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By Pekka Taskinen, Hannu Johto

"Copper sulfide concentrates often contain impurities such as lead and iron. The phase stabilities of the sulfide impurity systems in metallurgical process conditions are in many cases unsatisfactorily known. Thermodynamic information of a system gives better understanding of its behavior of metal making processes, but also has effects on the economic and environmental factors of the production process. In this study, isothermal equilibrium and quenching experiments of the stable phases of the system Cu2S-FeS-PbS at 700 and 900 °C were carried out and based on the experimental results, Gibbs triangle of equilibrium phases of the system was outlined.IntroductionThe knowledge of stabilities of phases and the thermodynamic properties of many sulfide systems in the temperature range of 500-1200 °C are quite limited. Especially, the knowledge of liquidus surfaces of multicomponent sulfide systems is essential for making many metallurgical processes more environmental friendly and allowing the utilization of complex concentrates. In this work, the aim was to investigate the phase stabilities of the quasiternary system CU2SFeS- PbS using evacuated silica ampoules. Of greatest interest were the properties of the liquidus surface in the system, in order to be able to predict better the formation of a liquid phase in metallurgical processes."

Jan 1, 2012

By Rafael Padilla

The recovery of copper from chalcopyrite concentrates by leaching is difficult due to the slow dissolution kinetics of this mineral in most leaching media. However, recovery of copper from sulfidized chalcopyrite (a mixture of CuS and FeS2) by leaching is faster and could be selective depending on the leaching media. In this paper, the result of an investigation on the H2SO4-O2 pressure leaching of sulfidized chalcopyrite is presented. The variables considered in the study were stirring speed, concentration of sulfuric acid, temperature, and partial pressure of oxygen. The experimental data indicated that stirring speed over 500 rpm and sulfuric acid concentration over 0.1 M had very little effect on the leaching rate. An increase in temperature from 90 to 100 ºC increased both copper and iron dissolution; however, further increase to 120 ºC affected negatively the copper dissolution. Oxygen partial pressure was found to be the main variable that controls the copper/iron selectivity of the leaching. An increase in oxygen partial pressure increased significantly the rate of copper dissolution but deteriorated the copper/iron selectivity. The analysis for sulfur of the leaching solid residues indicated that most of the copper sulfide sulfur in the sulfidized concentrate oxidized to elemental sulfur.

Jan 1, 2006

By Teruo Tanabe

The hydrogen-absorbing materials are expected to have the following properties at moderate conditions, (a) a large capacity of hydrogen absorption, (b) the absorption rate of hydrogen is large and (c) hydrogen-absorbed materials can easily desorb hydrogen. Thus the three concepts of capacity, rate and reversibility seem to be indispensable to clarify the mechanism of hydrogen absorption by the materials. In this work, the amount of absorbed hydrogen, the absorption rate and the reversibility of hydrogen absorption- desorption reaction were measured for binary R-M systems (R = Y, La, Ce; M = Co, Ni). These experimental results were discussed by the following three physical properties that were calculated by the extended Hückel method, i.e. the density of states unoccupied by electrons, the cohesive energy and the energy fluctuation. The major results are as follows: (a) the amount of absorbed hydrogen increases with the density of states in the energy range between -9 and -4 eV, (b) the R-M compounds of which energy fluctuations are large show a large value of rate of hydrogen absorption, and (c) when the cohesive energy is large, the compound has a tendency not to easily desorb hydrogen, i.e. its reversibility is poor.

Jan 1, 2006

By Marshall Khan

The Goodfellow Expert Furnace System Optimization Process (Goodfellow EFSOP?) is a proprietary process that uses real-time and continuous off-gas analysis, along with process monitoring to optimize the operation of electric arc furnaces (EAF) for steelmaking. With the exception of off-gas composition, dynamic process measurements within the EAF are not possible due to the harsh operating environment. The Goodfellow EFSOP? system provides a dynamic indication of the operating conditions within the EAF. Continuous measurement of furnace off-gas composition, along with other furnace operating parameters is used to elucidate the fate of chemical energy usage within the EAF including: the evolution of carbon from the molten steel bath; the in-leakage of air into the furnace; the extent of combustion above the molten steel bath and the occurrence of dangerous water-leaks from the furnace cooling system. The ability to measure the process reliably and continuously enables Techint Goodfellow Technologies Inc (TGTI) to implement dynamic process control of combustion within the electric arc furnace and to optimize the overall operation through adjustments to the EAF process based on off-gas measurement. This paper discusses the methodology and results achieved from several recent Goodfellow EFSOP? installations in South East Asia.

Jan 1, 2006

By Damien Wagner

To reduce the emission of greenhouse gases by the steel industry, particularly for ironmaking, the production of DRI (Direct Reduced Iron) using hydrogen as the reducing gas instead of carbon monoxide is being considered. In this context, the reduction of pure hematite by hydrogen was studied at the laboratory scale, varying the experimental conditions and observing the rate and the course of the reaction. All the reduction experiments were performed in a thermobalance and supplementary characterization methods were used like scanning and transmission electron microscopy, X-ray diffraction, and Mössbauer spectrometry. The influence of rising temperature in the range 550-900°C is to accelerate the reaction; no slowing down was observed, contrary to some literature conclusions. A series of experiments consisted in interrupting the runs before complete conversion, thus enabling the characterization of partially reduced samples. Interpretation confirms the occurrence of three successive and rather separate reduction steps, through magnetite and wustite to iron, and illustrates a clear structural evolution of the samples. Finally, the influence of the sample type was revealed comparing a regular powder, a nanopowder and a sintered sample. The regular powder proved to be the most reactive despite its larger grain size, due to a more porous final structure.

Jan 1, 2006

By Patrick R. Taylor

In the search for the development of more "environmentally friendly" and more intensive waste disposal approaches to meet more and more stringent environmental regulations, thermal plasma-based processes? are considered one of the most promising alternatives to well-established technologies such as incineration. This paper presents an overview on the research and development status of thermal plasma-based waste remediation technologies. The properties of thermal plasma are described. Due to its unique feature of high-energy intensity and super high temperature, thermal plasma is particularly capable of destroying organic-containing wastes. Its potential and promising application to waste remediation may include: treatment of incinerator ashes; metallurgical dusts (especially, electric arc furnace dust); medical wastes; radioactive wastes; and other Resource Conservation and Recovery Act (RCRA) listed hazardous wastes. Many research institutes and vendors have been involved in the development of thermal plasma-based waste treatment-technology encouraged by the cleanup programs supported by the Environmental Protection Agency (EPA), the Department of Energy (DoE) and the Department of Defense (000). More recently, thermal plasma-based waste treatment technologies (sometimes called plasma-enhanced pyrolysis) are focused more and more on not only just destroying organic wastes but also on how to practically, and economically recover energy contained in the organic waste materials in addition to the recovery of metals in order to offset the high operating costs.

Jan 1, 2003

By Gordon A. Irons

"Powder injection for melt refining is widely practiced in the steel industry, and is gaining acceptance in the non-ferrous industries. In these commercially-important systems, the thermodynamics and kinetics may be very complicated. More than one element may be removed by refining, and often the refining agents are not just one compound. In this paper, the thermodynamic and kinetic aspects of these processes are reviewed. A number of examples are given, such as the desulphurization of iron with a variety of reagent mixtures, and selenium removal from copper with several different reagent combinations.IntroductionI am very pleased and honored to present a paper at this Symposium recognizing the many contributions of Professor Howard Womer. Even at the time I was an undergraduate student, the WORCRA process was part of the curriculum. I remember at the time that I was fascinated by the concept, and due to it and the many other rapid developments in Process Metallurgy, I chose it as my field of study. I think the Symposium is testimony that Professor Womer has touched the lives of many others as well.My original assignment was an overview of the basic aspects of gas and solids injection. However, I reviewed most of this material at the Savard/Lee Symposium [1]. In the present paper, I will present some of the basic issues related to refining with powder injection, using work that we have recently completed in both ferrous and non-ferrous systems."

Jan 1, 1996

By Patrick R. Taylor

In the search for the development of more "environmentally friendly" and more intensive waste disposal approaches to meet more and more stringent environmental regulations, thermal plasma-based processes are considered one of the most promising alternatives to well- established technologies such as incineration. This paper presents an overview on the research and development status of thermal plasma-based waste remediation technologies. The properties of thermal plasma are described. Due to its unique feature of high-energy intensity and super high temperature, thermal plasma is particularly capable of destroying organic- containing wastes. Its potential and promising application to waste remediation may include: treatment of incinerator ashes; metallurgical dusts (especially, electric arc furnace dust); medical wastes; radioactive wastes; and other Resource Conservation and Recovery Act (RCRA) listed hazardous wastes. Many research institutes and vendors have been involved in the development of thermal plasma-based waste treatment technology encouraged by the cleanup programs supported by the Environmental Protection Agency (EPA), the Department of Energy (DoE) and the Department of Defense (DoD). More recently, thermal plasma-based waste treatment technologies (sometimes called plasma-enhanced pyrolysis) are focused more and more on not only just destroying organic wastes but also on how to practically, and economically recover energy contained in the organic waste materials in addition to the recovery of metals in order to offset the high operating costs.

Jan 1, 2003

By George Oprea, Tom Troczynski, Joe A. Rigby, Waiman Lo

The refractory lining of the tuyere line in Peirce Smith converters have usually much shorter life in service than the rest of the lining, above or below it. There are already recognized chemical, thermal and mechanical factors which contribute to the wear of the lining. Our study presents the experimental results on microstructural changes occurring on these tuyere line bricks in a nickelcopper converter. The experimental bricks, after use at the tuyere line, were investigated using SEM/EDS and XRD techniques, to identify the mineralogical changes due to interactions with the nickel-copper matte or fayalite type slag at the process temperatures. The microstructural changes were correlated with physical and mechanical properties of the brick before and after use and a wear mechanism was suggested. Although the matte does not theoretically react with the mineralogical components of the brick, a partial oxidation of the Ni-Cu sulphides was identified using a line analysis by SEM/EDS in the densified layer at the hot face, which allows for mineralogical changes at the matte-refractory interfaces, with a high probability of microcrack formation due to the thermal cycling during use. These microcracks were also identified to open through inter-granular fractures parallel to the hot face, which appeared to be the main cause of lost lining during use. The reactions between the fayalite slag and refractory brick could eventually play a role in chemical dissolution of the brick only in the superficial layer at the hot face, as no slag components were identified deep into the brick.

Jan 1, 2009

By Katsukiyo Marukawa, Manabu Iguchi, Sigeta Hara, Shinichiro Yokoya, Sigeo Takagi

"A numerical analysis and water model study of the mold region of a continuous casting apparatus was performed with a novel injection concept using swirling flow in the pouring tube, to control the heat and mass transfer in the continuous casting mold.As a result, the following results were found:1) By changing swirl strength, it is easy to control the flow pattern as well as the direction of the flow.2) Uniform velocity distribution can be obtained within a very short distance from the outlet of the nozzle.3) Heat and mass transfer near the meniscus can be remarkably activated compared with a conventional straight type immersion nozzle without swirl.4) Swirl helps the superheat in the melt dissipate.S) Penetration depth of nozzle outlet flow is decreased remarkably by the application of swirling.6) For the case without swirl, the peak of the flow moves near the mold-wall with flowing down from the outlet of the nozzle due to the Coanda-effect. On the other hand, peak of the flow moves near the mold axis with flowing down from the nozzle-outlet within considerable short distance, namely axi-symmetric velocity distribution can be obtained within very short distance from the nozzle-outlet.Those findings mentioned above are very useful to control the flow pattern in the billet and bloom continuous casters."

Jan 1, 2001

By D. M. Hausen

It has been demonstrated that microscopic techniques can be applied in a practical manner to the study of spodumene liberation in the processing of pegmatitic ores at the Kings Mountain spodumene plant, Kings Mountain, North Carolina. Spodumene and associated non-opaque gangue minerals are identified and quantified by microscopic point-counting of polished thin sections of heads, concentrates, middlings and tails fractions. Specially prepared polished thin sections? provide uniform thickness of particles for measurement of diagnostic optical properties and the alternate use of incident and transmitted light in distinguishing the various gangue and ore minerals. Spodumene is commonly associated and interlocked with quartz, albite, microcline and muscovite. Concentrate grade depends on the degree of spodumene liberation, which in turn depends on the crystal size and textural association of interlocked minerals. The liberation of spodumene can be measured as a function of screen size by means of microscopic point-count data. Microscopic data also provide useful metallurgical information about the nature of diluent minerals in spodumene concentrates, and the form of lithia losses in the tails. Lithium assays correlate closely with microscopic spodumene analyses in various flotation products from Foote Mineral's Kings Mountain plant, and confirm the applicability of quantitative optical microscopy to the study of liberation and recovery of spodumene from pegmatitic ores. A better understanding of recovery-grade relationships was developed as a result of quantitative microscopy studies.

Jan 1, 1981

By V. Gornitz

The Orphan mine uranium deposit, Grand Canyon, Arizona, is a cylindrical collapse-breccia pipe, 70 to 150 m in diameter and 500 m deep. Pipe fill was derived from the Supai Group, Hermit Shale, and the Coconino Sandstone. Uraninite, with Cu, Fe, Pb, Zn and Ni-Co sulfides is concentrated along the pipe boundary ring fracture (annular ring) and within the central porous sandstone matrix. There is some suggestion of vertical and lateral zonation of U with respect to Cu. Reduction of ferric oxide cement from red beds and recrystallization of carbonate, with formation of kaolinite preceded major ore deposition. Early Ni sulfides, arsenides and disseminated pyrite were followed by massive pyrite, and botryoidal uraninite, which in turn was suc-ceeded by Cu, Zn and Pb sulfides. A second, later generation of uraninite was closely intergrown with hematite and base metal sulfides. Oxidation of primary minerals may have been associated with Tertiary regional uplift. The paragenetic sequence closely resembles that of other Grand Canyon breccia pipes, except for the extensive development of the distinctive uraninite-hematite association. Mineral assemblages at the Orphan suggest possible mixing of the metal-bearing solution(s) with a more oxidized fluid, containing soluble uranyl complexes. Homogenization temperatures of fluid inclusions in calcite (GO-lIO?C) at the Orphan fall within the lower end of the range observed at other breccia pipes.

Jan 1, 1987

By Julian Johnson

The effect of changing redox potential (Eh) on the high temperature sulfuric acid leaching of Western Australian dry-land nickel laterite ores has been investigated. In particular, the effect of added reductant (sulfur, sodium sulfite) or oxidant (potassium chromate) on Eh, leaching kinetics, metal extractions, acid utilisation and leach residues has been determined. Three separate ores - nonhonitic ores from Murrin Mumn and Bulong, and limonitic ore from Cawse - were used in the study. Sulfur addition varied from 0 to 7.8 kg/t ore. The total acid loading was kept constant at 430 kg/t (Murrin Murrin ore) and 330 kglt (Cawse ore), whilst acid loading for Bulong ore was varied according to the presence of either reductant or oxidant. The extraction of both nickel and cobalt from limonite ore remained unaffected when small amounts of sulfkr were added, but addition of even small amounts of reductant to nontronitic ore decreased both nickel and cobalt extraction. Increased manganese and iron dissolution were observed as the levels of reductant increased, accompanied by a decrease in chromium dissolution. As the iron dissolution increased, free acidity decreased, with a subsequent decrease in nickel extraction. In contrast, addition of oxidant lead to reduced iron and manganese dissolution and slower extraction of nickel and cobalt. Keywords: Limonite, Nonhonite, Eh, Nickel Extraction

Jan 1, 2004

By H. J. Garcia

Biodegradation of cyanide by microorganisms isolated from solids previously exposed to cyanide has been investigated. Initial sodium cyanide concentration was 300 ppm at pH 10.5. The kinetics of biodegradation were found to be first order with respect to cyanide concentration, and the overall reaction rate constant is k = 0.102 day-1. The activation energy and the frequency factor were determined to be { A }Ea = 5.45 Kcal/mol and A = 1.28 x 10-2 sec-1, respectively. Based on these values, thermodynamic properties of an intermediate activated complex were assessed. All tests resulted in cyanide concentrations less than 0.1 ppm in about 35 days at 250C, whereas at 350C the time of biodegradation to reach this cyanide level was 30 days. Kinetic data were also established to relate biodegradation to amount of inoculum. The maximum theoretically-attainable rate, Vm , and the optimum amount of inoculum, K , were determined to be 4.8 x 10-4 M NaCN/day and 7.5 % of amount of inoculum. With respect to the mechanism of biodegradation, cyanide was shown to decompose to carbonate, bicarbonate and ammonia. Titrimetric analyses revealed concentrations of 5.6 x 10-3, 4.8 x 10-3 M, and 70.2 ppm for carbonate, bicarbonate and ammonia, respectively. The average cell population was determined to be 3.75 x 108 cells/mL.

Jan 1, 1994

By M. A. Gimenes

The utilization of chlorination in extractive metallurgy and advanced ceramics areas has been widely investigated as a preparative route in order to obtain intermetallic compounds, which are used as precursors in the development of new materials and process. The major processes of decomposition of rare-earth ores use sulfuric acid and sodium hydroxide at high temperatures, however there is not much work concerning chlorination. In this work, a systematic study of the reaction between xenotime (REPO4), chlorine and carbon has been performed. Particular emphasis was on kinetic studies to establish optimized conditions for the reaction. The kinetics of chlorination of xenotime raw material by rare-earth elements/compounds has been studied over a temperature range from 600°C to 950°C. The influence on the rate of conversion of xenotime to RECl3 on temperature, partial pressure of chlorine, carbon content, and particle size were investigated. A global rate equation that includes these parameters has been developed. The results show that the process follows the unreacted core-shrinking model with a formation of a porous product layer. The powder X ray-diffraction technique corroborated this model showing clearly the patterns related to the formation of yttrium oxychloride (YOCl), indicating that the reaction mechanism involves the presence ofan intermediate step before the formation of lanthanide chloride.

Jan 1, 2000

By J. Etay, S. Daugan, Y. Fautrelle

"New type of electromagnetic parametric instabilities arising at the free surface of liquid metal in the presence of a low frequency magnetic field are presented. First, the mechanism of the instability is analysed in an idealised case. Then, the experimental device working with mercury is described. Various shapes, both regular and irregular, of free surface are found. A experimental stability diagram is obtained. Measurements of the deformation performed on photographs are compared with physical orders of magnitude.IntroductionWhen a liquid metal pool of electroconductivity a is submitted to an A.C. magnetic field B = B0 cos mt, electrical currents j are induced in the liquid metal and interact with the applied magnetic field to create electromagnetic body forces F = j x B. Those Lorentz forces comprise both a mean value (time average) and an oscillating part. Those forces are widely used in many metallurgical processes to stirr a liquid metal or to control its free surface, e. g., in aluminium continuous casting or electromagnetic levitation problems (1-3). When liquid metal free surfaces are submitted to AC. magnetic fields, the shape of those interfaces may interact with the applied field and leads to a various instabilities. A review of these instabilities may be found in Fautrelle (4). That instabilities may be a problem for the control of processing as electromagnetic levitation or quasi-levitation."

Jan 1, 1999

By Deborah A. Kopsick

Several minerals were observed and collected in a small gully originating from a weathered coal processing waste (gob) pile in Barton County, Missouri. The rapid alteration of these various minerals after collection suggested that they might represent a dehydration sequence. X-ray diffraction of the dehydrated and rehydrated minerals deposited on the gob pile indicated the presence of the monohydrate and heptahydrate forms of ferrous sulfate, szomolnokite and melanterite respectively. The occurrence of melanterite (FeSO4.7H2O), was limited to isolated areas of ponded water while szomolnokite (FeSO4.H2O), was associated with the outwash areas of the pile. Laboratory dehydration of melanterite collected at the gob pile revealed the formation of rozenite (FeSO4.4H2O), an intermediate form of ferrous sulfate. Szomolnokite was shown to be the stable form of these ferrous sulfates during these experiments while melanterite and rozenite were shown to alter readily. Chemical analysis of szomolnokite revealed enrichment in Fe, Mg, Zn, Cd, Cu and Mn relative to the chemical composition of the gob ad the lechate generated from the gob wastes. Although this gob pile had been weathering for more than 35 years, significant concentrations of trace metals were still being released from the pile through the generation of leachate and the formation of various soluble metal enriched ferrous sulfate minerals.

Jan 1, 1982

By Stavros A. Argyropoulos, Henry H. Hu

"The assimilation of exothermic additions in liquid metals exhibit an array of unique coupled heat, mass and momentum transport phenomena. These phenomena are further complicated by the presence of a moving boundary.This paper describes a) A mathematical model which simulates the complex phenomena, and b) An extensive verification of the mathematical model. The SIMPLER algorithm was employed to solve numerically the pertinent partial differential equations. The computational results indicated that the exothermic heat of mixing led to a rapid increase in temperature around the moving boundary, which produced an enhanced convective flow in the liquid phase. The intensification of fluid flow around the moving boundary resulted in an acceleration of the melting process.Verification of the model was carried out in two contexts. The first was, in a low temperature physical model consisting of ice immersion in different sulfuric acid solutions. In this physical model, both temperature and velocity measurements were carried out. The model results were compared with experimental measurements and they were found to be in excellent agreement. The second context employed high temperatures, involving the assimilation of silicon in high carbon liquid iron. The model was also applied to predict fluid flow, heat and mass transfer for these high temperature experiments and a good agreement was obtained.In addition new dimensionless heat transfer correlations that quantify these complex phenomena will be presented."

Jan 1, 2001

By F. K. Letowski

Leaching in froth is a particular case of a three phase (liquid-solid-gaseous) process which combines flotation with leaching by using a reactive gaseous reagent as a flotation carrier and a leaching solution as the reactive liquid medium to fonn the foam (froth) in' which the solid particles are suspended. Some physico-chemical and engineering aspects of leaching in froth are discussed and illustrated by its application for cleaning the mineral graphite. Leaching of the graphite concentrate containing 4L4% of the elemental carbon and 3.16% of the sulphidic 'sulphur was canied out in the froth fonned by: (a) a concentrated chloride solution, with a small addition of nitric acid, in the foam state; (b) a mixture of gaseous O2, NO., and H20 encapsulated in the foam; and (c) notable particles of graphite suspended in the foam. The laboratory experiments werecanied out in a "flotation column"-type reactor ala temperature from 80 to !08°C and under total pressure of 100 to 200kPa. In the 3-stage leaching-flotation process, the non-flotable fraction of particles was separated three times from the notable fraction. The concentration of carbon and elemental sulphur in the final flotable fraction was 96% C and 0.38% S respectively. The expected advantages and possible application in hydrometallurgy are suggested.

Jan 1, 1995

By J. R. Donald

Surface and interfacial phenomena play a significant role in refractory performance. For example, the wettability of the refractory material with slag, matte, and metal influences infiltration and interfacial reactions. Yet, very little fundamental information regarding the surface properties of refractory materials and slag is available. Thus, in the present work, the sessile drop technique incorporating a high temperature furnace equipped with X-ray fluorescope was employed to investigate the surface and interfacial phenomena of fayalite-type slags on solid alumina at 1200?C. The iron to silica (Fe/SiO,) ratios employed were 1.4 and 2.0, and the oxygen potentials used were log p02 =-11 and log p02=-9 atmospheres. The contact angle between the fayalite-type slags and the alumina were determined to be relatively low, at about 16.9 to 19.6 degrees under the experimental conditions. The surface tension of fayalite slag (Fe/SiO2=1.4) at an oxygen potential of log -11 was 0.298, which agreed with the work of previous researchers. The surface tension of the fayalite was observed to increase with time. The spinel FeAl2O4. was determined to be the product of the interfacial reaction, and 8.8 to 15.8 mass percent alumina was dissolved into the slag after 40 minutes.

Jan 1, 1996