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By P. T. Velu

Solubility of metal oxides in the molten salt electrblytes is an important parameter in the electrochemical processing of metals and alloys. The efficiency of an electrochemical process primarily depends on the quantity of metal oxide present in the electrolyte in the dissolved form and its thermodynamic properties. The activity of CeO2 was calculated using the free energy of fusion of CeO2,{ AG°m, CeO2. The AGOm,CeO2 }was deduced from the values of enthalpy, heat of fusion and melting point of Ce02. The activity coefficients of CeO2 as a function of temperature and melt composition were calculated. The thermodynamic data such as integral molar enthalpy, entropy and Gibbs energy of formation were calculated as a function of composition and temperature.

Jan 1, 1994

By Fumitaka Tsukihashi

Increasing amounts of steel scrap are being used as resources for steelmaking. Therefore, there has been a growing interest in the removal of harmful tramp elements such as antimony, zinc, tin, arsenic, bismuth, lead and copper from the molten steel. The problem that should be solved is the economic removal treatment of residual tramp elements in the steelmaking processes and the production of high quality steel by reducing the effect of the contaminated tramp elements and satisfying the environmental regulations. In this paper, the available thermodynamic data of the residual tramp elements in the molten steel arc summarized and the possibility of the removal of residual tramp elements from the molten steel is thermodynamically estimated.

Jan 1, 2003

By Takaaki Shibata

The Tamano Refinery has developed two new processes for removing the impurities, arsenic, antimony, and bismuth from an electrolyte. The first process involves bleeding the surface electrolyte in the electro-refining cells. The copper concentration level in the outermost layer is lower than that in any of the other layers, while the impurity levels are almost the same in all layers. Bleeding the surface electrolyte increases the amount of impurities removed in the liberator by approximately 20%. The second process involves adsorbing antimony and bismuth from the electrolyte by means of chelating resin. As the electrolyte passes through the packed column of chelating resin, antimony and bismuth are selectively adsorbed. They are then desorbed by means of hydrochloric acid, and then recovered in the form of a highly concentrated antimony chloride solution by means of evaporation. This process almost doubles the capacity for removing antimony from an electrolyte.

Jan 1, 1987

By Luis M. Chia

The direct dissolution of zinc in an organic solution of di-(2-ethylhexyl) phosphoric acid (D2EHPA) and kerosene was studied. The objective was to gain a better understanding of the fundamentals involved in the anodic step of the galvanic stripping process. Results showed that metallic zinc does dissolve spontaneously at ambient temperature by an electrochemical mechanism and the presence of additional oxygen activated the process. When oxygen was removed by prior nitrogen sparging, dissolution did not occur indicating a depolarizing cathodic reaction is necessary. The concentration of water in the organic also affected the rate of dissolution. A factorially designed experiment was made using four variables at two levels selected by evaluating results from previous screening tests. D2EHPA concentration, surface area and agitation were all found to be significant for the values chosen. Temperature was less significant and it was found that zinc dissolution is probably a diffusion or mixed controlled process, as indicated by the calculated activation energy of 6 kcal/mole.

Jan 1, 1995

By Goran Vukovic

The use of gas purging plugs in the copper industry is a widely used practice. They provide substantial improvements especially in anode refining furnaces, where savings in process time and energy are obtained as well as refractory wear and buildups inside the furnace are minimized. The newly developed system, enables purging plugs to be implemented in both stationary and tilting furnaces, is in operation in vessels on three continents. An additional advantage in these furnaces above all other benefits is the significantly improved melting rate. This innovative and patented gas purging system consists of a purging plug cooling device and a slidable, cooled piping system. It provides compensation for any thermal expansion in the furnace lining and minimizes the risk of undesirable copper infiltration. User experiences and results of this widely used system are reported in this paper.

Jan 1, 2014

By Ryosuke O. Suzuki

A new cell concept for calciothermic reduction is proposed in which the titanium dioxide instead of TiCl4 is used as the raw material for reduction, Metallic calcium is needed as the reductant of a thermochemicaily stable oxide, such as TiO2. CaCl2, is selected as the solvent of Ca and simultaneously as the solvent of CaO. The reduction system consists of a single cell where both the reduction reaction and the electrolytic reaction for recovery of reducing agent coexist in the same molten CaCl2 bath. A few mol%Ca dissolves in the melt and gives the media a strong reducing power. Sufficiently deoxidized metallic titanium deposits and forms a slightly sintered granular sponge. Both mechanisms of the halide flux deoxidation and the electrochemical deoxidation work efficiently for these fine precipitates, The reducing agent is in situ recovered by electrolysis of CaO because the molten CaCl2 he a relatively large solubility for CaO Some cell designs and modifications are proposed for industrial applications.

Jan 1, 2003

By J. P. Evans

The modem 'copper smelter today utilizes tonnage oxygen for smelting concentrates. ,generating a high strength S02 off-gas leaving the smelter vessel. This gas stream. which also contains any unreacted oxygen, plus CO2; N2 and H20. also carries with it the volatilized portion of heavy metals in the feed, plus partly oxidized sulfide concentrates, The time/temperature history and subsequent treatment of this off-gas stream emerging from the smelting furnace exit up to the acid plant can influence the partitioning and segregation of heavy metals, in the off-gas circuit. Depending on this history. the type and characteristics of the chemical and physical reactions which occur in the gas handling system 'can be influenced. This fact can also be used as a tool to adjust the separation of copper from heavy metals. In this paper, the impact of different time/temperature histories of the gas, due to different furnace geometries and design. on the subsequent formation and characteristics of the smelter dust is examined. Based on the available data. several case histories drawn from examples using both bath and flash smelting technologies are analyzed from this perspective.

Jan 1, 1992

By Fumitaka Tsukihashi

Increasing amounts of steel scrap are being used as resources for steelmaking. Therefore. there has been a growing interest in the removal of handful tramp elements such as antimony, zinc, tin, arsenic, bismuth, lead and copper from the molten steel. The problem that should be solved is the economic removal treatment of residual tramp elements in the steelmaking processes and the production of high quality steel by reducing the effect of the contaminated tramp clements and satisfying the environmental regulations. In this paper, the available thennodynamic data of the residual tramp elements in the molten steel are summarized and the possibility of the removal of residual tramp elements from the molten steel is thcnnodynamieally estimated.

Jan 1, 2003

By Bora Derin, Sertac Yazici, M. Seref Sonmez

"In this study, the recycling conditions of waste liquor obtained after the production of tungsten boride powder from calcium tungstate by self-propagating high temperature synthesis (SHS) and the following hydrochloric acid leaching were investigated in detail. Environmentally unfriendly and extremely acidic (pH~ -0.3) liquor consisting of calcium, magnesium, and boron ions was treated with 1 M sodium carbonate solution to precipitate magnesium carbonate and calcium carbonate phases. The obtained amorphous precipitates were heated up to the temperature of 400°C for re-crystallization. As a result, MgO, CaC03 and CaMg(C03)z phases were obtained, while sodium, boron, chlorine ions were remain in the solution. The present study is still in progress.IntroductionSelf-propagating high temperature synthesis (SHS) is one of the techniques used in the production of a variety of advanced ceramics, inter-metallic, organic and inorganic compounds, oxygen free single crystals, and polymers [ 1, 2]. The reaction becomes selfsustaining and propagates in the reactant mixture, after initiation in SHS process. SHS products may contain the mixture of several unwanted compounds and elements. Therefore following acidic leaching process may be needed to purify the target product. In the previous study, calcium tungstate (Ca W04), magnesium (Mg) and boric acid (B20 3) mixture were reacted to produce tungsten boride powder by SHS process according to the Reaction 1. Then, magnesium and calcium containing byproducts (i.e. MgO, Mg3B206 and Ca3B206) found in the SHS product were leached out by using concentrated hydrochloric acid (HCl) solution to obtain pure tungsten boride powder [3].Ca W04 + 0.5B203 + 4.5Mg = WB + 4.5Mg0 + Cao (1)After the leaching, filtrate solution consisting of different amounts of magnesium, calcium, and boron requires additional treatment for the environmentally acceptable disposal.Several works were carried out about magnesium precipitation conditions and kinetics from brines. Rabadzhieva et al. investigated the precipitation of Mg(OH)z from brines by using NaOH as well as caustic soda [ 4]. Turek ve Gnot investigated the precipitation efficiency of Mg(OH)z for the temperature range between 10-40°C, while the reaction was kinetically experimented by Alamdiri et al [5, 6]. Homogeneous precipitation of nesquehonite (MgC03.3H20) by the reaction of MgCli with (NH4)2C03 in supersaturated solutions and factors that influence the precipitation of MgC03.3H20, such as reaction temperature, initial concentration, stirring speed, titration speed, equilibration time, have been studied by Wang et al [7]. The precipitation of Mg(OH)z by calcium hydroxide from aqueous solutions was studied by Baird et al. [8]. Stratful et al. focused on conditions influencing the precipitation of magnesium ammonium phosphate from wastewaters [9]. 1031"

Jan 1, 2011

By Flávia Paulucci Cianga Silvas, Otávio da Fonseca Martins Gomes, Viviane Tavares de Moraes, Denise Crocce Romano Espinosa, Jorge Alberto Soares Tenorio, Guilherme Apostólico Bortolini, Stoyan Gaydardzhiev

"Printed circuit boards (PCB) are particularly problematic to recycle because of the heterogeneous mix of organic materials, metals, and glass fiber. PCBs are found in almost every electroelectronic equipment and their recycling process involves a pre-treatment to separate the products which contain targeted metals. In this work, a physical processing involving sequential shredding and hanuner milling were used to obtain a comminuted sample from scrap printers PCBs. The thus prepared sample was analyzed for particle size distribution and by optical microscopy as well was subjected to pyrolysis, leachabilty and chemical composition determination by XRF. The metals concentration was determined by ICP and AAS. The PCBs have been also analyzed by SEM-EDS (micro-analysis and X-ray mapping). The results show that the studied PCBs are lead free, multilayer with 4 copper layers, have 45% of metals and the copper is present in significantly higher concentration than the rest of the metals.IntroductionThe global generation of e-waste (electrical and electronic equipment waste - WEEEs) grows at a rate of about 40 millions of tons per year [ l].Among this e-waste there are PCBs that are present in almost all electronic equipment. Their composition is heterogeneous and varies according to several factors, including: kind of EEE, when and where it was produced, fabrication technology [2], etc. In printers, the PCBs represent about 6.6- 8 wt.% [3].The PCBs treatment may include physical, pyrometallurgical, hydrometallurgical, ectrometallurgical and more recently bio-hydrometallurgical process. Normally there is a combination between these processes [2, 4, 5, 6, 7, 8, 9, 10].The diversity between the different PCBs composition complicates the recycling process since the composition of metal and others materials can vary according to the models. So characterization is an indispensable step before any processing of PCB to begin. Owing to the above said, the main goal of this work has been set to characterize representative samples of PCBs from printers through physical, chemical and microstructural analyses."

Jan 1, 2014

By L. I. Rosato

A novel hydrometallurgical process for the recovery of silver and gold from neutral leach residue that is based upon leaching with thiourea, is described. Laboratory and pilot plant studies have shown that 80-90% of the silver and 60-70% of the gold can be recovered by:? ( i) leaching zinc calcine with 'Spent electrolyte at pH 2.0-3.0 to generate a precious metal-bearing zinc ferrite residue, (ii) leaching of the thickened zinc ferrite with 3-5 g/L thiourea in a six stage carbon-in-pulp circuit, (iii) elution of silver and gold from the loaded carbon with a thiourea- butanol solution, (iv) thermal regeneration of the stripped carbon and (v) recovery of the precious metals from the pregnant eluate by cementation with zinc dust. The reasons for adopting the thiourea CIP leach and the preferred operating parameters for each process step are presented. The requirements for the destruction of any thiourea transferred to the zinc circuit are outlined, and the results of an integrated one tonne/day pilot plant operation at Canadian Electrolytic Zinc are given.

Jan 1, 1990

By A. H. Castillejos E., F. A. Acosta G.

Filtration is widely used as a terminal refining step for metals, particularly for the casting of aluminum alloys, but still more knowledge is required to understand how several factors affect the efficiency of removal of inclusions. In this study, both, initial and long term filtration efficiencies of a ceramic foam filter have been obtained from the computed trajectories of solid particles suspended in molten aluminum. The complex structure of the foam filters is represented by a unit cell which is formed by a pair of pores with average dimensions. The fluid flow field was determined from the numerical solution of the Navier-Stokes equation, and periodic fully developed flow was assumed at the inlet of the calculation domain, as a boundary condition. This flow field corresponds to laminar flow as that found in ceramic filters operating under normal conditions. Computed initial filtration efficiencies showed that filtration efficiency decreases sharply with fluid velocity for particles larger than 30 µm, but smaller particles are better trapped at higher fluid velocities. Finally, it was found that long term filtration efficiency for particles of 8 µm decreased with time, in spite that perfect particle-wall attachment was assumed. Filter aging was considered in this study, and it was found that the distorted flow field, around the already trapped small inclusions prevented further collection.

Jan 1, 1999

By Fuming Wang, Xin Lu, Hao Bai, Hebin Zhu

"In this study, CO2 emissions and carbon footprint of a typical steel works with integrated process and iron and steel industry in China was calculated and analyzed by a carbon footprint method based on the model of process CO2 emissions in iron and steel making. The carbon footprint of iron and steel industry from 1991 to 2010 in China showed a rapid increasing tendency. In 2008, the CO2 emissions of iron and steel industry in China was 1.289 billion tons, 19.71% of the national total CO2 emissions, and the corresponding carbon footprint was 159.13 million hm2 of green area. Carbon deficit of iron and steel industry also go up gradually if considering the carbon storage by green vegetation. Thus, the internal carbon reduction strategy, such as energy structure optimization and energy saving technology, was mainly encouraged for the sustainable development of iron and steel industry in China.IntroductionThe Global Warming resulting from the increase of Greenhouse Gases (GHGs), in particularly CO2, in the atmosphere has become the main reason of global climate change, and large emission reductions are required for sustainable development [ 1]. The iron and steel industry is the largest energy consuming manufacturing [2] in the world and the largest emitter of CO2 emissions. In 2005, it accounted for about 20% of global industrial energy use and 30% of energy and process CO2 emissions from industry [3]. In China, the crude steel has firmly been ranking at first of the world recent years and kept growing tendency year by year. With the production growth, the CO2 emissions of iron and steel industry also increased significantly and hence the steel industry has become one of the most sources of CO2 emission in China [4], which has attracted more and more attention to seek the carbon reduction strategies.Carbon footprint is an important and useful concept originating from Ecological Footprint, which was used efficiently to quantitatively analyze the impact of the human activities on ecological system, in particularly impact of the human energy activities [5]. In the view of Life Cycle, the carbon footprint is efficient to analyze the direct and indirect CO2 emission in the whole life of various products used in human activities. As to the iron and steel, the important materials and products in the human life, the carbon footprint analysis is quite necessary to evaluate the CO2 emission impact on the corresponding ecological system and global environmental."

Jan 1, 2013

By Robert Vidal

The performance of a laboratory-scale cell for the electrolysis of an aqueous chrome alum solution was studied. Electrode potentials, pH, and Eh were recorded. An optimum catholyte pH of about 2.5, consistent with information from the literature was observed. Values exceeding this range resulted in a precipitate formation and are detected by wavering cathode potentials. The role of anodically produced dichromate ions was investigated by chemical analysis. It was found that the steady state concentration of dichromate ions varies inversely with fluid flow from catholyte to anolyte. This concentration was also reduced with the use of precious metal coated titanium anodes.

Jan 1, 1994

By R. R. Odle

A laboratory and pilot-scale investigation of direct smelting of copper concentrates was conducted to determine the effect of concentrate analysis and the degree of roasting on the yield and quality of copper produced in a subsequent smelting step. A stoichiometric :mOdel of direct smelting is presented which predicts the? quantity of copper; slag, and white metal' prOduced'and the distribution of copper in these phases as a function? of the concentrate '(calcine) analysis.

Jan 1, 1983

By Derek J. Fray

"In order to extend the application of fused salts in\the electrowinning and electrorefining of metals, it is necessary to maximise the current density, minimise the voltage drop and greatly increase the area of electrode surface so as to compete with the space-time yield of pyrometallurgical reactions. The various designs of electrowinning cell are reviewed and it is shown that by the application of a modest centrifugal field it is possible to reduce the anode to cathode interelectrode spacing to 4 mm whilst still maintaining a current efficiency of 85-90%.The thermodynamic potential for electrorefining is far less than for electrowinning yet fused salt electrorefining is only applied in limited cases. The reasons for this are discussed and the important design parameters evaluated. It is concluded that by using packed bed electrodes, separated by a diaphragm, the possibility of electrorefining with very low energy consumption can be achieved. Carbothermically-produced metals are always cheaper than those produced by electrolysis but suffer from the disadvantage of low purity. It is proposed that fused salt electrorefining may offer an energy efficient way of upgrading the metal. IntroductionThe majority of metals can be deposited from fused salts (1,2) but as commercial production is restricted to the more reactive elements, it is worthwhile considering the advantages and disadvantages of fused salt electrolysis as' compared to smelting and aqueous electrolysis. The advantages over aqueous extraction are as follows:1) the much higher conductivities and diffusivities result in much lower IR losses and higher current densities can be achieved at modest voltages;2) the elevated temperatures of operation result in larger exchange currents which give rapid kinetics and lower activation polarisation for the electrode reactions;3) the absence of water as a solvent means that it is not necessary to consider the evolution of hydrogen as a competing cathodic reaction. Furthermore, alkali halide salts, often used as solvents in fused salt electrolytes, have high deposition potentials;4) molten salts generally are mutually soluble and, therefore, concentration polarisation effects are minimised."

Jan 1, 1988

By David M. Davidson

Seven intrusive phases have been mapped to date in the 1 b.y. Red Bluff Granite Complex (RBGC) near El Paso, Texas. This batholith is 20 km2 in area and intrudes older supracrustal units as well as a trachyte ignimbrite cap. Two early microgranite sills are spatially separated 6 km from a porphyritic, three-phase "ring complex" by a tin-bearing, biotite granite which cores the RBGC. These units are intruded, in turn, by a riebeckite granite which locally exhibits lineated and pegmatitic textures as well as exceptionally high light REE and Zr values (800 ppm La; 3,000 ppm Zr). The riebeckite granite is exposed in three separate occurrences within the Franklin Mountains. REE values in the RBGC are depleted in HREE and show distinct negative Eu anomalies. Typical La/Yb ratios are 5:1-2:1 with Eu values ranging from 10-80 ppm. The mineral source of the high REE values in the riebeckite granite has not yet been specifically identified, but is believed to be zircon.

Jan 1, 1988

By Jie Li, Zhongliang Tian, Xun Hu, Kai Zhang, Yanqing Lai, Hongliang Zhang

The Al-Sc Alloys show many advanced properties for a wide range of engineering applications. But the metal Sc must be added into the metal Al in the form of the Al-Sc master alloy, which is usually produced by the thermal reduction process. In this paper, the decomposition voltages of Sc2O3 and Al2O3 in Na3AlF6-K3AlF6-AlF3 melt were calculated based on the Nernst equation. And the Al-Sc master alloy was prepared in the melt at 950°C by electrolysis. The results show that the Al-Sc master alloy can be prepared by the co-deposition of Sc3+ and Al3+ at the cathode if the concentration ratio of Sc2O3 to Al2O3 in the melt is more than 2:1 under the condition of the aluminum electrolysis. SEM and ICP analysis of the product indicates that the Al-Sc master alloy is made of the phase Al and the phase Al3Sc.

Jan 1, 2016

By Chunlin Chen

Nickel-sulfide minerals are normally associated with copper and iron sulfides and often contain a minor amount of valuable metals such as cobalt and detrimental impurities such as arsenic. Metal losses in slag vary from process to process during the pyrometallurgical production of nickel and, depend on the feed composition, slag chemistry and operating conditions. Maximiz the metal recovery is one of major considerations to optimize operating condition for nickel smelting/ converting processes. At the same time, the deportment of minor elements between various phases during nickel smelting is of great importance by smelter operators. The Multi-Phase Equilibrium (MPE) is a thermodynamic package developed by CSIRO for simulating reactions between phases in multi-component and multi-phase systems [1]. Over the years the capability of the MPE model has been extended to cover the behavior of a large number of elements in high temperature systems. The sulfide smelting module of the MPE, which covers the minor elements such as As, Bi, Sb, Pb, Se, Te, Sn, Co and Zn, is capable of modeling the deportment of major and minor elements between various phases during nickel smelting. In this article the application of the MPE model in modelling the nickel smelting process is presented. The modelling results on the majors and minors are compared with the plant data. The deportment behaviour of arsenic in nickel smelting was analysed and the impact of slag chemistry on slag properties was modelled. These results can assist process metallurgists in exploring the optimum fluxing strategy for smooth operation and the potential practices for improving arsenic removal.

By Joseph Goodwill

1. PURPOSE The objective of this paper is to summarize a study undertaken by the EPRI Center for Metals Production (CMP). The overall purpose of the study was to identify electrolytic opportunities that might merit consideration for joint development by industry and EPRI. 2. SCOPE The electrolytic technologies of interest to this study include: Electrorefining, Electrowinning, and Fused-salt electrolysis. Recovery from primary, secondary, and waste materials were included in this effort; however, we excluded from consideration: Plating and coating operations, such as electrogalvanizing; Mining and milling operations in which electric energy is predominantly used for comminution; Electrothermal processes in which submerged-arc, open electric-arc, and plasma-based smelting processes use electric energy largely to provide a melting or refining ("heating") capability; and Aluminum electrotechnologies since these were the subject of a separate study (CMP 86-2). We recognize that there may be some "gray areas" between these excluded areas and the electrolytic sectors of interest. For this reason, a secondary criterium was used, namely, if the major use of electric energy was to extract or refine the

Jan 1, 1990