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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 William A. Hockings

This report describes the results of laboratory studies on leaching of copper ores.tlf These studies are the first step of a program for the investigation of in situ leaching of tabular, metalliferous ore bodies.(2) The basic steps required in the development of an in situ process are: 1. Leachability - the ability to dissolve the metal values from the ore under in situ conditions must be demonstrated. 2. Ore Preparation - the ore must be prepared so that sufficient contact with the solution can be attained. 3. System Design - integrated in situ systems must be designed and studied for engineering feasibility. 4. Economic Feasibility - the economics of the system must be shown to be economically feasible and competitive. 5. Environmental Feasibility - the loss of reagents into the environment must be investigated. 6. Pilot Scale Testing - the feasibility of the system must be demonstrated on a sufficiently large scale. The studies described in this report were concerned only with the first step of the program, viz., leachability. Native and sulfide copper ores from the Michigan copper district were selected as model ores for these studies. Aqueous amnonia solutions were chosen as the solvents to be investigated. In this study carbonate (CO3, HCO3, H2CO3) was used exclusively as the anion. In keeping with custom it is referred to as carbon dioxide and concentrations are ex- pressed in terms of CO2. When leaching native copper the reaction is

Jan 1, 1976

By D. H. Rubisov

The neural networks modelling approach is one of the most elegant black-box type methods to model industrial processes. In this paper, this approach is applied to model the performance of the CEZ zinc electrowinning plant. The model that was built was found to exhibit an excellent predictive ability for voltage and current density. The model was also used to investigate the sensitivity of the process to various key variables such as temperature, current density, zinc and sulphuric acid concentration, etc. Optimal regimes for zinc production were identified from the power consumption standpoint.

Jan 1, 1996

By Pengfu Tan

A thermo-chemical model of the copper P-S converter and a viscosity model for the converter slag have been developed to predict the behavior of magnetite in the converter slag, amounts of slag and matte, compositions of slag and matte, volume of the bath, bath temperature, slag blow endpoint determination, SEMTECH OPC signals, and the viscosity of converter slags. The predictions of bath temperature, slag and matte compositions, and magnetite content in the slag have been validated by the industrial data. The effects of fluxing strategy, returns and skim charges, oxygen enrichment, and temperature on the magnetite formation in the slag have been predicted and discussed. The effect of oxygen potential, SiO2/Fe in slag, detection of slag blow endpoint, and temperature on Fe3O4 content in converter slag, slag viscosity, liquidus temperature of converter slag and skimming operation has been modeled and discussed as well. Some applications of the industrial operations have been presented.

Jan 1, 2009

By Rajesh Kumar Mishra

About 500,000 troy ounces of Platinum Group Metals (PGM) will be available for recycling each year from spent automobile catalytic converters in North America alone. Platinum Group Metals? from spent catalyst can be extracted by Hydrometallurgical, Pyrometallurgical or Gas Phase volatilization processes. This paper is a review and comparative study of various processes investigated for PGM extraction. A number of processes described in this paper have already been commercialized. The technical and environmental aspects of the important processes are discussed.

Jan 1, 1989

By Rina Kim

There are many factors which affect the gold cyanidation mechanism— mineral composition, free cyanide and dissolved oxygen (DO) concentrations, heavy metal additions, etc. This study combines electrochemistry and surface analysis methods to examine the effectiveness of the above factors on gold cyanidation process. Three gold ore samples were used in this study. Sample 1 was a pyrite concentrate, contained mercury and silver. Sample 2 also contained sulfide minerals, including galena. Sample 3 contained pyrite with sphalerite and galena. In the case of samples 1 and 2, the presence of heavy metals enhanced gold cyanidation kinetics, though the addition of higher DO was not effective on improving the kinetics. Sample 3 showed an opposite behavior: the kinetics was not enhanced by galena, because of its relatively small amount, however, the use of higher DO made improvement in the gold leaching kinetics, likely caused by iron species generated by pyrite oxidation.

By Yotamu Stephen Rainford Hara

"The aim of our work is to investigate a low energy and clean route for the recovery of copper and cobalt from complex sulphide mineral concentrates. The mineral concentrates were roasted in air, in the presence of CaO (MS + CaO + 202 =MO+ CaS04) at temperatures below 973K. The roasted products containing CuO, CoO and Fe203 were carbothermically reduced at 1073K within an hour to preferentially reduce copper and cobalt. The kinetics of reactions were studied using the thermogravimetric technique and by characterisation ofreaction products using the XRDSEM-EDX techniques. The effects of MS:CaO ratio, roasting temperatures and physical nature of the mineral concentrates were analysed. The method for capturing S02 by forming CaS04 was analysed for reuse in the process. The energy balance for the above process is compared with that of conventional continuous smelting/converting process.1.0 IntroductionCopper sulphide mineral concentrates from Zambia contains substantial amouot of cobalt. The cobalt metal content in the concentrates ranges between 0.7 and 2 % weight, which corresponds to 3 and 9 % weight copper, based on the spot price of copper ($7 386/tone) and cobalt ($31 000/tone). Although the traditional approach using a combination of roasting-leaching-electrowining steps can be applied to recover copper and cobalt from sulphide mineral concentrates [1-4], there are two major draw backs of the traditional process: (i) the S02 emitted during roasting is too lean for economical conversion for sulphuric acid manufacture, which causes serious environmental pollution. (ii) silver and gold which are normally present in the sulphide concentrates are lost out [5] because they are not leachable by H2S04 or HCl which are the common leachants. The above two problems have been overcome by adopting flash smelting in which a rich S02 gas above 20% is produced [1, 5] and successfully converted into sulphuric acid. The precious metals tend to partition to blister copper and recovered during refming. However, nearly all cobalt is lost into the slag phase uoder oxidising condition which prevails during flash smelting. It is important to note that the cobalt content in the slag can be up to 2.6 % weight [6]. The recovery of cobalt from the slag is a process which requires huge amouot of energy since the slag is smelted above 1873K [6]. With a view of minimising the amouot of energy and S02 emission during metal recovery, our investigation involves roasting the sulphide concentrates in the presence of lime and reducing the roasted samples with carbon."

Jan 1, 2013

By A. K. Riihimäki

The description deals with duplex stainless cast steels and austenitic high molybdenum steels used in pumps for severe condition service. The main modem nitrogen alloyed duplex cast steels are presented in the ASTM standard A-890. Two grades of high molybdenum austenitic stainless steels there are presented in ASTM A-744 (-96) standard i.e. CN-3MN and CK-3MCuN. The latest and most corrosion- resistant stainless steel grade is AVESTA 654 SMO?. Avesta Sheffield the trademark owner has granted Ahlstrom Pumps license to produce the material. This new stainless steel as pump material for severe service has improved properties in the hydrometallurgy and electrorefining processes of metal and especially in the copper industry compared to duplex stainless steels. The paper deals briefly with the foundry process to manufacture high alloy stainless steel pump castings. The AOD-method (AOD= Argon Oxygen Decarburization) is an important prerequisite for the melting of low carbon, high chromium and molybdenum alloyed nitrogen steels. The properties of these steels are included. The main topic is the corrosion resistance of the above-mentioned pump materials in severe service. Results of short-time erosion and corrosion tests are discussed and compared with the results of plant tests. Practical results of pump materials performance in severe service for the copper industry are given. The new high alloyed cast stainless steel (main elements; Cr-24%, Ni-22%, Mo-7,3% and N-0,5%) has shown improved corrosion and erosion properties as process pump material in several severe service applications e.g. in the metal industry.

Jan 1, 1999

By E. W. Lithgow

Commercial volumes of nickeliferous laterite ores overlie part of a 90 km long belt of peridotites in central Dominican Republic. Protores are serpentinized harzburgites and dunites, with lesser serpentinite. The ore mineralogy consists mostly of goethite, serpentine-group minerals, quartz and poorly crystallized, x- ray amorphous materials. Minor constituents are hematite, gibbsite, olivine and enstatite. In the Ore Dressing plant the mine feed is subjected initially to proper sizing and blending to produce a homogenized mix. Subsequent drying and upgrading, by selective crushing and screening of rock fragments through a Barmac circuit, complete preparation of the ore for pyrometallurgical processing.

Jan 1, 1993

By I. C. Howard, E. J. Palmiere

"Heat transfer and friction in hot flat rolling have traditionally been characterised by an average heat transfer coefficient (h) and an average friction coefficient (p.). However, the presence of oxide scales and asperities at the interface question the use of such averages. The apparent irregularity and lack of pattern of interactions at the interface has prompted this present investigation to move away from averaged h and 11 values, and to study their local evolution based on probabilistic rules. The approach is based on the probability of finding the workpiece surface in a specific configuration at a particular instance of time in the roll gap. These rules are based on observations of surface phenomena such as scale behaviour during hot rolling. The model is implemented using user-subroutines integrated with the commercially available finite element program ABAQUS™. The results show the strong dependence of h and u on the local scale interactions. In particular, the effect of scale thickness, material behaviour and processing conditions on the evolution of hand 11 are discussed. Finally, the development of a Cellular Automata based Finite Element (CAFE) model is proposed to model the combined interfacial phenomenon of friction and heat transfer at the tool-work piece interface.IntroductionIntricate interactions between process variables in hot rolling of steels make it a challenge to the modelling community. For a given material and geometry combination, reducing interfacial power losses can increase the efficiency of the rolling process. The roll-strip interface, therefore, forms the critical zone and is currently the domain of intense investigation, especially to characterize interfacial frictionl • 2 and heat transfer3 • 4 . These interfacial phenomena are inter-related and cannot be studied in isolation. However, very few mathematical models4 • 5 combine an analysis of friction and heat transfer and deformation of the strip-roll interface taking into account the role of asperities and oxide scales."

Jan 1, 2001

By Zhang Hengzhong

Based on thermodynamics of surfaces and a proposed two-dimensional state equation for surfaces, the relationship between the surface tension (Y) of a solution and the activity (a1) of its component (i) was derived: (1/Y)r2-.¬E (ai/Yl) The derived equation was verified with reported experimental data of water-alcohol systems and water-acetone system, the calculated results showed astonishing coincidence with experimental. Applications of the equation to the five matte systems Cu2S-FeS, Ni3S2-FeS, FeS-PbS, Cu2S-PbS and FeS-Cu22S-PbS also demonstrated that at given matte compositions the calculated surface tensions agreed with experimental fairy well.

Jan 1, 1993

By Bruce H. Baker

Studies of used or unused refractory materials are excellent examples of applied mineralogy in industry. Refractory materials are mineral substances containing ceramic or chemical bonding systems. Knowledge of the mineral composition, bonding, and textural relationships often explains the resulting physical property values of a refractory and contributes to the interpretation of refractory wear mechanisms occurring in steel plant service.

Jan 1, 1982

By Guan-zhou Qiu, Shui-shi Liu, Yu-feng Guo, Tao Jiang

"The preparation of high-quality synthetic ruitle from electric furnace titanium slag was systematically investigated by activation roasting followed by acid leaching process. The results showed that impurities such as Ca and Mg in titanium slag can be effectively removed and TiO2 grade of the product was markedly improved by the process. High-quality synthetic rutile containing 88.54% TiO2, 0.42% (CaO+MgO) was obtained under the conditions that roasted with 7.5%(wt) H3PO4 at 1000 oC for 2h, followed by two-stage leaching in boiling dilute sulfuric acid for 2h. Mechanism studies showed that anosovite solid solution and silicate minerals were reacted with phosphoric acid in the roasting process. As a result, titanium components in titanium slag turned into rutile (TiO2) and impurities were transformed into acid-soluble phosphate and quartz.IntroductionWith the gradual depletion of natural rutile and the rapid development of titanium industry in China, the natural rutile reserves cannot satisfy the requirement for production of titanium pigment and titanium sponge. Ilmenite is, therefore, becoming main raw material for titanium industry. However, because of its low TiO2 grade, it generally requires preconcentration to titanium-rich material such as titanium slag or synthetic rutile [1-3].Ilmenite resources are extremely rich in Pan-xi area of China, which account for 90.54% of total ilmenite reserves in China [4]. The titanium slag produced by electric smelting of ilmenite concentrate has high contents of Ca and Mg, and is not suitable as a raw material for chloride process and titanium sponge production. Therefore, upgrading titanium slag to prepare raw material suitable for chloride process and titanium sponge production has important significance for the development of China's titanium industry."

Jan 1, 2011

By N. Gopalakrishnana, R. Beccard, S. Lourdudoss, R. Holz, M. Deschler

"Rapid growth of conducting and/or insulating InP, GaAs, Gao.47In0.53As, and GaAs0.6Po.4 on one or more of (001), (110), (111)A, (3ll)A and (3ll)B surfaces by Hydride Vapour Phase Epitaxy (HYPE) is demonstrated. The maximum growth rate of the binaries lies between 12 and 300 µm/hr and of the ternaries between 7 and 170 µm/hr. A simple model is developed to describe the influence of crystallographic orientation on temperature dependent growth rates. The growth rates predicted by the model is compared with the experimental values. Room temperature resistivity of insulating InP:Fe can be as high as 5xl09 ohm cm. Temperature dependent differential resistivity is also analysed. This feasibility of growing conducting and insulating layers rapidly on different orientations is very useful for electronic and optoelectronic devices.IntroductionRecently there is a renewed demand for very thick layers of III-V compound semiconductors for high performance electronic and optoelectronic devices [1]-[2]. Long wavelength high speed lasers that can be modulated up to 30 GHz necessitate epitaxial growth of semi-insulating (SI) layers [3]. There is also an increased interest on the growth of epitaxial layers on surfaces other than (001) surface. Epitaxial growth of these materials on such surfaces is of theoretical importance besides being technologically relevant. These demands led us to focus on the growth of conducting and insulating III-V compounds by Hydride Vapour Phase Epitaxy (HYPE). lnP, GaAs, Gao.471no.s3As on lnP and GaAso.6Po.4 on GaAs were grown as conducting materials using Low Pressure HYPE (LP-HYPE) on (001) 2° off substrates. Gao511no.49P on (001) GaAs substrate and lnP on lnP substrates of (001), (110), (l 11)A, (31l)A and (3 ll)B orientations were grown as semi-insulating materials using Atmospheric Pressure HYPE (AP-HYPE). In this report we present the growth aspects of these materials. We also present a simple model on the growth of InP on substrates of various orientations. The theoretically obtained temperature dependent growth rates are compared with the experimental values. Differential resistivities of semi-insulating lnP grown on substrates of various orientations as a function of temperature are also summarised."

Jan 1, 1998

By Z. R. Llanos

This paper presents a review of industrial and experimental processes for the recovery of molybdenum, vanadium, nickel, cobalt and aluminum from spent hydrotreating or hydrodesulfurization catalysts. Numerous processes have been developed in a laboratory and pilot scale. However, worldwide, there are only four well established commercial facilities currently in operation. The installed capacity of these facilities exceeds the availability of spent catalysts and may be sufficient to assimilate future increases of spent catalysts. Despite liability risks; significant quantities of spent catalysts are still being landfilled. Changing regulations that may affect the future handling and disposal of spent catalysts are also reviewed.

Jan 1, 1995

By Noel A. Warner

Modern steelmaking is based on direct use of oxygen in high intensity batch reactors. A totally new approach is proposed in this paper, based on the view that pursuit of high intensity is unlikely to lead to successful coal-based continuous steelmaking. By substituting carbon dioxide and water vapor as the oxidants rather than using oxygen directly, the intensity is greatly reduced. Accordingly, subsurface formation of carbon monoxide bubbles can be avoided by careful manipulation of the three participating rate processes, gaseous diffusion, interfacial chemical kinetics and liquid phase mass transfer. Steelmaking can then be carried out without explosive ejection of molten droplets and the generation of micro-spray but rather in a controlled and fume less fashion. The vital component is the introduction of generic melt circulation technology. Three melt circulation loops in series are envisaged. Starting with a composite feed of iron ore fines, pulverized coal and lime flux, a metallized solid raft floating on molten iron is propelled out of the ironmaking loop onto the first of two downstream steelmaking loops. In the first, a liquid slag is formed, primary decarburization is undertaken not with oxygen but rather with CO2 and H2O and the melt is desulfurized. The semi-product stream enters the third melt circulation loop, where open-channel decarburization is effected along with dephosphorization to yield a low carbon steel product. Alternatively, the melt leaves the last loop to irrigate a packed tower countercurrent to argon at around 100 mbar to continuously produce ultra-low carbon (ULC) steel.

Jan 1, 2003

By Dieter Neuschiitz, Pengfu Tan

"In order to understand the sintering phenomena during iron ore sintering process, a CFD model of iron ore sintering has been developed, combining with the kinetics of 15 relevant chemical reactions with the aim of describing the temperature fields and the gas flow patterns in the sintering bed. This CFD model can be used to simulate the concentrations of the gaseous and solid species, temperatures of the gas and solid, melting and molten fractions of the mixture, gas velocities, temperature zones and residence times of the gas in each temperature zone. IntroductionThe off-gas analyses clearly revealed that the off-gas of a sinter strand does not have a composition corresponding to thermodynamic equilibrium, for example, the CO, CO2 and O2 concentrations are not the mutually consistent equilibrium values. Apparently the chemical reactions in the sinter bed are controlled kinetically. Therefore kinetic modeling of sintering reactions combined with CFD modeling is necessary to understand the sintering phenomena during iron ore sintering process.Several models of iron ore sintering have been developed since 1970 [l-l 4l, each being more refined than its predecessor. The models were formulated as a series of differential equations to describe chemical and physical changes occurring at a point in the bed. These equations were solved numerically in a vertical plane along the strand. The present CFD model, based on the Nath's model [14], has been published in the reference [15]. In this work, some new chemical kinetic models of gas-solid reactions are incorporated in the present CFD model. The concentrations of gaseous and solid species, temperatures of gas and solid, melting and molten fractions of solid, velocity of gas, and residence time of gas in each combustion zone can be calculated by this model."

Jan 1, 2004

By D. E. Karvelas

Argonne National Laboratory is conducting research to develop a cost-effective and environmentally acceptable process for the separation of high-value plastics from discarded household appliances. The process under development has separated individual high purity (greater than 99.5%) acrylonitrile-butadiene-styrene (ABS) and high-impact polystyrene (HIPS) from corruningled plastics generated by appliance-shredding and metal-recovery operations. The process consists of size-reduction steps for the commingled plastics, followed by a series of gravity- separation techniques to separate plastic materials of different densities. Individual plastics of similar densities, such as ABS and HIPS, are further separated by using a chemical solution. By controlling the surface tension, the density, and the temperature of the chemical solution, we are able to selectively float/separate plastics that have different surface energies. This separation technique has proven to be highly effective in recovering high-purity plastics materials from discarded household appliances. A conceptual design of a continuous process to recover high-value plastics from discarded appliances is also discussed. In addition to plastics separation research, Argonne National Laboratory is conducting research to develop cost-effective techniques for improving the mechanical properties of plastics recovered from appliances.

Jan 1, 1996

By Jose F. Hevia

This study is part of a broader project on the hydrothermal conversion of copper concentrates to metallic copper by solid state reactions in which the copper remains localized in the solid phases. The kinetics of the solid/solid hydrothermal hydrogen reduction of tenorite (CuO) and cuprite (Cu,O) to metallic copper are presented. After an induction period, the process is governed initially by a nucleation step followed by rapid solid state reduction. Nucleation promoter agents decrease the induction period and control the particle morphology. Separate nucleation and reduction rate processes have been identified. Following nucleation, reduction follows a shrinking core process.

Jan 1, 1994

By Y. Y. Liu, H. M. Domanus, W. T. Sha

"Casting is fundamental to manufacturing of many types of equipment and products. Although casting is a very old technology that has been in existence for hundreds of years, it remains a highly empirical technology, and production of new castings requires an expensive and time-consuming trial-and-error approach.In recent years, mathematical modeling of casting has received increasing attention; however, a majority of the modeling work has been in the area of heat transfer and solidification. Very little work has been done in modeling fluid flow of the liquid melt. This paper presents a model of fluid flow coupled with heat transfer of a liquid melt for casting processes. The model to be described in this paper is an extension of the COMMIX code and is capable of handling castings with any shape, size, and material. A feature of this model is the ability to track the liquid/gas interface and liquid/solid interface. The flow of liquid melt through the sprue and runners and into the mold cavity is calculated as well as three-dimensional temperature and velocity distributions of the liquid melt throughout the casting process.IntroductionBower et al. (1), in their 1969 review of the evolution of some of the casting techniques, stated that:""The evolution of technology requires alternatives to be available so that choices can be made that lead to changes. The role of solidification science and other disciplines related to casting technology is to develop a better understanding of process and product, so that a wider range of alternatives is possible.Alternatives, whether from science or from invention, must lead to improvements in casting ""utility."" Utility, or economic advantage, must include consideration of total system costs, and final product value. The cost of materials, melt processing and finishing should be optimized with casting costs, since all are part of the production system. It is the favorable relationship between total processing costs and product value that makes a change in casting technology viable, but the best change is not possible unless technology has provided an understanding."""

Jan 1, 1986