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By Ian M. Ritchie

Right across the universities of the developed world, the traditional disciplines of physics and chemistry are losing ground. Extractive metallurgy, which depends so heavily on chemistry, is also contracting despite a clear need for people with this kind of training in the mining industry. Reasons for this loss of popularity are discussed in this paper. High on the list is one of image. The extraction of metals is widely seen as a dirty, polluting, sunset industry which involves working in remote and uncomfortable corners of the earth for inadequate compensation. Ways in which the image problem can be overcome are considered. It is concluded that a concerted effort needs to be made by the universities and industry to redress this situation. The importance of extractive metallurgy, both now and in the future, when a greater emphasis will be placed on sustainability and recycling, needs to be stressed. In addition, courses need to incorporate training for a career path that leads on beyond extractive metallurgy.

Jan 1, 2003

By Jeff M. Kuhn

A new solvent extraction process for the removal of halides from zinc sulphate solution was tested in pilot plants at both a 0.1-L/min scale and at a 3-L/min scale. Teck Cominco?s process is called the HalogonTM process, for which patents are pending. Mixer-settlers were used for the 0.1-L/min pilot scale and two BATEMAN pulsed columns for the higher rates. Pilot testing was performed with commercial zinc sulphate solutions containing variable amounts of chloride and fluoride. Sulphate extraction was also controlled and deleterious halides were loaded and stripped into a form suitable for disposal. The engineering aspects and economics of this solvent extraction process for halide removal are also reported.

Jan 1, 2003

By T. Manlyama

The Tamano Smelter of Hibi Kyodo Smelting CO., Ltd. went into operation in 1972. The Flash Smelting Furnace that was originally adapted was equipped with electrodes that were attached to the settler substitute of the slag cleaning furnace. Later the development of our own original coke combustion technology was promoted and a new Tamano Type Flash Smelting Furnace (T-FSF), without electrodes, was put into operation in 1988, T he technology of coke combustion and combustion the burner have continued to improve. As a result the copper losses in the Wag have been reduced as well as a stable operation has been achieved, Furthermore; this has been accomplished while increasing the concentration feed and the matte grade. The current objective is to continue to strive for high matte grade operation and to raise production efficiency while paying attention to the important subject of copper losses in the slag. In this report, the data related to the copper loss in the slag reduction are presented along with the influence of the thickness, settling time and coke. The recent operation conditions of the T-FSF are also presented.

Jan 1, 2003

By C. P. Manning

This paper reports recent progress in the development of a unique metal extraction technology utilizing zirconia-based inert anodes for the electrolytic reduction of metals from their oxides. In this process, the target metal oxide is dissolved in an ionically conducting liquid solvent phase. An extended anode consisting of an oxygen-ion-conducting stabilized zirconia membrane in intimate contact with a catalytically active electronic phase and an inert electronically conducting cathode are inserted into the molten flux containing the oxide. When the appropriate electric potential is applied between the electrodes the target metal is reduced at the cathode and oxygen ions are selectively transported across the stabilized zirconia membrane and oxidized at the anode. When the process is conducted at temperatures between 1200-1400°C, the ohmic resistance drop across the stabilized zirconia membrane is low, and high current densities on the order of I A/cm2 or greater can be obtained. In addition, the process efficiency can be increased further by directly reforming hydrocarbon fuel over the anode. Laboratory experiments at Boston University have demonstrated the technical viability of employing zirconia-based inert anodes for environmentally sound production of metals such as magnesium, tantalum, aluminum, etc., directly from their oxides. Significant progress has been made in the application of this concept to the electrolytic reduction of magnesium at 1300°C. The research topics covered include stability of the zirconia membrane in the selected molten solvent (flux), volatility of the flux, electrochemical characterization of the electrolytic cell, and analysis of the metals produced.

Jan 1, 2003

By Michael Zinigrad

The quality of metallic materials depends on their composition and structure and these are determined by various physico-chemical and technological factors. To effectively prepare materials with required composition, structure and properties it is necessary to carry out a research in two parallel directions: Comprehensive analysis of thennodynamics, kineties and mechanisms of the processes taking place at the solid-liquid-gaseous phase interface during welding processes and development of mathematical models of the specific welding technologies. We have developed unique method of mathematical modeling of phase interaction at high temperatures. This method allows us to build models taking into account the thennodynamic characteristics of the processes, the influence of the initial composition and temperature on the equilibrium state of the reactions, the kinetics of heterogeneous processes, the influence of the temperature, composition, hydrodynamic and thennal factors on the velocity of the chemical and diffusion processes. The model can be implemented in the optimization of various technological processes in welding, surfacing, casting as well as in manufacturing of steels and non-ferrous alloys, materials refining, alloying with special additives, removing of non-metallic inclusions.

Jan 1, 2003

By Mitsutaka Hino

The contents of gangue minerals, such as Al2O3. P2O5, crystalline water and so forth in the iron ore imported to Japan tend to increase year by year. Though the increments of such gangue contents arc approximately 0.1-0.2 mass%, some problems for the blast furnace operation in ironmaking process have already been reported, In order to clarify the mechanism of harmful effect caused by the small increment of gangue minerals, mainly Al2O3. on the blast furnace operation, the dripping behavior of Fe,O-CaO-SiO2-Al2O3-MgO slag from the iron funnel, which simulated the micro-porosity in sinter ore, has been observed with the wide range of basicity, Al2O3, Fe2O and MgO contents. The effect of MgO on the dripping behavior of slag has been summarized in this paper. It was found that the addition of 2mass% MgO resulted in large increase of hold-up on the most of the conditions. When Fe2O content was less than 20mass% and the basicity was lower than 0.8, MgO lowered the hold-up even if the slag contained 10mass% Ah03. Every slag hold-up showed the minimum at the basicity of less than unity on the conditions of constant Fe2O and Al2O3 contents, This trend became remarkable when the slag contained 2 mass% MgO.

Jan 1, 2003

By Zdzistaw MiGzkowski

At KGHM Polska Miedi S.A. a direct flash smelting process is used for smelting of chalcocite concentrate for the production of blister copper. The paper presents a model of complex oxidation process of single concentrate grains smelted at KGHM. The description covers main chemical reactions, phenomena of heat and mass ex-change inside the grains and between a grain and the surrounding space. In the model, two zones describing the course of process inside the grain were distinguished: ? The first one, which moves faster towards the centre of a grain, both organic and carbonate carbon are freed. The process takes place without the presence of oxygen and results in an increase of the temperature in the core of the particle. ? The second zone moves slower into the grain and the rate of the movement is deter-mined by the presence of oxygen. In that zone the sulphur is eliminated and the oxidation of the organic compounds vapours moving from deeper layers of a grain takes place. Based on the results of laboratory tests, the coefficients that describe the oxygen transportation into the grain and decide the progress in the chemical reaction were determined. The paper contains the results of model calculations for single grains reacting in environment of various content of oxygen as well as the results of model calculations for the laboratory reactor system.

Jan 1, 2003

By Mônica Suede Santos Silva

This work describes characterization of the performance of the tundish of a six strand continuous casting unit of the Companhia Siderúrgica Belgo Mineira, João Monlevade, Brazil using physical modeling. Permanent and transient conditions, due to ladle metal composition changes are considered. Pulse and step tracer addition techniques are employed to assess the control variables. For transient conditions the degree of inter-mixing and the minimum residence time are determined with a view to optimize the process especially during the grade changes of steel.

Jan 1, 2003

By Helmut Antrekowitsch

Nowadays nearly the half of the world zinc production is used for galvanizing. After their life span most of the galvanized products return as scrap to the steel mill During the steel process the zinc is collected in the flue dust It is astonishing to notice that between 40 and 50 % of the zinc produced is brought into the steel processing cycle by the coated scrap while only 3 to 5 % of the zinc production can be covered by the recycling of the zinc-bearing steel mill dusts. Responsible for this worse ratio is the fact that the established recycling technologies suffer from high energy consumption, low zinc yields, halogen problems and hardly any iron recovery. A development of new or an optimization of current recycling procedures for the dusts is unalterable because of increasing zinc amounts in these residues and the rising costs for the disposal. Different pyrometallurgical recycling technologies are tested in rotary kilns and vertical retorts at the Department of Nonferrous Metallurgy, University of Leoben, Austria. Various reducing agents from carbon monoxide to hydrogen and combinations are used. The results should make it possible to draw conclusions that allow an economical and ecological judgement of the different varieties. The goal is to support the affected industry to increase the low recycling rate and prevent a loss of high zinc values in the steel industry filter dusts.

Jan 1, 2003

By Ian M. Ritchie

Cementation or metal displacement reactions such as Cu2+ + Fe Cu + Fe2+ are among the oldest known hydrometallurgical reactions. They are still used in the recovery of some metals and in the purification of process liquors and waste water streams. However, they are often more complex than the stoichiometric reaction would suggest because they involve the simultaneous deposition of one metal onto a second which is dissolving. For example, sometimes a cementation will not take place, even though it is thermodynamically favoured. On other occasions, a cementation reaction will start but come to a halt as the depositing metal blankets the reacting surface. On yet other occasions, side reactions, catalyzed by the deposit, can be important. In this paper, the electrochemical basis of cementation reactions is described. The conditions for each of the complications encountered in these reactions are described and illustrated by examples drawn from a number of hydrometallurgical processes. The cementation reaction between activated carbon and gold thiosulfate is also briefly described, this reaction being unusual in that no dissolution of the carbon occurs.

Jan 1, 2003

By Supachai Surapunt

The distribution behavior of V A minor elements (As, Sb and Bi) in the smelting stage of the Mitsubishi process were evaluated thermodynamically based on thermodynamic data and operating data. The fractional distributions between the gas, slag and matte phases considered as the degree of vapor saturation of 1.0 are as follows: 53.8, 27.2 and 19% for As, 23.6, 56.6 and 19.8% for Sb, and 91.3, 1.1 and 7.6% for Bi, respectively. Arsenic is mostly distributed to the gas and slag phases. It is effectively eliminated by volatilizing and slagging. Antimony is mainly in the slag phase, which is suitably removed by slagging. Bismuth is easily vaporized to gas phase. The degree of vapor saturation has a large effeet on the distribution behaviors of the three elements between the three phases. The amount of a minor element in the charge has an effect on the distribution of As but no effect on the distributions of Sb and Bi. Increasing matte grade and temperature results in the change of distributions for As and Sb, significantly. The change in the distribution ratio between slag and matte phases also considerably affects the distributions of As and Sb. The distribution behavior of Bi is not significantly changed by the change in matte grade, temperature and distribution ratio.

Jan 1, 2003

By Chu Yong Cheng

Synergists can be used in solvent extraction to improve the selectivity of extractants for metals. Research work carried out by the SX group at the AJ Parker Cooperative Research Centre for Hydrometallurgy / CSIRO Minerals has shown that the pH isotherm of nickel with Versatic 10 was significantly lowered by the addition of the synergist Acorga CLX50. The paper discusses how this synergistic shift can be used to alleviate a gypsum formation problem at Bulong nickel laterite operation in Western Australia. Metal pH isotherms were obtained with Versatic 10 and synergist CLX50 using synthetic leach solutions. In terms of pH50, the extraction order of the metals with 0.5 M Versatic 10 alone was Cu > Zn > Ni > Co > Mn > Ca > Mg, whilst the extraction order with Versatic 10 and 20% by volume CLX50 was Cu > Ni Zn > Co > Mn > Ca > Mg with the pH50 (Mn-Co) significantlyincreased. This is significant because the isotherms of valuable metals Ni, Cu, Co and Zn shift more towards low pH than those of the waste metals Mn, Mg and Ca, resulting in a possible good separation of Ni, Cu, Co and Zn from Mn, Mg and Ca. The use of intermediate precipitation, solids/liquid separation and re-leach in the three Western Australian nickel plants make these processes complicated and costly in capital and operation. The research work carried by the SX groupat the AJ Parker Centre has led to the development of direct SX (DSX) processes to recover nickel and cobalt from leach solutions using synergistic organic systems. Semi-continuous tests with a BHP Billiton pilot plant leach solution showed that Ni and Co together with Zn and Cu were separated from the major impurities, Mn, Mg, Ca, and Cl, in the first SX circuit. The co-extracted impurities were easily scrubbed. After stripping, Ni and Co together with Zn and Cu were concentrated, resulting in a much smaller second SX circuit in the down stream processes.

Jan 1, 2003

By A. González

Arsenic is one of the main contaminants present in Chilean copper concentrates and its abatement represents a challenge for the process metallurgy, particularly under the strong environmental requirements in the global community. The possibility to form ferric arsenate directly from a gas phase by means of a heterogeneous reaction between an arsenic gas bearing and iron oxide was studied at laboratory scale. A thermodynamical analysis for the system Fe-As-O-S has been initially made, in order to obtain the stability conditions for the ferric arsenate or other FexAs2O2 type compounds. Experiments were made using an hematite sample suspended in a thermogravimetric device. AS4O6 gas generated from solid AS203 that was passed through the iron oxide sample and its instantaneous weight change was recorded directly. A kinetic study for the AS4O6 volatilization was made to control the gas composition. A chemical control between 300 and 600°C with an apparent activation energy of around 14 Kcal/mol As2O3 was determined. The samples after the reactions were chemically and XRD analysed. Arsenates detected corresponds to complex compounds. Results shows a dependence on temperature and oxygen content in the gas phase. The kinetics for iron arsenates formation is slow, reaching an arsenic capture of 6% after 80 minutes of reaction when an oxygen content of 50% is fed continuously at 800°C and 3,56% As in the gas. Experiences made at the same temperature but under higher oxygen content in a closed reactor, allowed arsenic capture close to 60%. For higher temperatures the capture is considerably lower.

Jan 1, 2003

By Vladimir Kislik

Competitive complexation/solvation theory of solvent extraction constitutes a general framework for interpretation and quantification of ion-molecular interaction data in extraction systems. Depending on extracting metal -- solvent affinity constant and metal concentration ratios, four possible stages of extraction behavior and interacting mechanisms, are considered. Affinity constant ratios are easily acceptable through the independent measurements of three-component systems. Once determined and tabulated, the affinity constant ratio data may be used in any system of interest. Mathematical descriptions of the results are introduced for different interactions. Active solvent (including water) concentrations in the organic phase and temperature are included to the quantitative consideration. The theory allows direct comparison of the complexing/solvating power (competition order) of various extractants, active solvents and diluents. As a result, predictions for the extraction effectiveness and selectivity are possible. Some metal extraction systems are analyzed on the base of the theory. Analysis gives a key for preliminary quantitative prediction of suitable extraction systems.

Jan 1, 2003

By Guo Xueyi

The electrochemical couple behavior of manganese dioxide with ferrous/ferric ions in acidic chloride medium was investigated, It was proven that the dissolution of Mn01 is due to the electrochemical couple reaction between MnO2/Mn2+ and Fe2+/lFe3+ in the solution, The driving force for the process originates from the rest potential difference of the two couples. The reduction of Mn02 is controlled by clectrochemical kinetics, whereas the conversion of F e2+ to Fe3+ is limited by diffusion, The factors such as the Mn2+, Fe2+, Fe3+, Cl concentration, pH of the solution and the temperature, have much influence on the kinetics of the couple process, This study will be useful to elucidate the mechanism for the leaching of manganese nodule from the deep ocean as well as manganese dioxide ores in land,

Jan 1, 2003

By Jerome P. Downey

Technologies developed within the field of extractive metallurgy to recover, concentrate, and purify metals and industrial minerals from ores, have served as the foundation for all of the subsequent environmental remediation, materials recycling, and waste management technologies. This paper discusses the application of classical extractive engineering principles to the development of a thermal process for the recovery of mercury from solid wastes. Process development is presented as a series of logical stages, which begin with a thorough characterization of the site-specific waste, move on to bench and pilot scale testing of the process options, and end with a functional process flowsheet. This paper also presents thermodynamic data on many mercury species of interest to the minerals, power, and chemical industries. These data can be used to model the speciation and recovery of the mercury as a function of various process parameters.

Jan 1, 2003

By Catherine Williams-Beam

Thallium is more toxic to humans than mercury, cadmium, lead, copper or zinc. Its chemical behavior resembles the alkali metals (K, Rb, Cs). It occurs almost exclusively in natural waters the monovalent thallous cation. The solubilities of thallous compounds are relatively high so that monovalent thallium is readily transported through aqueous routes into the environment. The major sources of thallium are the base metal sulfides and precious metal bearing sulfides. Therefore, it is often present as a contaminant constituent in waters emanating from heavy metal sulfide bearing deposits. Thallium can be effectively removed from wastewater to <2 µg/L by reductive precipitation of thallium sulfide. Effective thallium sulfide precipitation requires a controlled solution potential/pH combination. The required potential can be effectively achieved by utilizing a particulate iron slurry or packed column environment. Experimental results will be presented and discussed.

Jan 1, 2003

By C. A. Morais

The present work describes the development of an efficient and relatively simple process to obtain high grade CeO2 from a mixed rare earth chloride solution. The process involves cerium oxidation and precipitation by addition of a KMnO4-NaCO3 solution. The experiments were carried out at room temperature (25 1° C). The results indicated that the major parameters affecting cerium recovery are the molar ratio of KMnO4/Ce, the initial acidity of the chloride feed solution and final pH of Ce(OH)4 precipitation. In strong acid solutions (pH < 1), the oxidation of Cl to Clo took place in addition to the oxidation of Ce(III) to Ce(IV), so increasing the permanganate consumption. Conversely, low acidity (pH >3) led to coprecipitation of the other rare earth elements. Under the selected conditions, cerium was selectively precipitated as ceric hydroxide, together with some manganese dioxide. Further purification was carried out by the dissolution of Ce(OH)4 in HCl, followed by precipitation as cerium carbonate. The filtrate was neutralised with a Na2CO3 solution in order to recover the associated rare earth elements for further separation. The final product, assaying 99.7 % CeO2, was obtained with a recovery of nearly 100%.

Jan 1, 2003

By Patrick R. Taylor

The synthesis of high-purity ultra-fine barium strontium titanate powders (BST: BaO6Sro.4TiO3) has been performed in a non-transferred are D.C. thermal plasma reactor. Slurries of aqueous solutions of dissolved barium and strontium nitrates and solid titanium dioxide powders were used as precursors. Oxygen and argon were used as carrier gases, and pure argon and combinations of argon and nitrogen were used as plasma gases. The plasma torch power was varied, as well as the oxygen flow rate and the total molar concentration of the precursors. A graphite plate was designed to protect the torch electrode and lower the level of impurities in the product. A thermochemical analysis of the Ba(NO3)2-Sr(NO3)2-TiO2-H2O-O2 system was performed to predict the conditions for the formation of BST and the feasibility of the reaction, The powders collected from the different sections of the reactor were characterized using Transmission and Scanning Electron Microscopy, X-Ray Diffraction, and ICP chemical analysis. The powders produced showed high conversion to BST, ultra-fine particle size (< 30 rim) and high purity, which makes this a potential process to produce ceramic materials for electronic devices.

Jan 1, 2003

By Sang Han Son

The vapor pressures of FeCI2 and ZnC12 in the FeCl2-ZnCl2 system were measured by the transpiration method at 873K and 917K. The vapor pressure data were interpreted to indicate the formation of complex ions in the FeCl2-ZnCl2 melts. It is presumed that the complex molecule FeZnCl4 as well as FeCI2 and ZnCI2 exists in the vapors in equilibrium with molten FeCl2-ZnCl2 mixtures. The activities in the FeCl2-ZnCI2 system are shown a negative deviation from Raoult&apos;s law. These results suggest the formation of complex ions such as ZnCl42- in molten FeCI2-ZnCI2 mixtures.

Jan 1, 2003