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By Klas G. Hultbom

Mercury is present as trace contaminant in many raw materials for metallurgical plants. When such materials are treated with pyrometallurgical processes the mercury is volatilised. Mercury has a high vapour pressure, even at low temperatures, and therefore it is removed only partly by normal gas cleaning processes. The Boliden Norzink scrubbing process removes elemental mercury by converting it to calomel. It is widely used in the base metals industry. This paper gives examples of the application, and also outlines the background for the development of the process. Another technology developed by Boliden for mercury removal is the Selenium filter. This is a fixed bed filter based on the reaction between elemental gaseous mercury and selenium, by which mercury selenide, HgSe, is formed. The mercury selenide is a highly stable compound with extremely low solubility in water and very low vapour pressure. Mercury is removed selectively without any side reactions. Special applications for the selenium filter technology include mercury removal from gases containing sulphur dioxide and geothermal off-gases.

Jan 1, 2003

By Takahiro Miki

Soldering material widely used is Sn-Pb alloy, which have low melting point and excellent electrical, strength properties and wettability. However, Pb is one of the toxic elements, which is undesirable due to environmental and safety reasons, thus Pb-free alternative alloy is preferred for new soldering materiaL Sn-Ag and Sn-Zn based alloys have been viewed as very promising candidates, among many potential substitutes. Addition of third element to these alloys will decrease melting point of the alloys. Hence, Sn-Ag-In and Sn-Zn-Mg alloys are expected to be suitable for replacing Sn-Pb solder alloy. In order to dcsign new Pb-free soldering materials, it is crucial to understand precise thermodynamic properties and phase diagrams of alloy systems. In the present work, ion current ratios of Ag to In and Mg to Zn were measured for Sn-Ag-In and Sn-Zn-Mg alloys by mass spectrometry, respectively. Also, the authors reviewed the thermodynamic properties of terminal binary alloys determined by other researchers and evaluated a thermodynamic functions to express the excess Gibbs free energy of each binary alloy. Thermodynamic functions to express the excess Gibbs free energy of liquid Sn-Ag-In and Sn-Zn-Mg ternary alloys were determined, utilizing the assessed Gibbs free energy of terminal binary alloys with the measured ion current ratios using mass speetrometer.

Jan 1, 2003

Achieving continued economic growth with social equity within the natural limits of the Earth's 'eco-systems is the major issue facing the world today. The material and energy needs of the world cannot be met with the current ways of addressing this issue. The need for metals, an important class of materials, will continue into the future because their unique properties make substitution by other materials impossible in many applications and this need will continue to be met from primary metal production and recycling. However, the recycling rate will increase and the usage pattern of metals will change to reflect the environmental impact of their production and use. Pyrometallurgy has an important role in meeting the metal needs of the future since some metals can only be produced pyrometallurgically; the energy required to produce some metals pyrometallurgically is significantly less than by other methods; most metals are most efficiently recycled pyrometallurgically; and the release of harmful and toxic elements into the biosphere can sometimes best be controlled through pyrometallurgical processing. The development of strategies for pyrometallurgical processing for the future lies in the recognition that sustainable development calls for large step improvements in value delivered per unit of environmental impact over the entire supply chain. Pyrometallurgists can respond to this challenge by contributing to reducing the environmental impact of meeting metal needs using three broad strategies: "end-of-pipe" approaches to convert emissions into benign materials for storage or disposal; flowsheet redesign to limit or eliminate emission production; and improved recycling technologies. A number of examples are discussed to illustrate how the sustainability driver is already influencing the technological development of pyrometallurgical processes, and how these will develop further as the sustainability driver strengthens.

Jan 1, 2003

By Daniel Helm

The first industrial application of direct solvent extraction of nickel from hypersaline sulfate feed solutions has highlighted the need to investigate the influence of chloride on the extraction behaviour nickel in the presence of calcium using Versatic 10 and the solubility characteristics of gypsum. Temperature-solubility curves for gypsum in various aqueous electrolytes were prepared. The solubility of gypsum is increased significantly by the presence of sulfate ions, while chloride ions decrease it for a given temperature. The anion effects of chloride and sulfate on the extraction of calcium and nickel by Versatic 10 corresponded well with the complexing ability of the anions. It was shown that the presence of chloride shifts the extraction isotherms for both metals significantly to the left, while decreasing the selectivity of Versatic 10 for nickel over calcium. The loading of nickel onto Versatic 10 in this system was shown to be at a maximum within 3 seconds, while calcium extraction took between 4 ? 5 seconds to load to a maximum. Chloride ions had no influence on loading kinetics of nickel, but depressed the rate of calcium loading. It was shown that in the presence of an excess of nickel, calcium loading is effectively eliminated, and that calcium is scrubbed from Versatic 10 within 2.5 seconds of contact with nickel electrolyte.

Jan 1, 2003

By P. J. Harrington

The recovery and recycling of low concentration metal and other ions has traditionally been carried out using adsorption or ion exchange processes which, however, become uneconomical at higher concentrations, such as those that occur with many intermediate or waste streams where recycling is now being required. This paper describes the development of a process based on non-dispersive solvent extraction for the recovery of chromium (VI) from electroplating rinse water. During the chromium plating of steel, the concentration of chromium (VI) in the rinse bath rises to concentrations in the order of 100 mg/L when it becomes unusable and is then disposed of. The aim of this work was to investigate processes for recovery and recycling of the chromium in the rinse bath. The recovered chromium is required to be concentrated and purified before reuse. Tertiary amines have been shown capable of concentrating and purifying the chromium (VI) in solution. However, solvent extraction processes that have been applied to the recovery and reuse of metals from waste streams have had only limited success in the past, primarily because of the relatively high solvent losses when existing contacting equipment is used on low feed concentrations. Attempts to eliminate losses by immobilizing these complexing agents on substrates have not been successful. In order to control the losses and maintain specificity, a hollow fibre-contained liquid membrane has recently been trailed in a pilot plant to recover chromium from chromium plating waste streams. Details of the trial and modeling of the results are presented, and show that the level of losses is significantly reduced. However, issues relating to fouling still need to be addressed. This type of equipment has many applications in the recovery and recycling of a range of materials in the manufacturing processes.

Jan 1, 2003

By Takeshi Azakami

By combining the iron reduction process with the usual rotary kiln process, the direct production of metallic zinc from EAF dust is proposed. After thermodynamic estimation and desk-top experiments it is confirmed that the process is hopeful under suitable conditions. In order to get some practical test data the enlargement of the process scale was planned and the bench scale tests were carried on successfully. In these experiments a zinc ingot of PW grade was produced from EAF dust.

Jan 1, 2003

By R. M. Luna-Sánchez

Electrochemical studies, particularly Evans? diagrams, have been employed in hydrometallurgy to simulate and explain the redox phenomena that take place at mineral and metal surfaces during operations such as leaching and cementation. However, despite their utility, in some cases, the combination of the cathodic and anodic branches, determined separately, does not reproduce the chemical environment present when both processes occur simultaneously on a specific surface. In the present paper, limitations of Evans? diagrams are analyzed through two examples: silver sulfide cyanidation and gold cementation on zinc. In both cases, the surface kinetics are sensitive to the local pH and cyanide levels. When the electrochemical oxidation of silver sulfide or the reduction of gold are performed in the absence of its corresponding redox reaction, the local pH obtained does not simulate the real situation and the combined reaction kinetics may be very different from those determined from the Evans? diagrams.

Jan 1, 2003

By David Melgaard

A significant emerging recycling, waste minimization problem stems from legacy waste from the nuclear weapons program and from production of power using nuclear fuel. Premium quality metals used in nuclear plants become contaminated, making them unsuitable for reuse. Consequently, decontamination studies were conducted to evaluate the decontamination capacity and partitioning effeetiveness of Electroslag Remelting (ESR). Eight laboratory melts were conducted to evaluate the efficacy of using ESR to transport radionuclides from the liquid metal phase to the liquid flux or slag phase. To determine the decontamination effectiveness, several surrogate compounds for uranium, plutonium and other fission products were added to the melts. During the melts, the melting rate was varied, typical slag additives were used, and two different slag compositions were evaluated. The resultant post-test ingots and slag were then analyzed to determine the partitioning of the surrogates. ESR generally proved very effective in removing contaminates from the metal with a few noted exceptions. -

Jan 1, 2003

By W. D. Cho

The slag chemistry in steel processing plays an important role in terms of the removal of impurities including alumina particles. In the present study, the dissolution of solid alumina particles in CaO-based fluxes at the temperatures between 1450 and 1550 °C has been investigated to determine dissolution kinetics and mechanism. Alumina particles were added directly in the slags and the size of alumina particles was measured as a function of time using optical and scaru;ling electron microscopes. The dissolution rate has also been obtained as a function of Si02, CaF2, MgO and MnO contents in the slags. The diffusion boundary layer between alumina and bulk slag phase has been observed and analyzed using SEM and EDX. In addition, some experiments have been performed for the dissolution of alumina in BaO-based fluxes.

Jan 1, 2003

By Junji Shibata

Through-hole copper plating is performed to make a multi-layer printed circuit board. The through hole plating is first carried out by Pd catalyst treatment, followed by copper non-electric plating. The amount of Pd catalyst used in one plant is about 0.25-2 m3/month (8 g/dm3 PdCl2 base) depending on the plant scale, and the cost of the catalyst reaches 17,000¬I35,000 US$/month. In this study, the flow and material balance of a Pd in Pd catalyst treatment process was investigated. About 60% of Pd catalyst adheres on the through-hole and other part of setup, while 25% is released into the washing liquor. Pd in the washing liquor should be collected by a suitable method like a pressure filtration using diatomite. The material balance of Pd in Pd catalyst treatment process and the recovery method of Pd from waste solution containing Pd catalyst was investigated.

Jan 1, 2003

At its Copper Cliff Smelter, Inco Limited processes a bulk copper-nickel concentrate in two Inco oxygen flash furnaces, The furnace matte is converted to low iron matte for further processing, and the molten converter slag is recycled to the flash furnaces. The flash furnace slag is discarded. Natural gas or coke supplies a minor proportion of the process heat requirements, thus limiting the flash furnace matte grade to the target 45% CuNiCo. Coke addition to the furnace offers a potential means of establishing a reducing barrier on the surface of the molten bath. Such a practice would be conducive to producing sulfur deficient (partially metallized) matte. At the same iron content, the iron activity of sulfur deficient matte is higher than that of regular matte. A supernatant coke barrier could, therefore, be expected to lead to higher nickel and cobalt recoveries, reduction or even elimination of magnetite furnace bottom build-up and increased sulfur elimination as S02 in the flash furnace. Preliminary experiments were conducted in a miniplant flash furnace to investigate the effect on process metallurgy of the suggested modified scheme. This paper presents the experimental results and discusses key aspects of the possible operation of the Inco flash furnace with a coke barrier separating the freeboard from the molten bath.

Jan 1, 2003

By M. B. Mesina

Mechanical separation systems are widely used nowadays for scrap metal processing, but they have natural limitations in product quality. The quality of the final product is considerably improved when sensors are used in the separation process. This paper describes new methods using sensors for scrap metal sorting and quality control. An example is the electromagnetic sensor, which uses the electrical and magnetic properties of materials to distinguish between different non-ferrous metals. The measurement results of two prototypes are reported. The benefits and the possibility to integrate such systems into practical applications regarding the processing of secondary raw materials are also described.

Jan 1, 2003

By J. Rajek

The novel multi-component, multi-particle, multi-phase precipitation model developed recently is used to predict the precipitation kinetics in complex 9-12% Cr steels investigated within the European COST 522 project. These steels are used for tubes, pipes, casings and rotors in USC (ultra super critical) steam power plants for the 21st century. In the computer simulations, the evolution of the precipitate microstructure is monitored over the entire production heat treatment starting with the casting process, including austenizing, several annealing treatments and in-service conditions. The main interest lies on the concurrent growth and coarsening interaction of different types of precipitates. Keywords: Precipitation kinetics, heat treatment, power plant steels, simulation

Jan 1, 2003

By Kiyoshi Takai

The Para-Eco Incinerator Ash Processing System for cleaning slag has been developed after a seven-year pilot plant study. The major part of the system is an electric furnace heated to 1773 K. The feed material consists of a municipal solid waste incinerator ash mixture containing a reducing agent of a coke and an inorganic flux of calcium and magnesium. With this furnace system, three kinds of products are produced. They are an inorganic molten salt that is slag, molten iron alloy absorbing non-ferrous metals, and fly ash. Due to the reducing atmosphere in the furnace, the slag does not contain any metal components as well as chlorine components just like natural rock and/or aggregate. A retreatment plant modifies this slag into a practically useful aggregate. The plant consists of a slow cooling step for crystallizing the slag as well as a water granulation step. The iron components in the ash are reduced to molten iron droplets, which concentrate at the furnace bottom. The non-ferrous metal components such as copper, chromium, and others are absorbed into the molten iron but not into the molten slag. Volatile metals such as lead, zinc, cadmium and others as well as sodium, potassium, and chlorine go back into the fly ash. A solvent extraction method and/or other appropriate procedures can be used to extract the metal components from this fly ash.

Jan 1, 2003

By Masatoshi Ogasawara

Saganoseki smelter & refinery operated two flash smelting furnaces, producing a combined 330,000 metric tons per year (hereinafter mtpy) of copper. [n 1996, however, it successfully shifted to a single fumace operation while maintaining production at the same level. Since then, the production capacity has been further increased to the present 470,000 mtpy by technological improvements. Also, in order to reduce the converter load which represents a bottleneck in efforts to increase production, the matte grade was gradually increased and currently runs at 65 to 66% attaining the low copper content in the slag (hereinafter slag loss) of 0.7 to 0.8%. This ' paper introduces some improvements, recent operation results and thermodynamic analyses.

Jan 1, 2003

By Corby G. Anderson

In nature, mercury is quite commonly found in association with antimony ores. This can be as a separate mineral such as cinnabar or in direct association with the antimony ore. The most common antimony-mercury mineral is livingstonite that occurs in places such as Algeria, Mexico, USSR and China. In the Roznava deposit in eastern Slovakia, tetrahedrite ore containing mercury ore has historically been processed pyrometallurgically for its silver and copper values. As well, in Tajikistan, major antimony deposits there contain significant mercury ore concentrations within the stibnite ore body. The mercury contained in these materials poses both a processing and environmental challenge. This paper will outline the processing of these types materials by industrial alkaline sulfide hydrometallurgical methods. The economics relevant to this potential application at Roznava in Slovakia will be outlined.

Jan 1, 2003

By N. M. Komkov

The main operation of obtaining zinc from sulfide raw materials by hydrometallurgical technologies is the oxidation roasting of zinc concentrates in fluidized bed furnaces. The technical-economic parameters are determined by the parameters of the roasting process, which depend on the composition of the initial raw materials, the temperature of the bed and on other factors. The predetermined roasting temperature is maintained due to the change of specific efficiency as well as to the quantity of the heat removed from the bed. The efficiency of caissons depends at a high degree on the composition and the thickness of the accretion formed on the surface of the caissons. Forecasting the roasting results is impossible unless we know the mechanism of the accretion formation. The aim of the present paper is the thermodynamic analyses of the behavior of the charge compositions under roasting and the determination of the potential mechanism of the accretion formation. The thermodynamic analyses show that under conditions of the oxidation roasting the thermodynamic probability of the formation of zinc sulfate is higher than the probability of the oxide formation until a temperature of 873°K is reached. The thermodynamic probability of the formation of the lead sulfate is higher than the probability of oxide formation in the entire temperature range of roasting. The probability of formation of ferrites and silicates of zinc decreases only insignificantly the sulfate stability. The results of the investigation of the accretions composition formed under roasting of concentrates with particle sizes less than 0.02 um (60%), containing 65% of sphalerite (ZnS), 12% of pyrite and chalcopyrite (FeS2 and CuFeSz2 each, 3% of galenite (PbS), 7% of silica and other non-ore minerals, have shown that the composition of accretion varies depending on the depth of the accretion layer. The accretions on the caissons and the thermo-siphons consist mostly of zinc sulfate (more than 50%). The accretions of forchamber consist mostly of zinc oxide. They also contain ferrites and silicates. The formation of the sulfate zinc accretion in the cold parts of the fluidized bed furnace (the caissons and thermo-siphons) may be explained by a lower temperature on the surface and probably by a catalytic influence of the present oxides in the formation of S02 and sulfates. The nature of the structure of the accretion in the hotter parts of the furnace may supposedly be explained by the formation of elemental vaporous zinc during roasting.

Jan 1, 2003

By Huaming Yang

Infrared materials are a special kind of material widely used in military, biological engineering and chemical industry. However, the problems associated with them such as unstable properties, high cost and a high thermal expansion coefficient seriously restrict the development and the wide application of the traditional infrared materials with the SiC or ZrSiO4 matrix. The ultrafine quartz powder is normally used to prepare the infrared materials by hot-pressing technology. The aim of the paper is to investigate the thermal expansivity, the effect of the SiO2 size and the addition of Al2O3 or Fe2O3 on the infrared emissivity of the quartz matrix of the infrared material (QMIM) in a 8-25um wavelength range. The results indicate that 89% of infrared emissivity and 0.4x 10-5/°C of thermal expansion coefficient of QMIM can be obtained. The affecting mechanism of A1203 and Fe2O3 on the infrared emissivity of QMIM were also discussed.

Jan 1, 2003

By R. Hurman Eric

Within the Ag-Pb-S ternary system, the boundaries of the immiscibility region together with the tie-line distributions were re-established at 925°C by the equilibrium-quenching technique where samples were kept in evacuated and sealed silica capsules. Activities of Pb were measured by the dew-point method along the Ag-Pb binary at 925°C, 1100° and 1200°C. positive deviations were observed and the results were modeled by the Krupkowski formalism. Activities of Ag, Pb, and S, along the ternary miscibility gap were calculated at 925°C by utilizing the boundaries binary thermodynamics, phase equilibria and tie-lines. Activities of PbS within the pseudobinary Ag2S-PbS mattes were also measured by the dew-point technique and the results were again modeled by the Krupkowski formation Where negative deviations were observed.

Jan 1, 2003

By Peter Forschner

Classical Mixing Theory is based on applying many fundamental correlations to standard baffled dished bottomed vertical cylindrical vessels with high degrees of symmetry. Horizontal autoclaves operating at elevated temperatures and pressures have been used for more than two decades. All compartments and especially the first and last compartments are asymmetrical. To date no comparison of the effects of the asymmetric geometry on mixing system design and scale-up has been published. The results of investigating solids suspension, mixing time, momentum transfer from the impeller to feed slurry and feed inlet location in the first autoclave compartment are presented as influences on residence time distribution. CFD modeling was developed and verified with the test apparatus.

Jan 1, 2003