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By Shun Myung Shin, Kang Jeong, Kyoungkeun Yoo, Jin Koo, Dong Hyo Yang, Soo Sohn

"The optimum discharging condition to dismantle the batteries without explosion was investigated to recycle the lithium primary batteries, which could be exploded by heating too much or crushing. The 3 waste lithium primary battery cells were discharged with 500 cm3 of 0.5 kmol·m-3 sulfuric acid. Fe concentration and pH increased rapidly after 3 days at 35? and after 1 day at 50?. Chromium concentration increased by 4 days at 35? and 2 day at 50?and then decreased, and nickel concentration was very low. Because Li concentration increased gradually, Li became dissolved after the dissolution of cover material. When the discharged batteries were shredded, the batteries discharged at 50°C were not exploded and those discharged during 3 days at 35°C were exploded. This result shows that the waste batteries could be stabilized within 1 day at 50°C and 4 days at 35°C. Introduction Lithium has some advantages for battery e.g. it is the lightest metals and also has the highest electrochemical potential at 3.04V[1]. For over thirty years lithium primary batteries became famous for their performance in various applications such as IT, medical, and military[2,3]. They gained a reputation for their long shelf life, constant voltage, wide operating temperature range, and low self-discharge characteristics[3-5]. World primary lithium battery market was expected to grow from $820.6 million in 2003 to $1,1355.3 million in 2010 (http://www.frost.com, Frost & Sullivan)[2-4]. The lithium primary batteries have very various sizes and components. Lithium batteries are made with lithium metal as anode active material and non-aqueous solvent as electrolyte. As cathode active material, various kinds of materials were used such as manganese dioxide (nominal voltage, 3.5V), thionyl chloride (3.6V), and carbon monofluoride (3.0V). In Korea, 50 % of the spent lithium primary batteries must be recycled because spent lithium primary batteries have been listed in EPR (Extended Producer Responsibility) of the enforcement degree of the act on the promotion of saving and recycling of resources. However, the batteries have been landfilled since there is no economic method to recycle the batteries in Korea[2,3]. When the batteries were heated too much, charged, pierced, over discharged, or short-circuited, the batteries explode because lithium reacts violently with water or air and because contents such as lithium, electrolyte, and sulfur become flammable by high temperature[4]. Therefore, it is so difficult to recycle safely the spent lithium primary batteries."

Jan 1, 2008

By Itavahn Alves da Silva, Izabela Diniz Duarte, Carlos Antonio da Silva, Varadarajan Seshadri

Mathematical modeling using computational fluid dynamics has been employed to assess the thermal losses in a steelmaking ladle. Thermal losses lead to thermal stratification and convective flow inside the ladle. The effects of preheating, mineralogical and physical characteristics of the lining as well as thickness of slag cover have been studied and the results obtained from application of the model have been discussed.

Jan 1, 2016

By F. Kongoli

Viscosity is an important parameter of copper smelting and converting processes. It affects the settling of matte or metal droplets in the slag, distribution of elements etc. Despite this importance, confusion exists on the viscosity of copper smelting slags as a result of disagreements found among the measured viscosity data of several authors especially in the slags of high ferric iron content and close to magnetite precipitation. In this work a critical review of the existing data on the viscosity of copper smelting slags has been first carried out and the effect of oxygen potential on the viscosity of copper smelting slags has been clarified through a coupled quantification of viscosity and liquidus temperature. The confusion in the literature has been clarified and the importance of the relation between the viscosity and the liquidus temperature is discussed.

Jan 1, 2003

By llya Perederiy, Vladimiros G. Papangelakis, Indje Mihaylov

"Nickel slags obtained from various smelting furnaces and converters differ in terms of their chemical composition and microstructure. The microstructure of the slag is largely affected by how fast the slag is cooled after being discharged from the furnace. Slow cooling is known to promote crystallization and growth of phases such as crystalline fayalite (Fe2Si04), magnetite (Fe3Ü4) and vitreous silica (S1O2). Slag granulation causes rapid solidification of the melt in the form of either an amorphous solid or highly intergrown crystalline silicate and oxide phases. Smelter slags contain entrapped Ni, Co and Cu in the form of dissolved oxides and matte inclusions. Extraction of the entrapped metals by high pressure oxidative acid leaching (250°C, 70 g/L initial H2SO4, up to 90 psi O2, 45 min) relies on the dissolution of the metal bearing minerals. The impact of the slag microstructure on the accessibility of these minerals to leaching, as well as the morphology of the produced residues is discussed in this paper.IntroductionIt was shown previously that entrapped base metals can be efficiently extracted from naturally cooled (as opposed to granulated) crystalline nickel smelter and converter slags using high pressure oxidative acid leaching operating at 250°C, ~40 g/L terminal acid and 60 to 90 psig oxygen overpressure [1, 2,3,4, 5, 6].Mineral characterization work performed on a naturally cooled crystalline nickel furnace slag from Vale's operations in Sudbury (ON, Canada) was previously reported [4]. Fayalite (Fe2Si04) and magnetite (Fe3U4) were detected using powder X-ray diffraction. These two minerals as well as silica (S1O2) and matte ([Fe,Ni,Cu]Sx) were also identified with the help of energy dispersive X-ray spectroscopy (EDX) on cross-sectional images obtained with a scanning electron microscope (SEM) operating in the backscattered mode. Nickel converter slags obtained from Vale's operations in Sudbury were found to be mineralogically similar to the furnace slag, but with higher contents of matte entrainment and magnetite based on the SEM-EDX observations [6]."

Jan 1, 2012

By K. J. Richards

The converting of copper mattes to blister copper has seen few technical advances since the introduction of batch furnaces using submerged tuyeres over a hundred years ago. The first side-blown converting vessel, operated by P. Manhes in 1882, was an offshoot of the 'Bessemer steelmaking process, and subsequent improvements in the conversion of molten mattes resulted In the Peirce-Smith converter, still the Industry standard today. While Peirce-Smith' converting has served the industry well since the early 1900!s, increasingly stringent environmental regulations, burgeoning energy costs, and a trend toward continuous processing have set the stage for a major improvement in this area of copper production. In contrast to a growing number of approaches for continuous converting using molten copper mattes, Kennecott is developing a process for treatment of solidified matte which allows improved' control, higher oxygen enrichment and a separation or decoupling of smelting and converting operations not possible with the other converting technologies. The new process known as Solid Matte Oxygen Converting, or SMOC, eliminates the need for molten matte transfers, minimizes fugitive emissions, and produces high strength SO2 off gases which substantially reduce offgas handling requirements. The SMOC process, despite additional matte solidification and size reduction steps, offers both capital and operating cost advantages for new smelters and the upgrading of existing plants, when compared with conventional converting technologies. Capital cost reductions of up to 35% in converting, gas handling, and sulfur fixation are indicated. Kennecott has successfully tested the new process concept and continued' development work is now under way to commercialize the technology. This paper reviews the limitations of batch copper converting with emphasis on the need for a continuous process, previous industry approaches to continuous converting of molten mattes, and the new Kennecott development.

Jan 1, 1983

By Ricardo Melamed

Metallic mercury has been extensively used for gold recovery. Although the solubility and mobility of metallic mercury is low, this metal can undergo many transformations, leading to mercury contamination in humans. The complexity of Hg chemistry in the environment reflects its different possible oxidation states and species, with different physical-chemical properties. The interaction of Hg in the terrestrial system, as well as in the aquatic environment, is important to understand the mercury cycle. This paper reports data on the adsorption of Hg onto an Oxisol soil. Results show that the interaction of Hg(II) at the soil-solution interface depends strongly on ligand concentration in solution, which can affect Hg mobility. The presence of the chloride anion in solution increases the mobility of Hg(II) through the soil, due to a relative lower affmity of mercury chloride at the oxide surface. In the absence of chloride, Hg(II) form strong complexes with the surface, and its adsorption behaviour is similar to the adsorption of other hydrolizable cations.

Jan 1, 1996

By F. Kongoli

Viscosity is an important parameter of copper smelting and converting processes. It affects the settling of matte or metal droplets in the slag, distribution of elements etc, Despite this importance, confusion exists on the viscosity of copper smelting slags as a result of disagreements found among the measured viscosity data of several authors especially in the slags of high ferric iron content and close to magnetite precipitation. In this work a critical review of the existing data on the viscosity of copper smelting slags has been first carried out and the effect of oxygen potential on the viscosity of copper smelting slags has been clarified through a coupled quantification of viscosity and liquidus temperature. The confusion in the literature has been clarified and the importance of the relation between the viscosity and the liquidus temperature is discussed,

Jan 1, 2003

By R. Steven Izatt

Green chemistry principles will be discussed, and examples will be given of the use of Molecular Recognition Technology (MRT) to selectively separate specialty metals such as cobalt, nickel, bismuth, rhenium, molybdenum, indium and germanium from various primary and secondary feed streams. Recovery of these metals has numerous advantages including (i) conservation of valuable resources, (ii) prevention of environmental damage, and (iii) elimination of capital and operating expenses due to re-processing or disposal of metal-bearing streams.

By Yasushi Sawada

An experimental investigation was carried out to study the rates of reduction of iron oxides dissolved in liquid Ca0-SO2-A203 slags by Fe-C droplets at temperatures ranging from 1325 OC to 1550 OC. The %FeO in the slag was varied from 5.5 to 18. Flash X-ray images were employed to observe the behavior of Fe-C droplets in the slags during the reactions and for determining the slag-gas-metal interfacial area. Effect of P205 in the slag and sulfur in the droplet was also investigated. The reduction rates were determined by measuring the volume of CO evolved as a function of time and the estimated slag-gas- metal interfacial area. The reduction rates have increased with increasing %FeO in the slag and the slag temperature. The experimentally established relationship between the reduction rates and FeO (wt%) in slag is given by

Jan 1, 1992

By R. Boom, Y. V. Meteleva-Fischer, B. Kraaijveld, H. Kuntzel

"Segregation of impurities during refining of metallurgical grade silicon (MG-Si) is an option to produce solar grade silicon (SG-Si). Directional solidification is a last step in production of SG-Si effective for removal of metallic impurities. The possibility is investigated to use metallic impurities originally present in MG-Si for removing boron and phosphorus. MG-Si has been treated using two methods: 1) alloying with calcium and 2) refining with Na2O-CaO-SiO2 slag, both by controlled cooling. The microstructure of silicon and the impurities distribution have been studied before and after the treatments. Using EPMA phosphorus and boron have been detected in 1-2 wt% concentration range in several intermetallic compounds in grain boundaries after both treatments. This observation points to a different possible mechanism of silicon refining from boron and phosphorus. Controlled cooling improves migration of phosphorus and boron to the silicide phases in grain boundaries, which can be removed by acid leaching treatment.2. IntroductionStandards for silicon solar cells and growing demand on “green” energy require economical and efficient route to the production of solar grade silicon. Refining of cheap metallurgical grade silicon is one of the promising options, where application of existing metallurgical approaches can result in cost-efficient production on industrial scale. Focus in refining is on impurities, which are most difficult to remove: B, P, Al, Ti, due to their large segregation coefficient in silicon and low vapour pressure [1]. Moreover, more environmentally friendly technology in comparison to the traditional Siemens process [2] will be in accordance with societal needs. Based on properties of common impurities in metallurgical grade silicon, alloying refining and slag refining are suggested as competitive techniques having potential effect on removal of impurities harmful for conversion of solar energy [3, 4]. Alloying with Ca followed by acid leaching was found to be effective for removal of Fe and Ti from silicon [5] and to enhance also removal of boron [6] and phosphorus [7, 8]. In the work of Inoue et al. [8] drastically increasing removal of phosphorus from silicon has been observed with an increase of Ca content and a thermodynamics-based explanation was provided. Since phosphorus has been found to condense in the secondary precipitate mainly composed of CaSi2, it can be removed together with iron and titanium by consecutive acid leaching treatment. Slag refining is one of the metallurgical methods proposed to be effective for refining of metallurgical grade silicon from boron [9, 10]. Slags with additions of the following oxides to silica have shown positive effect on removal of boron: CaO [11-13], Na2O [11,14]. Mechanism of slag refining from boron is based on oxidation of boron followed by its incorporation in the slag network [9,11]; the same mechanism is suggested for refining from phosphorus taking into account that oxides of boron and phosphorus are known as network-formers [15]."

Jan 1, 2012

By W. Kunda

A laboratory study was carried out on the treatment of sulphidic copper concentrates in aqueous chloride systems under elevated temperatures and oxygen overpressure. Exploratory tests showed that chalcopyriteoxidizes with various chloride salts to form, depending upon the pH of the system, soluble copper chloride or insoluble copper oxychloride salts; the copper can then readily be recovered from the solution or residues respectively. During the leaching, iron was oxidized to iron oxide and remained in the leach residue while the bulk of the sulphide sulphur was oxidized to the elemental form with a minor portion oxidized further to sulphate. The presence of metal chloride salts in the system increased the oxidation rates of chalcopyrite and depressed the solubilization of iron in the system. A systematic oxidation leach study carried out in (1) ammonium chloride and (2) sodium chloride systems showed that the former system required little or no HC1 addition while the latter required 2 mol of HC1 per mol of dissolved copper (plus zinc). The copper was recovered from the cuprous or cupric chloride leach solutions by cementation with iron. Extractions of 99% copper and zinc, 97% silver, and negligible iron were obtained. Sulphur was oxidized to the elemental or sulphate form; the relative proportions of the total sulphur were 60 and 30% for system (1) and 80 and 10% for system (2). A flowsheet for a conceptual process with minimal reagent requirements was proposed.

Jan 1, 1976

By Moto Goto

Onahama Smelter of Onahama Smelting & Refining Co., Ltd. has two green- charge reverberatory furnaces; the old furnace was constructed in 1965 and the new one in 1973. This paper discusses the use of oxygen-oil burners in a green-charge reverberatory furnace and also compares the copper loss in slag between the two furnaces at Onahama Smelter. During the past ten years of operation, no shutdowns of the old furnace were necessary and the smelting capacity was increased by 25% by the use of two oxygen-oil burners. These burners are suitable for a green-charge reverberatory furnace to in- crease the smelting capacity without causing an increase of the exhaust gas volume and refractory erosion. After two years of operation of the old furnace, a bottom build-up in the charging zone of approximately 50 centimeters was experienced, and this build-up has stayed at this level since then. In 1973, a new additional reverberatory furnace was put into operation. Copper content in slag of the new furnace was lower by approximately 0.15% than that of the old one during the first several months after the start-up. Investigations were then made on the effect of the bottom conditions in the charging zone on the copper content in slag.

Jan 1, 1976

By Wang Shulan

The synthesis process of BaTiO3 from TiO2 and BaCO3 in the molten NaOH-KOH at 350oC was studied by the A.C impedance technique. The A.C. impedance of molten NaOH-KOH (xNaOH = 0.36) and the variation of the conductivity of the salt with time during the synthesized process were measured. The synthesized reaction of the BaTiO3 and the decomposition reaction of BaCO3 are fast and were finished in 10min. The interaction between TiO2, BaO and BaTiO3 and the molten salt was confirmed by the variation of the conductivity.

Jan 1, 2005

By Gudrun A. Saevarsdotti

For decades tile aluminium industry has been practicing gas treatment of aluminium melts. This treatment is of great importance because of its influence on 'impurity" and inclusion removal from the melt. The gas-melt interaction is greatly influenced by the gas composition, melt temperature etc. This paper gives an overview of the interaction between argon-chlorine gas mixtures and the aluminium melt. It covers the thermodynamics of the reaction between the chlorine and a number of different elements commonly found in liquid aluminium, and discusses the behaviour of reaction products in the melt. The paper reports an experimental study of the behaviour of the chlorine-molten aluminium interface, using sodium contaminated aluminium melt with and without the addition of grain refiner.

Jan 1, 1996

By Shawn A. Cefalu, Matthew J. M. Krane, Kent J. VanEvery

"Segregation during electroslag remelting (ESR) of a nickel-chromium-molybdenum alloy (Ni-8 wt% Cr-25 wt% Mo) has been modeled. Features of the model include species transport and AC electromagnetic effects coupled with fluid flow, heat transfer, and solidification. The effect of varying ingot diameter and melt rate, on macrosegregation patterns, local solidification time, and liquid pool profiles obtained from this model are demonstrated. The results show that the macrosegregation in the ingots correlates to the filling velocity.IntroductionElectroslag remelting (ESR) is a secondary melting process used to refine the chemical composition and the microstructure of metals. Macrosegregation of solute elements causes defects in ESR ingots, including freckles and the maldistribution of phases. These defects are not correctable through heat treatment due to the large length scales over which they occur. However, the frequency and distribution of these defects may be minimized, or even prevented, through process control based on an understanding of the conditions that lead to their formation.In the past, studies have been conducted on the effect of the process parameters on the shape of the melt pool and the thickness of the mushy zone [1-7]. In these studies, the shape of the liquid pool is determined by consideration of the heat and fluid flow induced by electromagnetic (Lorentz) force and thermal buoyancy. The transport of solute and the resultant solutal buoyancy effects were not considered in these macroscopic models. Defect formation is tied to formation of secondary phases (e.g., freckling and white spots in nickel superalloys) [5,8]. In cases where secondary phase formation is calculated (e.g., [6]), phase fractions are determined using a micro-scale model given the local solidification time (LST) and local thermal history from the macroscale model.Using the local thermal history from the macroscopic transport model to predict microstructure increases the importance of the accuracy of those results. This investigation models the macrosegregation of molybdenum during the ESR of a Ni-Cr-Mo alloy. The effect of macrosegregation on pool shape and depth is demonstrated, along with its effect on the local solidification time. By comparing the relative effects of the melt rate and ingot radius, a better understanding of the factors that affect macrosegregation, and ultimately secondary phase formation may be obtained."

Jan 1, 2004

By Torma A. E.

Biotechnological processes are considered to be cost effective especially for situations where the recovery of metals from 'Very large volumes containing trace metal concentrations (less than 10 ppm) is concerned. Microorganisms, alive or dead, or their products can be highly efficient and selective biosorbents for metal concentration. It is important that the metal bound to the biosorbent can be stripped by suitable agent(s) and regenerated for repeated use. The stripped solution should be concentrated enough to be introduced into the common metal recovery circuit. The industrial acceptance of biosorption processes is dictated by increased competitive advantage over other processes. This paper reviews the pertinent literature?, regroups the information, and points out future possibilities for the mineral and metal processing industries.

Jan 1, 1992

By Andres Vikdahl

The Rönnsktär smelter has recently undergone a series of technical and operational changes. This changes are caused by our own will to remain and gain in competivety and to adapt to the ever changing surroundings. To be able to remain competitive in surrounding with high wage costs, high inflation and high environmental standards thorough cost management is needed. The Swedish economic policy in the beginning of the 80'ies consisted amongst other things of two devaluations. The exchange rate of the Swedish Krona was reduced with approximatively 25 %. This boosted the profits of our export industry, some even believed we entered the land of milk and honey ... And working in this promised land where everything turns into profit it is very difficult to be careful and restrictive with your spendings. Apart from some healthy and fruitful investments we allowed ourselves yearly steady increases in salary for ever reduced number of worked hours and we of course employed more people. Inflation rates went up and so did property prices. In 1986 finally reality catched up on us. Reality in the form of too high costs started to hit Swedish export industry 5-6 years after the big devaluations. Furthermore the high inflation rate also hit the domestic industry a couple of years later. Together with other important factors Sweden faced a severe home-made recession in the beginning of the 90'ies. With this background we now report and analyse our smelter's performance and operating results, shown in fig 1 The main constrictions on smelting and refining at Rönnsktär are today: * Income restrictions by governmental production level Limit * Throughput resmctions by governmental emission limit * High capital costs in the aftermath of Swedish high inflation in the recent decade * Low work force turnover Below we will illustrate how we tackled with these issues along the following lines: * People * Quality * Technology

Jan 1, 1993

By Guanghui Li, Xuling Chen, Zhiyun Ji, Min Gan, Tao Jiang, Xiaohui Fan, Zhiyuan Yu

With the increase of proportion of biochar(without modified) replacing coke breeze, the physical strength of sinter decreases due to the faster burning speed of biochar. An investigation upon passivating biochar with boric acid was then conducted to strengthen sintering in this paper. A layer of thin film of B2O3 distributed in the surface of biochar was observed, which could reduce the contact between reaction gas and biochar. So the burning speed of biochar was decreased properly after passivation, and the combustion efficiency increased due to the inhibition of carbon gasification. The comprehensive effects of above changes could increase the maximum temperature of sintering bed, which facilitated to the mineralization of sintering mixtures. Eventually sintering indices got reinforced. Thus the indices of sinter as applying 40% passivated biochar were comparable with that of 100% coke breeze.

Jan 1, 2015

By Adam Powell

A Cahn-Hilliard phase field model is formulated to describe transport-limited electrochemical reactions coupled with fluid flow in a metal reduction cell. When the reaction is limited by mass transfer of metal ions from the electrolyte to the cathode, the metal-electrolyte interface at the cathode exhibits a Mullins-Sekerka instability, leading to the growth of dendrite-like "streamers" of liquid metal into the electrolyte, which in turn significantly enhance the apparent mass transfer coefficient there. Model results for iron reduction from ferrous oxide in slag show formation of these streamers. Although the double-layer is not included in this model, the related phenomenon of electrocapillarity can be represented by a gradient penalty term which includes the electric potential gradient, such that interfacial energy is a function of the electric field normal to the interface.

Jan 1, 2003

By Simon N. Lekakh, D. G. C. Robertson

A new integrated CFD-combined reactors approach is proposed for the description of processes in metallurgical vessels. CFD simulations were used to obtain the melt flow pattern in the vessels (ladle, tundish, and continuous caster mold). From these simulations, the characteristic curves were derived: (i) the residence time distribution curves (RTD) for flow-through systems (at tundish exit or at dendrite coherency surface in the mold) and (ii) the mixing curves for closed systems (ladle). In the next step, the melt flow was represented in a “combined reactors” system consisting of a combination of unit reactors (Plug Flow, Mixer, and Recirculated Volume). An inverse simulation was used to define the volumes of the reactor units and the melt flow rates between them by fitting to the characteristic curves from both methods (CFD and combined reactors). The suggested approach is demonstrated for multiple designs of Ar-stirred ladles, tundish, and SEN. This methodology can be used to enhance traditional post-processing CFD analysis and also as a tool for on-line process control.

Jan 1, 2014