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By G. B. Harris

Much has been written over the past decade concerning the disposal of arsenic from metallurgical processes. In Canada, there are proposed regulations which would classify arsenic in the Primary Group of twenty one persistent, toxic pollutants to be banned or phased out. Since many nickel and cobalt ores, not to mention those of copper, gold and uranium, contain significant amounts of arsenic, it is pertinent to assess the current state-of-the-art of its disposal. The literature is reviewed, and it is demonstrated that from a purely chemical point of view, the family of ferric arsenates largely immobilize arsenic. There is clear evidence from laboratory studies that both crystalline ferric arsenate (scorodite) and amorphous ferric arsenates in which the molar Fe/As ratio is at least three (Fe/As = 3) have very low arsenic solubility; plant data are given to support this. The debate over the long term stability of these compounds continues however; the evidence presented for long term stability and for compound breakdown is critically reviewed in the light? of the recent structural studies, and the role of base metals in these compounds evaluated. Finally, conclusions are drawn as to the viability of a purely chemical process for the long term disposal of arsenic from metallurgical processes.

Jan 1, 1993

By Dong Joon Min, Joo Hyun Park, Mi Sun Choi, Jae Hong Shin

Sublimation of ZrCl4 is important for the production of nuclear grade metallic Zr in Kroll’s process. The sublimation kinetics of ZrCl4 was investigated by TGA under both isothermal and non-isothermal conditions. The sublimation rate of ZrCl4 increased with increasing temperature under isothermal conditions. ZrCl4 sublimation was confirmed to be a zero-order process under isothermal conditions, whereas it was first-order kinetics under non-isothermal conditions. The activation energy of ZrCl4 sublimation under isothermal conditions was 21.7 kJ/mol. The activation energy for non-isothermal sublimation was 101.4 kJ/mol and 108.1 kJ/mol with the Kissinger method and Flynn- Wall-Ozawa method, respectively. These non-isothermal activation energies were very close to the heat of sublimation (103.3 kJ/mol). Sublimation occurs by two elementary steps: surface reaction and desorption. Therefore, the overall activation energy of ZrCl4 sublimation is 104.8(±3.4) kJ/mol. The activation energy of the surface reaction and desorption steps are proposed to be 83.1 kJ/mol and 21.7 kJ/mol, respectively.

Jan 1, 2014

By Fumitaka Tsukihashi

Phase diagrams of the CaO-SiO2-FeOx-MgO, Al2O3 systems arc necessary for the analysis of copper smelting reactions and sintering process of iron ore. The effect of MgO and Al2O3 addition on the liquidus of the phase diagram of the CaO-SiO2-FeOx system at low oxygen partial pressure was observed. The liquid phase area changed bi the addition of MgO and Al2O3 with a changing oxygen partial pressure from 10-8 to 10-3 atm (10-3 to 10 2 Pal at 1573K. The effect of Fe3+ / Fe2+ ratio on the melting mechanism is discussed.

Jan 1, 2003

By Emil H. Geus

A process has been developed to recover aluminum from dross which does not require the use of salt flux as commonly employed, This results in a salt-free residue which has potential industrial uses or alternatively can be safely land-filled. The dross is first heated by an air-fuel or oxy-fuel burner in a sealable rotary furnace. At a suitable temperature the burner is turned off and the temperature of the dross thereafter controlled by means of an atmosphere of oxidative and inert gases. When the free metal has agglomerated it is first discharged from the furnace, followed by the residues.

Jan 1, 1995

By Barry Welch, Kai Grjotheim

"The capital intensive nature of the present process for aluminium smelting, the low productivity per unit reactor, and pressure to reduce the electdcal energy demand have motivated the search for an alternative process. Optional routes include carbo-thennal reduction of alumina (using an alloy phase immediate), chlorination followed by electrolysis of aluminium chloride, and electrolytic decomposition of alumina using inert electrodes. Materials performance and reactor design constraints have been a major limitation for alternatives. However parallel research has led to considerable advances in the process efficiencies and scale of both the Bayer process and the Hall-Heroult cells.Future development of alternatives is dependent on breakthroughs in Materials Science such as the development of stable conducting anodes and stable wettable cathode materials. However if successful it is probable that some spin-offs will be retrofitted to existing cells. Therefore the basic Hall-Heroult technology will continue as the dominant process for at least the next half century.IntroductionThe present Bayer/Hall-Heroult process for production of aluminium is just over 100 years old. Frequently, during the century of its technological development questions have been raised as to whether it is the ideal route for metal production. The questioning was particularly intense in the period between the mid-1950s and the mid-1060s when the limitations of the Hall-Heroult electrolytic stage were evident. Then the cells were only 30 to 35 % efficient with respect to the utilisation of the hydro-electricity (requiring 16 18 kWh/kg, thus making it strongly dependent on cheap electrical energy), while the size of cells being installed were 80 to 130 kA. Hence the process was capital intensive, the productivity per reactor volume low, and the process was labour intensive (requiring about 15 man hours per tonne of aluminium). In addition, the use of pitches for Soderberg anodes and the fluoride electrolyte were creating problems through emission. At that time material science had paid little attention to the manufacture and use of carbonaceous materials or the development of alternatives that were corrosion resistant to cryolite or liquid aluminium. Hence cell lives were short - typically 600 to 1000 days - thus adding to operating costs. Thus the grass over the fence, as foreseen in 1960s vintage crystal balls appeared much greener for alternative processes."

Jan 1, 1988

By Kenneth S. Coley, Michael Pomeroy, Elaine Chen

Recent work on modeling of BOF steelmaking is reviewed, highlighting the critical aspects of each approach. It is concluded that the most successful models should be based on a deep understanding of the mechanisms and kinetics of the critical reactions. The importance of the decarburization mechanism is discussed with particular reference to its role in droplet swelling or bloating which has a profound influence on the droplet residence time in the slag. Conditions which cause bloating are discussed and the rate determining step is proposed to be primarily nucleation of CO bubbles inside the metal droplet with some influence from growth by reaction at the bubble/metal interface. The discrepancy in the super-saturation ratio required for classical nucleation is discussed and an approach using a surface tension modifying parameter is illustrated. Finally, the role of CO nucleation in controlling the driving force for dephosphorization is discussed.

Jan 1, 2014

By E. Krystad, G. Tranell

"The kinetics of boron removal from liquid silicon during slag refining, as a process step in the production of solar grade silicon, has been investigated by means of small scale mass transfer experimental series at 1600°C, using a graphite crucible. The slags were SiO2-CaO based, with or without addition of approx. 19 wt% MgO. Experiments were carried out at slag-metal ratios of 1 or 2, where the silicon initially contained approx. 250 ppm boron. The metal-slag mass transfer coefficients for boron were found to be in the order of 1-3 · 10-6 m/s and were largely influenced by slag composition. The mass transfer rate was higher for the MgO-containing slag than the slags without MgO. The final equilibrium distribution of boron between metal and slag, LB, was determined to be in the order of 2.3-3.3.I. INTRODUCTIONRecent years have seen a race in industry and research aimed at obtaining a reliable metallurgical route for production of silicon for solar cells (SoG-Si) from metallurgical grade (MG) silicon. Metallurgical routes can successfully challenge the traditional chemical routes for production of SoG-Si if they generate metal of sufficient purity while being less expensive in terms of production cost and energy consumption. Efficient removal of boron is one of the greatest obstacles in the refining of silicon by a metallurgical route, because the segregation coefficient of boron in silicon makes directional solidification unfeasible; in addition, the vapour pressure of boron is not high enough for removal by vacuum refining. However, the thermodynamic properties of boron makes removal from silicon by oxidation possible, and thus the process of slag refining of silicon has been receiving increasing attention as a method for boron removal."

Jan 1, 2012

By Ravi Vancheeswaran

The consolidation of ceramic fiber reinforced metal matrix composites is a key process step in the synthesis of high performance composite systems. A simulation tool has recently been developed for predicting the evolution of the composites internal state microstructural variables (eg. relative density, fiber microbendinglfracture, and chemical reaction layer thickness at the fiber-matrix interface) during the consolidation processing of spray deposited composite mono-tapes. A Generalized Predictive Control (GPC) scheme is used in conjunction with the simula-tion tool to design near optimal process paths that minimize fiber damage and reaction product thickness while simultaneously maximizing the composites relative density. The microstruc-tural evolution depends nonlinearly on the process conditions and therefore the scheme uses a constantly updated linearization of the model to optimize the input process variable vector. A control simulation is presented to illustrate the performance of the design scheme and to assess the feasibility of its use for the achievement of goal state microstructures at the completion of consolidation cycles.

Jan 1, 1996

By Cang Daqiang, Li Yu, Liu Xiaoming, Zong Yanbin

"Utilization of high-quality heat in melting slag is a great challenge for iron and steel industry. In the paper, a new method is put forward to concurrently utilize heat and slag by converting the melting slag directly into high valued materials, slag glass-ceramic. A glassceramic with a higher basicity of 0.7 than traditional basicity of 0.45 was prepared from steelmaking slag in order to utilize more hot melting slag. Effects of Alz03 on its crystallization processes were researched by XRF, DTA, XRD and SEM. Results show that Alz03 in glassceramic would have great effected on its property. When the Alz03 content ranges within 12%-15%, glass-ceramics with basicity of0.7 could reach the best performances. The change of dominant phase in glass ceramics from akermanite and wollastonite to akermanite and gehlenite would significantly degrade its mechanical property. An increase of Al2O3 content leads to a rise of the viscosity and crystallization activation energy of the glass, while results in increasing sintering temperature and crystallization temperature of glass, which contributed to its fully crystallization and densification process.IntroductionSteel slag is a by-product under a process of converting iron to steel at above 1600°C, and 0.1-0.15 ton molten steel slag would be discharged for producing per ton of steel in the process. The discharged steel slag at 1600°C has heat of 68 kgce/t. In 2012, China's steel output reached 716 million tons, and produces about 100 million tons of steel slag and 68,000 tee of heat in it [1,2]. But at present, utilization of both slag and its heat at 1600°C is a great challenge for iron and steel industry.Dry granulation of melting steel slag by air and then recovering the heat of the hot air are a traditional technology which have not yet been put into practice for very low heat conductivity of the slag and low efficient of heat exchange among the different processes [3,4]. Therefore, a new method for high efficient utilization of both steel slag and its high temperature sensible heat is put forward [5,6], which is on-line reducing and extracting iron from molten steel slag and then directly preparing glass-ceramic by use of the residual molten slag."

Jan 1, 2014

By Gordon A. Irons

"Powder injection for melt refining is widely practiced in the steel industry, and is gaining acceptance in the non-ferrous industries. In these commercially-important systems, the thermodynamics and kinetics may be very complicated. More than one element may be removed by refining, and often the refining agents are not just one compound. In this paper, the thermodynamic and kinetic aspects of these processes are reviewed. A number of examples are given, such as the desulphurization of iron with a variety of reagent mixtures, and selenium removal from copper with several different reagent combinations.IntroductionI am very pleased and honored to present a paper at this Symposium recognizing the many contributions of Professor Howard Womer. Even at the time I was an undergraduate student, the WORCRA process was part of the curriculum. I remember at the time that I was fascinated by the concept, and due to it and the many other rapid developments in Process Metallurgy, I chose it as my field of study. I think the Symposium is testimony that Professor Womer has touched the lives of many others as well.My original assignment was an overview of the basic aspects of gas and solids injection. However, I reviewed most of this material at the Savard/Lee Symposium [1]. In the present paper, I will present some of the basic issues related to refining with powder injection, using work that we have recently completed in both ferrous and non-ferrous systems."

Jan 1, 1996

By Richard B. Diver, Mark D. Allendorf, Daniel E. Dedrick, James E. Miller, Roy E. Hogan, Andrea Ambrosini, Eric N. Coker, Anthony H. McDaniel, Nathan P. Siegel, Gary L. Kellogg

"Converting carbon dioxide and water to hydrocarbons is an attractive option for storing solar energy and, coupled with appropriate CO2 capture technology, for recycling carbon and impacting atmospheric CO2 concentrations. For any process, high solar-to-fuel efficiency is necessary for large scale viability and favorable economics. Thermochemical approaches for solar-to-fuel conversion are potentially highly efficient as they avoid the inherent limitations of photosynthesis and also sidestep the solar-to-electric conversion necessary to drive electrolytic reactions. Solar-driven two-step metal-oxide-based thermochemical cycles for producing the components of syngas, CO and H2, from CO2 and H2O are the basis of the “Sunshine to Petrol” project. Multi-cycle production of both H2 and CO has been demonstrated over several iron- and cerium-based compositions fabricated into monolithic pieces both in the laboratory and at the National Solar Thermal Test Facility. These compositions are being developed for deployment in a unique and continuous solar-driven reactor prototype, the counter-rotating-ring receiver reactor recuperator or CR5.IntroductionThe interconnected challenges posed by increasing global competition for petroleum and the increasing concentration of atmospheric carbon dioxide are now widely recognized. Meeting these challenges requires recognition that although hydrocarbon fuels are ideal energy carriers, they can no longer be thought of as primary energy sources. It is necessary to take the realistic view that our conventional fossil fuels are in fact “stored sunlight” in the form of “sequestered carbon.” This view leads to a search for options to use and store sunlight more directly.Sunshine to PetrolIn combusting hydrocarbons we unlock the energy for utilization, but we also release the carbon to the atmosphere. However, nature teaches us that with an appropriate persistent energy source, e.g. solar irradiation, it is possible to effectively reverse the combustion process and “reenergize” CO2 and H2O back into hydrocarbon form."

Jan 1, 2010

By G. G. Krishna Murthy

Interactions of wustite and hematite pellets with Fe-C melts were investigated experimentally by examining the effect of pellet size and bath temperature on the reduction rates of the pellets. Experiments were carried out in the temperature range 1473-1923 K. A flash X-ray equipment was used to obtain images of the melt surface during its reaction with an oxide pellet. The reduction rates were calculated using experimentally estimated time for complete reaction of a pellet, tR. The value of tR was determined employing gas mass flow rate, or pressure rise in the sealed furnace, versus time traces. The value of tR was the same for both wustite and hematite pellets of equal weight at or above 1723 K and it decreased with increasing melt temperature. But the reduction rate was substantially lower at temperatures below 1651 K, the melting point of wustite. The rates were defined as the rate of moles of oxygen removed from the pellet per unit area of bath free surface and it was found that the bath surface area affects the reduction rates. It was established that the overall reaction followed nth-order rate kinetics with the values of n falling between 0.3 and 0.4 for temperatures above the melting point of wustite. The apparent activation energy determined using the apparent rate constants obtained from the experimental data was 76.2 + 27.7 kJ/mol-O.

Jan 1, 1992

By Zhucheng Huang, Ronghai ZHONG, Tao Jiang, Jun ZOU

The method of reduction roasting and magnetic separation of low-grade, micro- fine disseminated refractory iron ore following granulation with coal produced unexpected success. Pellets of iron ore with diameter between 3 and 8mm were granulated with coal, bentonite and water. The raw pellets and reduction products were analyzed by scanning electron microscopy and x-ray diffraction. Results show uniformly distributed coal powders inside the pellets improved the kinetics of the reduction process and accelerated the reduction rate. Reduction time was higher at temperatures below 890℃, which resulted in the formation of substantial amounts of fayalite. When temperature was increased, micro- fine hematite was then quickly reduced to iron metal and the amount of fayalite decreased sharply. When pellets were reduced at 950℃ for 25min, reduction products with 56.73% metallization rate were obtained. After grinding and magnetic separation, a concentrate with 72.18% Fetot was obtained.

Jan 1, 2015

By Zhigan Deng

Cooling crystallization was used to separate iron (III) and nickel (II) from acidic sulfate solution produced by leaching of molybdenum-nickel black shale. The effect of K2SO4 concentration, crystallization temperature, solution pH and crystallization time on recovery of nickel (II) and precipitation of iron (III) was investigated, in order to obtain effective separation of nickel and iron. The optimum parameters determined were as follows: 200 g/L K2SO4, 10 °C crystallization temperature, solution pH of 0.5 and 24 h crystallization. Under these conditions, 97.6% nickel (II) was recovered as K2Ni(SO4)2, 6H2O crystals and only 2.0% of the total iron (III) was precipitated. Recrystallization yielded K2Ni(SO4)2, 6H2O crystals with a purity of 98.4%.

By E. O. Ávila-Davila, F. R. Barrientos-Hernández, I. A. Lira -Hernández, Miguel Pérez-Labra, M. Reyes-Pérez, J. Antonio Romero-Serrano

Slag from smelting reduction processes were characterized by chemical analysis, XRD, SEM-EDS and XRF. The results revealed Ag concentrations of 362 g/t of slag, the slag mineralogical characterization by XRD and SEM-EDS showed mineralogical species oxidized complex containing Pb, Zn, Ca, Si, Fe, As, S in its structure, silver was found in globules associated lead in the slag and the furutobeite specie. The leaching study was conducted to evaluate process variables such as NaCN concentration: from 7.8x10-3M - 1.26x10-1M, temperature: 25-50°C, particle size: +140 mesh to -400 mesh, stirring speed of 750 rpm - 900 rpm. All studies were performed with a NaOH concentration of 0.2 M. The optimal values of silver recovery encountered in conditions of 7.8x10-3M NaCN, agitation rate of 750 rpm, temperature of 35°C and with a treatment time of 240 min. We also observed that a particle size -400 mesh will have optimum recoveries compared to +140 mesh, +200, +270 and +325.

Jan 1, 2015

By Gregory A. Knapp

Treatment of industrial wastewaters generally advances with specific chemical concentration and mass-flow targets, established by National Pollutant Discharge Elimination System (NPDES) permits. Treated discharges must also address toxicity to test and receiving water organisms. Various parameters might need consideration during treatment design and planning, such as the known toxicants, hardness, alkalinity, solids, nutrients, metals in both the dissolved and particulate state, and even flow. Since toxicity is used as a "catch all" regulatory monitoring tool, design of treatment systems should focus on the various factors contributing to toxicity.

Jan 1, 1996

By Eoghan T. M Doyle

Oxide mixtures of nickel (NiO), cobalt (COO) and chromium (Cr203) were prepared with graphite in stoichiometric amounts and the powder mixtures were compacted to produce cylindrical pellets. The composition of chromium oxide in these mixtures were varied. Pressed pellets were reduced in a flowing stream of argon-4% hydrogen gas (500 ml/min). Both slow and rapid heating methods were adopted to raise the temperature of a pellet during reduction of oxides to form superalloy powder. The reduction temperature was varied between. 1523 and 1623K. The effect of heating rate and niobium oxide addition on the microstructure of the superalloy produced was studied by using ordinary light and scanning electron microscopes. New phases formed as a result of reduction were identified by X-ray powder diffraction technique. The mechanism of reduction of oxides together with the microstructure of NiCrCo alloy are discussed. The thermodynamics of formation of ternary alloy phase is elucidated on the basis of binary phase equilibria and Gibbs free energy of mixing data for the constituent alloy compositions.

Jan 1, 1992

By B. Mishra, W. A. Averill

"The application of various hydrometallurgical, pyrometallurgical and electrochemical processes in the extraction, purification and production of radioactive metals as well as the use of various materials, ego metals and alloys, ceramics, polymers, etc. in the process, construction and handling equipment in the nuclear industry has generated a large stockpile of radioactively contaminated waste material and scrap metal which can not be directly discarded, recycled or considered for long-term storage due to its volume and potential hazards, without the separation of radionuclides. This paper reviews the emerging methods that have been investigated and suggested for dealing with some of these wastes and scrap material.The separation technologies studied for the recovery of radioactive components from the pyrometallurgical and electrochemical processing wastes have been discussed in details with results from some of the recent theoretical and physical modeling work as well as the data obtained from the actual waste treatment. Specific processes shall be described in terms of its advantages and limitations. These emerging separation technologies are being considered by the US Department of Energy as alternatives for dealing with the issues of environmental management [EM] and decontamination and decommissioning [D&D].IntroductionThe high temperature carbothermic or metallothermic smelting reduction methods for metal production are associated with the generation of significant quantity of waste as slags, flue dusts, sludges, residues, effluent salts etc. Certain hydrometallurgical processes also generate lots of aqueous waste due to the inherent nature of the technique. Also, the gas-based reduction processes are not applicable to many stable metal compounds, such as alumina, titania, beryllia, lanthanide and actinide oxides, etc. due to thermodynamic considerations. All these methods cause substantial environmental hazard. There is a need to develop alternative processes which have low waste or ideally a ""zero-waste"" generation.Pyrochemical processes using molten salts provide a unique opportunity for the extraction and refining of many reactive and valuable metals either directly from the beneficiated ore (aluminum, beryllium, neodymium, plutonium, uranium, etc.) or from other process effluent that contain reactive metal compounds. The processes reduce metal compounds electrolytically (A12O 3 and BeCI2) on a carbon anode or by calciothermic reduction (Po, Nd). The by-product, in the latter case, is a calcium oxide saturated halide salt. The waste-treatment to recycle the halide has to be done as a separate step or stored as a contaminated waste. A successful separation technology can provide a new insight to the waste minimization strategy for the nuclear industry."

Jan 1, 1996

By Fabiola Alvarez, Ana E. Bote, Daniel Pasquevich

"The oxidation of aluminum and its alloys was extensively studied for improving the corrosion resistance in structural materials having high specific strengths. But this reaction involves the formation of a very thin barrier layer on the metallic pieces. Furthermore, the ·recent development of the directed melt oxidation process for producing metal-ceramic; composites has renewed the interest in the study of interaction between gases and metals. Oxidation experiments in the presence of different chlorine partial pressures and at different temperatures were performed in ·a thermogravimetric balance, and microstructures were analyzed by electronic microscopy and X-ray diffraction. The oxy-chlorination kinetics was determined and the oxide formed W(IS amorphous at temperatures below 600 °C and crystalline .at higher temperatures. The appropriate experimental conditions for the fastest completed oxidation was further determined.IntroductionThe use of fine powders for the manufacture of ceramic components has significant advantages. They include excellent sinterability; low sintering temperature and better microstructure leading to improved mechanical properties. The conventional method of producing fine oxide powders involves controlled precipitation and pirolysis of suitable salts. The main limitation of the high temperature decomposition route is the evolution of environmentally unacceptable and corrosive gases. Controlled precipitation of hydroxides from solutions of salts, followed by thermal treatment involves large volumes of solutions and the calcination step that can induce grain growth (1).Direct oxidation of aluminum metal for producing alumina powder requires high temperatures for the direct oxidation of molten Al alloys by a vapor phase oxidant process (2, 3) or high technological process like thermal plasma reactor ( 4).Oxidation of high purity aluminum (5, 6) below the melting temperature· is initially characterized by a nearly linear reaction rate, followed by a rate which decreases rapidly with further weight gain. However, the oxidation rate of an aluminummagnesium alloy is much faster and it does not conform to any common oxidation law, but it is nearly parabolic at temperatures between 200 and 400 °C, an nearly linear· above 400 °C."

Jan 1, 2000

By Bryce Clark

Cobalts history from the 14th Century is outlined, with a look at its various sources over that period. The present sources and quantities are given, when in 1994 it is an equal co-product of copper in Africa and nickel elsewhere (Canada, Australia, Russia). Future trends in this scene are also examined. The final section deals with cobalts uses in superalloys, magnets, colours, electronics, chemicals, and examines trends in its markets. Supply and demand in co-product cobalt are shown, based on the latest production figures.

Jan 1, 1995