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By Wenliang Cao, Jidong Li, Mingjie Zhang, Yiyong Wang

In CaC12-CaF 2 System, we studied the electrode process and discharge mechanism of preparation of Al-Ca alloys by fused salt electrolysis with CaO as raw material. The change of back electromotive force after adding CaO was measured by continuous pulse oscillograph method and the discharge process mechanism was also investigated by cyclic voltammetry. The finial results indicate that back electromotive force decreases by 0.6V after CaO of 1 % is added and there was a peak of oxidation current ahead of the potential at which the negative chlorine ions precipitated. According to thermodynamic calculation, it was determined that current peak was caused by the CO2 produced by 0 2 - ionic discharge due to CaO addition.

Jan 1, 2014

By R. Kramer

During foundry sand reclamation process development, molds formed from reclaimed chromite sand showed a rapid decline in tensile strength during thermal cycling tests. Because this characteristic could limit reuse of chromite sand in the. foundry, the sand was examined in detail Scanning electron microscopy, x-ray mapping, magnetic susceptibility, and x-ray diffraction were utilized to evaluate processed chromite sand. It was found that process variables such as binder composition, reclamation temperature, and processing method had a significant effect on the chromite sand particle surface. X-ray diffraction indicated a crystallographic change in the processed sands. Magnetic susceptibility also increased after processing. Diffusion of iron to the particle surface and increased surface roughness were identified as potential causes of the decreased tensile strength in the molds.

Jan 1, 1991

By H. Virtanen

Outokumpu copper refining operations have a long history of expansions and application of new technologies. Outokumpu is a name known around the world for technological excellence in the field of base metals, and part of the policy of operations is continuous investment and investigation in new technologies. The results of this hard work sometimes are immediate and sometimes take years. The work done during the last years at the Outokumpu Harjavalta Metals copper refinery, together with a sister technology group Outokumpu Wenmec, has started to bear fruit in terms of the following radical developments and advances that are and will be applied to assure Outokumpu's position as the technology leader and a low cost and safe producer. Some of the developments discussed include the new anode and cathode design, mechanised electrode handling, cell design incorporating features facilitating full automation, automated short circuit detection and removal, automated on line anode slime removal, and high efficiency and intensity refining.

Jan 1, 1999

By Ted H. Eyde

Natural Zeolites are a less expensive and in certain applications a superior alternative to organic ion exchange resins. Mining and metallurgical waste streams are difficult to treat because the effluents which contain potentially valuable heavy metals such as copper, lead, and silver are often highly acidic and contain significant quantities of suspended solids. Under rigorous operational conditions, certain natural zeolites can remove the metals, which if desired can be recovered by either elution or conventional smelting techniques. There are significant differences in cation exchange rate, selectivity and capacity as well as resistance to either high or low pH, blocking cations and tolerance to elevated or depressed temperature and pressure not only between different zeolite minerals but between the same mineral from different deposits. Applying natural zeolites to the treatment of mining and metallurgical waste streams depends on matching the specific zeolite to the effluent by characterization of the zeolite minerals.

Jan 1, 1993

By Matthew Tunnicliffe, Akram Alfantazi, Paul Nesbitt, Farzad Mohammadi

"Lead and its alloys are proper candidates for anodes in electrowinning processes mainly because they are insoluble in the leach solutions and relatively cheap. However, the annual cost of corrosion problems associated with these anodes is millions of dollars. In this study lead-silver and lead-calcium anodes were tested under typical nickel electrowinning conditions and the effect of chloride on the corrosion performance of the anode materials was investigated. Corrosion rates of the anodes were calculated using the discharge plateau (reduction of lead dioxide to lead sulfate) after galvanostatic experiments. It was found that lead calcium anodes have the highest corrosion rate both in the presence and absence of chloride. Surface morphology of the electrodes was studied using SEM and the corrosion products were characterized using XRD.IntroductionLead (Pb) is usually the preferred material for commercial anodes since it is insoluble in the leach solution and the costs are manageable. One advantage of using an insoluble material as an anode is the higher purity of the cathodic deposits and better quality of the end product. During nickel electrowinning, metallic nickel is deposited on the cathode while oxygen evolution reaction (OER) takes place on the anode. In practice, relatively high potentials are necessary for the reaction to proceed at the desired rate because of the high overpotential of OER on lead. Lead anodes get oxidized in typical electrowinning conditions and usually have two to three years of lifetime. Although the price of each anode is insignificant, the overall cost of corrosion of these anodes is considerable, which is due to the large number of anodes used in a plant, typically two to three thousand. Therefore, corrosion is a significant problem associated with lead anodes in commercial nickel electrowinning plants and industries show interest in addressing this problem. Corrosion of lead electrodes in acidic environments has been previously the subject of many research studies [I-7]. It has been reported that, during the anodic polarization of lead, several phases may be present on the surface, depending on the potential range that is being studied [8]. Lander showed that lead is oxidized at potentials higher than 0.252 YsHE with tetragonal lead monoxide being the main reaction product [9]. At 0.666 YsHE lead can transform to lead dioxide; however, it is not stable and transforms to lead sulfate and lead oxide. At potentials higher than 1.684 YsHE, lead dioxide is eventually a stable phase and forms a protective layer on the surface [I 0, 11]. Under conditions of a typical nickel electrowinning plant, usually a 200 A/m2 current density is passed through the electrodes."

Jan 1, 2012

By Saskia Duyvesteyn

Small ion-exchange resin particles provide faster mass transport than conventional-sized beads. Unfortunately, high pressures are needed to pump solutions through columns containing small resin particles. It is preferable to disperse fine resins in the solution being treated. Screens have been used to separate the resin from the solution, but screens do not retain fines created by attrition of the resin particles. We have developed a separation process based on flotation, which relies on the surface characteristics of the resin, instead of size. The resin is conditioned with a surfactant before dispersing it in the solution to be treated; this increases the hydrophobicity of the resin sufficiently for froth flotation, without introducing surfactant directly into the solution. The surfactant adsorbed on the resin surface does not appear to impair the kinetics of metal ion removal. A flowsheet for an effluent treatment process is proposed; other applications are clearly possible.

Jan 1, 1998

By Baozhong Zhao

In-situ vitrification (ISV) is a new technology used for treating radioactive, organic and inorganic contaminated soils. In this process, electricity is applied through electrodes buried in the contaminated soil to melt it and form an environmentally stable glass-like solid. The organic contaminants and volatile metals are vaporized during heating up, the non-volatile inorganic elements are dissolved and incorporated into the melt. In present full-scale operation, the ISV process can treat 4 to 6 tons of soil per hour at consumption of about 1000 kwh per ton of soil. In this study, various configurations of electrodes were examined in a mathematical model. The results may be used to optimize the ISV process.

Jan 1, 1994

By B. Q. Li, S. P. Song

"Numerical models are developed to represent complex electromagnetic, free surface deformation and fluid flow phenomena in floating zone refining processes with radio frequency inductive heating. The computational methodology is based on the coupled finite/boundary element method for the electromagnetic field distribution and the Galerkin finite element method for magnetically driven fluid flow and free surface profiles of the molten zone. With the models, the complex transport and free surface phenomena in a floating zone system can be studied as a function of various operating conditions including applied current, frequency, inductor position and shape, surface tension, floating zone diameter and height. Results show that the equilibrium shape is sensitive to the height of the molten zone and that the free surface shapes can have a significant effect on the melt flow in the molten zone. Our extensive simulations also suggest that to ensure accurate results, the same mesh should be used, whenever possible, for both the electromagnetic forces and fluid flow calculations.1. IntroductionThe floating zone processes have been widely used in the materials industry to grow ultra-pure rare earth metal or semiconductor single crystals for sensor or electronic applications that have a tough demand on purity. Developed based on the principle of magnetic melting/levitation, the processes possess a main advantage that the molten zone is supported in air by the electromagnetic forces generated by the coil (see Figure 1), and therefore is free from contamination from a container. Consequently, the final products made from the floating zone processes have higher inherent purity than those by other techniques [1-4].Complex physical phenomena occur in the floating zone processing of materials. These include free surface deformation, magnetically-driven melt flow, which may be turbulent or mildly turbulent [5] depending on the applied conditions, and solidification. Thermal stresses also develop in the single crystals, which are affected by the flow and temperature field and which can have direct implications to qualities of single crystals [6]. An understanding of the fundamentals governing these physical phenomena can be of critical value in elucidating the physics that controls the properties of the metal or semiconductor crystals being produced, thereby providing a rational basis for process improvement and quality control."

Jan 1, 1997

By Roderick 1. L. Guthrie, Mei Li

"A mathematical model was developed to study the role of orifice shape in the detection of inclusions in LiMCA (Liquid Metal .cleanliness Analyzer) system. The fluid flow field within the ESZ was obtained by solving the Navier-Stokes equations. The trajectories of entrained particles were calculated using the equations for motion of particles. A numerical study of the effect of orifice shape on signal shape generated by inclusions passing through orifice showed that the signals in a parabolic orifice are gaussian in shape, while those in a cylindrical orifice are trapezoidal in shape. This signal shape difference needs to be taken into account when performing particle discrimination. Orifice shape influences also pass-through fraction of inclusions. Finally, a study of the orifice shape on critical conditioning currents suggested that as the polynominal coefficient of the parabolic orifice increases, the critical conditioning current, which is also the maximum operating current, decreases dramatically. These critical conditioning currents also increase as the fluid flow velocity within the ESZ increases. IntroductionThe presence of non-metallic inclusions in metals often leads to impaired mechanical properties such as a reduction in fatigue strength, and to processing problems such as tear-offs in deep drawing and increased breakage rates in wire drawing operations. Similarly, inclusions cause a variety of surface defects in rolled or extruded products.Prior to the development of the LiMCA system (1) at McGill University in the early 1980's, it was not possible to measure inclusions, in situ, in liquid metals. Compared with other techniques, such as sedimentation, filtration and metallography, which require considerable amounts of labor and time, the LiMCA method has the advantage of providing not only information on the volume concentration of inclusions, but also on the size distribution of inclusions immediately and quantitatively."

Jan 1, 2001

By Tor Lindstad

Specific C02-emissions are given for the production of silicon-metal, ferrosilicon, ferromanganese and silicomanganese. Emissions taken into account come from reduction materials, from coke production and generation of electric energy. C02-emissions can be abated by direct and by indirect methods. A direct method is to replace fossil carbon as reduction material wholly or partially by endogenous carbon (biocarbon, charcoal). Another possibility is to produce metals by electrolysis instead of the present electric smelting furnace. Indirectly CO2-emissions can be reduced by energy recovery, thus saving coal, oil or natural gas for heat generation. Some reduction in global C02-emissions can be obtained by giving credit for the use of silica dust partially replacing cement in concrete. In addition to give an overview of possible methods, costs will be discussed.

Jan 1, 1999

Pyrometallmurgical reactors constitute a key processing component in the total primary and secondary resource cycle, being involved both in primary smelting, converting and extraction, as well as the reprocessing of scrap, from aluminum cans to end-of-life automobiles. To effectively control the overall resource cycle, one needs to take a systems modeling approach of the whole cycle, seeking to also understand the dynamic process behavior of the individual components of the cycle, and then especially the part that contributes most to the chemical conversion, namely the pyrometallurgical reactor. This paper highlights the role of pyrometallurgical thermodynamics, in the whole resource cycle and specifically places equilibrium thermochemistry in the context of process dynamics where large variable inventories are recycled or maintained within the system. This paper will therefore review the semi-empirical dynamic modeling tools, which are used to model complex systems with the specific goal of developing dynamic predictive models, which also include slag-alloy chemistry, towards controlling the recycling in a feed forward manner. To illustrate the primary processing side, high carbon ferrochrome will be presented as a brief case study. It also will show how the distributed nature of the chemistry of melts in the case of primary extraction, and secondary materials such as recycled end-of-life vehicles, have a significant impact on the process outcomes and model predictions. It is therefore argued that the fundamental thermodynamics and kinetics in metallurgical reactors playa final crucial role in modeling the closed material cycle, but only when it is used in conjunction with process systems theory based on reconciled data for parameter estimation and model calibration.

Jan 1, 2003

By Jürgen Antrekowitsch

Typical zinc oxides recovered from wastes like steel mill dusts and neutral leaching residues are of a low quality because of impurities like fluorine, chlorine, lead and others. Therefore, they are not comparable to technical grade zinc oxides produced in “French” or “American Process”. Some new developments, most of them still in pilot scale, try to establish processes where higher qualities of the product should be achieved. Zinc oxides are not only supposed to be an input material for electrolytic zinc production. Far more, they should find their way into the zinc oxide market as a substitute for technical grade zinc oxides. Furthermore, a new field of application for these oxides has been investigated at the department of Nonferrous Metallurgy, University of Leoben. Because of a higher acceptance concerning different impurities in relation to zinc winning electrolyses, a use in electrolytic galvanizing shows an interesting option. Therefore, synthetic zinc oxides with different impurities were generated to study the effect of these impurities especially on the quality of the zinc layer. Typical steel sheets, as used for car bodies, were electrolytically galvanized and the resulting layer was analysed, as main impurities compounds of fluorine, chlorine, iron, lead and calcium were used for the investigations. Beside the layer quality, the current efficiency and the possible galvanizing speed were examined. The results give an indication, weather such an alternative application can be feasible from a technical and economical point of view or not. 597

Jan 1, 2008

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 R. E. Aune

In the present work, a critical assessment of the thermodynamic information available for the ternary system Ni-W-0 has been carried out; This was complemented by experimental measurements of the standard Gibbs energy of formation of the ternary compound NiWO, by solid state galvanic studies involving Zr02-CaO solid electrolyte. The assessed thermodynamic data, together with the phase diagram information available in literature, were employed to generate the ternary phase diagram for the system Ni-W-0 in the temperature range 1073-1273 K. The calculation of the phase diagram was carried out by computer optimization according to the "CALPHAD" method. The computed phase diagram has been confirmed at isothermal sections by identification of the phases present in samples equilibrated at defined temperatures.

Jan 1, 1994

By R. K. F. Lam

Unacceptable levels of impurity were noted in high purity chromium melting. Analysis of recent melting data determined that oxygen content in chromium is the critical parameter. Thermodynamics studies identify zirconia to be the most stable oxide in the presence of liquid chromium, followed by alumina and silica. Iron oxide reacts readily with liquid Cr. A certain degree of chemical reaction between liquid chromium and oxides does occur, contamination by the crucible is therefore unavoidable. Equilibrium constants indicate that a chromium oxide addition decreases 'ceramic dissolution and reduces impurity contamination. Safe operating conditions with oxygen content between 1190 ppm and 2500 ppm were identified. Additions of chromium oxide (Cr2O3) of 161 grams and 264 grams to liquid chromium yielded acceptable levels of impurity, and oxygen content was respectively increased to 1624 ppm and 2 179 ppm. A new process of melting high purity chromium with chromium oxide addition for controlling the activity of Cr2O3 is recommended.

Jan 1, 1997

By Robert S. Gärtner

The selective aluminum extraction by 3 different calixarenes (p-tert-butyl-calix[4]arene-tetra¬2-acetic-acid-ethyl-ester, p-tert-butyl-calix[4]arene-tetra-2-acetic-acid and p-tert-butyl-calix-[4]arene-di-2-acetic-acid-ethyl-ester) from an industrial pickling bath solution was studied. The pickling bath solution contained hydrofluoric and phosphoric acid as its main components. The aluminum removal was not successful and also no significant extraction of trace metals present was observed.

Jan 1, 1999

By Gökhan Demirci, Ishak Karakaya

"Energy consumption in electrolytic magnesium cells is well above the theoretical values. However, the mechanism of the back reaction, the main cause of the current losses, has not been fully understood yet. Magnesium dissolution into the melt is generally regarded as the limiting step for the back reaction. Accordingly, present cell designs are made with priority given to fast magnesium removal from the cell. However, experimental data and modeling results in this study indicate that the limiting step for the back reaction between magnesium and chlorine is the chlorine dissolution into the electrolyte when physical contact between electrolysis products was eliminated. Effects of chlorine bubbles on the current efficiency and the cell potential were investigated. Results show that the extent of back reaction is proportional to the chlorine surface area in contact with the electrolyte per unit time, and the cell potential increases with the amount of chlorine bubbles inside the electrolyte.1. IntroductionMagnesium is less dense than the electrolyte in electrolytic magnesium production. Therefore, both electrode products, magnesium and the chlorine gas, move upwards inside the molten salt electrolyte during electrolysis. The upward motion of electrode products promotes the most important current loss mechanism, the ""back reaction"". Separation of the highly reactive species; liquid magnesium and the chlorine gas in the cell, to prevent their recombination is one of the main concerns in cell designs. The employment of large inter-electrode distance or a separation wall in early cell designs; decreased the extent of recombination, but increased the cell voltage and energy consumption. Recent cell designs, on the other hand, make use of lifting action of chlorine gas [1,2] by utilizing smaller inter electrode distances to separate the magnesium and chlorine gas faster. Although energy consumption was reduced, but more physical interactions between electrode products make electrolytic magnesium cells still highly inefficient when energy consumptions are compared with the theoretical values. Today, the most efficient industrial cells utilizing high purity feed operate at 10.5-11.5 kWh kg-1 Mg [3-5] and it is considerably higher than the theoretically attainable value of about 6.0 kWh kg-1 [6]. This large gap demonstrates the necessity of more research on physics and chemistry of magnesium cell electrolysis."

Jan 1, 2011

By V. Montenegro

Smelting of copper concentrates in Teniente Converter produces highly oxidized slag, containing from 4 to 10 % Cu and from 15 to 25 % of Fe304. Copper recovery requires magnetite reduction at a level of 5%, determining the degree of cuprous oxide co-reduction and the liberation of copper matte inclusions. The rate of slag reduction is controlled by the mass transfer to the reaction interface. Slag stirring affects the rate of reduction and enhances coalescence of mechanically entrained copper matte inclusions. Slag reduction and sedimentation in the AC electric furnace is a commonly used method of slag cleaning. Utilization of DC electric furnace creates beneficial conditions introducing slag electrolysis additionally to chemical reductions with carbon of coke and electrodes. Application of external magnetic field, interacting with a direct current in an electric furnace, induces magnetohydrodynamic phenomena, such as intensive stirring and electromagnetic buoyancy force acting on inclusions. Laboratory scale research in simulated DC electric furnace with a superimposed magnetic field showed a significant acceleration of the rate of slag reduction and copper removal. Continuous measurement of gas flow and composition allowed for determination of the reduction rate along the time. Application of external magnetic field in the reduction of the industrial slag in a crucible simulated DC electric furnace results such as the increase of the reduction rate from 2 to 3 times, compared with the identical conditions in the AC electric furnace. Interaction of non-homogeneous electric field with crossed permanent magnetic field induces vigorous slag stirring, enhance mass transfer and accelerate the rate of the slag reduction. Additional participations of the slag electrolysis in the magnetite and cuprous oxide reduction as well as the acceleration of the settling of the inclusions by the electromagnetic buoyancy force affect the slag cleaning intensification.

Jan 1, 2003

By M. Olper

Today, copper production from direct leaching of oxidized copper ores followed by solvent extraction-electrowinning (SX-EW) accounts for about 15% of the total primary world output. SX-EW is a well-accepted process with an operating cost in the range 16-20 cents/lb. copper for small and medium size plants, depending on the plant size and local conditions. However, this technology presents some drawbacks that affect the operating cost and cause environmental concerns. ENGITEC and Paques Bio Systems have developed a new process that avoids the solvent extraction step and operates the copper electrowinning step at a lower cell voltage because of the depassivation of the anodic reaction. The consequence of this new concept is that the direct operating cost is in the range 10-12 cents/lb. copper. This new process is composed of the following steps: ? Selective precipitation of copper from leach solutions by biogenic H2S, yielding CuS and regenerating acid ? Leaching of the CuS with a ferric fluoborate solution to dissolve copper and produce elemental sulphur that is recycled back to the H2S biogeneration step ? Electrowinning of copper fluoborate solution in a diaphragm cell with the ECUPREX® Process, producing copper cathodes and regenerating the ferric fluoborate solution to be recycled back to the leaching step ? Biogeneration of H2S from the elemental: sulphur generated during the leaching step, with the nutrient source for the anaerobic bacteria selected form a wide range of organic substances and/or some industrial by-products containing carbon and hydrogen This paper describes all process steps with particular reference to the biological H2S generation technology. Also discussed' is the capability of the ECUPREX® Process to treat copper sulphide concentrates and copper matte.

Jan 1, 1999

By N. J. Tannyan

Laboratory bath smelting tests were conducted to determine the feasibility of smelting nickel- copper concentrate directly to a low iron matte in one step. Concentrate, air/oxygen and a silica flux were fed to a matte-slag bath kept in MgO crucibles at 1300°C. Various oxygen enrichments and smelting rates were used to maintain 0.5 to 2 wt"10 iron in the product matte. The slag losses are comparable to those obtained under similar industrial conditions. Due to the highly oxidizing conditions required to produce mattes with low iron contents, it is not recommended to target iron contents below about 2% in the matte. The specific bath smelting rates were equal to or higher than those in various industrial bath smelting processes.

Jan 1, 2003