electronic equipment (WEEE) are still difficult to obtain because the estimates should take into consideration the historical production and sale of various products and the rate at which they reach the end of their life cycle, whose duration depends on the behavior of consumers [1]. Thus, the estimated overall WEEE generation varies between 25 and 50 million tons each year, which corresponds to more than 5% of all municipal waste generated [2], and this amount will increase at a rate of 3 to 5% per year, approximately three times faster than other individual types of waste [3].Printed circuit boards (PCBs) are essential parts of electric and electronic equipment (EEE), being found in virtually all electronic products, as well as in weapons systems [4]. A PCB is a basic component, which consists of a board where copper tracks are deposited. While the board behaves as an electrical insulator, the tracks connect electrically the various components attached to the board [ 5]. In addition to glass fibers, paper and resins, the PCBs contain significant amounts of metals, such as copper, iron, nickel, lead, stain, silver, gold and palladium [6]. In general, the weight fraction of metal is around 28% and the remainder of the boards is composed of plastic (19%), bromine (as flame retardant - 4%) and ceramic material (49%) [7]."

Jan 1, 2014

By Baozhong Zhao

Laboratory experiments have been conducted on the removal of As, Sb and Bi from molten copper by SF 6 injection. The results showed that the impurities can be removed by SF6 injection in the? sequence of Sb >As >,Bi and the rate of Bi removal is affected significantly by the concentration levels of As and Sb in the copper melt. Analysis of the experimental data indicates that the impurity removal process is under chemical reaction control rather than by mass transfer of impurity through the molten copper phase. On the basis of experimental results, a kinetic model was developed and the order of chemical reaction and the volumetric chemical reaction rate coefficients of impurity removal were determined.

Jan 1, 1996

By A. Ballester, F. Gonzalez, M. L. Blázquez

Pyrometallurgical process are usually used to recover valuable metals from metal sulphide concentrates. However, their use is diminishing as the cost of energy rises and pollution controls become strictes. An alternative method of treatment sulphides could be bacterial leaching due its simplicity and negligible contamination (1-2). This process is presently used commercially to re cover metals such as Cu and U from low grade ore concentrates. In spite of numerous researchs during recent years (3-5) there exists very little kinetic data concerning the speed of bioleaching process. The kinetic analysis of bacterial activity is related with the metabolism and growth of microox ganisms . This fundamental information permits ma- king the best utilization of bacterial oxidation and to suggest techniques which might increase the production of the products desired. However, bio- kinetic models are especially complicated due to the existence of many metabolic routes and parallel reactions which are important for the life of the bacteria. Microbiological oxidation of a mineral substrate is influenced by its own inicial concentration: This influence can be determined by means of a kinetic study. In a medium with sufficient concentration of nutrients (nitrogen, phosphorous and potassium) and an adequate supply of 0, and CO2, as the only & L source of carbon for the biochemical synthesis, the substrate concentration would remain the only limitation in the rate of leaching. In this case the Michaelis-Menten model could be applied (6). The model is based on an association of the enzyme (El with the substrate (S) with consequent decomposition of the latter into enzyme and products [ ] The rate of dissolution is defined by the equation : [ ] Were V is the rate of metal extraction (mg 1-1 1 h-1 ) ; S is the pulp density Mn is the maximum rate for metal extraction (mg 1-1 h-1) and K is the constant of Michaelis (concentration of substrate that yields Vm/2). This method is applicable only when the rate of bacterial growth is similar to the rate of metal extraction. It would therefore be sufficient to control the concentration of metal in the medium over the period of time. In the present work a systematic study of the kinetics of ZnS and CuFeS bioleaching in sphalerite and complex ore concengrates was carried out. The rate of dissolution of the Zn and Cu as function of the pulp density and temperature was determined. However, most oxidations of sulphide dissolution take place with a very slow kinetic; but, this can be accelerated considerably by the addition to the solution of suitable catalytic ions, as was Suggested many years ago by Bjorling (7). Such ions can exercise an important influence on the rate of the oxidation-reduction reactions, both homogenous and heterogenous, which take place during the leaching of sulphides; they also affect the nature of the reaction products. The action of catalytic ions has been fully developed in aqueous systems, but in the absence of bacteria (8 - 11) although the actual machanisms is not totally known. The mechanisms proposed as hypotheses in the literature (8) indicate that, in the case of ZnS, the catalyst ion act through an electrochemical mechanism according to the reactions: [ ]

Jan 1, 1989

By Mamookho Elizabeth Makhatha, Mbal Henock‑Michel Mwanat, Kubangala Brest Kasongo, Ntumba Edward Malenga

This study investigated the operating parameters that affect the kinetic dissolution of copper and cobalt from sulfidic ores. The sulfuric acid concentration, temperature, sodium chloride concentration, particle size range, and leaching time were selected to deduce the kinetic mechanism of the leaching reaction. Other parameters, such as a stirring speed of 250 rpm and the percentage solid 10% w/v, remained constant. The results reveal that an increase in acid concentration enhances the leaching rate of copper and cobalt. Copper and cobalt dissolution was positively affected by the addition of sodium chloride. The highest leaching rates of copper and cobalt were 24.71% and 15.65%, respectively. The chemical control and diffusion control by shrinking core models are well fitted as the kinetic models representing the dissolution of the minerals. The respective activation energies for copper and cobalt dissolution of 10.92 and 31.023 kJ mol− 1 for the chemical control and 18.83 and 37.28 kJ mol− 1 for diffusion reaction control were established from temperature-based experiments.

Aug 26, 2022

By Inkap Choi

Asbestos is a broad term embracing a number of fibrous silicate minerals. These minerals look extremely fragile, yet their fibers have a tensile strength equal to that of piano wire. Chrysotile asbestos is the only mineral that can be woven into cloth, and its fibrous structure is, if anything, even more amazing than its remarkable ability to withstand heat. Because of its unique physical properties asbestos has achieved great industrial importance, and more than 3,000 current uses are known, ranging from use in the kitchen to use in space missiles. Because their minuscule fibers are eminently respirable, asbestos minerals have also found their way into the lungs of humans, where they apparently produce serious biological effects such as asbestosis and lung cancers. 1, 2,3 Because of both their usefulness and their hazardous properties, these minerals have attracted a good deal of attention from research workers during recent years. For example, the surface properties of asbestos minerals have been studied by many investigators. 4, 5, 6, 7, 8, 9 However, even for the important mineral chrysotile, the literature data are more or less conflicting. Pundsack4 measured a PZC (point of zero charge) of 10.1; Martinez and Zucker5 measured 11.8; Chwastiak reports 10.8-11.0; and Raddick measured three sepa-rate apparent PZCls at about pH 8.3, 10.0 and 10.9. More recently Trivedi8 reports 10.11. Naumann and Dresher9 have studied surface charge enhancement of chrysotile by metal ions, and describe how the mineral reacts with contaminantions. In the present paper, the mode of dissolution of magnesium and hydroxyl ion from asbestos minerals placed in water was studied by kinetic experiments involving rate at which these items leave the minerals. Also, some study was made of interaction between dissolved species.

Jan 1, 1972

By Dewa Putu Agus Sudarmaja, Widi Astuti, Januarti Jaya Eka Putri, Yayat Iman Supriyatna, Himawan Tri Bayu Murti Petrus, I Wayan Warmada, Siti Nurul Aisyiyah Jenie, Ferian Anggara, Anisa Maulidia, Vincent Sutresno Hadi Sujoto, Sutijan

With the rapid development of renewable energy technology, such as electricity reserves, to store energy for electric or electric vehicles, environmentally friendly energy sources are expected to continue to be fulfilled according to mobility and stationary energy needs. Lithium is the most attractive candidate for energy storage development. The presence of lithium in Indonesia in the Sidoarjo mud content is interesting to be used as an alternative source of raw materials. During the research, sulfuric acid acted as a solvent, and hydrogen peroxide acted as an oxidation agent. Lithium recovery will be studied using a leaching process at various temperatures (30, 45, and 60 °C) and sulfuric acid concentrations (0.5, 1, 2, 3, 4, and 6 mol/L). The increasing temperature, sulfuric acid concentration, and hydrogen peroxide concentration will directly affect the lithium recovery. An increase in sulfuric acid concentration will be directly proportional to the recovery of lithium in the solution. Optimum conditions were obtained at varying 6 mol/L sulfuric acid concentrations and 60 °C temperature variations. The shrinking core model (SCM) studied leaching kinetics, and ash layer diffusion acted as a rate-controlling process. The activation energy of the leaching process was obtained at 38.90 kJ/mol.

Jul 25, 2023

By R. Baker

A novel electrochemical half-cell and corresponding working electrode were designed to evaluate the electro-catalytic activities of catalysts in an environment close to that of an operating proton exchange or polymer electrolyte fuel cell (PEMFC). Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) techniques were employed using the novel cell to characterize various methanol electro-oxidation parameters that contribute to the overall reaction on a fuel cell anode. The effect of temperature on methanol oxidation kinetics was examined in the potential range of 0.31 to 0.65V (vs. NHE). The data was collected in the temperature range of 20 to 80°C. Based on the experimental analysis and literature data, an equivalent circuit model (ECM) for methanol oxidation was proposed and was used to fit the EIS experimental data. The experimental data and ECM electrochemical data was used to extract electrochemical kinetic parameters for methanol oxidation such as the exchange current density, Tafel slope, and energy of activation for the reaction. Kinetic data, especially at different temperatures, is very limited in the literature.

Jan 1, 2005

By Gerald Onyedika, Tochi Onwumere, Martin Ogwuegbu

"The kinetic study for the leaching of iron from cassiterite ore in KOH solution was studied. The effects of KOH concentration, particle size and reaction temperature on the leaching rate of iron were also examined. The results of leaching studies showed that the leaching of iron from cassiterite ore in KOH solution is significantly influenced by the reaction temperature, KOH concentration, and decrease in particle size. The study showed that 90.62% of iron ore was leached in 8M KOH solution at 80°C within 120 minutes. The experimental data were well evaluated using the shrinking model for surface chemical reaction and diffusion control through the product layer. The activation energies for the iron ore dissolution using the two models were calculated to be 32.06KJmor1 and 97.97 KJmor' respectively.IntroductionIn recent times, there has been increasing attention on the kinetic study of mineral dissolution. In most of these studies, the experimental results were analyzed with a suitable shrinking core model under the assumption that the ore is a homogeneous spherical solid phase [1-4]. A study of the dissolution kinetics of a Nigerian cassiterite ore by hydrochloric acid showed that increase in the hydrochloric acid concentration is accompanied with increase in the amount of cassiterite ore dissolved at various times [4]. The optimal concentration was found to be 4.0M HCl, after which there was a decline in the amount of the ore dissolved, which showed that the concentration of the reagent has a significant effect on the leaching rate of the ore. Also in studying the effect of stirring speed on the rate of cassiterite ore dissolution while keeping other conditions constant for 120 minutes, the result showed that the rate of cassiterite ore dissolution was dependent on the stirring speed over a range of 0 to 630 rpm. Above 360 rpm, the stirring speed no longer had any effect on the solid dissolution. The dissolution rates of cassiterite were analyzed using a suitable shrinking model. The results showed that the reaction was controlled by the diffusion of tin through the porous product layer, a reaction order with respect to hydrogen ion concentration of 0.92 M and activation energy of 50.05KJmor'. In another kinetic study on the leaching of a low grade niobium-tantalum ore with concentrated KOH solution the effect ofreaction temperature, KOH concentration, agitation speed, particle size and alkali-to-ore mass ratio on the dissolution rate of niobium were examined [5]. The result of niobium leaching from low grade niobium-tantalum ore with concentrated KOH, solution at different agitation speeds showed that the dissolution rate increased with increase in agitation rate. In the case of particle size effect, the results show that small particles require much shorter time for complete dissolution than the large ones."

Jan 1, 2013

By J. B. Hiskey

The principle oxide minerals of molybdenum are wulfenite (PbMoO4), ferrimolybdite (Fe2(MOO 4)3.nH2O), powellite (CaMoO4), and ilsemannite (Mo304). Wulfenite is found in Arizona, New Mexico, Nevada, Utah, California, and Montana. It is also found in the states of Sonora and Chihuahua, Mexico. Prior to 1915 wulfenite ores were the primary source of molybdenum. The solubility of wulfenite in hot sodium sulfide was first noted by Bonardi(1) during attempts to sulfidize wulfenite material prior to flotation. He identified lead sulfide and soluble sodium molybdate as reaction products. Bacon (2) sulfidized wulfenite in preparation for flotation and by X-ray analysis found the reaction product to be lead sulfide. Holmes(3) made an extensive investigation of the extraction of molybdenum from wulfenite concentrates by leaching. Nearly 100% molybdenum extraction was possible from -100 mesh samples leached for 15 min with 10% sodium sulfide solution at room temperature. Molybdenum extraction from -100 mesh samples after leaching 30 min at a temperature of 45°C using 2, 4, and 6% sodium sulfide was about 32, 79, and 98% respectively. The extraction showed little sensitivity to time, temperature, or particle size using 10" sodium sulfide solution.

Jan 1, 1976

By A. P. Mehta

The role of microorganisms in the leaching of metal sulfides is well established (Torma, 1977; Murr, 1980). However, this established knowledge applies mostly to chemolithotropic microorganisms such as Thiobacillus ferrooxidans which function optimally in leaching catalysis between 25-35° C, and in a pH range of 2-2.5. Although leaching with thermophilic microorganisms capable of extending the range of catalytic viability beyond 35° C is also documented, there are few if any attempts to optimize or extend sulfide concentrate leaching with thermophilic microorganisms. When mixed metal sulfides or other materials having different rest potentials (referenced to the standard hydrogen electrode, SHE, in the electromotive series) make contact in a conducting, aqueous medium, the contacting members will act as an electrochemical cell, with the member having the higher rest potential assuming the role of an electrical cathode. In leaching reactions involving such galvanic couples, the cathode becomes passivated, while the anodic member reacts vigorously due to the electro- chemical reaction which occurs (Hiskey and Wads- worth, 1975). Serry, eta1 (1978) observed that when chalcopyrite and pyrite were in intimate contact in natural ores, the chalcopyrite reacted vigorously by galvanic conversion as a result of the higher rest potential (~ 0.63 V) as compared to the chalcopyrite (~ 0.53 V). In addition, it was postulated that because of the elemental sulfur which can form on the anodic chalcopyrite in this galvanic conversion process, reactions in acid-bacterial medium would be expected to have accelerated copper extraction because of the conversion of any sulfur product layer on the chalcopyrite anode to sulfuric acid according to the following general reactions: [MS?M2+ + S° + 2e- (1) and 2S° + 302 + 2H20 bacteria?-2H2SO 4 (2)] where M in reaction (1) designates the metal (or metals in the specific case of chalcopyrite) to be released to solution by galvanic conversion.

Jan 1, 1982

By S. N. Shahcheraghi

Bioleaching method makes use of bacteria in solving metallic sulphides, so that these bacteria tend to convert insoluble metal sulphides into soluble sulphates. Since the kinetics description of this process is inevitable for better interpretation of relation between metabolism and growth of live organisms, as well as optimization of metals extraction processes, in this paper, this description is represented and designed in mathematic (kinetics) model for copper sulphide minerals based on Monod kinetics model. According to this model, special growth rate of bacteria (?) is a hyperbola function of restrictive substrate concentration (S). By Solving and developing of Monod kinetics model, a comprehensive kinetics model for bioleaching of copper sulphide minerals results. The designed is also applicable for other metal sulphides.

Sep 1, 2012