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By D. Van Dooren

The final goal of the research project is to develop a 3D FEM model that is able to predict the kinetics and micro-structural evolution during the bainitic transformation. The input parameters consist of thermodynamic and atomic mobility data obtained from the ThermoCalc and mCTRA databases combined with structural mechanics data extracted from the stress-strain curves of the fcc and bee phases. In this paper the general principles of the model are outlined and some interesting preliminary results are shown and commented. The full implementation of the model has presently not been achieved yet. In the model the bainitic transformation is considered as a sequence of martensitic (re)nucleation and growth of a ferritic subunit followed by the carbon rejection into the surrounding austenite. The (re)nucleation of the subunits will be described through a non-classical martensitic nucleation criterion. Once a nucleus has been activated at a specific location in the material, a full-sized subunit is instantaneously formed through a displacive mechanism. The stress state in the system that arises due to the transformation strain can be calculated by a 3D FEM programming code. Immediately after the formation of the subunit, another 3D FEM programming code calculates the carbon diffusion from the supersaturated ferrite into the surrounding austenite. The resulting stress state and carbon profiles will be used to determine where and when a new subunit will nucleate based on a renucleation criterion. Keywords: Bainitic Transformation, Modeling, Eshelby, Carbon Diffusion

Jan 1, 2003

By A. E. M. Warner

Inco Limited has long and extensive experience in converting nickel-copper primary smelting mattes over a broad range of nickel/copper weight ratios and combined nickel-copper-cobalt contents. At the Copper Cliff Smelter, the composition of the converter product matte has to meet the requirements of the matte separation process; at the Thompson Smelter, converter matte of a different composition is cast into anodes for nickel electrorefining; and in Soroako, Indonesia, a very low copper product matte is granulated for the Japanese market. Recently, Inco has conducted pilot plant testing of three possible nickel-copper matte continuous converting routes, namely flash converting, oxygen top blowing-nitrogen bottom stirring, and tuyere blowing. This test work has generated substantial new information on nickel-copper matte converting chemistry. This overview paper reviews the metallurgy of nickel-copper matte converting, in particular the behaviour of cobalt and the operating conditions required to meet the iron and sulfur specifications of the product matte. The relevant thermodynamic information is used to discuss the industrial data.

Jan 1, 2003

By Mikiya Tanaka

This paper outlines our attempt to establish a recycle process of nickel in the spent baths and waste rinse water of electroless nickel plating plants using solvent extraction and solvent-impregnated support, Solvent extraction studies of nickel from actual spent baths revealed that (i) nickel is efficiently extracted by a hydroxyoxime extractant such as LIX84I at a pH greater than 6 and is readily stripped with sulfuric acid, and (ii) the mixtures of LIX63 and acidic organophosphorus extractants (D2ERP A, PC88A, and Cyanex 272) enhanee the nickel extraction efficiency to a sufficient degree without pH adjustment, but at the same time, reduce the stripping efficiency. The application of acidic organophosphorus extractants to selectively remove impurity metal ions (iron and zinc) from a real spent bath before extracting nickel lead to the finding that PC88A and Cyanex 272 effectively remove iron and zinc without pH adjustment leaving nickel in the raffinate. The removal of nickel from the waste rinse water was also studied. Solvent-impregnated supports with a macroporous resin and oil sorbents made of natural kapok fiber and synthetic fiber as supports were applied using D2EHPA and LIX860 as the extractants. During the batch operation, nickel is removed with a high efficiency without pH adjustment. During the column operation, however, the effective removal is hindered by (i) the dissolution of the nickel-D2EHPA complex into the aqueous phase in the high loading region, and (ii) the slow removal rate of the LIX860-impregnated support.

Jan 1, 2003

By Guo Xueyi

The reaction mechanism for the manganese dioxide reductive dissolution in acidic chloride media in the presence of ferrous/ferric ions are based on theoretical delineation and dual cell experiments. In terms of the Buttler-Volmer equation and chemical kinetic principles, a electrochemical kinetic equation was deduced, which successfully provided a theoretical basis for describing the role of Cl-, Fe2+, Fe3+ and H+ in solution, as well as their interrelationship in manganese dioxide reductive dissolution. Dual cell experimental studies indicate that the increases of Cl- and Fe2 in solution are helpful to accelerate the couple process; while, Fe3and Mn2+ hinder the coupled reaction to some degree. Higher acidity in solution is beneficial to the dissolution of MnO2. All the dual cell experimental results are consistent with the theoretical deduction. This study will be useful to understand the mechanism for the leaching of manganese nodules from the deep ocean, as well as the leaching of manganese dioxide ore from land.

Jan 1, 2003

By Joe Milbourne

The potential for treating copper-nickel-cobalt-platinum group metal concentrates by a fully hydrometallurgical route is discussed. Processes specifically developed for treating these feeds and the potential application of the processes developed for the treatment of chalcopyrite copper concentrates are included in the evaluation. Block flowsheets are provided and the technical characteristics of various processes are compared. The current state of development for each process is summarized and probable economic impacts of the technical features are qualitatively assessed. Perceived risks and rewards associated with each technical concept are provided in the conclusions.

Jan 1, 2003

By G. A. Brooks

Increasing interfacial area through gas injection is one of the main methods for accelerating reaction between slag, metals, and gases in modern pyrometallurgical reactors. In slag-metal reactors, the generation of a large number of metal droplets into the slag phase through high gas velocity has a much larger effect on the overall kinetics compared to the enhanced mass transfer through mixing. Top blowing technology generates large interfacial areas (>300 m2/tonne) through high impingement gas velocity at short distances between the exit of the injection lance and the metal-slag interface. Phase separation may become a limit at the case of very high interfacial areas, though there is still only limited understanding of the trajectories of metal droplets in slag-metal-gas emulsions.

Jan 1, 2003

By Gabriel Plascencia

Copper was oxidized in the temperature range from 300 to 1000 °C under different pressures of oxygen, In the range from 300 to 500 °C, copper oxidizes following the logarithmic rate law; while in the range from 600 to 1000°C oxidation follows the parabolic rate law. Transition from logarithmic to parabolic growth occurs at about 525°C. X-ray diffraction was performed on oxide scales to account for the CuO/Cu2O ratio at different temperatures. Activation energies found in this work are in good agreement with reported values.

Jan 1, 2003

By Sabine Knoll

The thermodynamic properties of four liquid ternary zinc alloys, Au-Sn-Zn, Ag-Sn-Zn, AI-Sn Zn and Cu-In-Zn were measured with an electromotive force (emf) method at three or four cross-sections with an constant X:Sn or Cu-In ratio. At the Au-Sn-Zn and AI-Sn-Zn system calorimetric measurements were also carried out in order to compare the integral enthalpy of mixing from the direct measurements with the data of the emf measurements, which were derived by Gibbs-Duhem integration.

Jan 1, 2003

By Gabriel Plascencia

Copper was oxidized in the temperature range from 300 to 1000 GC under different pressures of oxygen. In the range from 300 to 500°C, copper oxidizes following the logarithmic rate law; while in the range from 600 to 1000°C oxidation follows the parabolic rate law. Transition from logarithmic to parabolic growth occurs at about 525°C. X-ray diffraction was performed on oxide scales to account for the CuO/Cu2O ratio at different temperatures. Activation energies found in this work are in good agreement with reported values.

Jan 1, 2003

By Rodney J. Ishak

The reduction of Mn3O4 to MnO has been investigated in a thermobalance apparatus, The charge was composed of manganese ore (decomposed by heating/calcination or pre-reduction to mainly Mn3O4) and coke. The material was charged to a crucible, which was suspended in the balance. CO-gas was distributed through a grid in the bottom of the crucible. Two sizes of ores were used; 2.4-4.8 mm and 6,7-9.5 mm. Coke particles were in the size range 4.8-6.7 mm. Experiments were conducted in the 900-1100°C temperature range. The composition of the product gas was monitored continuously. External mass transport between bulk gas and particle surface does not seem to limit the rate of reduction. Assuming that both diffusion through product layer and chemical reaction at the interface between MnO and Mn)04 are rate controlling, the data was tried both in a shrinking core model and in a grain model using regression. The grain model gives the best physical description of the process, because the reactant is in fact a porous medium. With this model the effective diffusivity was calculated to be in the 1.5-6.10.5 m2/s range. The pore size was mainly between 0.1 and 10 um,

Jan 1, 2003

By Dan Adams

A number of gas-liquid processes require high intensity agitation systems to provide uniform blending and dispersion of reactants in order to achieve desired end products. Processes such as hydrogenation, fermentation, and minerals processing have used conventional down pumping or radial agitation systems with some success. In 1996, LIGHTNIN introduced the concept of Up-Pumping to the industrial marketplace as an improved mixing technology for these applications. For processes requiring gas-liquid mass transfer, such as those listed above, conventional mixing technology requires the use of gas introduction devices (sparges) below impellers. These devices can be a maintenance concern due to plugging and erosion in the presence of solids. Up-Pumping impeller systems are able to draw in a significant amount of gas from the headspace, much more so than conventional vortexing impellers designed for headspace gas incorporation. This paper will demonstrate the effectiveness of Up-Pumping impeller systems that have the potential to eliminate need for sparge devices entirely. It demonstrates the ability of Up-Pumpers to re-entrain gas for higher utilization compared with conventional impeller technology. This is significant in applications using costly gases such as enriched oxygen or hydrogen, reducing overall operating costs of production.

Jan 1, 2003

By V. A. Luganov

The behavior of arsenopyrite under heating has been studied by many scientists. It has been already established that under heating at more than 650°C and without air access the arsenopyrite dissociates with the formation of one atom arsenic. Under vacuum the dissociation process begins at 550 DC with the formation of elemental arsenic. The residue of dissociation process contains pyrrhotite and throilitc. In the presence of pyrite, arsenopyrite dissociates under lower temperature and with a higher velocity than without it. The industrial realization of fool scale processing of arsenic bearing raw materials is possible only by the use of standard equipment and oxygen containing blast In this view the paper presents the results of the study on the effect of oxygen in the gaseous phase and its addition into the charge of pyrite in the process of arsenopyrite decomposition. Thermodynamic analyses showed that under thermal processing of arsenopyrite in the presence of pyrite and limited quantities of oxygen in the gaseous phase the formation of arsenic sulfides is possible according to the following reactions:

Jan 1, 2003

By R. E. Molnar

A number of flowsheets have been designed and operated, or are currently being considered, to extract copper from leach solutions having much more copper than the 4 g/L levels typically found in heap leach liquors. Dealing with these solutions has required that the envelope for ?normal? copper solvent extraction be pushed beyond the usually considered limits. Others have published information on flowsheets to recover copper from leach liquors containing over 25 g/L copper. Secondary solvent extraction circuits are often required to attain satisfactory overall recoveries. This paper reviews some of the issues faced in three pilot plant circuits that were operated by SGS Lakefield Research to produce cathode copper from solutions containing 8 to 20 g/L Cu. The primary objective was to maximize copper extraction using one solvent extraction circuit. The role of feed acidity and the disposition of impurities such as iron and chloride are considered. The challenges of running short SX piloting campaigns are discussed.

Jan 1, 2003

By Devon A. Hannan

Thermodynamic modeling calculations were undertaken for the recovery of mercury from HgTe using a vacuum retort reactor. However, discrepancies were noted in the available thermodynamic data which introduced uncertainty in the model results. Consequently, a series of transpiration experiments were first undertaken on the thermal decomposition of HgTe into an inert carrier gas stream according to the following reaction: HgTe(s) Hg(g) + Te(s) From the measured weight loss of the HgTe samples, the Gibhs free energy change for the above volatilization reaction was determined as a function of temperature. The experimentally determined Gibbs free energy values were found to be approximately 30% larger (more posi-tive) than the values available in databases such as HSC Chemistry. By conducting a second-law analysis on the experimental data, the heat of formation of HgTe at 298.15 K and the en-tropyat 298.15 K were determined, which then formed the basis for a new database for the modeling calculations. The results of this study showed that HgTe was more stable at elevated temperatures than was generally indicated in the literature. The new database is given in a for-mat for direct insertion in HSC Chemistry. Using the new database, modeling calculations were conducted to examine the effects of the re-tort pressure and the molar ratio of purge gas to HgTe on the volatilization of mercury from HgTe. A diagram is presented that shows the minimum temperature for 100% volatilization of mercury from HgTe as a function of retort pressure for different molar ratios of purge gas (N2) to HgTe. For example, it was found that the minimum temperature for 100% volatilization could be decreased by 175 K, at a retort pressure of 0.05 bar, if the molar ratio ofN2 to HgTe is increased from 1.0: 1 to 100.0: I.

Jan 1, 2003

By Takahiko Okura

Most non-ferrous raw materials are associated with sulphur. To extract the metals, the sulphur is recovered typically as Sulphuric acid or liquid S02. On the other hand, natural gas may contain over 20% of hydrogen sulphide (H2S) and a huge quantity of elemental sulphur is produced through oil and gas refining processes in the world. A large fraction of the sulphur mined from natural sources is eventually returned to the earth as fertilizers, by-products of desulphurisation and neutralisation processes, or as fugitives to the atmosphere. However, the supply and demand for sulphur are in imbalance. Such situation urges to develop a new smelting process without sulphuric acid production. This paper briefly reviews the global sulphur balance and the technologies for recovering elemental sulphur. The core of this paper is a proposal to convert S02 gas to elemental sulphur by using organic materials. Some results of thermodynamic calculations and experiments are presented.

Jan 1, 2003

By Satoshi Itoh

Phase equilibria and activities of the components in the liquid lead-antimony-oxygen ternary system, which is of fundamental importance for discussing the' recovery of lead and antimony from a used lead-battery, have been investigated at 1173 and 1223 K. The two liquid phases of metal and oxide were observed at the temperatures studied, and the tie lines indicating isoactivities were determined. The activities of PbO, SbO1.5 and Sb2O3) in the PbO-SbO1.5 and PbO-Sb2O3 pseudo-binary systems were then obtained by applying the Gibbs-Duhem equation to the phase relation of metal-oxide equilibrium. Both in the pseudo-binary systems the activities exhibit negative deviations from Raoult's law. The vapor pressures of lead, antimony and lead oxide, antimony oxide were calculated by using the activities of the components in the lead-antimony-oxygen ternary system. As a result, an oxidation of antimony concentrated in an anode slime followed by evaporation as antimony oxide Sb406 was found to be considerably effective for the recovery of lead and antimony from a used lead-battery.

Jan 1, 2003

By Brajendra Mishra

Molten Salt electrolytic processes offer unique opportunities to extract and refine metals where gaseous or metallothemlic reduction, hydrometallurgical extraction and aqueous electrolytic methods are thermodynamically constrained. Production of aluminum and magnesium by molten salt electrolysis are well known commercial processes. Several other reactive metals, such as lanthanides and actinides, as well as beryllium and calcium, make use of molten salt processing for extraction and refining. This presentation describes the science of molten salt chemistry and electrochemistry for winning and refining of several metals. In addition, recovery of metals from waste process salts by molten salt reduction as well as oxidation have been discussed. Material issues in design of molten salt reactors have been included. Various applications have been presented through case studies. Experimental data have been included to justify the suitability as well as limitations of these specific processes.

Jan 1, 2003

By Varadarajan Seshadri

The performance of mould fluxes in satisfying its quality requirements can have a significant effect on the efficiency of the continuous casting process and on the surface quality of the products. This performance is affected by various parameters including the characteristics of the mould fluxes, the quality of the steel being cast and the operational conditions of the caster. The extremely complex relationships involving the parameters mentioned above make it very difficult to have simple criteria for selecting mould fluxes for casting a certain grade of steel in a continuous casting machine. These difficulties led steelmakers and mould flux suppliers to select mould fluxes based mainly on plant trials. In the present work, a software to help in the analysis and development of mould fluxes for continuous casting was developed_ This software includes several models for prediction of mould flux viscosity and consumption. A mathematical model was also used to predict the heat flux through the mould flux. The proposed methodology was applied to continuous casting of crack sensitive steels_ Some of the results given by this software are presented, discussed and compared to plant data.

Jan 1, 2003

By Florian Kongoli

The production of a homogeneous self-fluxing sinter is an important step in iron making processes. A good sinler should have good permeability and reducibility and has to keep those characteristics for a certain time. An early melt down of the sinter in the blast furnace, where its solid state reduction is essential, would cause many problems such as low permeability and reductibility. Nevertheless, the important factors that influence these characteristics, such as the chemistry of the sinter and the fluxing effect during sintering and sinter reduction conditions have not yet been clarified, In today's new reality where many new minor components such as Al2O3 and MgO enter to the sinter through raw materials, the quantification of the fluxing effects during sintering becomes even more important. In this work, the liquidus surface and phase relations of the sinter primary melts in the CaO-FeO-Fe203-Si02 system at sintering conditions have been quantified. The fluxing effect of oxygen potential, Al2O3 and MgO has also been quantified by the means of some practical diagrams that can directly help the optimization of the sintering processes.

Jan 1, 2003

By R. W. Lawrence

A high rate biological reduction technology has been developed to provide low cost hydrogen sulphide for various uses in water treatment and metallurgical processes. Commercial operations produce sulphide safely at a fraction of the cost of chemical sulphide. The biologically produced H2S is used for treatment of acid wastewater and selective metal recovery whereby metals present in wastewater streams are recovered in high grade metal sulphide concentrates that are sold to smelters. The combination of biological H2S production and selective metal recovery is currently marketed under the process name BioSulphide-Thiopaq. The process can be applied on a stand-alone basis or in conjunction with a conventional lime water treatment. Process advantages include: reduced lime treatment costs, reduced volume of waste sludge free of toxic metals leading to reduced long term environmental liabilities, selective recovery of metals and, in some cases, net profit from water treatment achieved through the sale of metal concentrates. Three case studies are presented to provide examples water treatment and metal recovery: the Caribou Mine, New Brunswick; the Phelps Dodge Bisbee operations, Arizona; and Falconbridge?s Raglan nickel mine in Quebec. A fourth case study is presented to highlight environmental control for treatment of ARD in the Leadville mining district of Colorado. Process flowsheets, capital and operating costs are presented for the four case studies

Jan 1, 2003