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By François Larouche

Since their commercialization in the early 1990s, lithium-ion batteries (LIBs) have become ubiquitous for powering a myriad of portable electronics. Their usage now extends to the automotive industry and stationary energy storage market. With an average life of 6.2 years and the strong demand, the volume of spent LIBs has increased exponentially, making recycling mandatory. Currently, recycling/ recovery of spent LIBs is limited in comparison to all other types of batteries. The current processes focus mainly on the recovery of the most valuable metals such as cobalt and nickel, leaving lithium and phosphate in a low value end-product. It is necessary that new advanced recycling technologies are developed for the recovery of spent LIBs both from an economic and environmental perspective. In this paper, the current R&D status of LIBs recycling is reviewed with the emphasis placed on hydrometallurgical processing opportunities for Li-ion and Li-solid state batteries.

By Larry M. Southwick

Steel mill electric arc furnace dust is a RCRA listed hazardous waste and its treatment and/or disposal are regulated by a complex set of rules. These regulations were originally established to encourage recovery and recycling of valuable components. For EAF dust, the more valuable constituents include zinc, lead, cadmium and iron. In fact, current trends are in the opposite direction, as the regulations have complicated the ability to commercialize new treatment technologies and created substantial roadblocks and liabilities for processors. As a result, almost half of the EAF dust generated in 1997 will be landfilled. The problems are compounded by difficult processing requirements, less than sterling examples of technology development and mechanical and operating problems. This paper explores some options to simplify the processing requirements and thereby easing difficulties in commercializing new technologies and expediting the recycling of recovered metals. Dust processing usually includes a simple step followed by two complicated steps. The simple step is fuming of heavy metals away from iron and other residues. The complex steps are (1) separating and purifying the heavy metals and (2) upgrading the iron residue. The first complex step can be simplified by producing an intermediate product that is amenable to processing by zinc refiners. This route benefits from the currently underutilized (by dust processors) resource offered by refiners, who have experience in and existing processes for separation and purification of zinc-based heavy metals. Various processes and their associated product options are reviewed and compared. Future directions for dust processing developments are suggested.

Jan 1, 1998

By O. Forsén

In the first part of this paper is studied the behaviour of small amounts of impurity elements? in the solidification of copper anodes. In the second part the dissolution of these impure anodes in sulphate based electrolysis is discussed. The first part is introduced with practical examples, the .model of solidification of impurities during the solidification of anode copper. According to this model the solidification structures of anode copper are strongly influenced by both thermodynamic and kinetic factors. Thermodynamics determine the microstructure of anode copper, but kinetics can alter the composition of melt to such that there is formed unequilibrium structures during the solidification, especially when the residual melt is solidified. The electrolysis experiments have clarified the behaviour of impuririties in the electrochemical dissolution in sulphate. Based copper electrolysis. In this study it is widely investigated to what extent any impurity elements or oxides will dissolve. In copper electrorefining. With the aid of the electrochemtcal experiments it was possible to fulfil quantitatively the qualitative results accomplished by microstructure studies.

Jan 1, 1985

By G. D. Sandrock

The science and technology of roan temperature rechargeable metal hydrides began about 1969 with the discoveries that the intermetallic Compounds LaNi5 and TiFe could be, conveniently hydrided and dehydrided at roan temperature and modest H2 pressures. Subsequently, this lead to the development of a broad family of REE-containing AB5 hydrides and numerous applications that make use of the extraordinary H2-absorption and reaction-heat properties of these materials. Some of the applications include H2 storage, compression and separation, as well as heat pumping, heat to mechanical energy conversion and electric energy storage. This paper briefly reviews the fundamental phenomenology of metal hydrides, the history of the use of REE's in rechargeable metal hydrides, the practical engineering properties of these materials and the applications that have evolved around them. The rechargeable nickel metal hydride battery, a new vial alternative to NiCd cells, stands at the forefront of the applications.

Jan 1, 1992

By Derek J. Fray

"In order to extend the application of fused salts in\the electrowinning and electrorefining of metals, it is necessary to maximise the current density, minimise the voltage drop and greatly increase the area of electrode surface so as to compete with the space-time yield of pyrometallurgical reactions. The various designs of electrowinning cell are reviewed and it is shown that by the application of a modest centrifugal field it is possible to reduce the anode to cathode interelectrode spacing to 4 mm whilst still maintaining a current efficiency of 85-90%.The thermodynamic potential for electrorefining is far less than for electrowinning yet fused salt electrorefining is only applied in limited cases. The reasons for this are discussed and the important design parameters evaluated. It is concluded that by using packed bed electrodes, separated by a diaphragm, the possibility of electrorefining with very low energy consumption can be achieved. Carbothermically-produced metals are always cheaper than those produced by electrolysis but suffer from the disadvantage of low purity. It is proposed that fused salt electrorefining may offer an energy efficient way of upgrading the metal. IntroductionThe majority of metals can be deposited from fused salts (1,2) but as commercial production is restricted to the more reactive elements, it is worthwhile considering the advantages and disadvantages of fused salt electrolysis as' compared to smelting and aqueous electrolysis. The advantages over aqueous extraction are as follows:1) the much higher conductivities and diffusivities result in much lower IR losses and higher current densities can be achieved at modest voltages;2) the elevated temperatures of operation result in larger exchange currents which give rapid kinetics and lower activation polarisation for the electrode reactions;3) the absence of water as a solvent means that it is not necessary to consider the evolution of hydrogen as a competing cathodic reaction. Furthermore, alkali halide salts, often used as solvents in fused salt electrolytes, have high deposition potentials;4) molten salts generally are mutually soluble and, therefore, concentration polarisation effects are minimised."

Jan 1, 1988

By Noel A. Warner

Modern steelmaking is based on direct use of oxygen in high intensity batch reactors. A totally new approach is proposed in this paper, based on the view that pursuit of high intensity is unlikely to lead to successful coal-based continuous steelmaking. By substituting carbon dioxide and water vapor as the oxidants rather than using oxygen directly, the intensity is greatly reduced. Accordingly. subsurface formation of carbon monoxide bubbles can be avoided by careful manipulation of the three participating rate processes, gaseous diffusion, interfacial chemical kinetics and liquid phase mass transfer. Steelmaking can then be carried out without explosive ejection of molten droplets and the generation of micro-spray but rather in a controlled and fumeless fashion. The vital component is the introduction of generic melt circulation technology. Three melt circulation loops in series are envisaged. Starting with a composite feed of iron ore fines, pulverized coal and lime flux, a metallized solid raft floating on molten iron is propelled out of the ironmaking loop onto the first of two downstream steelmaking loops. In the first, a liquid slag is formed, primary decarburization is undertaken not with oxygen but rather with CO2 and H2O and the melt is desulfurized. The semi-product stream enters the third melt circulation loop, where open-channel decarburization is effected along with dephosphorization to yield a low carbon steel product. Alternatively, the melt leaves the last loop to irrigate a packed tower countercurrent to argon at around 100 mbar to continuously produce ultra-low carbon (ULC) steel.

Jan 1, 2003

By W. William Culver

James Douglas became known in the nineteenth century for two reasons fundamental to his mining career: (1) his experimental work with copper hydrometallurgy, and (2) his grasp of the idea that the quantity of copper ore matters more than the quality. On the first reason, there is a moment for any technology that’s critically important—when it moves from an area of scientific interest to one that companies are founded on. This paper examines the original 1869 Hunt and Douglas Copper Process in the context of science and engineering as they were in the 1860 and 1870s. It was a “humid” process, developed at Quebec’s Harvey Hill Mine. Chemically, the Hunt and Douglas vat leaching process succeeded, but not the original companies using it. On Douglas’ understanding of ore quality versus quantity, luck had it that the first company to field test the Hunt and Douglas Copper Process was in Chile. The Hunt and Douglas patent made that transition from experimental model to operational plant in 1870 when the Compañia de Minas de la Invernada was organized in Valparaíso. As a joint-stock company, Invernada spread the risk of investing in the revolutionary, but untested, Hunt and Douglas Process. The company brought Douglas to Chile as a consultant in 1871. His experience with hydrometallurgy, combined with what he learned about the copper business while in Chile, set him off on a career in metal mining that both surprised Douglas and made him wealthy.

By Noel A. Warner

Modern steelmaking is based on direct use of oxygen in high intensity batch reactors. A totally new approach is proposed in this paper, based on the view that pursuit of high intensity is unlikely to lead to successful coal-based continuous steelmaking. By substituting carbon dioxide and water vapor as the oxidants rather than using oxygen directly, the intensity is greatly reduced. Accordingly, subsurface formation of carbon monoxide bubbles can be avoided by careful manipulation of the three participating rate processes, gaseous diffusion, interfacial chemical kinetics and liquid phase mass transfer. Steelmaking can then be carried out without explosive ejection of molten droplets and the generation of micro-spray but rather in a controlled and fume less fashion. The vital component is the introduction of generic melt circulation technology. Three melt circulation loops in series are envisaged. Starting with a composite feed of iron ore fines, pulverized coal and lime flux, a metallized solid raft floating on molten iron is propelled out of the ironmaking loop onto the first of two downstream steelmaking loops. In the first, a liquid slag is formed, primary decarburization is undertaken not with oxygen but rather with CO2 and H2O and the melt is desulfurized. The semi-product stream enters the third melt circulation loop, where open-channel decarburization is effected along with dephosphorization to yield a low carbon steel product. Alternatively, the melt leaves the last loop to irrigate a packed tower countercurrent to argon at around 100 mbar to continuously produce ultra-low carbon (ULC) steel.

Jan 1, 2003

By Finlay Campbell

Nickel laterite pressure acid leach plants and reduction roast plants have had a checkered history in their engineering, construction, startup and operational reliability. Many potential projects have been the subject of detailed studies over the last thirty to forty years but relatively few have advanced to commercial production. Four reduction roast plants are currently operating, an additional one was partially constructed but never completed, and another was started up in 1974 and shut down after 12 years operation. Three acid leach plants have been built and commissioned in the last five years, trying to follow the example of the Moa Nickel plant in Cuba. An additional acid leach plant project is currently on hold, following limited construction work, its future subject to review by the owner because of potential cost over-runs. This paper attempts to discuss difficulties that may be encountered as a project is developed and will address factors which may affect production ramp-up schedule, long term production performance and overall production success. Comparisons are made with ramp-up performance at other large metallurgical plants that employ some comparable unit operations. Keywords: Caron, PAL, nickel laterite ore, ramp-up, reliability, process development, equipment design, step-out, commissioning, startup.

Jan 1, 2004

By Patrick R. Taylor

A non-transferred arc thermal plasma assisted cyclone reactor has been designed, built and operated to evaluate its use in vitrification of wastes. Simulated waste (liquid, slurry or fine particulate) is injected near the plasma flame, where nearly instantaneous dehydration and calcination reactions happen. A non-transferred arc plasma torch was attached tangentially to the cyclone and is utilized as both an enthalpy source and to provide the gas velocities required to generate the cyclonic gas flow patterns. The closed top cyclone flow sends the solid particulates to the wall, where they are captured by a thin film of molten glass that is injected as a powder at a position lower in the reactor. The molten glass is then collected in a crucible. The feasibility of simulant injection directly into the flame zone and its effect on electrode lifetimes has been studied. Several candidate refractory systems have been evaluated for their suitability for extended use under the demanding conditions present in the cyclone reactor.

Jan 1, 2002

By E. Gutierrez-Miravete

A computational method for the simulation of mold filling processes is described. The method is based on the representation of the flowing or deforming medium as a collection of mutually interacting parcels of material. Instantaneous positions of individual material parcels are calculated by numerical integration of the dynamic equations, subject to appropriate initial and boundary conditions. So far, the method has been used to produce qualitative simulations of some flowing and deforming systems encountered in mold filling technology, and our findings are summarized herein. In all cases, individual material particle motions can be followed in detail, allowing critical examination of potentially problematic mold design features.

Jan 1, 1992

By Jinrong (Patrick) Mang

Three of the most challenging problems in phosphate beneficiation are discussed: flotation efficiency, resource conservation and environmental impact. Some new flotation machines offer the opportunity of reducing power and reagent consumption significantly, while increasing specific capacity many fold. Efficiency might also be improved dramatically by replacing the "double float" process with a single-collector scheme. Model based software control is a powerful tool for improving overall plant efficiency. Recovery of phosphate values from the phosphatic clays could extend phosphorus reserve life significantly. phosphate recovery from the slimes might be achieved by sizing-flotation, selective flocculation and bioleaching. Reducing the volume of phosphatic clays produced is another key stop to minimizing phoephate logs. Such a reduction may be realized by floating at finer cut size. Although an ideal' dolomite separation process is yet to be developed, a cationic flotation process may prove to 'be economically feasible. Loss of phosphate in the desliming stage is the major problem with most of the flotation schemes for removing dolomite.

Jan 1, 1995

By J. A. Holmes

Due to varying and complex mineralogy, the flotation tailings from the Chingola Concentrator have, for some years, contained upwards of 0.4% acid soluble copper. In 1968, an investigation was initiated, to determine a method for recovering this acid soluble copper. This initial investigation concluded with a recommendation to install a leach-solvent extraction-electrowinning plant at Chingola, to treat up to 900 000 tonnes of material per month, for an additional copper production of some 4 500 tonnes per month. The process consists basically of six stages :- Materials reclamation handling and preparation, acid leaching in air agitated pachucas, solid-liquid separation by countercurrent washing in thickeners, solution concentration and purification by solvent extraction, copper recovery by electrowinning, and residue neutralisation and disposal. This paper describes the development of the main parameters for design of each of the six sections, and gives details of the final plant design. Problems encountered in commissioning and initial operations are commented on, particularly insofar as they indicated any errors or misjudgements in the design. The choice of materials of construction is commented on in some detail.

Jan 1, 1976

By N. L. Piret

Primary and secondary copper smelting dusts are being generated in varying quantities with very dissimilar characteristics due to the different compositions of feed materials and the type of process utilized. After categorizing the multitude of dust types, the criteria for on-site and off-site recycling of smelter dust in terms of type and concentrations of the accompanying elements are established. Thereby, consideration is given to the important aspects of: ? optimization of copper recovery ? quality of copper product ? valorization of accompanying elements ? elimination and disposal of deleterious impurities ? minimization of impact on operation ? effects on operating costs ? environmental impact of dust treatment on overall process Existing commercial, emerging and proposed copper smelting dusts, pyrometallurgical as well as hydrometallurgical, treatment schemes are reviewed and evaluated technically, economically and environmentally in an attempt to streamline the vast number of proposed options. Thereby, the high selectivity achievable in hydrometallurgical dust processing due to it being complementary to the smelting process is expected to be given increased consideration.

Jan 1, 1995

By KNona C. Liddell

The ion interaction model Pitzer proposed twenty years ago is today the most widely used method for calculation of osmotic coefficients and electrolyte and single ion activity coefficients in aqueous solutions. This is due in part to the accuracy of the results that have been obtained for many concentrated electrolytes. An additional factor is that, compared to alternative activity coefficient models, there are many more parameter values available for the Pitzer equations. The important features of this model are reviewed. Published parameter values for Co, Ni, Cu, Zn and Fe are tabulated, and applications of interest in the aqueous processing of these metals are described.

Jan 1, 1993

By Corby G. Anderson

In the majority of industrial operations recovering gold and silver by hydrometallurgical means, cyanide is the predominant lixiviant. However, as an economic alternative, production of massive quantifies of silver chloride was done on an industrial scale in the nitrous-sulfuric acid pressure leaching of a refractory precious metals concentrate. This proven process required no cyanide. Thus, because of the large volumes encountered during day-to-day plant operation, the need for efficient and low cost methods of silver chloride precipitation, reduction and materials handling was mandatory. As such, this paper covers the evolution of plant scale precipitation, filtration, washing, reduction and control of silver chloride processing. As well, an in-depth description of the unique leaching system is included.

Jan 1, 1998

By Paul C. Turner

In 1998, approximately 57,000 tons of titanium metal was consumed in the form of mill products (1). Only about 5% of the 4 million tons of titanium minerals consumed each year is used to produce titanium metal, with the remainder primarily used to produce titanium dioxide pigment. Titanium metal production is primarily based on the direct chlorination of rutile to produce titanium tetrachloride, which is then reduced to metal using the Kroll magnesium reduction process. The use of titanium is tied to its high strength-to-weight ratio and corrosion resistance. Aerospace is the largest application for titanium, and titanium cost has prevented its use in non-aerospace applications including the automotive and heavy vehicle industries.

Jan 1, 2001

By George P. Demopoulos

In this paper the production and stability of crystalline scorodite (FeAsO4·2H2O) is discussed both on the basis of previously published work as well as recent work performed in our laboratory. The production of scorodite, especially from arsenic-rich and iron-deficient sulphate solutions offers a number of operational advantages such as high arsenic content, stoichiometriciron demand, and excellent dewatering characteristics. In addition to hydrothermal production of scorodite the work done over the last 10 years in our laboratory has determined that it is feasible to produce scorodite by step-wise lime neutralization at 90°C. The atmospheric scorodite possesses the same structural and solubility characteristics with the hydrothermally produced scorodite. Long term equilibration tests (up to 66 weeks) in the pH range 5 to 9 and temperatures from 22 °C to 75 °C revealed scorodite to undergo slow incongruent dissolutionyielding a highly metastable nano-sized 2-line ferrihydrite phase. The equilibrium arsenic concentration with this phase was 0.35, 0.96 and 5.87 mg/L at pH 5, 6, and 7 respectively at 22°C. In the presence of gypsum slightly lower concentrations were measured, this being more pronounced at pH>7. It was tentatively deduced that a Fe-Ca-AsO4 association (in the form of a phase resembling the mineral yukonite) contributes to the lowering of As concentration. Finally thermodynamic calculations determined that scorodite is stable in the presence of ferrihydriteunder oxic conditions up to pH 6.75 at 22 °C or higher pH at lower temperature and gypsum-saturated solutions. Keywords: Scorodite, Crystallization, Arsenic, Solubility, Stability, Precipitation, Disposal, Extraction, Processing, Metals, and Environment.

Jan 1, 2005

By F. Elgersma

Hydrometallurgical zinc winning processes ?are frequently based on iron containing concentrates which yield a goethite, jarosite or hematite residue. Jarosite or goethite are mostly stored in waste ponds which ,are lined with foil. Water percolating through the pond is withdrawn from the deposit ,and decontaminated before discharge. Despite these measures, more and more pressure is put upon zinc companies to treat their (historical) residues and to produce environmentally acceptable residues. The criterion which determines this acceptability is the potentiality of leaching out hazardous elements by natural processes. This paper provides the comparison of five different process designs for integrated jarosite treatment in a hydrometallurgical zinc winning plant leading to environmentally acceptable residues. The processes are esigned for producing 200 ktons/yr zinc and for treating 80 ktonslyr historical jarosite. Mass and energy balances are used to determme parameters such as: the energy use per ton waste treated and the amount and composition of final residues. The conclusion of the work is that. pyrometallurgical jarosite treatment integrated in hydrometallurgical zinc winning is preferable to hydrometallurgical jarosite treatment. Integrated pyrometallurgical processes lead to a ?smaller quantity of remaining hazardous residues and require less energy.

Jan 1, 1992

By E. A. Thiers

The causes of structural changes in the markets for high technology alloying metals are discussed in terms of technological, economic, and financial trends. Recent market imbalances have affected producers in developed and developing countries differently. Possible response strategies for suppliers in the two types of countries are examined that may alleviate future market imbalances.

Jan 1, 1988