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By Vitalij K. Pecharsky

Recent interest in complex aluminohydrides as potential near ambient, ultra-high capacity, solid-state sources of hydrogen (e.g., for fuel cells) calls for an improved understanding of the processes occumng in these hydrogen-containing materials during both the release and the uptake of hydrogen. Lithium aluminohydride (LiAlH4) rapidly releases 5.2 wt. % of hydrogen (i.e., nearly four times more than LaNis-based alloys) during mechanochemical processing at ambient conditions in the presence of transition metal catalysts. Using a variety of solid-state characterization techniques, the mechanochemical transformations in a series of LiAlH4 - metal catalyst systems have been examined and preliminary insights on the mechanism have been obtained. Surprisingly, the well-known hydrogenating-dehydrogenating catalysts, such as Ni and Pt, are practically inactive in the mechanochemical dehydrogenation of LiAlH4.

Jan 1, 2002

By F. Elgersma

A high purity electrolysis solution is essential for hydrometallurgical zinc winning processes. For this reason ferric iron containing compounds such as jarosite are precipitated as iron and impurity collector during the calcine leaching. Jarosite thus forms a chemical waste and creates environmental problems. This research contributes to the development of a wet jarosite treatment process, where less contaminated jarosite is produced which can act as an iron source. The present work studies jarosite precipitation kinetics and the uptake of zinc cations in batch and continuous experiments. The distribution coefficient for zinc in continuous experiments is constant for a wide ratio of zinc over ferric ions in the solution. Addition of NH, + ions in batch experiments accelerates the conversion rate equivalent to the driving force increment. Addition of 50,2-ions above the stoichiometric ratio increases the conversion rate less then could be expected from the increase in the estimated driving force. Zinc ions tend to retard the conversion rate. An increasing reaction temperature increases the conversion rate. Below 75 ?C the conversion rate approximates zero.

Jan 1, 1990

By C. J. Newman

The Kidd Creek Copper Smelter has been expanded from its original design of 59,000 tonnes of copper per year to over 120,000 tonnes per year. Modifications to the process gas handling system and acid plant have been made to accommodate this higher production rate and to generally optimize the operation. The gas handling system associated with the continuous smelting process is discussed in terms of boiler accretions and modifications to minimize their impact on operations; design changes to effect reductions in high pressure drop duct configurations; material changes to overcome corrosion and plant additions to improve gas cleaning capability. The acid plant is reviewed with references to changes? made to accommodate the increased SO2 gas strength resulting from the higher smelting rates.

Jan 1, 1992

By Florian Kongoli

Non-ferrous smelting slags .can contain magnesia, which substantially increases the liquidus temperature. One option to counter this increase is to flux with calcia. In this work, experimental liquidus measurements including new measurements on industrial slags have been compared with a FACT-based thermodynamic model, which predicts the liquidus surface of multi-component iron silicate smelting slags containing both magnesia and calcia. The predictions, which agree well with experimental results, are summarized in both isothermal and non-isothermal diagrams to give a quantitative description of the liquidus surface.

Jan 1, 1998

By R. J. St. Eloi

The Kidd Creek Copper Smelter has been expanded from its original design of 59,000 tonnes of copper per year to over 120,000 tonnes per year .. Modifications to the process gas handling system and acid plant have been made to accommodate this higher production rate and to .generally optimize the operation. The gas handling system associated with the continuous smelting process is discussed in terms of boiler accretions and modifications to minimize their impact on operations; design changes to effect reductions in high pressure drop duct configurations; material changes to overcome corrosion and plant additions to 'improve gas cleaning capability. The acid plant is reviewed with references to changes made to accommodate the increased S02 gas strength resulting from the higher smelting rates;

Jan 1, 1992

By Jingwei Lou, Bing Li, Suzhen Li, Miao Shen, Jianguo Yu

"As a main impurity in primary lithium metal, magnesium is difficult to remove because of the very close relative volatility of the two metals. Electrochemical refining provides a possibility to completely remove Mg in the LiCl-KCl melt prior to Li reduction. MgCl2 reduction processes in LiCl-KCl- MgCl2 melt were investigated by cyclic voltammetry (CV), square wave voltammetry (SWV), chronoamperometry and chronopotentiometry. Then potentiostatic electrolysis was carried out and Mg (II) ion was reduced onto a liquid lead cathode from the LiCl-KCl-MgCl2 melt at the Mg deposition potential. The results show that Mg ( II ) is reduced in one step with two-electron transfer. The reduction potential of Mg ( II ) was well defined. The reduction of Mg( II) results in Li ( I ) underpotential deposition at 0.2V more negative potential than that of Mg( II) reduction. Therefore, in order to prevent Li ( I ) from codeposition with Mg, accurately controlling Mg ( II) reduction potential during the potentiostatic electrolysis was necessary. Ninety three to 99 % removal rate of MgCl2 was achieved after 8-12 h electrolysis when liquid lead was used as cathode.IntroductionMetallic Li has been widely used in batteries, light weight alloys and in fusion reactors because of its excellent properties. Currently, the only way in industry to produce metallic Li is by electrowinning from molten LiCl-KCl at about 450 °C [l-5]. LiCl-KCl is the only electrolyte used, because they presents a lower eutectic temperature and KCl shows a slightly higher theoretical decomposition voltage than LiCl, as shown in Table l .The produced metallic Li generally contains 1-2 wt% impurities including Na, K, Al, Ca, Mg, Si, etc. [6l, which are derived from the corresponding metal chloride compounds or metal oxide compounds existing in the LiCl and/or KCl raw materials. These impurities have to be removed by subsequent vacuum distillation at high temperatures to meet the requirements for metal Li purity in the final products. Separation of Mg from Li by vacuum distillation is difficult because their relative volatilities are very close, as shown in Table 2."

Jan 1, 2011

By R. R. Odle

A laboratory and pilot-scale investigation of direct smelting of copper concentrates was conducted to determine the effect of concentrate analysis and the degree of roasting on the yield and quality of copper produced in a subsequent smelting step. A stoichiometric :mOdel of direct smelting is presented which predicts the? quantity of copper; slag, and white metal' prOduced'and the distribution of copper in these phases as a function? of the concentrate '(calcine) analysis.

Jan 1, 1983

By Flávia Paulucci Cianga Silvas, Otávio da Fonseca Martins Gomes, Viviane Tavares de Moraes, Denise Crocce Romano Espinosa, Jorge Alberto Soares Tenorio, Guilherme Apostólico Bortolini, Stoyan Gaydardzhiev

"Printed circuit boards (PCB) are particularly problematic to recycle because of the heterogeneous mix of organic materials, metals, and glass fiber. PCBs are found in almost every electroelectronic equipment and their recycling process involves a pre-treatment to separate the products which contain targeted metals. In this work, a physical processing involving sequential shredding and hanuner milling were used to obtain a comminuted sample from scrap printers PCBs. The thus prepared sample was analyzed for particle size distribution and by optical microscopy as well was subjected to pyrolysis, leachabilty and chemical composition determination by XRF. The metals concentration was determined by ICP and AAS. The PCBs have been also analyzed by SEM-EDS (micro-analysis and X-ray mapping). The results show that the studied PCBs are lead free, multilayer with 4 copper layers, have 45% of metals and the copper is present in significantly higher concentration than the rest of the metals.IntroductionThe global generation of e-waste (electrical and electronic equipment waste - WEEEs) grows at a rate of about 40 millions of tons per year [ l].Among this e-waste there are PCBs that are present in almost all electronic equipment. Their composition is heterogeneous and varies according to several factors, including: kind of EEE, when and where it was produced, fabrication technology [2], etc. In printers, the PCBs represent about 6.6- 8 wt.% [3].The PCBs treatment may include physical, pyrometallurgical, hydrometallurgical, ectrometallurgical and more recently bio-hydrometallurgical process. Normally there is a combination between these processes [2, 4, 5, 6, 7, 8, 9, 10].The diversity between the different PCBs composition complicates the recycling process since the composition of metal and others materials can vary according to the models. So characterization is an indispensable step before any processing of PCB to begin. Owing to the above said, the main goal of this work has been set to characterize representative samples of PCBs from printers through physical, chemical and microstructural analyses."

Jan 1, 2014

By P. Henry

A novel electrochemical cell has been developed for the recovery of MnO2 from residue of pyrolusite ore leading loaded with Fe, Al Ni, Co and Si impurities, This new process can be considered as an alternative to the traditional methods : S02, H2O2 or bioleaching. It has been observed to proceed fairly rapidly and could prove to be a more economically viable process, as well as being more environmentally acceptable. Electrochemical characterization and kinetic studies have shown that MnO2 is effectively leached by electrogenerated ferrous ions at high current density from a pulp containing less than 5 g8 Fe. The chemical reactions are : Cathode (inox) : 2F23+ + 2e ? 2 Fe2+ Bulk: MnO2 + 2 fe2+ 4H+ ? Mn2+ + 2 Fe3+ + 2 H2O Anode (Pb-Ag) : H2O ? ½ O2 + 2H+ + 2e Global: MnO2 +2H+ Fe2+ = Mn2+ + H2O + 1/2 O2 The catholyte (MnO2 pulp) circulates upward in the expanded mesh cathode separated from the sulfuric acid solution anolyte by a separator which shows high mechanical resistance, low porosity, low potential drop, and reasonable cost. Laboratory and mini-pilot tests have led to the construction of an OT crating pilot plant (100 kg/hr) able to leach more than 95% of Mn, Ni, Co at 1000-1200 A/m2, 50°C with high faradic yield (> 95 %) and low power consumption (3.2 kWh/kg kWh/kg &4D). New applications like the treatment of spent Zn-Mn batteries, polluted soils, spent catalysts and oxide ore (cobalt, nickel) with electrogenerated redox species are now investigated at a laboratory and mini-pilot scale.

Jan 1, 2000

By Brajendra Mishra

Molten Salt electrolytic processes offer unique opportunities to extract and refine metals where gaseous or metallothermic reduction, hydro metallurgical extraction and aqueous electrolytic methods are thermodynamically constrained. Production of aluminum and magnesium by molten salt electrolysis are well known commercial processes. Several other reactive metals, such as lanthanides and actinides, as well as beryllium and calcium, make use of molten salt processing for extraction and refining. This presentation describes the science of molten salt chemistry and electrochemistry for winning and refining of several metals. In addition, recovery of metals from waste process salts by molten salt reduction as well as oxidation have been discussed. Material issues in design of molten salt reactors have been included. Various applications have been presented through case studies. Experimental data have been included to justify the suitability as well as limitations of these specific processes.

Jan 1, 2003

By QIE Jun-mao, DONG Fang, DENG Hao-hua

The DIL402C thermal dilatometer and STA449C thermal analyzer were employed to test the linear expansion and contraction coefficient，CP and DSC curve of 304 stainless steel. The result showed that the linear expansion coefficient range was 20.9700×10-6～21.5712×10-6 and the linear contraction coefficient range was 21.2528×10-6～21.9471×10-6.The linear expansion and contraction coefficient were higher than other steel grade，so the 304 stainless steel belonged to the crack sensitive steel. Because of the crystal phase transformation occurred during the 1000~1400 ℃,the curve of CP fluctuated obviously and the defects of casting blank occurred easily. Chosen 1414℃ as the liquidus temperature of 304 stainless steel based on the analysis results of DSC. The curve of DSC was unsmooth during 1450～1100℃，the crystal phase transformation occurs and thermal stability of slab was inferior.When the initial solidified shell formed in this temperature range,the thickness of the shell would be nonuniform and the surface defects occurred more easily.

Jan 1, 2015

By J. P. Evans

The modem 'copper smelter today utilizes tonnage oxygen for smelting concentrates. ,generating a high strength S02 off-gas leaving the smelter vessel. This gas stream. which also contains any unreacted oxygen, plus CO2; N2 and H20. also carries with it the volatilized portion of heavy metals in the feed, plus partly oxidized sulfide concentrates, The time/temperature history and subsequent treatment of this off-gas stream emerging from the smelting furnace exit up to the acid plant can influence the partitioning and segregation of heavy metals, in the off-gas circuit. Depending on this history. the type and characteristics of the chemical and physical reactions which occur in the gas handling system 'can be influenced. This fact can also be used as a tool to adjust the separation of copper from heavy metals. In this paper, the impact of different time/temperature histories of the gas, due to different furnace geometries and design. on the subsequent formation and characteristics of the smelter dust is examined. Based on the available data. several case histories drawn from examples using both bath and flash smelting technologies are analyzed from this perspective.

Jan 1, 1992

By Lamar S. Todd

The direct production of metal from a sphalerite concentrate is an attractive route for primary zinc. A series of operations and conditions have been selected to efficiently cause the following overall exothermic reaction. The process uses a continuous circulation of molten copper for material and energy transfer between the unit operations. Sulfide concentrate is reduced with an excess of superheated copper to make a copper alloy and white metal. The alloy is stripped of volatile metals under vacuum and some metals can be separately condensed. The residual copper and the white metal are fed into a copper converter to be blown with oxygen for desulfurizing and the superheated copper is recycled. The paper will include a detailed material flow sheet for the process, discussion of the operating conditions of the individual units, behavior of minor elements, and zinc quality.

Jan 1, 1999

By A. S. Rao

In the original roast-leach-electrowin (RLE) circuit at the Chambishi Cobalt Plant, commissioned in 1978, the separation of nickel and zinc from cobalt in aqueous streams was achieved by successive stages of precipitation using lime. However, this technique was not able to meet the increasingly stringent metal quality requirements of customers whilst maintaining acceptable process recoveries. Intensive process development work was carried out and, in July 1988, an ion exchange circuit for nickel removal was commissioned using DOW XFS 4195 resin and for the first time Z.C.C.M. produced high purity cobalt metal containing less than 0.10% nickel. Following further work, a solvent extraction circuit for zinc removal, using DZEHPA, was commissioned in February 1991 in order to enhance cobalt recovery by reducing co-precipitated cobalt losses. This paper outlines the process development, design, commissioning and subsequent operation of these nickel ion exchange and zinc solvent extraction circuits.

Jan 1, 1993

By A. A. Bustos

A model was developed to simulate the blow-by-blow operation of the converting process. From the weights, compositions and temperatures of all converter feeds the model calculates the composition and tonnage of both converter matte and slag as well as bath temperature at the end of each blow. The development of the model and its application to the converter aisle operation are described. There is good agreement between model predictions and observed results. At the present time the model is being used to investigate different converting schemes and their effect on pay metal recoveries, slag chemistry and temperature of the bath. Future work involves the use of the simulation model as a process control tool for the converting operation.

Jan 1, 1988

By B. Bichel

For the last 70 years, molten blister copper has been transferred by rail in hot metal cars from the Copper Cliff Smelter to the Copper Cliff Copper Refinery (ex Ontario Refining Company) where it was processed in two (2) reverberatory anode furnaces by poling with logs, cast on four (4) wheels, and then electrorefined. This practice was modernized in 2001 with the installation of two (2) rotary anode furnaces at the. Copper Cliff Smelter which employ steam and. natural gas for reducing and which provide a significant reduction in emissions. A new casting shop with a single anode casting wheel is used to cast regular and stripper constant weight anodes which are transported by truck to the Copper Cliff Copper Refinery for anode preparation and electrorefining. This paper provides an overview of the copper circuit at the Copper Cliff Smelter and a description of the CDN$31 million capital project.

Jan 1, 2002

By Cledwyn Mangunda

Mining operations generate Acid Mine Drainage (AMD) that poses a significant threat to the natural environment. AMD treatment using Ca(OH)2 leads to the precipitation of a sludge dominated by a mixture of ferri-oxyhydroxides. This sludge has poor dewatering tendencies and is deposited in landfills with potential for metal remobilization. This study investigated the dewatering behaviour of a precipitate formed during elevated temperature treatment of a primary, pre-settled sludge from the neutralisation of aqueous acidic Fe2(SO4)3 and Ca(OH)2 solutions in an MSMPR reactor. The resulting treated precipitates were analysed for micro-properties, with results showing that an increase in the secondary reactor temperature from 25 °C up to 50 °C led to an increase in mean particle size, a decrease in the number of particles and improved dewatering behaviour at a ferric concentration of 300 mg/L. This was ascribed to the attainment of a circum-neutral surface charge that favoured agglomeration and a change in micro and nano-structure that allowed for better water passage.

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 Katsutoshi Inoue

The sulfuric acid leaching of spent hydrodesulfurization catalysts yields an acidic solution rich in rare metals such as molybdenum, vanadium, cobalt, and nickel in addition to aluminum. For the purpose of separating and recovering the rare metals from the solution, basic solvent extraction characteristics of the metals involved with commercially available acidic organophosphorus reagents like TR-83, PC-88A, PIA-8 and CYANEX 272 as well as aliphatic alpha-hydroxyoxime LIX 63 from sulfuric acid media were investigated in the present work. It was demonstrated that CYANEX 272, PIA-8 and LIX 63 possessed excellent selectivity for molybdenum and vanadium over the other metals at comparatively low pH. Further, recovery of molybdenum and vanadium from the total leach liquor by the selected extractants was discussed. Additionally, in order to achieve preferential separation and recovery of cobalt and nickel over an appreciable amount of aluminum from the raffinate obtained after recovering molybdenum and vanadium, a systematic investigation was conducted on synergistic extraction behaviors of the mixed solvents of LIX 63 in combination with a series of acidic extractants such as CYANEX 272, PIA-8, PC-88A, D2EHPA, TR-83 and OPEHPA for cobalt, nickel and aluminum. It was elucidated that all of these mixtures could exhibit a good synergistic effect for extraction of cobalt and nickel, and that the lower the pKa of the acidic extractants, the greater the synergism. Contrarily, the extraction of aluminum, was considerably suppressed by LIX 63. Effective extraction of cobalt and nickel away from aluminum was accomplished from the sulfate solution at low pH (1.0 - 2.5) with the mixtures. In particular, the mixtures consisting of LIX 63 and CYANEX 272 or PIA-8 appeared to be the most feasible and economic from an industrial point of view, yielding acceptable separation efficiency for cobalt and nickel over aluminum and .a low acidity requirement for stripping cobalt and nickel as well as negligible degradation of LIX 63. Aluminum can be readily recovered as sulfate salt from the raffinate obtained after recovering molybdenum, vanadium, cobalt and nickel as outlined above by conventional crystallization method.

Jan 1, 1995

By Gervais Soucy, François Quesnel, Pierre Hovington, Wen Zhu, Karim Zaghib, Jocelyn Veilleux

The properties of lithium titanates anodes in Li-ion batteries are highly dependent on their secondary constituents. While their main phase is usually constituted of Li4Ti5O12, significant quantity of lithium titanates compounds of various stoichiometry are often present, due to either the processing, usage or aging of the material. These may go underreported, as many of these spectrums overlap or display low signal in X-ray diffraction (XRD). Samples of nanosized lithium titanates synthetized by inductive plasma were characterized by XRD and scanning electron microscopy (SEM), as they provide a regular yet typical crystallite size and shape including multiple phases. A Rietveld refinement was developed to extract the composition of these samples. Mass balance through further annealing and differential scanning calorimetry (DSC) enthalpy measurements from phase transformations were also used as identification and validation techniques.

Jan 1, 2015