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By Fiseha Tesfaye, Pekka Taskinen

"Thermodynamics of the equilibrium phase assemblage Ago_9Cul.lS-Cu2-xS-CuS have been studied by an EMF -method. The ternary phase was synthesized from the pure Cu2S and Ag2S in vacuum furnace at high-temperature and mixed with appropriate compositions of Cu2S and CuS to form the cathode electrode. The EMF-measurements were made on the solid-state galvanic cell Pt(-) I Ag I RbAg,ils I Ago9Cu1.1S-Cu2-xS-CuS I Pt(+), in a temperature range from 316 K to 498K.Based on the measured EMF vs. T relations, thermodynamic functions (?fG° , ?fS and ?fH°) of stromeyerite (Ag0.9Cu1.1S) in equilibrium with Cu2-xS and CuS have been determined. The obtained experimental values have been compared with the available literature values. New experimentally determined thermodynamic properties of the solid solution (Ag,Cu)2Sss were determined.IntroductionDue to intense mining of high grade sulfide ore minerals in the past, recently, the available sulfide ores are poor in metals and becoming increasingly complex; such that, the production of high grade metals by the conventional pyrometallurgical processes is compromised. Consequently, smelters are in need to modify their operating flow sheets and strategies for processing more complex feed materials economically, while meeting the strict environmental regulations. To make the appropriate modifications, accurate thermochemical data of phases and phase assemblages which exist in these complex ore minerals are essential.Silver-bearing sulfosalts are encountered in ore minerals for the production of base metals and are common sources of silver. Among the silver-based sulfosalts, stromeyerite (Ag0_9Cu1.1S) is relatively common ore mineral in most hydrothermal vein and replacement deposits [1]. Recently, the ternary chalcogenide compound Ago0.93Cu1,07S has been studied, intensively, due to its high ionic conductivity and gradual disorder in the sequential phase transitions [2]. Therefore, accurate knowledge of the thermodynamic properties of stromeyerite has considerable fundamental and practical interest in many aspects of extractive, chemical and physical metallurgy."

Jan 1, 2014

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 Atul Kurnar

In the present research a two-cell polymer electrolyte membrane fuel cell stack (PEMFCS) with SS-316 bipolar plates has been tested. Different flow field designs were studied and a modified multi-parallel channel design is proposed. The stack is stable within ±3 mV even after 1000 hours of continuous operation, indicating efficient water management and effective removal of any metal ions from the stack. Also no iron is detected in membrane electrode assembly (MEA) by EDAX analysis after 1000 hours of cell operation. Results indicate that high operating pressures beyond 138 kPa didn't significantly increase the performance of cell, however added much to the pressurization cost of the system. Tests at different temperatures showed that at temperatures below 80°C, external humidification could be completely removed. The prototype stack is also tested under variable load conditions simulating highway-driving schedule. The experimental efficiency of PEMFCS is 48%, which is in good agreement with the model predicted efficiency of 53.8 %. Results show that 59% of the total losses are due to ohmic polarization in the cell. Further analysis on applications of the stack in automotive transportation system is in progress.

Jan 1, 2002

By J. Bostjancic

As wastewater discharge regulations become more stringent, power plants, manufacturing plants and other industrial sites are looking for ways to reduce makeup water requirements and to recycle and reuse as much wastewater as possible. In some cases, environmental regulations require zero liquid discharge, meaning all wastewater must either be retained on site or reduced to solids for disposal off site. Zero liquid discharge or "closed-loop" wastewater treatment systems using evaporators and other process equipment have been well-accepted in recent years. Often overlooked is the fact that zero discharge is not just the latest fashion--many commercial zero liquid discharge systems have been in operation since the mid-70's. This paper will give specific examples of zero liquid discharge operations from 1974 to the present, showing how evaporation equipment and processes have changed to meet the requirements of industry and environmental regulations.

Jan 1, 1996

By Ali Hasham

Reduction rates of FeO in CaO-SiO2-Al2O3 slags by Fe-C melts have been investigated experimentally at 1723 K. The rates were estimated using experimentally determined CO(g) evolution rates. Flash X-ray images were employed to visualize the behavior of the melt-slag interface during the reactions. The influence of melt interface was examined by conducting two types of experiments - (i) dropping one (or several) Fe-C droplet(s) weighing 2 g into the molten slag bath, and (ii) dropping a small amount (10-30 g) of slag onto a Fe-C melt weighing 400 g. The rates from both types of experiments were compared and analyzed to determine the rate limiting steps. It was established that neither the carbon transport in the Fe-C melt, nor the transport of gas species in the gas film adjacent to Fe-C melt was responsible in limiting the reaction rate. It is possible that the slag phase mass transport may be controlling the initial reduction rate in the droplet experiments. However, a, different mechanism was responsible in limiting the reduction reaction when the overall %C in the droplets fell to about 2-3.

Jan 1, 1992

The cleaning of copper containing fayalite slag using a CuFe alloy was studied under an oxygen pressure ranging from 10-7 to 5 X 10-11 atm at 1200º c. The reduction of copper from fayalite slags by Cu-Fe alloys was found to be very effective. For example, at a P 02 of 10-7 atm, the copper content in the slag was reduced from 4.1 to 0.402 wt. percent after 90 min. of reaction time using a Cu- 5.27 wt. percent Fe alloy. The copper reduction rates were found to be independent of P02 in the gas phase when using Cu-Fe alloys which exhibit an iron activity of greater than 0.4. A mechanism for slag c1eaning is proposed based on the concept that the Cu-Fe alloy lowers the oxygen potential of the slag according to Eq.1 1, fol1owed by the reduction of cuprous oxide by wustite as shown in Eq.2. Here X represents element X in the alloy phase while (X) represents the element in the slag phase. The copper and iron transfer behaviour obtained in this study are explained by a ?Stepwise equilibrium model.

Jan 1, 1985

By Finlay Campbell

Nickel laterite pressure acid leach plants and reduction roast plants have had a checkered history in their engineering, construction, startup and operational reliability. Many potential projects have been the subject of detailed studies over the last thirty to forty years but relatively few have advanced to commercial production. Four reduction roast plants are currently operating, an additional one was partially constructed but never completed, and another was started up in 1974 and shut down after 12 years operation. Three acid leach plants have been built and commissioned in the last five years, trying to follow the example of the Moa Nickel plant in Cuba. An additional acid leach plant project is currently on hold, following limited construction work, its future subject to review by the owner because of potential cost over-runs. This paper attempts to discuss difficulties that may be encountered as a project is developed and will address factors which may affect production ramp-up schedule, long term production performance and overall production success. Comparisons are made with ramp-up performance at other large metallurgical plants that employ some comparable unit operations. Keywords: Caron, PAL, nickel laterite ore, ramp-up, reliability, process development, equipment design, step-out, commissioning, startup.

Jan 1, 2004

By N. L. Piret

Primary and secondary copper smelting dusts are being generated in varying quantities with very dissimilar characteristics due to the different compositions of feed materials and the type of process utilized. After categorizing the multitude of dust types, the criteria for on-site and off-site recycling of smelter dust in terms of type and concentrations of the accompanying elements are established. Thereby, consideration is given to the important aspects of: ? optimization of copper recovery ? quality of copper product ? valorization of accompanying elements ? elimination and disposal of deleterious impurities ? minimization of impact on operation ? effects on operating costs ? environmental impact of dust treatment on overall process Existing commercial, emerging and proposed copper smelting dusts, pyrometallurgical as well as hydrometallurgical, treatment schemes are reviewed and evaluated technically, economically and environmentally in an attempt to streamline the vast number of proposed options. Thereby, the high selectivity achievable in hydrometallurgical dust processing due to it being complementary to the smelting process is expected to be given increased consideration.

Jan 1, 1995

By Rick Honaker

Rare earth elements (REEs) contained in coal and associated mineral matter exist in several forms including micro-dispersed minerals, ion adsorption onto clay surfaces, and chemically bound. Tests found that REEs can be effectively recovered from certain components of three coal sources by leaching under mild conditions followed by solvent extraction. A range of pH values were evaluated at solution temperatures of 25 and 75 °C. When using 1.2 M of sulfuric acid, nearly 85% recovery of the REEs was extracted from the middlings material collected from an operating plant. Acid leaching of a second middling source from another plant resulted in 60% of the total REEs being recovered under the same leaching conditions. Solvent extraction treatment of the leachate produced from six different coal sources resulted in products containing up to 50% total REEs from feedstocks starting with around 300 ppm.

By Mototsugu Matsuno

A new process has been developed to treat fly ash generated from municipal incinerators, which contains not only toxic metals such as lead and cadmium, but also dioxins. The process includes the following steps; fly ash is formed into green pellets with some additives and the pellets are then roasted to eliminate or stabilize the toxic metals and to decompose dioxins. A pilot plant with a capacity of approximately 100 kg/hr was used to test the process. The tests verified that heavy metals were either volatilized or stabilized and dioxins were decomposed by high-temperature roasting. The pelletized ash was found to be non-toxic, so that it can be recycled as artificial lightweight aggregate. It was also found that volatilized metals collected as secondary ash can be recycled as smelting resources.

Jan 1, 2003

By Rodney Hundermark, July Ndlovu, Lloyd Nelson, Phillimon Mukumbe, Paul van Manen, Whitey Seyanund, Bart Pieterse, Bertus de Villiers, Diale Mokwena

The 2003 redoubling in power to 68MW on the Polokwane Smelter furnace represented a significant intensification in platinum group metal (PGM) smelting. Combined with onerous ‘green’ PGM concentrate smelting requirements, this yielded conditions unusually corrosive to copper coolers and refractories. This presented unexpected operational and design challenges to reliable crucible operation and maintenance. Combined with specific operational control intervention, development of protective coatings has led to the life of water-cooled copper components improving from 9 to 40 months. The furnace matte endwall was extended in 2010 to address accelerated wear of refractories and the potential risk for contact of copper components by superheated matte. An 18 month planned endwall rebuild cycle has been demonstrated (versus catastrophic failure within 9 months). Finally, benefits including lower energy consumption, improved metal recoveries and higher productivity resulting from operational and in-house design developments will be described, that justify “Celebrating the Mega-scale” in PGM smelting.

Jan 1, 2014

By A. Dutta, B. Devulapalli, A. Mukhopadhyay, E. W. Grald

"Computational Fluid Dynamics (CFO) has matured over the past two decades as an analysis tool for conducting virtual experiments with significant time and cost savings. It complements and reduces physical testing. CFO has penetrated the diverse materials industry in much the same way as Computer Aided Design (CAD) did more than a decade ago. As the basic numerical algorithms used in CFO have steadily improved, so have the reliability, consistency and user-friendliness improved significantly, too. Other recent trends have also contributed to the rapid growth and widespread adoption of CFO. In this presentation, CFO applications from several materials processing industries will be presented using case studies. Emphasis will be on metals, glass and semiconductor applications.IntroductionThe term materials processing covers a diverse array of industrial applications and products today. From the continuous casting of steel, to the deposition of semiconductor materials atom by atom, to the extrusion of molten polymers, materials processing applications span an incredible range of length scale, process times, pressures, temperatures and velocities. The properties of the materials themselves, in terms of density, viscosity, thermal conductivity, etc., can be complex functions of temperature, shear rate, chemical composition and time. And the processing equipment may be very complicated in geometric shape.Computational fluid dynamics (CFD), the technique of solving the governing equations of fluid motion and other related phenomena using a computer, has enjoyed widespread and rapid growth, which started in the aerospace and automotive industries. More recently, CFD has also been successfully applied to a great many materials processing problems, in spite of the challenges described in the previous paragraph. The reasons for the growing usage of CFD in materials processing are many. Using CFD to test design options and reduce the number of physical prototypes can decrease the time and cost associated with new product and process development. CFD gives insight and provides detailed predictions of operating conditions in lieu of difficult, intrusive and often expensive experimental methods. CFD can be used as an aid to scale-up processes from lab or pilot scale to full production. Troubleshooting the performance of existing equipment is often carried out with the help of CFD. Determining how an existing piece of process equipment will operate under new conditions, or with new input ,materials, is also a common task for CFD."

Jan 1, 2004

By Vladimir Panjkovic, Ostrovski. Oieg, Campbell Cripps Clark, John Truelove

"Effects of properties of raw materials and blast on the performance of an iron bath reactor have been examined by a mathematical model. The model consists of three modules: 1) chemical reactions in the gas phase and heat transfer from gas to droplets ejected from the bath; 2) heat losses from the vessel and radiative heat transfer from the freeboard to the bath; and 3) heat and mass balances for the bath. The following parameters of the process are calculated: coal, ore, flux and oxygen consumption, post-combustion ratio and heat-transfer efficiency, temperature and composition of the off-gas, and slag and metal chemistry.IntroductionOne of the anticipated advantages of smelting reduction over conventional ironmaking is the use of lower-grade raw materials. In this work, the effect of-properties of raw materials on the performance of an iron-bath reactor is examined with a numerical model. The model is also used to assess the effect of properties of the blast (flowrate, temperature and oxygen enrichment) and ejected droplets (generation rate, size and ratio of total weights of slag and iron droplets) on the key parameters of the process. In the process coal, oxygen, ore (which may be partly prereduced) and fluxes for specified slag composition are charged to the bath. Slag and iron droplets are ejected from the bath into the gas phase, where they are heated before returning to the bath. Iron droplets undergo decarburisation and reoxidation with CO2 and H2O. Dust is also generated from the bath, and oxygen or preheated air for post combustion is injected from the top of the vessel.The model consists of three modules: 1) reactions in the gas phase and heat transfer from gas to droplets ejected from the bath; 2) heat losses from the vessel and radiative heat transfer from the freeboard to the bath; and 3) heat and mass balances for the bath. The structure of the model and the data exchange between the modules are shown in Fig. 1. The following parameters of the process are calculated: coal, ore, flux and oxygen consumption, postcombustion ratio (PCR), heat transfer efficiency (HTE), off-gas temperature and composition, slag and metal chemistry, and rates of decarburisation and reoxidation of the iron droplets."

Jan 1, 1996

By Józef Czemecki

Polish copper concentrates are characterized by high levels of impurities, particularly Pb and As. Two technologies are being used for copper concentrate smelting at KGHM Polska Meidz S.A., namely the shaft furnace process (Legnica Copper Smelter, Glogów I Copper Smelter) and a single-stage process for direct to blister concentrate smelting in a flash furnace (Glogów II Copper Smelter). Both technologies are used at different physical and chemical conditions which results, in different impurities behavior. The paper presents flow sheets for copper production in a plant using the shaft furnace process and in another in which a single stage flash process is used. The metals distribution in particular semi-products is given as well as a method for elimination of impurities from the copper production cycle. Methods are also discussed for alloy and matte converting and copper refining to obtain low Pb and As concentrations in anode copper (0.3% Pb and 1500 ppm As maximum) that are being used in the KGHM Polska Meidz plants. Useful co-operation between the plants using different technologies, aimed at the limiting the effect of undesired impurities on the quality of blister copper produced, is also described.

Jan 1, 1998

By Allan MacRae

Freeport-McMoRan Inc. operates an ISASMELTTM furnace for the smelting of copper concentrate at the Miami Smelter in Claypool, Arizona. In May 2017, the furnace was restarted after incorporating newly designed copper cooling elements from just above the tap hole to the underside of the roof. The objective of the improved cooling design was to extend campaign life by eliminating existing failure mechanisms with the wall refractory. In addition to upgraded bathline coolers and complete coverage of the gas offtake transition, or ‘kettle’, with plate coolers, a novel arrangement of coolers was installed in the remaining freeboard area. The shell required significant cutting and re-stiffening, as well as extensive modification of the cooling water piping. Based on performance observed to date, it is expected that smelter throughput will be increased due to extended ISASMELTTM refractory campaign life.

By Lenny Winkel

With the aim to develop a solar-driven process for the extraction of copper from sulfide concentrates research on the decomposition of copper sulfides under inert atmospheres has been initiated. Thermogravimetric measurements on chalcocite,(Cu2S) revealed that copper is formed already at 1823 K. Chalcopyrite (CuFeS2) also disintegrates at this temperature, although at a lower rate. Copper and iron have been identified in the solid residue. The results confirm the feasibility of copper extraction by direct decomposition of sulfides under atmospheric pressure. The decomposition under inert atmosphere prevents generation of SO2, it also alters the behavior of volatile impurities during decomposition of copper sulfide concentrates. Chemical equilibrium calculations for chalcopyrite contaminated with enargite (Cu3AsS4) have shown that the absence of an oxidic slag allows for a complete evaporation of arsenic and subsequent separation from intermediate sulfides. The need to better assess the potential of direct sulfide decomposition has prompted the development of an experimental setup for studying the decomposition reactions. The experiment has been devised such that data on the decomposition kinetics and on impurity removal can be obtained at temperatures up to 2500 K.

Jan 1, 2003

By A. E. M. Warner

In co 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 Mehmet Bu daycı, Onuralp Yücel, Ahmet Turan, Murat Alkan

In this study, iron based alloys (Fe, Fe-Cr-Ni-Mo, etc.) were produced by using metallothermic methods starting from Mill Scales obtained continuous casting processes. During the process, the combustion was realized by ignition and the produced wave propagates throughout the reactant mixture yielding the desired product. In this work, Mill scale used as an iron source, which includes +2, +3 values iron oxides. Aluminum, Magnesium and Silicon were used as reductants. In these metallothermic experiments, different ratios of reductants were examined, and their effects on the metal recovery and alloy compositions were investigated. The samples were characterized by using chemical analysis (AAS), XRD and XRF techniques.

Jan 1, 2016

By Larry M. Southwick, Phillip J. Mackey, A. E. (Bert) Wraith, Albert Pelletier

In 1881, the first commercial pneumatic Bessemer-type converter treating copper matte was successfully introduced by Pierre Manhes at the Eguilles copper plant near Vedène in France. This development followed over a year of testing on a smaller scale at a foundry in Vedène, during which the vertical tuyeres of the conventional Bessemer converter had been successfully replaced by horizontal tuyeres in an effort to avoid the freezing of copper which had occurred in the bottom of the vessel having vertical tuyeres. The Manhes Converter, as it became known, was the first successful large-scale adaptation of the Bessemer concept of using compressed air blown into a melt for metal refining and treatment. Within a few years, Manhes Converters utilizing horizontal tuyeres in either the original type of vertical converter, or a later and more enduring horizontal barrel converter, were in operation at over a dozen copper smelters around the world. It was this process that Messrs Peirce and Smith essentially improved with the introduction of the larger converter which bears their name and the development celebrated at this Symposium. The present paper briefly traces the original development by Pierre Manhes in the early 1880s and which set the stage for the later Peirce-Smith adaptation. The paper observes that the original development by Manhes was in part driven by the need to reduce coal (energy) consumption and hence the production cost in order for Eguilles to remain competitive with the larger plants in Swansea, Wales, where a ready supply of cheap coal helped keep smelter treatment terms of the day low. These themes are eerily resonant of today where booming copper production in China has impacted the industry, and also where energy consumption, closely linked to today’s more familiar theme of ‘climate change’ remains an important challenge currently confronting the entire industry. The paper concludes with comments on these seemingly parallel situations today and offers some thoughts for the future.

Jan 1, 2009

Kosaka Smelter & Refinery has a history of more than a century as a metallurgical department belonging to Kosaka mine. It has treated for a long time the "Black Ore" or the complicated concentrates dressed from it. The "Black Ore" is composed of black sulfides. It contains not only valuable metals such as gold, silver, copper, lead and zinc but also some impurities like arsenic, antimony and bismuth. With the development of Kosaka's floatation technology, five kinds of concentrates (copper, zinc, lead, pyrite and barite) have been separated from the "Black Ore" but the separation was not complete and each concentrate contained some unfavorable impuritie. In 1980s the highly appreciated yen and the drop of the metals priees forced many domestic mines to close their operations. Since then Kosaka Smelter has changed its way of operation to a custom smelter. Now more than 95% of copper concentrates are imported to take advantage of this technology of "Black Ore" treatment. It mainly treats the raw materials that contain high gold and silver like the "Black Ore". Recently, Kosaka has been working on the recycling of the metals from the printed circuit board scraps and sludge which contain some precious metals. The volume of the recycled metal is continuously increasing.

Jan 1, 2003