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By J. L. Jambor, H. W. Nesbitt

Oxidative dissolution of pyrrhotite and pyrite is largely responsible for the sulfate-rich waters of the vadose zone in the Waite Amulet tailings. Although the shallowest of the sulfate-rich waters are of the Fe-SO4 type, they change to Mg-SO4-type, near-neutral waters within 1-2 m of the tailings surface. Phyllosilicates and amphiboles are the only minerals present in sufficient quantity to ameliorate the amount of acidity produced. X-ray diffraction and microscopic studies of bulk sample indicate that quartz, chlorite, talc, amphiboles, magnetite, albite, and micas are the major and minor non-sulfide minerals, but their variations with depth do not give clear indications of depletion in the vadose zone. Mineralogical and bulk chemical compositions of the tailings confirm that Fe2O 3 has accumulated in large quantity in the vadose zone, with the Fe having been derived from Fe sulfides. When the effect of Fe2O3 is accounted for, the bulk compositions suggest that SiO2 is slightly more abundant in the vadose zone than in the saturated zone. This may be the result of residual enrichment of siliceous minerals such as quartz and albite in the vadose zone. Weathering of the tailings since the cessation of deposition in 1962 has resulted in a well-defined zone of sulfide depletion and secondary sulfate-mineral development. Although some silicate dissolution is indicated by pore-water compositions, the role of silicates in providing neutralization seems to have been minimal. The contribution by silicate minerals in laboratory tests of neutralization potential may be excessive relative to that in natural settings.

Jan 1, 1999

By Ralph H. Nafziger

The Bureau of Mines, in cooperation with the Idaho National Engineering Laboratory, has electroslag melted a V-5Ti-5Cr alloy using a fused CaF2, flux. The alloy is a candidate for use in future fusion reactors. One objective of this research was to evaluate the feasibility of the electroslag melting process in separating simulated radioactive isotopes from the V alloy to demonstrate recyclability. Small amounts of Ca, Y, and Mn were added as surrogates for radioactive isotopes. Results showed that this vanadium alloy can be electroslag melted satisfactorily. The impurities added intentionally were removed or decreased successfully. Among the major alloying constituents, Cr was retained but there were some Ti losses. The latter may be controlled with process refinements. This research suggests that the electroslag melting process could be a suitable method for recycling V alloys after use in future fusion reactors, or for processing other reactive metal alloys with more immediate applications.

Jan 1, 1996

By C. Pereira

Spent nuclear fuel (SNF) can be treated in a molten salt electro refiner for conversion into metal and mineral waste fonns for geologic disposal. The fuel is dissolved in molten chloride salt. Non-transuranic fission products in the molten salt are ion-exchanged into zeolite A, which is subsequently mixed with glass and consolidated. Zeolite was found to be effective in removing fission product cations from the molten salt. Breakthrough of cesium and the alkaline earths occurred more rapidly than was observed for the rare earths. The effluent composition as a function of time is presented, as well as results for the distribution of fission products along the length of the column. Effects of temperature and salt flow rate are also discussed.

Jan 1, 1996

By Michael J. Nicol

Growing environmental and occupational safety concerns about the use of cyanide in gold processing has increased the interest in more acceptable alternatives. The most likely of these is thiosulfate. However, the thiosulfate process lacks a proven in-pulp method of recovering the dissolved gold, because activated carbon is not effective for the absorption of the gold thiosulfate complex .. Anion exchange resins do offer a possible route for in-pulp recovery. This paper describes work aimed at the evaluation of the effectiveness of commercially available anion exchange resins for the recovery of gold from thiosulfate leach liquors? and pulps. It has been found that strong-base resins are superior to weak-base resins in that they have a larger capacity, which assists in reducing the competition from other anions within a leach solution. Further studies with a selected commercial strong-base resin have shown that competing polythionateanions (particularly tri-and tetrathionate). Lower the maximum possible gold loading but that gold is selectively recovered over other base metal anions in solution. Kinetic experiments found that while? competilig anibns did not affect the initial rate? of gold loading it was important to minimise the contact time of the resin in solution so to prevent displacement of loaded gold by competing anions over longer times. A small-scale resin-in-pulp plant investigation showed gold can be recovered from a leach pulp by a strong-base resin to yield gold loadings of 3000 mg/L, barren pulp containing less than 0.05 mg/L of dissolved gold and. copper loadings of 500 mg/L. Loaded copper was displaced gold and at a loading of 2000 mg/L gold the copper loading was minimal «500 mg/L). The resin was found to recover gold adsorbed on the solids that would, otherwise have. reported to tails if a solid/liquid separation method were used. A patented two-step elution process in which copper and then gold are separately eluted from the resin is also discussed.

Jan 1, 1998

By V. I. Lakshmanan

Wastes when produced can be reused or recycled prior to disposal. Industries that cause environmental concerns during manufacturing include primary materials and primary metals. Pollution prevention mechanisms to achieve waste reduction require new separation, reclamation, control and process simulation technologies. Substituting recyclables for virgin resources will reduce energy use, water pollution, air pollution, water use and mining wastes. Shrinking landfill space will spur new technologies for waste treatment and recycling. These situations hence offer opportunities for innovative flowsheets with appropriate separation technologies. Development of innovative flowsheets to treat recyclables offer unique opportunities for process/product development, obtain green products and hence market advantage. The paper will illustrate with selected innovative flowsheets to treat recyclables.

Jan 1, 1996

By R. J. Kuczynski

The U.S. Bureau of Mines operated a 2,000-9 (4.4-lb) batch process development unit for recovering platinum-group metals (PGM) from automobile catalysts. Virgin monolith, used pellet and used monolith catalyst samples were tested. Leaching twice with 1-pct sodium cyanide (NaCN) solution at 160' C for 1 h in a pressure vessel dissolved over 95 pct of the PGM from virgin catalysts and over 90 pct from used pellet catalysts. Over 85 pct of the PGM was dissolved from used monolith catalysts when a third leaching step was added. PGM concentrates as metallic powder containing over 99.8 pct of the dissolved PGM and analyzing greater than 70 pct PGM were recovered by heating the pregnant leach solutions from virgin catalysts to 250' C and used catalyst to 275" C for 1 h. The solution after heating contained primarily sodium carbonate from cyanide decomposition and less than 0.2 ppm total cyanide.

Jan 1, 1993

By S. Seetharaman, Du Siehen

"In the processing of molten metals, it is extremely important to monitor continuously the concentration levels of various minor elements. In the production of common metals like copper, iron and aluminium electrochemical sensors involving solid as well as liquid electrolytes are being increasingly used to measure the concentrations of minor elements. The present paper deals with the electrochemical principles underlying these measurements and the possible errors involved. One of the major difficulties in the case of the solid electrolytes is to correct for the consequences of the electronic contribution to the conduction of the electrolyte.The application of the electrochemical sensors for molten metals processing involves designing of these probes to withstand the industrial operating conditions. In this respect, significant achievements have been made with respect to the design of oxygen probes for liquid metals in general and liquid copper in particular. Some of the salient design features are discussed in the paper. The application of auxiliary electrodes for impurities in molten metals like phosphorus in copper and silicon in iron are taken up. The development of oxygen sensors for slags is given special attention. Recent developments in the field of sensor technology, as applied to metals processing are highlighted.1. IntroductionThe rapid technological advancement today require precise control of the process parameters and the impurity levels. Most of the molten metals processing in industrialized countries are often steered by suitable computer models, either phenomenological or simulations based on theoretical principles. These models often require that the process parameters are continuously monitored so that the progress is followed and modified suitably as and when required. It is common practice to measure temperatures by incorporating temperature sensors at the various strategic points of the reactor. In the case of monitoring the composition changes in the various phases, the method of sampling followed by routine chemical analysis involves a time lag as well as uncertainties in sampling and analysis. In this respect, electrochemical sensors have the advantage of generating accurate data when properly applied and increasing attention is being paid in the development of electrochemical sensors for various common species in molten metals processing. In the present paper, the developments in this area over the years are outlined and typical process applications are discussed. A greater emphasis will be laid on sensors based on oxygen conducting electrolytes and their application to the production of common metals like iron and copper."

Jan 1, 1996

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 K A. Pericieous

"Magnetic fields have many actual applications in the metals processing industry. Externally applied magnetic fields give rise to electromagnetic (Lorentz) forces formed by the cross product JxB, between the induced current density J and the magnetic field density B. When the metal is in liquid form, the Lorentz force generates motion in the fluid which in applications of practical interest becomes turbulent. In modelling terms, the Lorentz force appears as a source in the momentum equations. In addition, the induced current generates heat (Joule heating) in the metal that is in proportion to J2, with a corresponding source of heat in the energy equation. Whether as heat or as a force, these effects represent action at a distance - a most useful attribute when dealing with hot metal. The Lorentz force is used to stir solidifying alloys, pump liquid metal in conduits, dampen the flow in the meniscus of a continuous caster, levitate metal drops, induce artificial gravity conditions in suspensions or contain liquid metal. Elsewhere, the Lorentz force may be a by-product of some other operation, so leading to wave excitation in aluminium electrolysis cells, or altering the shape of the weld pool in arc welding. Joule heating is most commonly used with applied AC fields, to melt metal in induction furnaces.The author and his colleagues have been involved in the modelling of most of these processes in the past decade. Modelling is not however straightforward, since most of the examples mentioned represent genuine multi-physics challenges. There is a strong coupling between the flow field and electromagnetic field. The addition of a dynamically varying metal free surface and the moving solidus front means the flow, heat and electromagnetic fields need to be computed simultaneously. In situations involving metal containment, the metal free surface position is governed by the interplay of gravity, Lorentz force, surface tension and fluid inertia. Since all the interesting effects often happen in thin boundary layers at the surface due to the skin effect, mesh generation and mesh control during the computation become non trivial problems that need to be addressed. This paper presents a review of numerical methods used to model droplet levitation, semi-levitation melting and cold crucible induction melting of metals. The first method is based on spectral collocation techniques and the second is the traditional FV approach. Steps taken to validate the computations and typical transient results are also given."

Jan 1, 2001

By Sharif Jahanshahi

Calcium ferrite slags are often associated with Professor Yazawa due to his pioneering work on the thermodynamics of this type of melts. Over the past years CSIRO has invested some effort in studying physico-chemical properties of such melts to fill in some gaps in our knowledge and explore opportunities for application of the understanding developed. These investigations cover thermodynamics, transport properties of calcium ferrite based slags, as well as the kinetics of reactions of such slags with refractories. The present paper provides an overview of some of these studies and highlights some of the interesting behavior of such melts. The oxidation state of copper and arsenic in calcium ferrite based slags are predominantly Cu+ and As3+, respectively, at oxygen potentials below 10.1 atm. The concentration ofCu2+ in such slags becomes significant at oxygen potentials of greater than 10'1 atm at 1300 ?C. The activities of CuOo.s and AsOl.S in calcium ferrite slags show strong deviations from the Raoultian Law, while that of CoO is very close to ideal behaviour with respect to pure solid CoO. Addition of Si02 to calcium ferrite slags can have significant effects on the activities of FeO and Fe2O3 and hence the stability of magnetite phase. Transfer of oxygen in calcium ferrite slags is fast with diffusivity of 2xlO?3 cm2/s at 1350 °C and activation energy of 16 kcal/mol Presence of solid phases, such as magnetite, has pronounced effect on the viscosity of calcium ferrite slags. The observed dependence on solid loading and shear rate indicates deviation from Newtonian behaviour. The interfacial tension between copper mattes and calcium ferrite slags is strongly dependent on the matte grade, with the determined values being much lower than the corresponding ones for interfacial tension between similar mattes and iron silicate slags. MgO, Cr2O3 and MgCr2O4 have low solubility in calcium ferrite slags and their solubility increases with increasing copper oxide content of the slag at 1300 °c. The oxidation state of the slag has strong effects on phase transformation, dissolution rate and disintegration of refractories in calcium ferrite slags. Other key factors with major impact on slag-refractory interactions include viscosity and surface tension of slags as well as the contact angle between slag and refractory material.

Jan 1, 2003

By J. L. Watson

The composite nature of titanomagnetites found on the west coast of the north island of New Zealand is an important parameter in the beneficiation of the black beach sands for export to Japan. To investigate this composite nature, borehole and plant samples from the Waipipi Ironsands Ltd property were subjected to a series of separations in heated Clerici solutions at densities varying from 3.2 to 4.6 g/cc. The resulting density fractons were analyzed magnetically and a set of distribution curves for composite grains proposed. In addition the experi¬mental data was plotted to produce titanomagnetite sand 'washability curves" which illustrate the possible problem areas in beneficiation that may arise due to composite titanomagnetite grains. From this data a set of guidelines are suggested for interpreting the curves in terms of ease of gravity concentration. The composite nature or liberation of titanomagnetite grains is shown to favor high and low grade composites with few intermediate compositions being isolated. The relationships between grain size, borehole depth and liberation are examined and related to beneficiation procedures for the black sand deposit.

Jan 1, 1982

By Gerald K. Vellente

Producers of strip coated products are being approached by users to supply higher quality products and adhere to tighter specifications. Suppliers, in an attempt to assist the producers, must consider new technologies for equipment. In the past several years, the induction melting and heating industry has made great strides in developing new and innovative equipment, while improving existing technology. In the past several years, the induction melting and heating industry has made great strides in developing new and innovative equipment, while improving existing technology. In the past several years, the induction melting and heating industry has made great strides in developing new and innovative equipment, while improving existing technology. This paper will review recent developments to include improved refractory systems for ceramic pots, new channel-type inductors which are more efficient, new power control systems for existing channel-type pots, and innovative use of multi-purpose lines. Additionally, new heating applications such as galvannealing, edge heating, and post heating will be reviewed. Advanced math models for controlling heat will be discussed. Producers can easily meet the demands of their customers because of the flexibility provided by the equipment reviewed.

Jan 1, 1992

The U.S. Bureau of Mines investigated CaF2-assisted H2SO4 leaching to extract Mn from domestic silicate manganese resources. A pyroxmangite ((Mn,Fe)Sio3) ore containing, in pct, 34 Mn, 23 Si, 3 Ca, and 1 Fe was leached at 90° C for 3 h in a solution containing, in g/L, 12 Mn, 140 H2SO4, 130 (NH4)2SO4, and 5 CaFz. Manganese extraction of 92 pct was achieved. Manganese of greater than 99 pct purity was prepared by electrolyzing the purified pregnant solution at a current density of 50 mA/cm2. The current efficiency was 65 pct.

Jan 1, 1991

By Shilai Yuan, Huimin Lu, Liyuan Zhao, Zhijiang Gao

"A purification process was developed to removal impurity element boron from metallurgical grade silicon by electromagnetic induction slag melting. Vacuum melting furnace was used to purify boron in both Al2O3-MgO-CaO-SiO2 slag system and Al2O3-CaO-SiO2 slag system. The relationship between different slag chemistry and the removal of boron in silicon were studied using Back Propagation (BP) Neural Network model. The best slag chemistry for the removal of boron was predicted by Genetic Algorithm (GA) contributed by the use of Matlab. The results show that the mass fraction of Boron in silicon is reduced from 11.7496×10-6 to 2.3259×10-6 after slag melting in 28.96%Al2O3-3.43%MgO-36.24%CaO-31.37%SiO2 slag system. The relative error obtained with GA-BP Neural Network model was below 0.35%.IntroductionSolar energy, due to its low green house gas emissions, has been paid great attention. Accordingly, the demand for solar grade silicon (SoG-Si) has been growing rapidly. The quest for developing a low-cost method of producing SoG-Si has been moving forward in the last decade. Refining of metallurgical-grade silicon (MG-Si) attracts research interest due to its low material and energy costs, and more environmentally friendly technology in comparison to the traditional Simens process. As such, impurity elements in MG-Si must be removed to low levels for the photovoltaics (PV) cell to operate at optimum efficiency. Most impurities in metallurgical-grade silicon (MG-Si), especially metal elements, can be separated by directional solidification and the zone refining plasma-arc method [1, 2]. The main focus in refining MG-Si to SoG-Si is on the impurities which are the most difficult to remove. Boron has relatively high segregation coefficients (KB=0.8, concentration of Boron in solid silicon divided by its concentration in liquid silicon) [3] and higher vapor tension (the saturated vapor pressure of boron and silicon are 6.78×10-7 Pa and 0.4 Pa, respectively). The vacuum melting and directional solidification methods hence have no effects on boron removal.Slag refining involves melting MG-Si in the presence of a flux to produce a slag phase that can take up the impurity elements. The mechanism of slag refining is considered to include two main steps: the oxidation of boron and the absorption of boron oxide by slag materials. The oxidation of boron, described by the oxygen potential (PO2), resulting from the equilibrium Si and SiO2. The absorption of boron oxide, described as the slag basicity, is interpreted as expected to facilitate their extraction to alkali and alkali-earth oxides in the slag phase. Thus, effective removal may be obtained for a certain slag composition. Researchers [4-5] examined the effect of boron removal in CaO-SiO2 based ternary systems and showed that the addition of excess CaO can decrease the activity of SiO2. Researchers [6-8] studied the boron behaviors in CaO-SiO2-Al2O3, CaO-SiO2-Na2O, Al2O3-BaO-SiO2, CaO-SiO2-Li2O and Al2O3-CaO-MgO-SiO2 slag systems by adding boron in the silicon to a degree. Li2O, Na2O, MgO and BaO are thought to be associated with B2O3."

Jan 1, 2014

By E. Oshilna

The Mitsubishi process has many advantages pertaining to economical and environmental matters. These advantages have led to the installations of the Mitsubishi process in constructing new smelters: The Mitsubishi process utilizes highly oxygen enriched blast air and uses a special lime slag in the C?furnace. These characteristics change the . distribution of Impurities from other processes which use P.S. converters, Recently an Increased amount of secondary materials which contain impurities Is being treated at Naoshima Smelter. In order to cope with an Increment of the Impurities load and maintain the cathode quality, many Improvements have been Implemented. This paper discusses the impurities behavior In the Mitsubishi process and describes the measures taken to treat an Increased ?amount of secondary materials:

Jan 1, 1998

By Arsenio Enriquez, Adrian Deneys

"Rio Tinto through its subsidiary Kennecott Utah Copper Corporation (KUC) and Praxair have implemented the CoJet® gas injection system for copper anode refining. The system provides the capability to melt on average 60 to 70 tons of scrap copper per heat (with acceptable NOx emissions). The system has demonstrated the potential for tuyere-less sulfur and oxygen removal using coherent jet technology.This paper describes the process concept, system development, laboratory testing, implementation, current operation and ongoing developments."

Jan 1, 2009

By Fumitaka Tsukihashi

Increasing amounts of steel scrap are being used as resources for steelmaking. Therefore, there has been a growing interest in the removal of harmful tramp elements such as antimony, zinc, tin, arsenic, bismuth, lead and copper from the molten steel. The problem that should be solved is the economic removal treatment of residual tramp elements in the steelmaking processes and the production of high quality steel by reducing the effect of the contaminated tramp elements and satisfying the environmental regulations. In this paper, the available thermodynamic data of the residual tramp elements in the molten steel arc summarized and the possibility of the removal of residual tramp elements from the molten steel is thermodynamically estimated.

Jan 1, 2003

By R. G. Henley

Mount Isa copper concentrate was combusted in a laminar-flow furnace. The conditions simulated those likely to be encountered in flames in flash smelters of the Outokumpu (air as oxidant) and INCO (oxygen as oxidant) types. The range of conditions studied was as follows: T 400-1400°C, 02 0-100%, SO2 0-95% for residence times up to 0.23 s. The distribution of sulfur, arsenic and lead between the particles and the gas phase was studied. Combustion was very rapid provided the concentrate was adequately dispersed, i.e., no agglomerates. The importance of the latter is discussed. It was possible to oxidize 80% of the sulfur present in the con¬centrate after only 0.1 s reaction time at 1000°C in an atmosphere contain¬ing 8.5% 02 and 12.5% SO2. Best volatilizations (90% of the As, 52% of the Pb) were obtained under localized conditions attained in an air-type flame. Average volatilizations were: air-type flame, As 50%, Pb 32%; oxygen-type flame, As 40%, Pb 30%. The substitution of oxygen for air reduced the arsenic volatilization. The products of combustion were mainly cuprospinel and cuprite; small inclusions of elemental copper were found in some of the particles. At high temperatures, there was a loss of copper due to vaporization of CU( g) CuO kg) (g)

Jan 1, 1983

By May Nyman

Due to the vast diversity of chemical media in which metal separations are executed, a wide range of ion separation materials are employed, This ,results in an ongoing effort to discover new phases with novel ion exchange properties. We present here the synthesis of a novel class at, thermally and chemically stable microporous, niobate-based materials. Ion exchange studies show these new phases are highly selective for Sr2+ and other bivalent metals.

Jan 1, 1999

By Sang-Beom Lee

For thermodynamic prediction, the deoxidation equilibrium of aluminum in Fe-36%Ni alloy was studied with a cold crucible under Ar gas atmosphere at 1773K. For the deoxidation reaction in liquid Fe-36%Ni base, i.e.: A12O3(s) = 2A1 + 3O The interaction parameters and the equilibrium constant between aluminum and oxygen in liquid Fe-36%Ni alloy are given in the following: eo Al = -3.8, roA1=0.9, eAl° = -6.4, rAl° = 700, rAIAIo = 3.1, roA1o = 833 within the composition range of [Al] < 1 mass%. The temperature dependence of the equilibrium constant was obtained in the range of 1773K < T < 1973K by using reported data and present results as follows: log KAo= 0.58-24463.7 / T The deoxidation equilibrium with aluminum in Fe-36%Ni could be thermodynamically well described in the range up [Al] < 1 mass% with first and second order interaction parameters as well as the equilibrium constant determined in this study.

Jan 1, 2002