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By Rajesh Kumar Mishra

About 500,000 troy ounces of Platinum Group Metals (PGM) will be available for recycling each year from spent automobile catalytic converters in North America alone. Platinum Group Metals? from spent catalyst can be extracted by Hydrometallurgical, Pyrometallurgical or Gas Phase volatilization processes. This paper is a review and comparative study of various processes investigated for PGM extraction. A number of processes described in this paper have already been commercialized. The technical and environmental aspects of the important processes are discussed.

Jan 1, 1989

By R. D. Brittain

In order to analyze and control the transport of harmful trace-element impurities in various smelting processes, it is necessary to have fundamental information about the chemical thermodynamic properties of the pertinent condensed and vapor phases. This paper describes recent thermodynamic studies of the gaseous arsenic sulfides and of the activity of arsenic in a copper-iron sulfide matte phase. These studies were carried out by high temperature mass spectrometry and by effusion vaporization techniques, which permitted clear identification of the molecular species involved, a decided advantage in such complex systems. The nature of the results obtained and comparisons with previous interpretations will be described.

Jan 1, 1983

By S. A. Davis

In July of 1996, the Kroll process began production again at TIMET's Henderson, NV, manufacturing facility. This, after being shut down for several years due to low market demand for titanium. Faced with limited pond capacity and increasing costs for water and wastewater disposal and storage; process changes were made to recycle water used to wash Kroll titanium sponge back into the sponge leaching process. This idea was revisited from 1992-93, when three consecutive attempts to recycle water for this application were unsuccessful due to early pump failure. Since it was uncertain why previous attempts failed, a complete understanding of the existing system was first sought. This included reviewing piping and flow diagrams; taking field measurements for all the piping, valves, and fittings; analyzing the wastewater composition; and modeling the fluid dynamics and control of the system. The fluid dynamics of the system were modeled by breaking the piping network up into nodes and applying the Bernoulli equation to each segment. The fluid flowrate control valves were modeled for this purpose also and the models were used to help specify the required processing equipment and control ranges and tolerances. Once the project was completed, an operating procedure was prepared for operation, startup, and shutdown of the washer water recycle system.

Jan 1, 1999

By Seetharama C. Deevi, Mohammad R. Hajaligol, Sarojini Deevi

"Carbides and nitrides of iron are being considered as magnetic materials for high-density recording due to their chemical stability and high-saturation magnetization values (> 100 emu/g). Iron carbides and iron nitrides with magnetic properties suitable for magnetic media were synthesized by employing a novel synthesis procedure based on fluidization of powders in reactive atmospheres. Fluidized-bed reactors of laboratory, bench, and pilot scale were employed for the synthesis of iron carbide, FeSC2, by reducing and carburizing U-Fe203 in the temperature range of 300 to 550 ºC. A temperature of 400· ºC and a reaction time of 2 to 3 h are found to be optimal for the synthesis of iron carbide. When the carburization was carried out in a reducing and carburizing atmosphere such as carbon monoxide, nucleation and growth of FeSC2 occurred directly from Fe304 with no intermediate phases such as FeO or Fe. Longer carburization times resulted in the deposition of carbon on the surfaces of FeSC2 particles due to Boudouard reaction, and higher temperatures favored the formation of a mixture of carbides such as FesC2 and Fe3C. Iron nitrides were synthesized by reducing u-Fe203 in the temperature range of 350 to 550 ºC, followed by nitriding in the temperature range of 350 to 550·ºC. The powders were characterized using X-ray diffraction, scanning electron microscopy, thermogravimetric analyzer, and a vibrating sample magnetometer.IntroductionRecent demand for high-quality recording of optical, electrical, and audio signals generated interest in magnetic tapes with high-recording densities as compared to the conventional magnetic tapes based on U-Fe203. At present, commercially available magnetic tapes contain maghematite, U-Fe203, as a magnetic material with a saturation magnetization of90 emu/g and a coercive force of 400 Oe. Recording of signals at a higher density per unit volume of magnetic material demands magnetic materials with high-saturation magnetization and a reasonable coercive force. Although metallic iron particles possess a saturation magnetization of 130 to 150 emu/g and a high coercive force of 1000 Oe, the gradual oxidation of iron-to-iron oxides (of lower saturation magnetization) prevents the use of iron particles for high-density recording. In contrast, iron carbides such as FesC2, Fe7C3 and iron nitrides such as Fe4N and Fe3N possess excellent magnetic properties coupled with good electrical conductivities and high hardness. The carbides and nitrides of iron have generated significant interest as magnetic materials for the next generation of magnetic tapes due to their unique magnetic properties and relatively greater oxidation resistance as compared to metallic iron particles [1-4]."

Jan 1, 1994

By Deepak Gupta, R. Kageyamat, J. W. Evans

"In electromagnetic casting, a liquid metal pool is partly supported by electromagnetic forces resulting from the interaction between induced currents and an alternating magnetic field. Stability of the metal surface is of paramount importance if the cast ingot is to be free from surface defects. Prior work by Garnier and Moreau had suggested that the magnetic field has no influence on the surface stability, but a more complete analysis at Berkeley suggested that surface perturbations are destabilized by the magnetic field once a critical magnetic field is exceeded. More recently we have employed a modified version of the software SOLA to compute the behaviour of a melt surface in the presence of an alternating field. The computed results support the theoretical analysis in predicting an unstable surface. Experimental work is now in progress to examine the stability of a mercury pool in the presence of an alternating field. Introduction and Previous InvestigationsElectromagnetic casting (EMC) is a technique widely employed in the aluminum industry to produce ingot for subsequent rolling. It is a ""continuous"" casting technique (illustrated in Fig. 1) producing ingots several meters high (and perhaps 1m by 2m in horizontal dimensions) at a casting speed of one or two mm. per second. The technology has gained acceptance because the metal is solidified without contact with a mold. Consequently the surface finish of the ingot is usually smooth and the ingot can be fed directly to rolling without machining, the surface (""scalping""). Scalping is necessary with alternative technologies (e.g., DC casting) where a mold is used. Consequently any disturbances that result in surface imperfections of EMC ingot are a serious matter. One type of imperfection is waviness on the surface of the ingot; a line drawn along the crest of a wave would run horizontally around the ingot. This imperfection may be caused by waves on the surface of the metal pool. As the waves reach the solidification line at the periphery of the metal they cause alternate outward and inward bowing of the meniscus at that point with attendant small (but significant) changes in ingot width. Elimination of building vibrations and similar disturbances minimize the occurrence of these surface waves but it is interesting to speculate whether there are disturbances of the metal pool that arise from the electromagnetic forces supporting the liquid metal. These forces are generated by the interaction of currents induced in the melt and the magnetic field produced by the current imposed on the inductor surrounding the melt. The present investigation has been concerned with whether the alternating magnetic field destabilizes the melt surface."

Jan 1, 1994

By Denis Shishin

The pyrometallurgical production and recycling of non-ferrous metals involves the use of complex feed stocks, having awide range of chemical compositions from sources that include mineral sulphide concentrates, high value obsolete materials and process wastes. The commercial viabilities of these operations hinge on the ability to extract value from these materials. Increasingly, modern computer-based tools are used to describe and predict process outcomes, including mass and heat balances, the partitioning of elements and phase equilibria. At the heart of these predictive tools are thermodynamic databases that describe the fundamental chemical properties of a system and all the components present. A comprehensive research program has been established to develop an accurate, self-consistent thermodynamic database describing all gas-slag-matte-metal-speiss-solid phases in the system Cu2O-PbO-ZnO-Al2O3- CaO-MgO-FeO-Fe2O3-SiO2-S-(As-Bi-Sb-Sn-Ag-Au). The database can be used in conjunction with the FactSage computer platform. The accuracy of the database and its application to industrial practice is demonstrated.

By Qingyu Deng, Shiwei Ma, Wang Hua, Guibao Qiu

"The flow properties of the blast furnace slag bearing high TiO2 at high temperature like the viscocity may change a lot due to the formation of the carbonitride inside, causing serious problems on the separation between the metal and the slag. Therefore, the critical condition of the formation of Ti(C,N) in blast furnace is vital importance for the ironmaking process with iron ore bearing titania. In this study, the formation of Ti(C,N) in blast furnace and the influences of various factors on the Ti(C,N) formation are investigated by FactSage. It is found that the mass of Ti(C,N) would reach the maximum at 1480 oC, and the product is mainly TiN below 1620 oC, while it is mainly TiC above 1620oC. The order of the factors by the importance from strong to weak was: temperature, the content of TiO2 in slag, basicity of slag, the content of MgO and Al2O3.IntroductionThe titanium dioxide (TiO2) in iron ore bearing titania will be partly reduced by carbon to titanium carbonitride (Ti(C,N)) in blast furnace, causing serious problems on the separation between the metal and the slag because of the change of flow property. Therefore, the critical condition of the formation of Ti(C,N) in blast furnace is vital importance for the ironmaking process, especially for the smelting of iron ore bearing titania. Extensive experimental data in regard to the formation of Ti(C,N) has been reported in numerous papers[1-6]. However, only some discrete data can be obtained by experiment, and it is difficult to detect the mass of Ti(C,N) in slag. In addition, the experiment is difficult to be proceeded when the temperature is above 1600oC. Therefore, it is very difficult to make clear the critical condition of the formation of Ti(C,N) by experiment."

Jan 1, 2012

By André L. B. Bittencourt

The copper content in the waste slag represents the greatest loss in the process of Caraíba Metais' Smelter. By identifying the variables responsible for copper stabilization in the slag, a minimization on these losses is expected, producing a granulated waste slag with a copper content lower than 0.7%. Statistics resourses such as control charts, Pareto's diagram and correlations curves were applied for the data obtained in the first semester of 1992. The magnetite and the calcium oxide contents in the slag of the Flash Smelter Furnace were most prominent variables. Some operational changes introduced during and after this investigation have shown good results.

Jan 1, 1994

By Albert F. S. Seboukens

A 5;6 MVA pyrometallurgical demonstration-scale pilot plant was commissioned at Mintek, South Africa, in 1994, using lead blast-furnace slag and coke as raw materials. The plant included a.d.c. power. supply, two plasma-arc furnaces' and an ISP lead-splash condenser. Slags containing typically 12 per cent zinc oxide and 3 per cent lead oxide are produced as a waste during the smelting of lead in a blast furnace. These slags are a potential: resource for the recovery of lead and zinc. During 1994, about 600 t of lead blast-furnace, slag was proceced through the pilot plant using the Enviroplas process. Zinc and lead oxides were reduced to their respective metals, volatilized, and collected in an. ISP lead splash condenser. Prime Western grade zinc and slags disposable in accordance with current US legislation, were produced. Zinc condensation efficiencies of about 80 per cent were achieved.

Jan 1, 1995

By Regina Krachler, Herbert Ipser

"The principles of the derivation of statistical-thermodynamic models to interpret the compositional variation of thermodynamic properties in non-stoichiometric intermetallic compounds are discussed. Two types of models are distinguished: the Bragg-Williams type, where the total energy of the crystal is taken as the sum of the interaction energies of all nearest-neighbor pairs of atoms, and the Wagner-Schottky type, where the internal energy, the volume, and the vibrational entropy of the crystal are assumed to be linear functions of the numbers of atoms or vacancies on the different sublattices.A Wagner-Schottky type model is used for the description of two examples with different crystal structures:For B'-FeAl (with B2-structure) defect concentrations and their variation with composition are derived from the results of measurements of the aluminum vapor pressure; the resulting values are compared with results of other independent experimental methods.For Rh3~ (with an NiAs-derivative structure) the defect mechanism responsible for nonstoichiometry is worked out by application of a theoretical model to the results of tellurium vapor pressure measurements. In addition it is shown that the shape of the activity curve indicates a certain sequence of superstructures.In principle, there are no limitations to the application of statistical thermodynamics to experimental thermodynamic data as long as these are available with sufficient accuracy, and as long as it is ensured that the distribution of the point defects is truly random, i.e. that there are no aggregates of defects."

Jan 1, 1996

By Etsuro Shibata

The saturated solubility of chromium oxide and the valence of chromium in the slag are important matters when considering how to effectively utilize chromium-containing slags. The experimental data of various types of slags cited in the literature were arranged according to the optical basicity in order to evaluate the effects of the oxygen potential and the slag composition. The saturated solubility of chromium oxide and the Cr2+/ Cr3+ ratio tend to decrease with the increase of the optical basicity of the slag at an oxygen potential below 10.5 atm. However, at an oxygen potential of 0.21 atm, the saturated solubility and the Cr6+/Cr3+ ratio tend to increase with an increase of the optical basicity. A practical approach was suggested to reduce chromium in the stainless steel slag and simultaneously recover it as a ferroalloy by the direct smelting reduction of chromium oxide in the molten slag using some reductant in a small furnace.

Jan 1, 2003

"The theoretical basis of ideal smelting reduction using coal as reductant in a process employing closed loop forced-circulation of hot metal is outlined. In the proposed process, an extensive area of relatively slag-free hot metal is available as a heat sink for absorbing the large amount of heat produced by complete combustion of CO within the furnace. Any slag that is formed within the oxidizing arm of the furnace loop is quickly swept away as a thin floating layer by the bulk movement of hot metal which is induced positively by forced melt circulation and sustained by causing the hot metal and the thin slag layer to overflow into a lower level hearth in which coal is carbonised and dissolved directly into the circulating melt.The proposed process is shown to offer very substantial cost savings over all other direct smelting technology. This is mainly because of its inherently low capital cost and its high energy efficiency. Furthermore, the favourable economics are not reliant on fuel gas credits as all the process gas is combusted within the reactor itself.IntroductionMetallurgical processes in the year 2000 will be compromise solutions to the metallurgical problems that already exist today. It is common knowledge that the mineralogical complexity of certain polymetallic sulphides, for example, precludes high degrees of separation and recovery by conventional mineral beneficiation. steps are therefore being taken towards the development of a truly polymetallic smelting process which will produce simultaneously zinc lead and copper as, metals from complex ores without prior beneficiation(l). In the ferrous extraction industry, the shortcomings of the highly efficient modern blast' furnace are well known and world-wide there is considerable effort being directed towards coal-based ironmaking without the requirement of metallurgical coke as a process intermediate. The current status 0f2Joal-based ironmaking has recently been reviewed by Smith and Corbett. (2)"

Jan 1, 1988

By Kazue Moriya

At the 1980 TMS-AIME world symposium, Dr. Davey mentioned that the traditional lead blast furnace is now being challenged by direct smelting processes. In the copper smelting field both the blast furnace and reverberatory furnace are also disappearing in favour of direct smelting processes such as Outokumpu flash smelting, Mitsubishi continuous smelting, Noranda furnace, Inco furnace and so on. Those new processes all have the following in common: (1) High degree of mechanization (2) Metallurgical reactions carried out in closed vessels (3) Application of oxygen and/or oxygen enriched air (4) Minimization of handling materials and gaseous volume (5) Minimum energy requirements (6) Removal of workers from near the furnace (7) Reduction of emissions of harmful gas to meet environmental regulations. (8) Improvement to the work place environment to avoid occupational hygiene hazards. Direct and continuous smelting of powdered concentrate in one vessel was a romance of the metallurgist since early times. However as mentioned above, in the copper field this objective is being achieved in practice. The industry however can't deny that the serious and severe regulation of environmental pollution in every country was the prime motive for the modernization of smelters. In early days, to meet regulations, it was anticipated that many economic difficulties such as higher capital and energy costs and extravagant use of resources and waste disposal would be the result. "Turn a misfortune into a blessing" is an old saying which reveals the current thinking and reacent developments in the nonferrous industries. In the last ten years in the lead smelting field, about two decades later than copper, commercial scale smelting using new furnance technology has started. The KIVCET process and QSL process, which is flash smelting and bath smelting respectively, are becoming major competitors. They will be sure to upgrade their processes to remain economically and environmentally viable in the comming decade.

Jan 1, 1990

By Omid Marzoughi

Chromium has a wide range of applications, including as an alloy addition in various steels and also as a corrosion resistance coating. Carbothermal reduction of chromite ore (FeCr2O4) in a submerged arc furnace is an important industrial process for extracting chromium, but the energy consumption is excessive. It is suggested that one area for future research is the low temperature carbothermic solid state reduction of chromite to produce an intermediate product, which can subsequently be upgraded to ferrochromium. In this regard, a thermodynamic model has been developed to investigate this process and the effects of temperature, carbon additions and ore composition on the recovery of chromium and the grade of the ferrochromium, have been studied. Further development of the model may allow it to be applied to the simulation of other processes for the recovery of chromium from chromite ores.

By Zhang Chuanfu, Tan Pengfu

"A thermodynamic model is developed to predict the distribution behaviors of Ni, Co, Sn, Pb, Zn, As, Sb, Bi, Au and Ag in copper pyrometallurgical process. In this model, as more as 21 elements (Cu, S, Fe, Ni, Co, Sn, As, Sb, Bi, Pb, Zn, Au, Ag, 0, N, C, H, Ca, Mg, Al, and Si) and 72 compounds (in fayalite-slag-making system) or 74 compounds (in ferrite-slag-making system) are considered. Accessory-element behavior is studied for two types of slag , fayalite and ferrite, and two levels of oxidation. The allowance is also made to account for physical entrainment in the melts.-Model simulations are carried out to study the effects of controllable process parameters such as feed composition, smelting temperature, degree of oxygen enrichment and volume of oxygen enriched air. The model can be used in copper flash process, Mitsubishi process and Noranda process. The predictions by the present computer model are compared with the known industrial data from Gui Xi Smelter in China, Home Smelter in Canada and Naoshima Smelter in Japan and excellent agreement between calculations and industrial data is obtained. In this paper, the effects of oxygen enrichment, matte grade, smelting temperature, and types of slag on accessory-element behavior among matte, slag and gaseous phase have been elucidated.I . IntroductionThe presence of trace quantities of minor elements such as As, Sb and Bi in copper significantly reduces its ductility, electrical conductivity, and lowers its thermal conductivity. Embrittlement of copper also occurs due to impurity-phase precipitates at the copper grain boundary interfaces. They deteriorate not only the electrical conductivity of copper but its workability in hot working."

Jan 1, 1998

By Avijit Moitra

The behavior of the solidifying shell in the early stages of solidification has an important influence on the final quality of continuously-cast steel slabs. In order to understand the thermal and mechanical behavior of the shell, a two-dimensional transient piecewise-coupled finite-element model has been developed. The model simulates a transverse section of the slab as it moves down through the mold and incorporates the effects of heat conduction, solidification, shrinkage, turbulent fluid flow, thermal distortion of the mold and the visco-plastic behavior of the steel. Coupling between the thermal and the mechanical model is based on the mutual dependence of heat transfer across the interface between the shell and the mold and the size of the gap. The effects of mold distortion and taper on the gap size are also included. The effect of fluid flow has been incorporated via a heat flux imposed at the solid-liquid interface, which is obtained from a separate fluid flow model. The high temperature creep and plasticity of the steel is incorporated through a unified constitutive law defining the inelastic strain rates as a function of temperature, time and stress state. The model can be applied to various problems in continuous casting, such as the formation of surface defects and the design of mold taper.

Jan 1, 1992

By Hong Yong Sohn, Miguel Olivas-Martinez, Zhixue Yuan

A novel flash ironmaking process that directly reduces iron oxide concentrate particles by gas is under development. The goal of this work was to study the possibility of reoxidation of iron particles in various gas mixtures. As the product iron cools down in the lower part of the flash reactor, conditions may become favorable for reoxidation because of equilibrium and high reactivity of iron particles. The effects of temperature (823 – 973 K) and H2O partial pressure (40 – 100 pct., Ptotal = 86.1 kPa) on the reoxidation rate were examined. The pressure dependence was first order with respect to water vapor, and the activation energy was 146 kJ/mol. A complete rate equation that adequately represents the experimental data was developed. For oxidation in O2-N2 mixtures, the effects of temperature (673 – 873 K) and O2 partial pressure (5 – 21 pct., Ptotal = 86.1 kPa) were determined. Reoxidation in pure CO2 was also investigated at 873 – 1073 K for comparison.

Jan 1, 2014

By S. Abe

An extensive study has been carried out to determine the true cause of floating slimes precipitation which sometimes occurs and badly affects the quality of copper cathodes. Soluhilities of floating slime compounds systematically measured for the ternary system As-Sb-Ri added solely or in combination with conventional copper electrolyte (63°C) and bench scale electrorefining experiments done by varying electrolyte composition, have shown conclusively that the level of Sb(V) ions plays a substantial role in the precipitation mechanism. It was, therefore, speculated that controlling the level of the less soluble S b ( V ) ions below a certain critical level should result in a complete elimination of the undesirable precipitation. This can be easily achieved, for instance, by the addition of a reducing agent such as SO2 gas and the simultaneous employment of a certain type of cheating agent that effectively removes excessive Sb and Bi from the contaminated electrolyte. Long-term pilot testing conducted in line with the above speculation has confirmed the SO2/chelating resin scheme to be industrially very attractive and feasible.

Jan 1, 1987

By L. A. André Santos

Atmospheric processing of nickel lateritic ores with low costs has been encouraged. In this work the kinetic of atmospheric acid leaching of a northern- Brazilian ore with 1.63% Ni and large amount of fine particles (d50 ≈ 0.075 mm and 40% below 0.038 mm) is presented. Chemical analysis showed a trend of Ni and Fe concentration in finer fraction (−0.075 mm) and Si and Mg in the coarsest one (−0.500 + 0.150 mm) associated to distinct mineral phases. Nickel is widespread in the mineral matrix. Distinct behaviors were observed as a function of particle size associated to the distribution of silicates and iron oxides in the ore. The kinetic modeling indicated that leaching is controlled by porous layer diffusion at 65 °C, but at 95 °C exhibits a mixed control by porous layer diffusion in initial minutes (60 min) and by chemical reaction or diffusion through the pore layer in final minutes (60–240 min) depends on metal evaluated.

By Noel A. Warner

Modern steelmaking is based on direct use of oxygen in high intensity batch reactors. A totally new approach is proposed in this paper, based on the view that pursuit of high intensity is unlikely to lead to successful coal-based continuous steelmaking. By substituting carbon dioxide and water vapor as the oxidants rather than using oxygen directly, the intensity is greatly reduced. Accordingly. subsurface formation of carbon monoxide bubbles can be avoided by careful manipulation of the three participating rate processes, gaseous diffusion, interfacial chemical kinetics and liquid phase mass transfer. Steelmaking can then be carried out without explosive ejection of molten droplets and the generation of micro-spray but rather in a controlled and fumeless fashion. The vital component is the introduction of generic melt circulation technology. Three melt circulation loops in series are envisaged. Starting with a composite feed of iron ore fines, pulverized coal and lime flux, a metallized solid raft floating on molten iron is propelled out of the ironmaking loop onto the first of two downstream steelmaking loops. In the first, a liquid slag is formed, primary decarburization is undertaken not with oxygen but rather with CO2 and H2O and the melt is desulfurized. The semi-product stream enters the third melt circulation loop, where open-channel decarburization is effected along with dephosphorization to yield a low carbon steel product. Alternatively, the melt leaves the last loop to irrigate a packed tower countercurrent to argon at around 100 mbar to continuously produce ultra-low carbon (ULC) steel.

Jan 1, 2003