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

"Alloying refining with rare earth elements followed by acid leaching was examined for the potential of upgrading of metallurgical grade silicon. Microstructure study of silicon alloyed with small additions of rare earths showed behavior relatively similar to the influence of calcium addition. After alloying with neodymium the phosphorus content was detected in various intermetallic silicides containing neodymium and iron. The content of lanthanum and neodymium in refined silicon was by several times lower than that of aluminium and calcium. Alloying with lanthanum and neodymium at smaller additions than calcium reduced the phosphorus content down to the same level. The efficiency of lanthanum and neodymium in removal of boron and phosphorus at the 1-2 wt% of their additions and their low solubility in silicon make the alloying with these metals followed by acid leaching an attractive option for the refining route of metallurgical grade silicon up to solar grade.IntroductionA striving for a cheap ""green"" energy directs the research interests in silicon solar cells towards new efficient refining routes for metallurgical grade silicon (MG-Si, -98% purity). The silicon price determines up to high extent the solar module's price, so that cheap and efficient metallurgical process is awaited. The research challenge is to fulfil the purity requirements of solar grade silicon (SoG-Si, 6N) by competing with the energy-consuming and environmentally unfriendly Siemens process. Most difficult impurities to remove are boron and phosphorus, so technologies dedicated to their efficient removal attract an attention of industry and academia.Alloying refining (also known as solvent refining) is one of the most promising refining options, which is based on a principle of solid-liquid extraction using limited solubility of impurity elements in solid silicon [ 1]. Various elements were proposed for alloying refining: aluminium [2], calcium [3], tin [4], iron [5], copper [6] etc. The attractiveness of the alloying refining is in decreasing a melting point of the metal mixture and an affinity of the alloying element to the most harmful impurities, especially to boron and phosphorus. However, the difficulties are still faced due to self-solubility of the alloying elements, their low affinity to boron and/or phosphorus, silicon losses and necessity of removal of the silicide impurity phases in an additional step, using acid leaching [7], fractional melting [ 8] etc."

Jan 1, 2013

By Akira Yazawa

The similarities and differences in copper, nickel and lead smelting processes are discussed based on the sulfur-oxygen chemical potential diagrams and the free energy minimization assessments using a thermodynamic software. The prominent features of copper smelting are ascribable to the fact that copper has a strong affinity for sulfur but weak for oxygen and the liquid phase immiscibility between Cu and Cu2S. During the oxidation of sulfides, nickel metal is not stable except at temperatures higher than 1500°C, well miscible with its sulfide, and is oxidized more easily than copper. Metallic lead looks as stable as copper during the oxidation of the concentrate but Pb and PbS. are much more miscible with each other and the vaporization loss is considerable. In the reductive smelting of oxides, the effects of oxygen potential and temperature on the copper contents in slag are not significant due to the monovalent character of copper and the reduction of copper content in slag is not easy in practice. The effect of the slag compositions on the oxidic metal contents of slag is much more significant for lead than either copper or nickel. Due to the immiscible nature between Pb and Fe, high grade lead bullion is easily obtained and lead is more tolerant to impurities.

Jan 1, 1998

By Tsembel Darjaa, Toru H. Okabe, Yoshiaki Umetsu

"With the purpose of extracting molybdenum and rhenium from molybdenum sulfide concentrate; .electrolysis of slurry, solvent extraction and ·precipitation operations were carried out. The slurry of the concentrate in 10 mass% NaCl aqueous solution was continuously circulated into a vertical type 10 stack bipolar electrolytic cell consisted of carbon electrode disks, and, the concentrate was dissolved by electrochemically generated oxidizers at 313 K. The current efficiency for molybdenum dissolution was 73 % after 10 hours electrolysis, and the leach solution was found to contain 0.2 mol/l of molybdenum and 4x10-5 mol/l rhenium. This result shows the dissolution is more than 8 times faster than that obtained using a single cell. The leach solution from electro-oxidation was then subjected to a solvent extraction for rhenium which is then recovered as sulfides. After rhenium separation, molybdenum was precipitated by pH adjustment, and solid MoO3 (H2O)x crystals, free of sulfate, were obtained from the leach solution containing large amount of so42-.IntroductionIn the past, electro-oxidation using a bipolar cell was applied for leaching molybdenite concentrate and ores at U. S. Bureau of Mines [1-3] and also at Bhabha Atomic Research Center [4]. In· these previous studies, Moebious type bipolar cells, in which electrode plates were vertically inserted into the free surface of the electrolyte, were employed and its effectiveness was demonstrated.Recently, the present authors studied on leaching of Mongolian molybdenite concentrate, and the effectiveness of leaching of the concentrate by electro-oxidation in alkaline and acidic NaCl solutions was demonstrated [5]. The leaching reaction during the process can be explained by the 18 electron transfer reaction of molybdenite (MoS2) with the oxidizers produced in-situ by electrolysis of NaCl aqueous solution. Further investigation was made with respect to various process parameters for electrooxidation such as pH, pulp density and temperature of the slurry, and the dissolution behavior of minor elements such as iron, copper, and rhenium [6]. Solubilities of molybdenum in the leach solution at, various temperatures and pH .was · studied, and feasibility of molybdenum recovery by hydrolysis of molybdenum species was demonstrated. By adjusting the pH of the leach solution, molybdenum oxides or hydroxides free from sulfate were successfully obtained from the solution containing large amount of sulfate ion. Rhenium present in the concentrate at a level of several tens of mass ppm was found to dissolve into the leach solution, and co-precipitate with the molybdenum compounds. Rhenium in the leach solutions, therefore, has to be recovered before precipitation of molybdenum, otherwise it is lost in the precipitate."

Jan 1, 2000

By Elli Miettinen, Markku Lahtinen, Ilkka Kojo

"The recent trends of decreasing energy consumption and environmental emissions and utilization of economies of scale are strong drivers favoring continuous copper converting processes. Flash Converting benefits from low off-gas volumes and low investment and operational costs for off-gas treatment. Separate matte and blister furnaces allow the adaptation to concentrate quality changes and flexibility in layout and maintenance.The stationary blister copper bath in Flash Converting furnace is less aggressive to the furnace linings than agitated processes, resulting in low refractory consumption, long campaign life and high on-line availability.Copper Flash Converting has been successfully applied in Kennecott with a campaign life now exceeding five years. A second FCF was started at Xiangguang Copper in China in 2007. The process itself is proven, as its features are similar to those in FSF, Direct-to-Blister and Direct Outotec Nickel Flash Smelting (DON), with one significant difference: it is the easiest of all to operate.The paper presents differences between continuous Flash Converting and conventional converting based on recent experiences and studies."

Jan 1, 2009

By G. J. Abbaschian, A. B. Gokhale, M. M. Kunjapur

"A laboratory scale model furnace was constructed for obtaining radially inward oriented columnar grains in disc shaped castings. The furnace consisted of eleven circular, concentric, equispaced resistance heaters on each half of a split graphite mold. Water or air flowing through a copper pipe along the periphery of the disc constituted the heat sink. After filling the mold, the heaters were turned off consecutively in top and bottom pairs from the rim towards the center, causing the temperature gradients to move inward. Equiaxed structure was obtained at the center by turning off the inner coils together when desired. Sn:15%Pb alloy was used to cast integral blade disc castings using the above technique to obtain dual-property discs with a central equiaxed structure and an outer columnar grain structure projecting inwards from the blades to the rim. A numerical technique was used to predict the temperature profile in the disc during solidification, and good correlation was obtained with the experimentally measured temperature profiles. The corresponding heat transfer coefficient values obtained were h = 544 Wm- 2k-1 (0.013 cal/cm2- ° C-sec) for cooling between metal and chill and h' = 71 Wm- 2k-1 (0.0017 cal/cm2- ° C-sec) for the heat input from the hot mold to the liquid metal. BackgroundHigh temperature alloys used in the current generation of gas turbine engines have evolved through two main stages of development: in 1950's, the increase in the efficiency of gas turbines was paced by improvements in alloy design, which led to the development of Ni and Co-based superalloys (1). By mid-1960's, it was realized that improved alloy chemistry alone was inadequate in meeting the increasingly stringent service requirements. The focus of research then shifted from alloy development to process development, and resulted in the introduction of directional solidification (DS) techniques for the production of turbine blades and vanes (1,2).Under typical operating conditions, the blades and vanes are subjected to aerodynamic loading, while the blades are additionally subjected to high centrifugal loading and vibratory stresses. The primary material requirements for blades may be summarized as follows (1,3):•,High creep resistance•,Good high temperature tensile strength (typically in the range of•,275 to 550 MPa at temperatures in excess of 750°C)•,Resistance to both low cycle and high cycle fatigue (LCF and HCF)•,Resistance to erosion, corrosion, and oxidation•,Resistance to thermal fatigue"

Jan 1, 1986

By M. Olper, M. Maccagni

"The crude zinc oxides (CZO) produced in any thennal process dealing with EAF dust also contain lead, cadmium, and a considerable amount of halides (chlorides and fluorides). The high halide contents make these crude zinc oxides less and less attractive, both technically and economically, and a further refining procedure is nece'ssary to meet the zinc and zinc oxide market requirements.Hydrometallurgical techniques commercially used to dehalogenate the crude zinc oxides are not effective enough to upgrade the crude zinc oxides to the required specification for their direct use in the traditional sulphuric electrolysis by primary zinc producers.The EZINEX® PROCESS has solved the problem of the halides contained in the crude zinc oxides. This process is the only proven technology electrowinning zinc from a chloridebased electrolyte in a conventional cell house. This paper discusses the process economics taking the data from feasibility studies of different size commercial plants."

Jan 1, 2000

By Kelly J. Driscoll

Impure zinc (98.5%) was electrorefined to high purity zinc (99.995%) using a fused salt electrolyte of molar composition 1: 1 : 1 :2 ZnCI2:KCl:NaCl:LiCl with a current efficiency of about 90% at 723 K. A recessed channel electrorefining cell was developed which achieved excellent mixing of both the metal and the electrolyte and by ensuring a very small anode to cathode spacing the voltage drop across the cell was 0.16 V and at a current density of 7kA m-2. The physical characteristics of the cell were observed using a low temperature model which showed the formation of droplets and rivulets which provided mixing. The application of this approach to the refining of other non-ferrous metals is discussed.

Jan 1, 1992

By Yuhsuke Mizukami

Crude high Cr containing steel such as tool steel, heat-resistant steel or stainless steel is produced by dissolution of high carbon ferro-chromium into molten crude steel. In the refining process, decarburization is performed at the first stage, and deoxidation is followed in the next stage. Therefore, the equilibrium relation between dissolved Cr and 0 in molten Fe-Cr alloy after decarburization is very important when yield of deoxidizer is considered for the ovemll control and optimization of the process. It is well known that the yield of deoxidizer does strongly depend on the kinds of refractories of furnace in the secondary refining process. In the present work, the equilibrium relation between dissolved Cr and O in molten Fe-Cr alloy has been measured in a Cr2O3, MgO or Al2O3 crucible at steelmaking temperature. O contents at given Fe-Cr components have been lower in order of Cr2O3, Al2O3 and MgO crucible. The present results have been discussed based on the activities of the constituents in pure solid Cr2O3, and FeO-Cr2O3, MgO Cr2O3 and (AI,Cr)2O3 solid solutions.

Jan 1, 2003

By Jr. Foot

The Bureau of Mines, U.S. Department of the Interior, investigated flotation methods for recovering fluorite and byproduct beryllium from the Fish Creek deposit of Nevada. The preferred method includes (l) fluorite rougher and cleaner flotation, (2) de sliming at 20 micrometers, (3) muscovite flotation, (4) silicate flotation, (5) hypochlorite wash of silicate concentrate, and (6) beryllium rougher and cleaner flotation from the silicate concentrate, Laboratory results showed that over 94 pct of. the fluorite was recovered in a concentrate containing 96 pct CaFz. Beryllium flotation produced .concentrates .containing in excess of 5 pct BeO with recoveries over 70 pct. A 1.00-lb/h continuous flotation unit was constructed to demonstrate this procedure,

Jan 1, 1985

By Jussi Vaamol

A commercial CFD-code was used to solve isothermal flow fields of gas and liquid in a Peirce-Smith converter. The model was validated with a 1/4 scale water model, and parametric study. Limits of the modeling technique used were recognized, but calculated results indicate that the present model predicts the general flow field with reasonable accuracy. The model was used to examine general flow conditions in an industrial scale PS-converter. Typical scaling factors of physical models were also evaluated with the aid of predicted bubble distribution, patterns of the flow fields and magnitude of flow velocities. The numerical simulations were found to open new viewpoints to the fluid dynamic related phenomena in the PS-process.

Jan 1, 1998

By James O'Brien, Lyman Frost, S. Elangovan, J. Stephen Herring, Joseph Hartvigsen, Carl Stoots, Anthony Nickens

"Carbon dioxide recovered from concentrated sources, such as metallurgical reduction furnaces, cement kilns and fossil power plants can provide a valuable feedstock for a synthetic fuels industry based on energy from nuclear, solar, wind and hydropower sources. High temperature co-electrolysis of CO2 and steam to produce synthesis gas has been demonstrated using reversible solid oxide fuel cell technology. Where a source of high temperature process heat is available, such as from an advanced high temperature nuclear reactor or solar dish concentrator, the endothermic electrolysis reactions can utilize both thermal and electrical inputs in such a way that the conversion efficiency within the cell is 100%. Synthesis gas produced in a coelectrolysis cell has been further reacted over a catalyst to produce conventional hydrocarbon fuels. Widespread implementation of synfuel production from CO2 will enable a much larger reliance on intermittent renewable energy than can be accommodated by conventional electric demand profiles.IntroductionFor the past several years, Ceramatec, Inc and the Idaho National Laboratory (INL), have been studying the feasibility of high temperature solid oxide electrolysis for large-scale, nuclearpowered hydrogen production under the U.S. DOE’s nuclear hydrogen initiative (NHI) as an alternative to the thermochemical process. Parallel to this effort, the INL and Ceramatec have been researching high temperature co-electrolysis of mixtures of steam and CO2 to produce syngas:"

Jan 1, 2008

By Rodney Clary

Building on work completed in earlier papers, the current paper presents a techno-economic evaluation of two recently demonstrated technologies for treatment of arsenic containing refractory gold concentrates. Using defined project parameters and inputs, the authors compare capital and operating cost estimates for pressure oxidation (POx), and the Albion Process™. The paper incorporates data now publicly available from the Albion Process™ plant, which has operated at the GeoProMining Gold (GPM Gold) project in Armenia since 2014, as well as recent POx circuits.

By P. Koskinen

Outokumpu Oy has 30 years' experience in nickel production. It is mainly based on the technology developed within the company. The production chain starts from the mines reaching to the high-grade cathode nickel and the stainless steel manufacturing. As a multi-metal producer Outokumpu has the advantage to exploit from nickel raw materials also other valuable metals and intermediate products which can be processed at the company's various plants. The main source of nickel concentrate is nowadays the Enonkoski Mine started up in early 1986. It is the most modern mine in Finland being provided with the latest Finnish high-tech systems. Nickel concentrates are smelted at the Harjavalta Works using Outokumpu's internationally well-known flash smelting method. Also nickel containing residues and secondaries' are used as raw materials. The high-grade nickel matte from the smelter is then refined at the nickel refinery in a hydrometallurgical process, which was also developed by the company's own research staff. These processes have been continually improved and capacities gradually enlarged to 18 000 mtpy of cathode nickel. Besides plating, melting and superalloying purposes part of the nickel ends in stainless steel at the Tornio Works. The production was started in 1976 and has reached an established position on the European market.

Jan 1, 1988

By Yasuhiro Konishi

Hydrolytic stripping is the process in which metal ions are simultaneously stripped from a loaded cation-exchange solvent extractant and precipitated as oxides or hydroxides. Hydrolytic stripping is usually effected by contacting the loaded organic phase with water at elevated temperatures. The possibility of using hydrolytic stripping to prepare ceramic powders with controlled size and morphology is now being evaluated for different systems, using carboxylic acid extractants. As part of this work, mathematical models were developed to describe the kinetics of nucleation and growth of nickel ferrite particles. This paper describes the development of the models, along with estimation of key parameters appearing in the rate equations from experimental data.

Jan 1, 1990

By Akira Yazawa

In the field of pyrometallurgy, the equilibrium evaluation has recently become easy by use of thermodynamic software, but it is strongly desired to estimate the amounts of non-equilibrium minor components to simulate practical processes. However, simple physico-chemical technique can not be applied to evaluate practical non-equilibrium components for many reasons. As an engineering solution for postulated equilibrium system, the activity coefficient is modified and introduced as the simulation parameter referred to as the "adjustment coefficient." This modified thermodynamic calculations were adopted to various sulfide roasting processes where many solid phases are participating and the system is not necessarily in equilibrium. Successful simulation was realized by assigning suitable adjustment coefficients for minor components which form a pseudo solid solution in the calcine. Some examples from sulfation roasting and dearsenizing roasting were discussed. In the smelting system, the loss of copper in slag is caused by equilibrium and non- equilibrium reasons, that is, chemical dissolution and entrainment of copper in slag. The total copper content of slag was simulated by use of the adjustment coefficient for entrained copper.

Jan 1, 1998

By Hang Goo Kim

A computer simulation has been carried out to predict the distribution behavior of minor elements such as Pb. Zn, Bi, Sb and As in recently proposed copper smelting and converting processes with submerged oxygen injection in which tonnage oxygen is used with a shielding gas. In this study the technique of stepwise equilibrium modeling was employed and some of the thermodynamic data were updated or reassessed. The volatilization and slagging of undesirable elements were investigated in copper smelting (steady-state) system, copper matte converting (batch) system, and the combined (smelting + converting) system at extremly high oxygen-enrichment levels. The predicted minor-element behavior under high oxygen- enrichment was compared with that in the Noranda process (normally 42% oxygen-enrichment in smelting and 24% in converting) and the reverberatory process using air. The effects of various operating parameters such as temperature, the final matte grade in smelting, the initial matte grade in converting and the O/Fe ratio in slag on the behavior of minor elements are discussed.

Jan 1, 1991

By Hideharu Fukunaga, Jin Pan

"The recognition of Metal Matrix Composites (MMCs) as a means of providing high specific strength, high specific stiffness, excellent wear resistance, low thermal expansion and improved high temperature properties has led to a number of new processing, not previously used for plastic and ceramic matrix composites. As a primary fabricating process, the liquid methods are the major ones, which are reviewed briefly from the view of processing terminology. One of them, squeeze casting process is the most traditional and well-developed, because it is rapid, versatile and near-net shape production of materials. Two of new squeeze casting processes are presented to offer the hardness· controlled MMC and the· functionally graded MMCs as well as a newly developed whisker preform.I .IntroductionA large number of liquid processes and techniques including semi-solid liquid process are proposed. The most primitive process is ''pressure infiltration casting” of liquid metal into the fiber preform. It is called as follows depending on pressure and its source squeeze casting (1-4) by hydraulic ram, gas pressure infiltration casting (5, 6), vacuum infiltration, centrifugal casting (7), Lorentz-force-driven infiltration (8). The pressurizing on the liquid metal requests a large and stiff equipment, so pressureless infiltration technique has been developed using K2ZrF6 flux (9,10) while the mechanical properties are not high enough, and using H2 gas with Mg alloying element called pressureless infiltration casting (11-13), spontaneous infiltration process (14) and PRIMEX (15). In those processes, no severe reaction occurred between the reinforcement and matrix molten metal. In early l 990's, the reactive processing with pressure or without pressure, in which one material is totally transformed into another of the required shape, eq. assisted oxidation, has been developed, called reaction squeeze casting (16,17), DIMOX (18) reactive infiltration casting (19,20), and in-situ process (21,22). Die casting of SiCp/Al alloy (23,24) and thixocasting of SiCp/Mg alloy (25) are also applied to produce the machine component of MMCs."

Jan 1, 2000

By Geoffrey Brooks, Ben M. Ekman, M. Akbar Rhamdhani

"Concentrated solar collectors including solar simulators have been studied to concentrate solar radiation to flux levels capable of reaching temperatures of 3000K. Currently, there are no industrial scale solar reactors used for material processing and only small research units have been tried. Various laboratory scale solar reactor designs are reviewed including their operating temperature and heat transfer efficiency. Solar reactor designs can be classed into directly or indirectly irradiated and single or double cavity construction. Thermal efficiencies of up to 40% have been achieved in experimental units while operating at 1500K. Problems are encountered that relate to the transfer of high heat flux. Hybrid reactor system should be considered in the future to overcome some of the practical issues associated with solar thermal reactors.I. INTRODUCTIONIn the high temperature processing of materials, such as the production of metals, cement, refractory or glass, the reactions are typically performed in the range of 500° to 2000°C. Metals are produced from minerals, which maybe oxides, sulphides, chlorides or silicates, and to recover the metals, these compounds have to undergo chemical reaction to liberate the metal. The thermodynamic stability of these compounds found in minerals necessitates the use of high temperatures to break down the bonds between the metals and other elements. Normally, the raw metals produced from smelting require refining, which is often carried out in the molten state. As new energy sources have been established, new furnace designs have evolved to incorporate the latest technology. Although solar energy has existed longer than all the current energy sources, it has not yet been incorporated into any industrial smelting; refining or melting processes. The solar radiation reaching the earth’s atmosphere, called the “Solar Constant” (SC), is defined as the rate at which solar energy is incident on a surface normal to the sun’s rays at the outer edge of the atmosphere when the earth is at its mean distance from the sun. The currently accepted value is 1367 W/m2 [1]. The earth intercepts only a small amount of this and 30% is reflected back into space, 47% is converted to low-temperature heat and reradiated into space and 23% powers the evaporative and precipitation cycle of the biosphere [2]. As a result, the solar energy reaching the earth’s surface is weakened considerably to about 1000 W/m2 or one sun, on a clear day and much lower on cloudy or smoggy days [3]. The thermodynamic limit for solar concentration is determined from the inverse square law [4] by the factor sin2? = 46,764 sun’s [5] where ? is the angular size of the sun and equals 0.0093 radians [7]. This would produce a steady state temperature equal to that of the sun’s surface of approximately 5800oC. In practice however much lower concentrations are achieved due to geometrical and optical imperfections, shading effects and tracking inaccuracies. Optical configurations based on parabolic-shaped mirrors are commercially available for large-scale collection and concentration of solar energy for the generation of electrical power. The most common configurations used for concentration of the sun’s energy in solar thermal applications are parabolic troughs, solar towers and parabolic dishes [8,9]."

Jan 1, 2014

By Ragnhild Aune

In fire refining of copper, the affinities of various impurity elements on dissolved oxygen is of great significance. Further, in the design of oxygen probes in liquid copper, the influence of solute interactions on the activity of oxygen need to be considered in order to evaluate the oxygen concentration in molten copper. The present paper presents a series of measurements of the activities of oxygen in liquid Cu-M-o alloys (where M stands for Mn, Zn, As, Se or Te) carned out by the present group employing the solid electrolyte galvanic cell technique. Extreme care was taken to control the oxygen potentials in the inert gas atmosphere, and to keep the oxygen levels very low in the molten metal. The oxygen content was determined by analysis of the samples taken out from the melt. The results obtained showed that Mn has a strong negative influence on the activity coefficient of oxygen in liquid copper. A similar, but less prominent effect was observed in the case of Zn. Arsenic had no influence on the activity of oxygen in Cu (liq.). Se and Te had slight negative effect on oxygen activities in copper at XQ >10-5, while at lower oxygen levels the interaction coefficients were found to be positive. The results obtained were compared with empirical models for the calculation of interaction coefficients available in literature.

Jan 1, 2003

By Reimers. Jan H.

Practically all the world's lead is produced by sintering and blast furnace smelting, or the Imperial Smelting Process which is a variant of the blast furnace process. Increased coke and labour costs and strict lead emission limits have, however, made blast furnace smelting undesirable in most countries. A change-over to other lead smelting processes providing better working conditions and lower emissions is, therefore,. expected to occur once economic conditions improve and the necessary capital expenditures can be justified. The need for new lead smelting processes has long been evident and a number of new processes have been proposed 'and advanced to various stages of development. One of the new processes is already proven on commercial scale, while several others are still being tested on pilot plant scale.

Jan 1, 1983