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By Merete Tangstad, Lars Klemet Jakobsson

"Slag refining is a promising refining method for boron removal from silicon as a part of a metallurgical route for production of silicon for solar cells. There is, however, limited data on the distribution of impurity elements between silicon and different types of slags. In the present study, the distribution of boron and calcium between silicon and slag were determined at 1600 °C for calcium silicate slags with a CaO/SiC>2 ratio between 0.65 and 1.3. An almost horizontal linear trend was found for the distribution of boron between silicon and slag, and the borate capacity was found to follow the relationln(CB0, ) = 30.8 + 2.96-V (1)where V\s the CaO/SiCh mass ratio within the range of the experiments.IntroductionSolar grade silicon feedstock contributes significantly to the total cost and energy required to make crystalline silicon solar cells. A less expensive and less energy requiring method of solar grade silicon production is therefore needed in order to make crystalline silicon solar cells more viable as an energy source. Silicon is an abundant element and the manufacturing cost of solar grade silicon is therefore mainly determined by costs related to purification of metallurgical grade silicon. The Siemens process is the most common process today, but it is an expensive and highly energy requiring process that gives silicon with a higher purity than is needed for crystalline silicon solar cells. A cheaper and less energy requiring method for production of solar grade silicon can either be achieved by modifying the Siemens process or by using a new production method. Purification of metallurgical grade silicon through a metallurgical route is a promising method that is already in use industrially. It has however proven to be hard to lower the boron content to 0.3 mg/kg or less, which is the requirement for most p-type crystalline silicon solar cell manufacturers. Slag refining is seen as one of the most promising approaches that can be used to bring down the boron content to the required level, but there is not much data on how boron is distributed between silicon and binary calcium silicate slags [1-4]. The distribution of boron between silicon and calcium silicate slags at 1600 °C has been studied in this work, and the obtained data has been used to calculate the borate capacity of binary calcium silicate slags."

Jan 1, 2012

By G. Gao

Flyash from municipal solid waste (MSW) incinerators is frequently classified as a characteristic hazardous waste due to its lead and cadmium content. Extensive investigation has therefore been carried out to detoxity the flyash by leaching and to recover lead, cadmium and zinc. Detoxification can be accomplished by leaching in HCI/NaCI solutions. Optimization of leaching conditions for effective detoxification and subsequent metal recovery can be achieved by controlling the acidity of the lixiviant and flyash to lixivaint ratio. Lead and cadmium In the leaching solution is recovered by cementation with zinc dust. Leaching and cementation experiments have shown that zinc concentrations suitable for electrowinning, > 15 g/liter, can be achieved. Experiments have also been performed to determine the effects of pH, particle size of the zinc dust used, quantity of zinc added and dissolved impurities on the cementation kinetics. After recovery of lead and cadmium, electrowinning or electrowinning coupled with solvent extraction can be used to recover zinc. A process flowsheet is presented.

Jan 1, 1991

By Patrick R. Taylor

Glass is used for immobilization of radioactive and hazardous wastes due to its durability and ability to accept a variety of waste constituents into its network structure. Alternative high temperature vitrification techniques have the advantage of increased throughput, increased waste loading and being applicable to variable and heterogeneous waste streams. However, the increased processing temperature places further concerns on the increased volatilization of contaminants, and increased corrosion and erosion of me Iter components. A database of melt properties at higher temperatures, such as partitioning, viscosity, density and electrical conductivity, in the temperature range of 1400-20000 K are being developed.

Jan 1, 2000

By R. A. Roberti

Most copper refineries use conventional wheel systems to cast anodes. over a period of time the copper moulds that are used become warped and cracks develop. To control mould warpage, the mould's are either rejected after a certain warpage is reached, or the shape is restored by mechanical means. The cracks, unless they are very severe, are repaired by a peening process. Even with regular maintenance to control warpage and cracks, the moulds have a limited useful life. If warpage and cracks are not controlled, anode quality deteriorates and tankhouse operations are seriously affected. -An intensive study was initiated to develop means of controlling mould warpage which culminated in the d?evelopment of technology to control mould warpage to within ±1. 5 mm, and at the same time effectively contr0l: cracking and significantly increase the mould life-. The warpage control has been achieved by using a unique mould design. Mould cavities are present on both sides of the mould and periodic inverting controls the wa-rpage in the cavities. The mould casting procedure has been developed and all production wheels have been converted to the new mould design. The performance characteristics of these moulds will be detailed. 21

Jan 1, 1987

By Federico Chavez

The process for recovering lead from battery residues used in several Mexican Plants include lead blast furnace and rotary furnaces. The formers are basically fed with recycled batteries together with the necessary additives to produce metallic lead. One of the by-products generated in the blast furnace is a dust mainly formed by lead sulfide. The rotary furnace is used to recover lead .from lead batteries, dross from the refining-alloying process and the leady fines produced in the blast furnace. This paper describes thennodynamic analysis made to the rotary furnace process to understand the effect that each component of the system has upon the lead recovery. In order to enhance the process, the influence of iron chips composition and excess coke on slag viscosity is discussed. A computer optimization program . has been developed to design the furnace charge based on material and energy balances, .together with the thennodynamic equilibrium calculation.

Jan 1, 1995

By R. Cavanagh

Studies relating to the fixation of sulfur by reaction of 4 to 8 mm diameter cylinders of calcined limestone or dolomite with high strength sulfur dioxide in the temperature range 880°C to 1020°C were undertaken. Dolomites are far superior in sulfate capacity and reactivity than dense limestones even at high strength SO2. The sulfation reaction was first order with respect to SO2 concentration below 100 percent. Zero reaction rate at 100 percent SO2 concentration indicates that sulfate was the exclusive reaction product and that sulfite had no role in the reaction. At relatively low SO2 concentrations gaseous diffusion through the reaction product layer has a marked effect on the rate. As SO2 concentrations were increased up to 100 percent more complex rate controlling mechanisms unfold. By sectioning partially reacted dolomitic limestone pellets a moving interface was observed. Reaction ceased because of pore plugging for dense non-porous limestones at 30% conversion. With dolomitic material virtually complete sulfation of the calcium was observed. S.E.M. analysis showed that the average atom ratio Ca:S was 1.01, thus supporting the argument that little if any of the magnesium was sulfated.

Jan 1, 1996

By Young-Dae Kim, Dong-Sic Kim, Jong-Jin Pak, Kyung-Hyo Do

"Sulfur is one of the most harmful elements in stainless steel (SIS) products and the specification of sulfur content is getting more severe for high grade SIS. In order to accurately control the desulfurization reaction in high chromium containing SIS melts, it is important to know the thermodynamic interaction between chromium and sulfur in Fe-Cr melts over a wide range of chromium content. In this study, the equilibrium sulfur distribution, Ls, between a Ca0-Alz03 slag and Fe-Cr-C,.,-S melts were measured under CO atmosphere in the temperature range of 1823-1923 K. The specific effect of chromium on the activity coefficient of sulfur in the melts was determined with the consideration of carbon effect on sulfur. A separate experiment was carried to determine. Ls between a slag and FeCr- S melts (Cr: 0-30 mass%) at 1873K to check the validity of the thermodynamic parameter determined in the present study.IntroductionFerritic stainless steels containing chromium (Cr) up to 30 mass% have been developed for a good corrosion resistance and a high formability to replace austenitic SIS. Especially, Sulfur (S) causes a reduction of high-temperature strength and the hydrogen induced cracking (HlC) in stainless steel for line pipes. [l]Many studies on the desulfurization of hot metal and liquid steel have been carried out for several decades and they used HzS-H2 gas equilibrium technique for measuring the effects of many alloying elements on the activity coefficient of S in liquid iron. However, the study on desulfurization of Fe-Cr melts was very scarce.[2] In order to accurately control the desulfurization reaction of high Cr stainless steel, it is essential to know the thermodynamic relation between Cr and S in Fe-Cr melt over a wide range of Cr content and temperature.In the present study, the thermodynamic interaction between Cr and S in liquid iron was determined by measuring the equilibrium distribution ratios of S between Fe-Cr-C,.1-S melts containing a wide range of Cr up to 30 mass% and a 55 mass%Ca0-45 mass%Alz03 slag of which the sulfide capacity was pre-determined using Fe-C,a1-S melts in the temperature range of 1823-1923 K. The validity of thermodynamic parameter determined in the present study was checked by measuring the S distribution between a Ca0-Alz03-Mg0 slag of known sulfide capacity and liquid Fe-Cr-S alloy at 1873 K. Using Wagner's formalism, the results of experiment were thermodynamically considered to determine the effect of a specific concentration of Cr on the activity coefficient of S in liquid iron."

Jan 1, 2014

By G. D. Sandrock

The science and technology of roan temperature rechargeable metal hydrides began about 1969 with the discoveries that the intermetallic Compounds LaNi5 and TiFe could be, conveniently hydrided and dehydrided at roan temperature and modest H2 pressures. Subsequently, this lead to the development of a broad family of REE-containing AB5 hydrides and numerous applications that make use of the extraordinary H2-absorption and reaction-heat properties of these materials. Some of the applications include H2 storage, compression and separation, as well as heat pumping, heat to mechanical energy conversion and electric energy storage. This paper briefly reviews the fundamental phenomenology of metal hydrides, the history of the use of REE's in rechargeable metal hydrides, the practical engineering properties of these materials and the applications that have evolved around them. The rechargeable nickel metal hydride battery, a new vial alternative to NiCd cells, stands at the forefront of the applications.

Jan 1, 1992

By Jürgen Antrekowitsch, Thomas Griessacher

"Heavy metal containing residues are typically hazardous wastes because on the one hand, a deposition gets more and more complicated and on the other hand, the large amounts of metals like Zn, Cu, Fe and Pb represent a significant value. Thus, a post-treatment of these materials with the recovery/recycling of the metals and stabilization of the waste is not only ecological but often also economical. The therefore typically applied recycling processes utilize pyrometallurgical steps, where carbon or carbon monoxide from fossil coal and coke is used as a reducing agent, which results in large amounts of CO2 emissions. An alternative option is the application of a hydrogen-rich gas emitted in biomass utilization processes as a carbon-neutral reducing agent. Investigations in a retort process which were done at different temperatures and times showed excellent results concerning the achievable reduction rates and final contents of the heavy metals for various residues.IntroductionNowadays heavy metal containing residues like electric arc furnace dust (EAFD), dust from cupola furnaces, waelz slag, etc. are declared as hazardous wastes in a growing number of countries due to the leachability of the heavy metals in these residues. For that reason it is no longer possible to landfill these materials or use them for road construction or disposal works. Some land filling activities, carried out until now, have only been realizable because of some process modifications or cost intensive post-treatment steps of these residues. But the disposal capacities for such materials are decreasing, therefore increasing the prices. The second point for the growing disposal limitations is the stringent environmental legislations and regulations, which restrict the number and amounts of materials which can be dumped [1 – 5].From the other point of view these heavy metal containing residues usually have high contents of zinc, lead, iron, etc., which represent a significant value and therefore a big potential to recover these metals. This is why in recent years the number of recycling processes and the amount of recycled heavy metal containing residues have continuously increased. These recycling processes have the target to recover the valuable metals from the residual materials in the form of a saleable product as well as the stabilization of the slag produced in these processes [5, 6]."

Jan 1, 2011

By R. W. Harnmack

Hydrogen sulfide generated by the anaerobic respiration of sulfate-reducing bacteria was used to treat pH 2.2 water from the abandoned Rio Tinto copper mine in Nevada. The untreated water contained 550 mg/L Fe, 140 mg/L Al, 90 mg/L Cu, 80 mg/L Mn, 60 mg/L Zn, 4 mg/L Co, and 2 mg/L Ni. The bench-scale treatment system examined consisted of a bioreactor for H2S generation and three precipitator/clarifier units for metal sulfide precipitation and recovery. The treatment system reduced the concentrations of all metals except Mn to less than 0.1 mg/L. Manganese concentrations were reduced by 96 percent to 3.3 mg/L. A CUS/SO concentrate (33 pct Cu) and a ZnS/5° concentrate (28 pct Zn) were produced that may be suitable for metal recovery at existing smelters

Jan 1, 1994

By W. Kasprzak

Modern light metals processing technologies are very complex and involve a diverse set of variables that must be quantitatively evaluated. The most effective way to design new casting processes that deliver specified metallurgical and mechanical properties is to develop a method of simulating the "real-time" process within a test sample of sufficient size. The results can then be analyzed and the required optimizations can be performed. This paper presents a novel method of simulating the industrial casting processes in a laboratory environment using an experimental apparatus based on the principle of high frequency induction heating. The applicability and accuracy of the proposed analytical method is demonstrated, for example, by simulation of the solidification and heat treatment of a test sample composed of two dissimilar materials. The simulation can be used to develop a stress model for an engine block made from an aluminum based alloy with iron cylinder liner inserts.

Jan 1, 2002

By Torn H. Okabe

A fundamental study was conducted with the purpose of establishing an environmentally sound recovery process for recycling of valuable metals, by combining scraps containing such metals. As an example, direct extraction and recovery of neodymium (Nd) in magnet scraps was investigated by utilizing liquid metal as an extraction medium. It was found that liquid magnesium (Mg) is a suitable extraction medium and can extract Nd from iron alloys with high efficiency at around I 100 K. The newly developed extraction apparatus for Nd is a mechanically simple and static device without moving parts, where the Mg extraction medium circulates due to differences in the temperature inside the reaction vessel. This developed device can simultaneously accomplish continuous extraction of metal Nd from scraps, re-extraction of Mg from Mg-Nd alloy and the eventual recovery of pure Mg. As a result, metal Nd with 98 % purity was directly recovered from magnet scraps under certain conditions. It was also shown that the extraction agent Mg could be reused. The results of this investigation show the possibility of establishing a new process for the direct extraction of Nd in pure metal form without oxidization.

Jan 1, 2003

By Yoichi Takeda

Copper solubility in SiO2-CaO-FeOx slag equilibrated with copper matte in 10% SO2 atmosphere at 1573K was estimated. Essential parameters are activity coefficients of copper oxide and sulfide, oxygen and sulfur potentials and activity of copper in the slag-matte system. A large number of experiments provide proper parameters to calculate copper solubility in slag, A classical thcrmodynamic model postulating CuO0.5 and CuS0.5 moleculcs assists in estimating copper solubility in slag. Additions of Si02 and CaO reduce copper solubility almost in any condition. Copper loss, that is function copper solubility and slag volume, in the silica saturated SiO2-FeO. binary slag is minimally equilibrated with less than 66% copper matte while copper loss in the 50% FeO.-SiO2-CaO ternary slag saturated with 2CaOSiO2 is minimally equilibrated with over 66% copper matte. This slag composition has potential for continuous copper converting, direct copper production or high-grade matte production.

Jan 1, 2003

By Bohumir Jelinek, Sergio Felicelli, Mohsen Eshraghi

"We present a parallel lattice Boltzmann - cellular automaton model of the two-dimensional dendritic growth during solidification of binary alloys. The model incorporates effects of solute and energy transport under melt convection. The parallel performance of the algorithm is assessed. A loss in the parallel efficiency is observed when multiple computational cores per processor are utilized. Excellent strong scaling up to thousands of computing cores is obtained across the nodes of a computer cluster, along with the near-perfect weak scaling up to forty thousand cores. The presented solidification model shows a good scalability up to centimeter size domains, including millions of dendrites.IntroductionLattice Boltzmann method (LBM) is an attractive numerical technique for solving fluid dynamics problems. Its advantages are simple formulation and locality, with locality facilitating parallel implementation. In the present model, interface kinetic is driven by the difference between local actual and local equilibrium liquid composition [1]. The cellular automaton (CA) technique is deployed to track the solid-liquid interface [2]. A serial version of the present LBM-CA model with a small number of dendrites was validated against theoretical and experimental results in the previous publications [3, 4]. In this work, it is the first time that simulations with millions of dendrites were performed, something not possible with the computationally much more costly phasefield method [5].This research effort examines a technique for simulations of millions of dendrites in centimeter size domains, including thermal, convection, and solute redistribution effects. Nearly ideal scaling properties of the model are demonstrated. This extensively large landmark was achieved because of• the CA technique being two orders of magnitude faster than alternative, phase-field methods [5]• highly parallelizable LBM method, convenient for simulations of flow within complex and time dependent boundaries• availability of the powerful NSF Extreme Science and Engineering Discovery Environment (XSEDE) supercomputing resources"

Jan 1, 2013

In low carbon TRIP steels, the formation of carbide-free bainitic ferrite is crucial for the stabilization of austenite. Based on experimental investigations modeling the bainite reaction is examined adopting diffusional and displacive mechanisms, as well as the semi-empirical JMAK approach. Transformation tests were carried out to study the isothermal austenite decomposition into bainitic ferrite for a model steel containing 0.6wt%C, 1.5wt%Mm and 1.5wt%Si which replicates the composition of remaining austenite at the start of the bainite reaction in a classical C-Mn-Si TRIP steel. In the diffusional approach, classical nucleation theory is employed and subsequent growth of bainite plates is modeled using the Zener-Hillert theory. In the displacive approach, the autocatalytic nucleation of bairtite plates is assumed to be rate controlling. The predictive capability of all models is evaluated for temperature ranges where different morphologies of bainitic ferrite have been detected, The shortcomings and inherent challenges associated with either of these modeling approaches will be delineated.

Jan 1, 2003

By Kenneth McGowan

"The aluminum industry is the 5th largest consumer of energy and the largest consumer of energy on a per-weight basis. Process heating accounts for 25% of the energy consumed to manufacture aluminum. Consequently, the generation of this energy results in the production of a significant amount of CO2 (over 3.75 million metric tons in 2003)1. As a result, the Aluminum Industry Technology Roadmap of 2003 listed the development of improved refractory materials as a goal to reduce energy use and decrease greenhouse gas creation. The result of a R&D effort addressing this desire is the development of patented microporous refractory materials for metal contact applications in all furnace areas including the belly band. It has been demonstrated that this material can reduce energy consumption up to 38% in furnaces and significantly reduce heat loss in launder and trough systems. Furthermore the material developed is non-wetting and remains un-penetrated by metal throughout its lifetime. The material does not contribute to the formation of corundum. As a result, the energy efficiency of an older lining remains intact compared to standard refractory materials which may have an initial high insulating value (such as lightweights and board) or standard dense refractory (even with penetration inhibitors) both of which show a rapid increase in thermal conductivity as the refractory is penetrated with aluminum and formed corundumIntroductionThe aluminum industry is the second largest producer of metal in the United States, behind the iron and steel industry. It is the 5th largest consumer of energy and the largest consumer of energy on a per-weight basis. Process heating is required to melt, hold, purify, alloy, and heat treat the metal and accounts for 25% of the energy consumed to manufacture aluminum. As such, process heating is the second largest energy consuming operation. Smelting, which utilizes an electrolytic reduction process is the largest energy consuming operation1.Most process heating is accomplished through the use of fossil fuels, either directly or indirectly. The choice of fuel is dependent on a plant’s location and fossil fuel availability. Table I shows the processes impacted by refractories and the calculated BTU’s generated by usage of the respective fuels as well as the Metric Tons (MT) of metal passed through each process in 20001."

Jan 1, 2009

By John H. Schloen

Copper refineries are constantly looking for methods to upgrade their plants to reduce refining costs and to improve the purity of their electrolytic cathodes at the same time that the purity of the anodes they refine is being lowered by the rehabilitation of reverberatory furnace smelters to one of the direct smelting processes. The comments given below are based on the answers to the questionnaire returned bf the 36 copper refineries that represent 66% of the western world s refining capacity. Eleven refineries employ some form of uniform weight anade casting, e.g., Outokumpu, Contilanode, Mitsubishi, Lurgi, or Hazelett. This type of anode casting presents the best possibility for improving cathode purity. The cathode press of Phelps Dadge can improve current efficiencies and cathode quality. The press is used on first-run cathodes, after 48-60 hours, on half-cells at a time without interruption of the cell current. One refinery interrupts current for sever.al hours to allow the anode slime to settle before the, cathode pressing. The cathode press is now used at eight refineries. Apart from periodic reverse current (PRC), it is not expected that current densities will be increased. Thirty refineries, using direct current, average 231 amps/M, with a low of 178 and a high of 350. Five refineries use PRC at an average of 338 amps/M, with a low of 290 and a high of 380. Current efficiencies are good at an average of 94%, with a low of 88% and a high of 99% for the 34 refineries that reported. It must be remembered that the cycle efficiency with PRC is about 93%., so that the effective current efficiency with PRC would be only .94 X .93 or 87% However, PRC should be considered seriously for refinery expansions because it can save about 25% on capital costs.

Jan 1, 1987

By Zhucheng Huang, Lingyun Yi, Bin Chai, Tao Jiang

"A high iron content manganese ore was reduced at 900~1200°C and followed by a magnetic separation process. SEM and EDS analyzes were employed to examine the transformation of microstructure and phase in reduced sample and the mechanism was revealed. Results showed that elements enriched during reduction. Iron existed in the metal iron phase and most of oxygen formed compound with manganese. Consequently a clear distinguish between iron phase and manganese minerals formed, which was beneficial to the separation of iron and manganese. But the iron phase can not be monomer dissociation in grinding process and manganese compounds turned into magnetic product as package and mechanic inclusion due to the isomorphism of iron and manganese and the small particle size. And MnO could be found partially in iron phase, which hindered the further separation of manganese and iron.IntroductionManganese is widely used in industry. The amount of manganese used in steel industry is very huge and 90% manganese is used in steel industry. Manganese ore resources are rich in China, yet with fewer rich ore but more low-grade ore which accounts for 93.6% and fine refractory ore. The constitution of the ore is very complex and more than 73% of all the manganese ore contains iron[l,2]. With the increasing of consumption of steel, the demand for manganese is becoming larger and larger and the imported ore accounts for more than 50%. Therefore, how to use the manganese ore efficiently has very significant meaning. The main method is manganese residual, which is simple and stable. However, the development of the method is limited by the quality of manganese ore, the huge amount of manganese residual, the technology of blast furnace process and economics[3,4]. Chemical benefication which may pollute environment and is difficult to recover iron is still being researched[5,6]. The paper investigated the process in which anthracite coal was the reducing agent for coal-based direct reduction and magnetic separation of the ore, and SEM with EDS measurements were employed to examine the transformation of phase in reduced sample and the mechanism was revealed[7,8]."

Jan 1, 2013

By Donald R. Sadoway

"Molten salt electrolysis is a proven technology for the extraction of metals -- all· the world's primary aluminum is produced in this manner. The unique properties of molten salts also make them excellent media in which to treat a variety of forms of waste. Of special note in this regard is electrolysis in molten oxides, a concept put forward by the author, initially as a ""clean technology"" for producing primary metal. However, in the context of waste treatment, electrolysis in molten oxides is a process offering the prospect of changing the-valence of dissolved heavy metals while making pure oxygen gas as the main by-product. Laboratory tests conducted at a temperature of 1550°C on chromate sludge dissolved in an melt composed of Al2O3, SiO2; CaO, and MgO have confirmed electrochemical production of oxygen on a carbon-free anode. IntroductionMolten salt electrolysis is the electrolytic decomposition of a compound dissolved in an ionic melt. The prime example of this process can be found in the production of aluminum. The compound, alumina (Al2O3)' derived from the mineral bauxite, is dissolved in an ionic melt comprising a multicomponent solution of cryolite (Na3AlF6)' aluminum fluoride (AlF3)' and calcium fluoride (CaF2,). The products of electrolysis are molten aluminum and carbon dioxide, the latter due to the attendant consumption of the carbon anode. Primary aluminum is produced in a reactor known as the Hall cell.' Alternatively, the compound undergoing electrolytic decomposition can be derived from waste. Processing in molten salts, with their capacity to dissolve materials to very high concentrations compared to those attainable in aqueous solutions, can be rather advantageous. High solubilities lead to high limiting current densities, and this, in tum, results in high productivities: For a primer on molten salt electrolysis and a review of the basic literature in the field of molten salts the reader is directed to an earlier publication of the author (1)."

Jan 1, 1996

By Ian M. Ritchie

Right across the universities of the developed world, the traditional disciplines of physics and chemistry are losing ground. Extractive metallurgy, which depends so heavily on chemistry, is also contracting despite a clear need for people with this kind of training in the mining industry. Reasons for this loss of popularity are discussed in this paper. High on the list is one of image. The extraction of metals is widely seen as a dirty, polluting, sunset industry which involves working in remote and uncomfortable corners of the earth for inadequate compensation. Ways in which the image problem can be overcome are considered. It is concluded that a concerted effort needs to be made by the universities and industry to redress this situation. The importance of extractive metallurgy, both now and in the future, when a greater emphasis will be placed on sustainability and recycling, needs to be stressed. In addition, courses need to incorporate training for a career path that leads on beyond extractive metallurgy.

Jan 1, 2003