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By Edouard Asselin, Guikuan Yue

"In the present study, electrochemical measurements, especially cathodic potentiodynamic polarization (CPC) and cyclic potentiodynamic polarization (CPP), have been employed to study the kinetics of ferric reduction on chalcopyrite in aqueous Fe( II )-Fe(III)-H2S04 solution at 25°C and 70 °C. Results from the calculation ofspeciation in the above solution reveal that, at both 25 °C and 70 °C, the real Fe3+/Fe2+ ratio is much lower than the nominal ratio, which leads to smaller values for the reversible potential of the ferric/ferrous couple based on the Nemst equation. Exchange current densities of the ferric/ferrous couple were obtained by extrapolating the cathodic linear Tafel line to the reversible potential and are on the order of 10-7·10-6 A/cm2 at 25°C and 10·6-10-5 A/cm2 at 70 °C, respectively. The transfer coefficients were about 0.35-0.38 at 25°C and 0.35-0.45 at 70 °C. Polarization plots of CPC and CPP under different nominal Fe3+/Fe2+ ratios are in good agreement at 25 ·c and at 70 °C. Based on the obtained exchange current densities, the rate constant k, was calculated and is on the order of 10-1 cm/s at 25 °C and 10 1 cm/s at 70 °C.IntroductionChalcopyrite is the most abundant copper mineral in nature, accounting for about 70% of copper reserves in the world [I]. In recent years, the metallurgical industry has been searching for a hydrometallurgical process as an alternative to pyrometallurgical treatment due to high emissions of S02 and capital costs associated with smelting. Activity in this area has increased recently due to some inherent advantages associated with hydrometallurgical processing, such as the possibility of treating low-grade ores (increasingly more abundant in the case of copper) and easier control of waste, with the attendant benefits to the environment [I]. Chalcopyrite is highly refractory under most hydrometallurgical conditions, owing to the formation of an anodic passivation layer on the chalcopyrite surface which renders the process kinetics very slow. Most of the currently proposed processes are based on sulfuric acid with ferric ions and/or dissolved oxygen as oxidants. Sulfuric acid is preferred over all other leaching reagents in terms of cost, environmental friendliness, and ease of its regeneration during electro-winning. Some of these processes have been piloted in attempts to implement these technologies on an industrial scale,"

Jan 1, 2012

By F. F. Lins

There is a large use of mercury in Brazil by the gold miners in the so called "garimpos" (non registered mining operations), where it is usual to recover the gold contained in the gravity concentrates by amalgamation, which is highly deleterious to environment if not conducted properly. Unfortunately, this is a common practice there. After presenting in brief the modus operandi generally practiced in the garimpos and the environmental problems, this work reviews some of the research conducted in CETEM according to two approaches: (i) replace amalgamation by other processes and (ii) develop technology to treat mercury-contaminated soils and effluents. Conventional processes like froth flotation, to recover gold from gravity concentrates, and centrifuges were considered. Also as alternatives to amalgamation, innovative process like the recovery of gold by coal-oil agglomerates and a technology that is currently under development in our laboratory, called gold-paraffin process, are described in brief, some results presented and their potential use assessed. To reclaim sites already polluted a technology was developed to float mercury selectively from contaminated soils. The potential use of centrifuges to pre-concentrate the mercury is also discussed. The scope for applying the last techniques is to concentrate the pollutants in a small volume of mass which would be suitable for recycling or isolation from the environment. A prospective technology to treat contaminated soils, or mercury concentrates, is the immobilization of mercury by adding inorganics. Concerning the ionic mercury which may be present in effluents, precipitation of the ions and flotation of the precipitates are being studied.

Jan 1, 1994

By Jie Li, Zhongliang Tian, Xun Hu, Kai Zhang, Yanqing Lai, Hongliang Zhang

The Al-Sc Alloys show many advanced properties for a wide range of engineering applications. But the metal Sc must be added into the metal Al in the form of the Al-Sc master alloy, which is usually produced by the thermal reduction process. In this paper, the decomposition voltages of Sc2O3 and Al2O3 in Na3AlF6-K3AlF6-AlF3 melt were calculated based on the Nernst equation. And the Al-Sc master alloy was prepared in the melt at 950°C by electrolysis. The results show that the Al-Sc master alloy can be prepared by the co-deposition of Sc3+ and Al3+ at the cathode if the concentration ratio of Sc2O3 to Al2O3 in the melt is more than 2:1 under the condition of the aluminum electrolysis. SEM and ICP analysis of the product indicates that the Al-Sc master alloy is made of the phase Al and the phase Al3Sc.

Jan 1, 2016

By Hiroyuki Matsuura

Treatment of electric arc furnace (EAF) dusts has become an important issue from the viewpoint of the environmental protection and recycling of variable resources because these dusts contain considerable amount of zinc and lead. A new recovery process of these metals has been proposed, in which the metals in the dusts react with waste polyvinyl chloride to form metal chlorides. Therefore, it is important to clarify the physicochemical properties and behaviors of zinc, lead and those chlorides and oxychlorides. In the present study, the kinetics of chlorination of ZnO, PbO and ZnFe2O4 mainly contained in the EAF dusts were investigated at 1023 K to 1273 K with Ar-O2-Cl2 gas. Based on these results, the selective chlorination and evaporation process of zinc and lead from the mixture of Fe2O3-ZnFe2O4-ZnO-PbO was examined and the high efficiency of selectivity has been demonstrated.

Jan 1, 2006

By Stig Petersson

Slag from the converting of copper matte is usually recirculated to the smelting furnace. This recirculation generally causes disadvantages as magnetite-build-up in the furnace, accumalation of impurities as antimony, lead, nickel etc in the process. The treatment of converter slag in a separate furnace in order to recover the copper and nickel content would be of advantage from several points of view. At the Mining and Metals Division, Boliden, testwork has been carried out to treat converter slag from the PS-converters in a separate furnace. The tests have been performed in laboratory and pilot plant scale. The pilot plant tests have been carried out in a TBRC with charges of 5 tons. Based on these tests a full scale TBRC has been projected in order to treat the slag from the PS-converters. This slag will be reduced with copper concentrates to give a matte and a final slag low in copper and nickel. The background and data from the testwork are presented. Also the lay out, technical data and flowsheets for the projected process are shown as well as some production data from the Rönnskär smelter.

Jan 1, 1976

By Ilija Ilic

Recovery of tin from tinplate and production of good-quality detinned-plate for further processing in ironworks has been the subject of interest for many years. Tinplates are mostly used for production of tin containers for food industry and consumer goods. The research carried out so far included determination of the parameters of dissolution of tin from tinplates by alkaline solution of NaOH and electrochemical recovery of tin from the alkaline solutions. During leaching, NaNO3 and methanitrobenzoic acid (MNBA) as oxidants were studied. By leaching the waste tinplate which contains 0.31 % of tin with a solution of 1.12 mol/dm3 NaOH, 0.26 mol/dm3 Na2CO3 and 0.09 mol/dm3 MNBA at temperature of 70°C for 60 mm, a degree of tin leaching of 97 % was attained. MNBA facilitates oxidation of Sn2+ into Sn4+ suitable for obtaining compact, and not spongy, Sn cathode deposit, as it was the ease earlier. Recovery of tin by electrolysis from solutions obtained by leaching was studied to determine the effect of electrolyte composition on the quality of cathode deposit and the degree of electric current efficiency. Experimental results obtained at a laboratory level were checked on an enlarged laboratory set up where continuos leaching of tin from waste tinplate and its electrolytic recovery from the solution obtained were carried out. The experimental set-up -operated under semi-industrial conditions, and about 500 kg of waste tinplate was processed yielding about 1.160 kg of tin (99 % Sn).

Jan 1, 2000

By Pekka Taskinen

The converter-less nickel matte smelting technology (DON) adopted more than 20 years ago in Boliden Harjavalta smelter has been since that applied successfully to the processing of large number of nickel sulphide concentrates of various Ni-to-Cu ratios and MgO contents. The operational point of the technology is far from the conventional primary nickel smelting in the smelting-converting route. Therefore, a careful scouting of distribution equilibria of the base and trace elements in the smelting conditions of DON process has been conducted, in order to obtain quantitative information about the equilibria and thermodynamic properties of the nickel mattes at low iron concentrations, less than 10 wt% [Fe] in matte. The series of investigations has included novel experimental and analytical techniques for increasing the reliability and sensitivity of the phase equilibria as well as the element distribution observations carried out in typical high-grade nickel matte smelting conditions.

By A. V. Tarasov

Investigations of thermodynamic properties of Cu-Ni and Cu-Ni-S systems and mattes have been conducted with the aid of a MC-130 I mass-spectrometer designed for studies of processes of vapor formation of hardly volatile substances. The instrument comprised a combination of an evaporator of Knudsen chamber type with a mass-spectrometer for analysis of the vapor phase. In the process of studies of molten Cu-Ni-S systems and commercial-grade mattes within a temperature interval of 1400-1800 K the partial pressure of sulfur was measured by means of complete isothermal evaporation and the partial pressure of copper and nickel by comparison of ionic currents. The partial pressure values of the components above the molten Cu-Ni-S were used for calculation of activities of the respective components in the melt. The copper and nickel activity data obtained was used for assessing the amount of dissolved losses of these metals in autogenous smelting slags.

Jan 1, 2003

By Akira Yazawa

The continuous converting has attractive advantages, but further experimental studies on the slag are required, when the process is considered thermodynamically. The summarized experimental results, obtained with iron silicate slag and with ferrite slag and results relating to actual operation are described and discussed in this paper. At first, equilibrium relations at controlled oxygen potentials among three melts of silica-saturated iron silicate slag, white metal and copper are investigated. The results obtained for slag agreed with the thermo-dynamical predictions. Namely, to suppress a magnetite separation, the system should be at high temperature; in the case of the S02 gas of 10 kPa, for example, magnetite did not separate from the slag at 1300°C, but at 1250 and 1200°C the slag was saturated with magnetite even at lower SO2 pressure. Copper losses caused by dissolution of its oxide increased with increasing 5O2 pressure, and were slightly lower than those reported in previous papers without the matte phase. When the continuous converting slag does not contain any appreciable amount of silica - in contrast to the conventional smelting slag ferrite slag would form, but there was no published fundamental work on-ferrite slags. Hence, the melting behavior and activities of the system CaO-Cu2O-Fe2O3 have been investigated. The liquidus diagram in nitrogen atmosphere was, constructed using both thermal analysis and quenching method. The low liquidus temperature region without magnetite separation was found in the part of low content of Cu2O in the section Cu2O-CaO-Fe2O3 and Cu2O?Fe2O3¬CaO?Fe2O3. The activity of Cu2O in the system was also measured. Slags, composed-of CaO, Cu2O and Fe2O3, in platinum crucibles were equilibrated at 1250°C and controlled oxygen pressures. After quenching, the-composition of slag and platinum crucible were determined qualitatively. On the thermo-dynamic analysis of the results, iso-activity lines were drawn, and it was shown that the slag in the converting furnace of the Mitsubishi process exists in an adequate region of the composition triangle.

Jan 1, 1976

By A. V. Tarasov

Investigations of thermodynamic properties of Cu-Ni and Cu-Ni-S systems and mattes have been conducted with the aid of a MC-1301 mass-spectrometer designed for studies-of processes of vapor formation of hardly volatile substances. The instrument comprised a combination of an evaporator of Knudsen chamber type with a mass-spectrometer for analysis of the vapor phase, In the process of studies of molten Cu-Ni-S systems and commercial-grade mattes within a temperature interval of 1400-1800 K the partial pressure of sulfur was measured by means of complete isothermal evaporation and the partial pressure of copper and nickel by comparison of ionic currents. The partial pressure values of the components above the molten Cu-Ni-S were used for calculation of activities of the respective components in the melt. The copper and nickel activity data obtained was used for assessing the amount of dissolved losses of these metals in autogenous smelting slags.

Jan 1, 2003

By Kuniaki Murase, Tetsuji Hirato, Yasuhiro Awakura

"Electrodeposition of CdTe was studied using aqueous ammonia-alkaline electrolytic baths in which Cd11-and Te1V-ions are dissolving as Cd11(NH3)/+ and Te1vol-ions, respectively. Ca-thodic polarization curves of the baths suggest the presence of strong interaction between the Cd11-and Te1V-ions; electrodeposition of tellurium is inhibited by the presence of Cd(NH3)/+ ions. The interaction makes it possible to electrodeposit CdTe films with stoichiometric composition. Polycrystalline CdTe thin film of about 1 µm thickness was electrodeposited at 343 K from ammonia-alkaline solutions (pH= 10.7) containing TeO32-(<20 mmol dm-3) and Cd(NH3)/+ ( < 60 mmol dm-3) ions. Increasing Cd(NH3)/42+/TeO32- mole ratio or decreasing total concentration of ammonia/ammonium-ion gave flat and smooth crystalline CdTe deposits at constant cathode potential-0.70 to -0.30 V vs SHE at 343 K.IntroductionCadmium telluride (CdTe) is well-known as a compound semiconductor whose band gap, i.e. 1.44 eV, is suitable for solar energy conversion with a photovoltaic cell. Various methods, such as CVD (chemical vapor deposition) and electrodeposition, of preparing CdTe thin films for solar cells have been investigated.Acidic sulfate solutions with a pH of 1-2 are usually employed for CdTe processing by electrodeposition.1-3) The electrodeposition of compound semiconductors is usually achieved (i) at a higher cathode potential than the redox potential of less-noble species, can in this case, and (ii) under the condition of diffusion-limiting current of a more noble species, Te1Y.4) There-fore, a suitable CdII/TeIV concentration ratio in the acidic electrolytic baths, resulting in the deposition of stoichiometric CdTe, is determined by the diffusion-limiting current density of TeIV- reduction, i.e. the concentration of HTeIVO2+ · Since the solubility ofTe1v species HTeIVO2+ in the acidic solutions is quite low, the rate at which CdTe is deposited from the acidic solutions is extremely slow."

Jan 1, 1998

By E. Burgos Cruz

The behaviour of S, N and P during refining of Fe-18 wt%Cr-10 wt%Ni with calcium carbide was investigated. The effects of the initial contents of C and N in the metal phase, as well as the supply method of calcium carbide to the melt on the removal degrees of S and P were evaluated. Heats were carried out at 1873K, in MgO crucibles, using a laboratory induction furnace. It was observed that simultaneously with S and P, N and O have also participated in the reactions. It seems that, in fact, O governs the behaviour of the other elements dissolved in the melt and that N is had to the removal of P with calcium carbide. It was also noticed that high C content in the metal phase have not altered the dephosphorization and desuffirization degrees, but that the supply of calcium carbide done by injection led to a lower dephosphorization degree than the one obtained by dumping it.

Jan 1, 1995

By Wiraseranee. Chompunoot, Kazuki Morita, Toru H. Okabe

"Aiming at the development of more effective recycling processes, dissolution behavior of rhodium into molten slag was investigated. Using a pure rhodium crucible and Na2O-SiO2 slag system, equilibration experiments were carried out for 18 h at 1423-1623 K under various oxygen partial pressures of 0.005-1 atm with varied slag basicity. Rhodium solubility increased with increasing oxygen potential, slag basicity, and temperature. Rhodium dissolved into slag as rhodate ion ([RhO2]-) by the endothermic reaction: Rh(s) + 3/4O2(g) + 1/2O2-(in slag) = [RhO2]-(in slag). In the dissolution reaction, the “rhodate capacity” of slag is newly-defined. The correlation between rhodate capacity and optical basicity is reported.IntroductionDue to its high chemical resistance and outstanding catalytic properties, rhodium (Rh), one of the platinum group metals (PGMs), is utilized in various applications such as catalysts, molten glass vessels and containers, and electronic devices. Owing to the rarity of Rh resources in nature, recycled Rh from scraps such as spent automobile catalytic converters is currently considered as an important source of Rh supply [1]. According to the recycling practices, Rh is currently mainly recovered from scraps along with other PGMs such as platinum (Pt) and palladium (Pd) by a dry process (e.g., smelting), a wet process (e.g., leaching and subsequent separation of PGMs from aqueous solution), or a combination of both processes [2]-[4]. Among these processes, smelting is commonly applied because PGMs can be effectively separated from a relatively large amount of various impurities coexisting in scraps. In the smelting process, Rh and other PGMs are collected in the collector metal (e.g., iron and copper), and impurities in scraps are removed into slag [4]-[6]. The process may be carried out at a temperature range of 1573-1973 K, in either an oxidizing or reducing atmosphere. Due to the high oxidation resistance at high temperatures, Rh is expected to be collected efficiently in the metal collector rather than being oxidized and forming RhOx in a molten slag. However, Rh loss into slag does occur in this process [7]."

Jan 1, 2011

By G. H. Khoe

Neutralisation of acid uranium mill tailings with lime or other alkaline materials is usually practised to reduce the dissolved concentration of heavy metals and radio nuclides. Computer modelling of this process was carried out using the geochemical equilibrium code MINTEQA2. Computed dissolved metal and sulfate concentrations were compared with laboratory-based experimental data. It was found necessary to include the modelling of adsorption of trace metals (such as uranium and lead) by the precipitated ferric hydroxide in order to obtain acceptable concentrations in the neutralised liquors. There were limitations of the modelling exercise due to important aspects which were not addressed or properly accounted for such as chemical reaction kinetics and the effect of high ionic strength. These are discussed in the paper.

Jan 1, 1991

By Dimitrios Fillippou

Magnesium hydroxide is used in a number of industrial applications, from the neutralisation of acid effluents to the production of pharmaceuticals. High-quality magnesium hydroxide powders can be produced by hydrating slow-reacting magnesia in dilute magnesium acetate solutions. The process of magnesia hydration shows many similarities with a typical hydrometallurgical leaching operation; however, its kinetics are crucial not only for process design and control, but also for the production of powders with a desirable particle morphology. This article shows the results of an experimental work whereby industrial heavily-burned magnesia powders were hydrated in 0.01 to 0.1 mol/L magnesium acetate solutions at temperatures ranging between 333 and 363 K. Examination of the magnesium hydroxide produced and the analysis of the kinetic data suggest that the hydration of heavily-burned magnesia in magnesium acetate solutions is a dissolution-precipitation process controlled by the dissolution of magnesia particles. The activation energy was estimated to be 60 kJ/mol, while the reaction order with respect to magnesium acetate concentration was found to be about one.

Jan 1, 1999

By A. M. T. S. Bandara

The solubility of rare earth (RE) salts in aqueous solutions depends on many factors including the type of cations and anions in solution, their concentrations, temperature and the type of solid precipitated. Experiments were conducted using anhydrous La2(SO4)3 and Ce2(SO4)3⋅8H2O as solids and lanthanum(III) perchlorate prepared by dissolving La2O3 in HClO4 solutions as RE-sources. Solutions of H2SO4, H3PO4 and their mixtures in the presence or absence of Na+, Ca2+, Fe(III) or Al(III) as perchlorates served as test solutions. Saturated solutions and precipitated solids were assayed and characterized using standard techniques to show that the La(III) and Ce(III) ions precipitate as hydrated sulphates, phosphates or double salts with sodium, depending upon the solution composition. The change in solubility of RE-salts with solution composition and temperature is the result of the composite effect of changes in solubility products (pKSP) of salts, pKa of acids and other equilibrium constants for ion-association.

By Z. Zhang, Zongshu Zou, Nan Wang

"Thermodynamic calculation is applied to make an investigation on the equilibrium phase relations and liquids of CaO-SiO2-Al2O3-FeOx system for different temperatures. The calculated results with FactSage6.1 show that the effect of temperature on the the equilibrium phase relations and liquidus of CaO-SiO2-Al2O3-FeOx system and its sub-systems is appreciable. The liquid phase regions enlarge with increasing temperature from 1573K to 1873K, while the primary phase fields reduce distinctly.IntroductionThe main oxide components of vitrified bottom ash slag are CaO, Al2O3, SiO2, Fe2O3, MgO, and Na2O, accounting for more than 90% of the bottom ash by weight[1]. During slag processing, the knowledge of thermodynamic properties and liquidus temperature in the related slag systems is highly required [2, 3], which is not yet available. Through literature survey [4-6], it is clear that the systematic information on the concerned complex slag system is scarce. So far the engineers in the field have to make assumptions of the thermodynamic properties of the simplified oxide system, without taking into consideration the interactions of the different oxide components, which hinders the development of the slag valorization and utilization. In order to provide thermodynamic properties for the application of the vitrified bottom ash, the six-component oxide system (CaO-MgO-Al2O3-SiO2-FeOx-Na2O) is highly required. A preliminary phase diagram of the CaO-MgO-Al2O3-SiO2-FeOx-Na2O system can be obtained from extrapolation of the thermodynamic functions of constituent subsystems such as CaO-SiO2-FeOx-MgO, CaO-SiO2-FeOx-Al2O3, CaO-SiO2-Na2O-MgO and CaO-SiO2-Na2O-Al2O3. In this work, the equilibrium phase relation and liquidus of CaO-SiO2-FeOx-Al2O3 system, one subsystem of the concerned complex slag system, are calculated and the effect of temperature is also discussed."

Jan 1, 2012

By John R. Goode

The fist part of this paper comprises a general discussion on refractory gold ores and their mineralogy. Processing methods now in use are reviewed and test procedures for the important methods are discussed. Factors determining the selection of a process are outlined. The paper includes a survey of production plants using pressure oxidation, roasting and biological oxidation to process refractory ore. The status of processes under development is briefly reviewed.

Jan 1, 1993

By Joseph Hamuyuni, Pekka Taskinen

We present experimental results for the liquidus in the system Cu2O - CaO -Al2O3 at 1250 oC. In this study, we quantified the liquidus by the equilibration/quench/analysis technique, with Cu2O, Al2O3, and CaO as primary materials exclusively. Experiments were conducted in air at an at oxygen pressure (p) = 21.3 kPa). Equilibrated specimens were quenched in brine solution of 10 wt% NaCl. We then quantified the liquid chemical compositions by means of Energy-Dispersive X-Ray Spectroscopy (EDS) and Electron probe micro-analyzer (EPMA). This study reveals inconsistences in liquidus surface of the present ternary diagram of the system here in mentioned. Differences of up to 10 wt % compositions of the species have been observed.

Jan 1, 2015

By Sergio Demetrio

Based on the current reality of the copper smelters industry, besides the advances that have been and are expected for the next few years, the authors present a futurist vision of the processing of copper concentrates and copper smelters in the years 2000. Outlined new development strategies and ways of improvement in this business, including research, development and management of the works that today posses characteristics of a profitable operation, as well as the changes expected with respect to the entry of new actors and the creation of new products The authors finally bet for small or tailor-made smelters with ad hoc technology for their raw materials and few units to coordinate -devoted to specific concentrates using high technology and low manpower. Considering the in-situ hydrometallurgical route, as well as the pyrometallurgical route in works or conversion facilities that buy or process white metal and produce copper and other metals associated with this such as gold and silver, besides sulfuric acid, plants which should be strategically located in zones with high sulfuric acid price to make this a product which contributes to the profitability of the business.

Jan 1, 1999