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By Sesha S. Srinivasan

Mechanochemical synthesis has been employed to prepare new light weight complex borohydrides, Zn(BH4)2. The thermal calorimetric and gravimetric analysis of these complex borohydrides shows the hydrogen decomposition temperature (Tdec) of about 100° C with theoretical capacity of ~8.0 wt%. This advanced materials based technology is considered to be suitable for attaining the US-DOE grand challenge technical targets. The powder x-ray diffraction analysis of the mechanically milled Zn(BH4)2 exhibits the presence of zinc borate and NaCl phase. The FTIR spectra of BH4-ion in NaBH4 has a characteristic band at 2290 cm-1,whereas in Zn(BH4)2, it occurs at ~2061 cm-1 (bridging B-H bonds) and ~2451 cm-1 (terminal B-H bonds) as well. The reversibility of hydrogen decomposition and recombination process is carried out by PCT measurements with multi-cycling procedure.

Jan 1, 2006

By Kwan Soo Han

A thermodynamic model for predicting the distribution coefficients has been developed by taking into account the extraction mech-.ism and the chloride complexation when Sm, Eu, Gd, Tb, Dy and Ho for single component systems are extracted from acidic chloride solutions by di-2-ethylhexyl phosphoric acid and 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester in kerosene, respectively. The model equation includes two constants, of which one corresponds to the apparent extraction equilibrium constant and the other is due to the variation of the activity coefficients of organic species. These values are determined from a few experimental data by the curve fitting method Then, the distribution coefficients under untried conditions have been predicted from only the initial data by iterative calculations. Bromley's formulation is used to estimate the activity coefficients of aqueous species and the interaction parameters for some rare earth chlorides are reported in terms of molality and molarity using data from Spedding et al. The validity of this method has been confirmed by excellent agreement between the experimental and the predicted distribution coefficients.

Jan 1, 1989

By Esa J. Peuraniemi

Copper smelting to form blister in one single step has been possible for a long time even from low grade concentrates. In spite of obvious benefits, it has been economically viable only with few special raw materials having high enough Cu/Fe and Cu/S ratio. Outokumpu Blister Flash Smelting is currently applied at three operations, and three others will be commissioned in the near future. With typical chalcopyrite concentrates two main obstacles have prevented wider adaptation of direct blister processing: slag formation and heat generation. Oxygen potential in the reaction shaft must be high in order to produce blister with targeted sulfur content below 1%. When large amount of iron is oxidized, as well as sulfur, copper is inevitably also oxidized into slag. High copper amount in substantial tonnages of slag lead on to costly down stream recovery operations to obtain discardable slag. Almost complete oxidation of sulfur and iron releases a high amount of heat which traditionally has been solved by lowering oxygen enrichment of the blast leading on to oversized off-gas line and acid plant. One challenge in direct blister smelting relates to the attack of aggressive high-copper containing slag against furnace refractory lining. In continuously operated Outokumpu Direct Blister Flash Smelting this is taken care of by preventing vigorous melt movement in the settler. Stable bath conditions and stationary slag against refractory lining enable the formation of a protective autogenous layer between aggressive slag and vulnerable refractory. These direct blister smelting challenges are addressed from equipment and process development point of view. New solutions to overcome the obstacles are presented and discussed.

Jan 1, 2006

By Guozhu Ye, Eric’ Burstrom

"Despite of numerous solutions for recovery of zinc from EAF dust have been suggested and tested in laboratory scale over the last three decades, Waelz kiln process is still the most dominating process for treatment of EAF dust. Few of the proposed alternative methods have gone beyond the laboratory tests. This paper will give you insights to some of the concepts that have been pilot tested at MEFOS. The innovative aspects of these concepts will be shown and the major results will be highlighted. These include the following concepts: - Production of a crude zinc oxide product with low halide content for zinc electrowinning using a DC furnace with hollow electrode- Production of a bypass filter dust containing more than 50%ZnO by injection of EAF dust to the electric arc furnace during refining combined with a bypass filter system- Elimination of zinc ferrite by CaO treatment for electrowinning with EZINEX process - Selective reduction of iron oxide in zinc ferrite for simultaneous recovery of ZnO andmetallic ironIntroductionRecovery of zinc from EAF dust is dominated by the Waelz process since EAF dust has been classified as hazardous waste by EPA in the early 1980´s. A large number of alternative processes have been suggested and tested without commercial success due to two major reasons [1]:- High content of chlorine and fluorine for the pyrometallurgical alternatives- High content of ZnOFe2O3 for the hydrometallurgical processesMany innovative concepts for treatment of EAF dust for zinc recovery have been pilot tested at MEFOS in the past 20 years. This paper will review some of the concepts focusing on the two problems mentioned above."

Jan 1, 2008

By Anita E. Lam

The thiosulfate leaching of gold generally requires the presence of a catalyst such as cupric tetraammine, Cu(NH3)42+, to obtain reasonable leaching rates and gold extractions. Unfortunately, this same catalyst that accelerates gold leaching also tends to accelerate thiosulfate oxidation to tetrathionate and other species. It is therefore imperative that a detailed understanding of the role of this catalyst and the factors affecting it is obtained. It is equally important for plant application that a method of assessing the catalyst be developed. In this work the role of the cupric tetraammine catalyst was studied using geochemical modeling for speciation prediction, thiosulfate leaching of gold ores, and chemical analyses of resulting leach solutions. It was found that the variables of pH, temperature, and the concentrations of ammonia, thiosulfate, and total copper all work in concert to affect the concentration of the cupric tetraammine species. It was also found that the presence of sufficient thiosulfate and cupric tetraammine was critical to the success of the leach.

Jan 1, 2003

By Steven E. Follin

In-situ leaching is commonly used to recover uranium from low-grade deposits in sandstone formations. Acceptable recovery rates can only be obtained if the formation retains its permeability during leaching. Field experiences indicate that microbial growth, stimulated by the leaching pro- cess, can cause plugging problems. To investigate this hypothesis, leach solution and solid samples from well casings and submersible pumps were obtained from four in-situ mining sites. Chemical and microbiological analyses were performed. Bacillus species, Micrococcus species, pseudomonads, and xanthomonads were isolated from these samples. A mixed culture of these organisms was inoculated into a uranium core that was being leached in the laboratory. The permeability of this ore sample decreased to one-third its original value after 16 days. The addition of hydrogen peroxide (0.2 g L-1) to the leach solution killed the microbes and restored the permeability to its original value. This suggests that periodic injection of hydrogen peroxide into production wells may reduce microbial plugging in these wells and the immediate surrounding formation.

Jan 1, 1985

By Sheng-hai Yang

The electrochemical synthesis was conducted in anhydrous ethanol solvent mixed with conductive reagent when tantalum plate was used as anode and stainless steel plate as cathode. The effects of different conductive reagents (such as NH4Br, (CH3)4NCl, (C4H9)4NCl), conductive reagent concentration and the space on the cell voltage and the current density were investigated. The current efficiency of electrosynthesis was more than 95%. The electrolyte, a mixed solution was then undergone air distillation and vacuum distillation to get the final product which was characterized by Fourier Transform Infrared(FTIR) spectroscopy, Raman spectra, 1H-Neclear Magnetic Resonance(1H-NMR) spectroscopy. Carbon and hydrogen contents in the product were determined by elemental analysis instrument. Results consistently show that the product was tantalum penta-ethoxide.

Jan 1, 2006

By D. C. Cupertino

Oxime based solvent extraction provides the user with a selective concentration process for copper prior to electrowinning. The selectivity required is largely for copper(II) over iron(III) and this is achieved by the preferential formation of the square planar copper-oxime complex in the organic phase. The copper/iron selectivity of oximes can however, be altered by modifiers or other types of oximes and may be enhanced in the presence of certain esters. Whilst the oxime based SX processes is important for operations leaching copper from laterite ores, the high selectivity will also be significant in processing streams arising from other leaching regimes which are currently under development, for example leaching of sulfide mineral ores. This paper presents some initial results using Molecular Modelling techniques to further our understanding of the nature of the copper/iron-oxime complexation processes together with some plant studies undertaken at a number of different mine sites investigating selectivity, and other properties, for some modified reagents. Some studies of the interfacial properties of the these systems are reported to explain in part the practical observations.

Jan 1, 1999

Environmental and public concerns and the banned use of cyanide for the recovery of gold in some parts of the world have heightened the search for an alternative lixiviant to cyanide. Thiosulfate appears to be the most promising alternative to cyanide due to thiosulfate being non-toxic, relatively cheap compared to cyanide and generally gold recoveries are similar to those of cyanide. The most widely researched thiosulfate process is one where copper ions and ammonia are added to the solution. This paper reviews the leaching of gold in thiosulfate solutions and the contributions of the research at Monash University to the understanding of the gold oxidation reaction in thiosulfate solutions, the solution chemistry when copper ions, ammonia and oxygen are present, the influence of the changing solution chemistry on the gold leach kinetics, and the application of thiosulfate in the leaching of gold from ores. It is clearly shown that the gold oxidation rate is hindered in thiosulfate solutions. In the presence of copper ions the gold oxidation rate though is significantly enhanced and thus is why copper(II) is more effective than other oxidants in the thiosulfate leach system. The copper-ammonia-thiosulfate leach solution chemistry is shown to be very complex, especially in the presence of oxygen as the rate of thiosulfate oxidation increases and the majority of the copper ions are not maintained in the copper(II) oxidation state. The thiosulfate oxidation rate must also be maintained low as an intermediate thiosulfate oxidation product hinders gold leaching. In optimising the recovery of gold from ores with copper-ammonia-thiosulfate leach solutions it is important to evaluate and minimise any negative effect an ore may have on the leach solution chemistry and hence gold leaching.

Jan 1, 2003

By C. K. Gupta

Electrometallurgical processes have a definite place in the extraction technology of rare earth metals and alloys. Some of the advantages of the molten-salt electrometallurgical processes include fast electrode reaction, providing accurately controlled large amount of energy to a relatively small reactor volume, negligible over voltage, simplicity of operation, and possibility of accomplishing continuous or semicontinuoue operations. This paper provides a vivid account of the theoretical and practical aspects of electrometallurgical processes for the production and processing of some of the rare earth metals and alloys. Reference has been drawn to the work reported on electrometallurgical processes as applied to the preparation of lanthanum, cerium and misch metal from author's laboratory.

Jan 1, 1992

By Katsunori Okaya, Gjergj Dodbiba, Hiroyuki Ono, Toyohisa Fujita, Seiji Matsuo

"In an attempt to raise the copper grade of Printed Circuit board (PCB) by removing other components, carbonization treatment was investigated. The crushed PCB without surface-mounted parts was carbonized under nitrogen atmosphere. After screening, the char was classified by size into oversized pieces, undersized pieces and powder. The copper foil and glass fiber pieces were liberated and collected in undersized fraction. The liberation of copper foil from the oversized pieces was also investigated. The copper foil was liberated easily from glass fiber by stamping treatment. Liberation rate of copper foil was high at high carbonized temperature. The experimental results indicated that 90% of oversized char was liberated and the copper foil recovery from PCB carbonized at 1073K was 110kg/t. The copper recovery from char powder by flotation was also investigated. 15% of the copper grade and 80 % of the copper recovery were obtained, whereas the removal rate of silicon was 55%.IntroductionWaste Electrical and Electronic Equipments (WEEEs) should be recycled because they have many kinds of valuable materials and most WEEEs include Printed Circuit Boards (PCBs). In Japan, about 30 km2 per year of Printed Circuit board (PCB) has been produced [1], PCBs are normally separated from WEEEs and picked up by hand and sold to non-ferrous metal market because PCBs include high grade of copper and other precious metal such as gold, silver and palladium [2]. However, PCB also has impurities such as silicon, aluminum and calcium which are slag materials in non-ferrous smelting process, and other harmful elements such as lead, bromine and antimony. Low grade PCBs are sold after removal of invaluable parts or sometimes land filled without any treatment"

Jan 1, 2011

By Yong Hack Lee

Electric Arc Furnace (EAF) dust is generated when scraps are treated in the electric arc furnace and usually classified as hazardous industrial waste in most countries. EAF dust usually contains 15 to 25% of zinc and 3% of lead. It is usually treated in rotary kiln (Waelz process) or landfilled after a solidification and stabilization treatment. Numerous methods have been proposed as the EAF dust treatment technology, but few of them are in operation as a commercial scale except the Waelz process. Korea Zinc performed a plant test in which 600 tons of EAF dust was treated using TSL (Top Submerged Lance) technology. The TSL technology is a low cost, proven technology for processing zinc-bearing residues. The EAF dust was first de-chlorinated and fed to the TSL furnace. Finally, clean slag satisfying toxicity criteria was generated and valuable metals such as zinc and lead were recovered as fume oxide. The fume oxide was de-halogenated by sodium carbonate and sent to zinc refinery to recover zinc and lead. The recovery of zinc and lead was 90% and 93%, respectively. Most of the dioxin in the EAF dust was discomposed so dioxin less than the Korean regulation limit was detected in the offgas, which proves that the TSL technology is the best solution to treat EAF dust.

Jan 1, 2006

By W. Gong

Their outstanding thermal stability and high energy product make Sm(Co,Fe,Cu,Zr),-type alloys attractive for advanced applications. The near net-shape production of Sm(Co,Fe,Cu,Zr), bonded magnets make them potentially superior to any magnets made by sintering. Although pioneering work done by Shimoda et al. and other investigators provide insights on the proper compositions and process control of this alloy system, additional work is still necessary to improve our understanding of alloy behavior at various processing stages and to increase the production yield during powder processing. In this paper we report on the development of anisotropic Sm(Co,Fe,Cu,Zr), alloy powders for the bonded magnet application. Our focus is on the development of a moderate coercivity powder requiring a relatively low magnetizing field to charge the magnets to their optimum Br, Hci and BHmax. The magnetic properties are related to the evolution of the microstructure at various processing stages and the average particle size and size distribution of powders.

Jan 1, 1997

By Varadajan Seshadri

Torpedo cars have been extensively used for pig iron desulfurization although its geometry is not considered to be ideal as far as mixing and mass transfer are concerned. Complications arise from scaffolds formed through aggregation of flux, slag and pig iron during operation. Following industry demand a 1:6 torpedo car physical model was operated to assess the optimum refining conditions for pig iron desulfurization. Similarity between the model and prototype were established through Froude and turbulent Reynolds criteria. Mixing times were evaluated by pulse tracer addition and the kinetics of metal/slag interactions were assessed from experiments investigating iodine transfer from kerosene to water. The influence of parameters such as level of metal, gas flow rate, lance penetration, lance orientation, presence of scaffold were evaluated. Mixing times were found to be shorter than regular desulfurization time and also not very sensitive to scaffold presence. Scaffold contributes to the reduction of the useful volume only. Mass transfer at the permanent reactor is more effective when the torpedo is operated at its full capacity. The experiments also highlight the dominance of the transitory reactor as compared with the permanent reactor.

Jan 1, 2006

By Ronald J. Roman

The shrinking core model for coarse particle leaching has been generally accepted as describing the leaching of a copper oxide or sulfide ore. However, when a mixed oxide/sulfide ore-is leached this model can not be used in its simple form because at least two and possibly three separate leaching processes are occurring simultaneously (dissolution of oxide copper minerals, secondary copper minerals and primarily copper minerals). It has been impossible to isolate their individual leaching curves from the recovery/time curve generated by the column leach test. This paper describes a tests program carried out at the Groupo Mexico, Mexicana de Cobre's La Caridad operation in which the individual recovery/time curves for the leaching of copper oxide mineral, secondary copper mineral and primary copper minerals were developed from standard column leach tests. Once the individual recovery/time curves were developed scale-up of the column leach test results to the commercial heap leaching operation is possible by using the shrinking core model.

Jan 1, 1999

By Catherine Williams-Beam

Thallium is more toxic to humans than mercury, cadmium, lead, copper or zinc. Its chemical behavior resembles the alkali metals (K, Rb, Cs). It occurs almost exclusively in natural waters the monovalent thallous cation. The solubilities of thallous compounds are relatively high so that monovalent thallium is readily transported through aqueous routes into the environment. The major sources of thallium are the base metal sulfides and precious metal bearing sulfides. Therefore, it is often present as a contaminant constituent in waters emanating from heavy metal sulfide bearing deposits. Thallium can be effectively removed from wastewater to <2 µg/L by reductive precipitation of thallium sulfide. Effective thallium sulfide precipitation requires a controlled solution potential/pH combination. The required potential can be effectively achieved by utilizing a particulate iron slurry or packed column environment. Experimental results will be presented and discussed.

Jan 1, 2003

By Ioannis Paspaliaris, Dimitrios I. Gerogiorgis, Dimitrios Panias

"Red mud fiberization is a process with remarkable potential, alleviating environmental pressure by transforming an aluminum by-product into mineral wool, thus to various marketable products. A promising mineral wool process is molten slag fiberization via an impinging air jet, which avoids mechanical wear and rotating parts. The molten slag which remains after pig iron casting flows out of a heated ladle orifice at a high temperature (1600 °C) and adjustable flowrate, and forms a free-falling vertical jet which visibly radiates its excessive heat: at a given distance, a high-velocity impinging air jet meets the vertical melt jet perpendicularly (or at an angle), inducing intensive droplet generation, subsequent fiber elongation, collection and processing.This paper focuses on high-fidelity CFD modeling of the molten jet flow under external cooling: the model encompasses all physicochemical phenomena (melt laminar flow, radiative cooling) and considers several temperature-dependent slag transport properties in order to understand which operational degrees of freedom (manipulated variables) are useful to process optimization."

Jan 1, 2012

The concepts of capacity and basicity have proved extremely useful in dealing with a wide range of solute species in metallurgical slags, and as a result have been widely applied. These two concepts are reviewed, and it is suggested that the Lewis approach to basicity has much to commend it. In some cases, it appears that the term capacity has been used without due consideration being given to the nature of the solution being formed, or even to whether a true solution was being formed at all. This paper proposes a rigorous definition of capacity, based on the true nature of the solution process in slags and glasses, and briefly reviews the repercussions of this approach on data available in the literature and the limitations which it may impose on future investigations in this area.

Jan 1, 1994

By Jafar Safarian

A new kinetic modelling technique has been applied to study the rate of MnO reduction from slags by dissolved carbon in liquid iron. Based on a consideration of the fundamental reaction kinetics, a general differential equation for the slag reduction process has been formulated, which then is solved analytically for certain special cases. By re-writing the solutions in a dimensionless form the poorly known kinetic constants are eliminated, which makes the model both flexible and applicable to a wide range of experimental conditions. For example, changes in process parameters such as temperature, metal composition, slag composition, gas composition can readily be captured along with variations in the crucible geometry. Based on a comparison with a series of experimental reduction curves being reported in the literature, it is concluded that the predictive power of the model is surprisingly good, yielding outputs that are both reliable and physically reasonable. An attractive feature of the model is that it provides an alternative way of calculating the activation energies from experimental reductions curves. For example, it suggests that the activation energy for the reduction of MnO by dissolved carbon in liquid iron is about 90 kJ/mol, which is different from the previously reported activation energies. The model also suggests that the crucible geometry, which affects both slag the volume and the resulting slag/metal interfacial area, has a significant influence on the overall reduction kinetics. This design parameter is a key to further optimisation of the process on an industrial scale.

Jan 1, 2006

By Jannie S. J. van Deventer

Geopolymers are novel engineering materials with the potential to play a highly significant role in the transformation of the construction materials and building products industry in the push towards sustainable development. These materials are formed by activation of industrial aluminosilicate waste materials such as coal ash or blast furnace slag with alkaline solutions. Geopolymers derived from coal ash can exhibit superior mechanical properties and chemical stability when compared to ordinary Portland cement (OPC). The use of waste-based geopolymers can also result in significant (up to 90%) reduction in carbon dioxide emissions when used in cement replacement applications. In addition to the formation of conventional pre-cast products, these high performance mineral binders are ideally suited to use in the encapsulation of mine tailings, immobilization of heavy metals and back-filling of mines due to their chemical stability and resistance to acid attack. A key attribute of geopolymer technology is the robustness and versatility of the manufacturing process; it enables products to be tailor-made from a range of raw material sources (waste and/or virgin) with specific properties for a given application at a competitive cost. Despite these key technical and environmental attributes, it is the ability to add significant value to coal ash or and/ or metallurgical slag waste streams which drives the commercial development and uptake of the technology.

Jan 1, 2006