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By R. N. O'Brien, E. Peters

"It has been discovered that copper concentrates can be leached in strong (40-60%) sulfuric acid with nitric acid, or with oxygen if nitric acid is present as a catalyst. Chalcopyrite is rapidly decomposed at temperatures well below the boiling temperature of the lixiviant (-150 C.) and the resulting copper and ferric salts are precipitated as CuS04.H20 and FeH(S04)z.4H20. Other metal sulfides such as zinc, lead, nickel, etc. are also converted to sulfates that are nearly insoluble. Sulfur is partially converted to elemental and partially to sulfuric acid. Reduction products of nitric acid can be recovered from the distillate with good recovery. Conversion of as-received copper concentrates is largely complete in about 1 hour. Introduction9 molar sulfuric acid is an unusual hydrometallurgical lixiviant: it has a boiling point of about 150 C. and a low solubility for base metal sulfates. Below about 6 molar acid, the boiling point falls below 120 C. and yields much higher sulfate salt solubility, while above 12 or 13 molar acid and at higher temperature sulfuric acid becomes an oxidizing agent, yielding gaseous S02' Thus, sulfuric acid within this range of concentration is capable of acting well above the temperature of boiling water without requiring autoclave conditions, and if typical oxidative leaching conditions are applied to suspended mineral sulfide concentrates, it is possible to obtain a conversion of these sulfides into 'crystalline sulfates. Thereafter, the sulfates can be separated by filtration or by solid - bowl centrifuge and the solution can be recirculated to the reactor vessel. Meanwhile, the solid sulfates can be treated in a typical hydrometallurgical circuit, i.e., dissolved in a return stream that is essentially water, separated from each other by, for example, solvent extraction, and recovered as metals by electrowinning."

Jan 1, 1997

By H. Kamarudin

The behaviour of cassiterite-sulphosuccinamate flotation system was examined in the light of zeta potentials measured by micro-electrophoresis method. It was observed that sulphosuccinamate substantially affects the zeta potentials of cassiterite, lowering its i.e.p. to pH 2.5 and indicating a specific adsorption and/or chemical interaction. The optimum concentration for flotation, as seen in micro-flotation tests, was found to be associated with the most effective lowering of the zeta potentials, the optimum pH being 3.0. The effect of cations in the pulp was examined for the presence of ferrous, ferric, aluminium and lead ions. The ions ferric and aluminium were observed to create an intense effect of increasing the potentials to positive side, possibly due to adsorption of cation hydroxy complexes, as indicated by their respective species distribution diagrams.

Jan 1, 1994

By Amy Nelson

In the electrolytic production of zinc, cobalt is removed from the zinc electrolyte by cementation with zinc dust prior to electrowinning. Although the thermodynamics for this reaction are favourable, kinetic barriers to cobalt reduction render the method almost useless in practice unless activators such as copper and antimony or arsenic are added. There is a large body of work studying the effect of these additives, yet the mechanism by which they act is still poorly understood. Even when the target conditions are met, zinc dust consumption is excessively high: satisfactory operation requires up to 300 times the stoichiometric amount of zinc dust. The objective of this work is three-fold: (1) to examine the effects of activators and elucidate the characteristics that make a good activator; (2) to identify new additives that could lead to a more efficient purification process; and (3) to test the new additives with synthetic and real electrolyte solutions. The present paper gives a status report on this project.

Jan 1, 1998

By Klaus-Markus Peters, James G. Hemrick, John Damiano

"Work was performed by Oak Ridge National Laboratory (ORNL), in collaboration with industrial refractory manufacturers, refractory users, and academic institutions, to employ novel refractory systems and techniques to reduce energy consumption of molten material processing vessels found in industries such as aluminum, glass and pulp and paper. The energy savings strategies discussed are achieved through reduction of chemical reactions, elimination of mechanical degradation caused by the service environment, reduction of temperature limitations of materials, and elimination of costly installation and repair needs. Key results of several case studies resulting from US Department of Energy (DOE) funded research programs are discussed with emphasis on applicability of these results to high temperature processing industries.IntroductionRefractory materials are limited in their application by many factors including chemical reactions between the service environment and the refractory material, mechanical degradation of the refractory material by the service environment, temperature limitations on the use of a particular refractory material, and the inability to install or repair the refractory material in a cost effective manner or while the vessel is in service. All of these limitations reduce the energy efficiency of the process as degraded refractory materials lead to loss of process heat (reduced insulation by refractories) and the need for maintenance through repair or replacement of refractory linings.This situation is conceptualized in Figure 1 which shows that when the thickness of the refractory wall is reduced by chemical or mechanical degradation, the heat losses through the wall increase exponentially. The subsequent maintenance to repair such conditions often requires cooling of the furnace or refractory lined vessel which entails loss of energy due to cooling and consumption of energy due to reheating. Additionally, production time and capability are sacrificed.Additionally, in most applications where refractories are used (metal melting furnaces, glass furnaces, steel making furnaces, gasifiers, etc.) wear of the refractory lining is not uniform. Very often, specific areas will wear (become thinner) more rapidly due to exposure to more corrosive or erosive conditions. This concept is illustrated in Figure 2, through the example of excessive metal line corrosion."

Jan 1, 2009

By M. Rubinstein, N. C. Koon, B. N. Das, V. G. Harris

"Copper and gold - based alloys having giant magnetoresistance properties were produced by melt spinning from arc melted and cast rods. The ribbon width varied between 1 and 2 mm and the ribbon thicknesses were in the range of 30 to 50 11m. The uniform microstructure of the cast rods indicated the composition homogeneity in the starting material. The ribbons showed composition uniformity across the cross section from EDX analysis. However, the spun ribbon microstructure changed from a 'frozen in' region near the wheel side to a nanosize spherically precipitated phase towards the freely frozen surface. The evolution of the microstructure from the spun ribbon state to the annealed ones was studied by optical microscopy, SEM and TEM. The structural information of the spun and annealed specimens was obtained from X - ray, electron diffraction, electron microscopy and ferromagnetic resonance. Magnetoresistance was measured by the four point probe method.IntroductionRecently. Giant Magnetoresistance. GMR. has been observed in sputtered thin films alloys of Ag. Au and Cu with Co and Fe [1. 2. 3]. The sputtered films are produced by condensation of the alloys from the vapor phase. These Ag. Au and Cu alloys are miscible and homogeneous in the vapor and liquid phase (except Ag alloys which exhibit phase separation even in the liquid phase) but immiscible and heterogeneous in the solid phase. In our work we have produced thin ribbons of the Cu and Au alloys about 30 µm thick from the miscible state in liquid phase by rapid solidification melt spinning. The microstructural development of the ribbons was investigated in the as - spun condition and on annealing. The other properties such as magnetization. GMR and Mossbauer Spectroscopy were also investigated in the various microstructural conditions of the ribbons."

Jan 1, 1994

"Recycling of solid wastes plays an important role in environmental protection. However, solid wastes are often contaminated with some undesired components so that many of these solid wastes are hardly economically recycled. Therefore, effective and efficient separation of undesired components from solid wastes becomes a crucial step for sustainable recycling of the solid wastes. There exist three general strategies of separation of undesired components from solid wastes: before-process separation, post-process separation and in-process separation. In this paper, different separation strategies are discussed in terms of energy requirement and availability, implementation complexity and additional need for environmental protection. It is concluded that of all separation strategies, in-process separation has the least energy requirement, the least implementation complexity and the minimum need for additional environmental protection.IntroductionIn industries, solid wastes almost come with every production process. Multi-million tons, if not billion tons, of solid wastes are being generated globally each year. These solid wastes are lowvalue materials in general, and often have very limited markets. As a matter of fact, many of these solid wastes have been stored on site or have been disposed of at landfills for many years, not only occupying lands, but also polluting environment. Therefore, effective and efficient recycling of solid wastes has been a very challengeable task and has played a very important role in environmental protection.One of the major barriers which hinder recycling of solid wastes is contamination of the solid wastes with some undesired components. These undesired components are components which are not wanted by production processes or applications where the solid wastes are consumed or recycled, since the undesired components often degrade qualities of the solid wastes, imposing negative effects on operations, facilities and product qualities of the production processes or applications. Sometimes, the undesired components may also pose severe environmental concerns. When undesired components are present in solid wastes at over-limit levels, the solid wastes tum to become destructive, useless and non-recyclable. Consequently, effective and efficient separation of undesired components from solid wastes becomes a crucial step for sustainable recycling of the solid wastes."

Jan 1, 2014

By Peter Hayes, Evgueni Jak, Ata Fallah Mehrjardi

Modern analytical tools, such as electron probe X-ray microanalysis (EPMA), are used in experimental characterization of phase equilibria and microstructures of complex slags. Integrated thermodynamic computer packages, such as FactSage, are used to provide more accurate descriptions of complex slag systems. These advanced methodologies have been applied to characterize dynamic steady state freeze linings in slag systems using submerged cold finger probes at controlled laboratory conditions, establishing the effects of bath chemistry, temperature, heat extraction rate and bulk fluid flow. It has been found that stationary freeze lining deposit interface temperatures at steady state conditions can be lower than the bulk slag liquidus temperature, and that stable operation below the liquidus is possible. A conceptual framework has been developed to explain the phenomenon and the range of interface temperatures that can be obtained in dynamic steady state conditions. These findings have important implications for the design of freeze linings and possible improvements to high-temperature metallurgical operations.

Jan 1, 2014

By John Nauman

Liquid ferrous silicates that are related to cop- per slags have been studied as media for the transfer of heat in pyrometallurgical processes. The effective thermal diffusivities have been measured from 1025Oto 1400°C, and values in the range of 0.004 to 0.007 cm2/ sec have been obtained. The heat-transfer characteristics of these slags have been determined by measuring the rise of temperature of a cold nickel sphere immersed in the liquid slag. The sphere is spun about its vertical axis to obtain a well characterized flow of liquid about the sphere. The principal barrier to the transfer of heat from the bulk slag to the metal sphere is a solid shell of slag that forms around the sphere and subsequently melts. It appears that the detailed nature of this shell is important to theheat- transfer process. A mathematical model is used to predict the rate of heating of the sphere, and to evaluate various aspects of the system that can influence the transfer of heat.

Jan 1, 1976

By R. P. King

The central idea presented in this paper is straight forward. Some fairly obscure mathematical techniques are presented from the fields of integral geometry and stereology and these techniques are shown to provide workable quantitative relationships from which the liberation spectrum of an ore after comminution can be determined. The experimental data that is required can be obtained very accurately and conveniently by image analysis of polished sections of the original ore. This quantitative mineralogical analysis provides a bridge that can link the worlds of the mineralogist and the mineral process engineer. This paper has been written to introduce this quantitative approach to a wider audience in the hope that the approach will be used more widely and that the basic linear intercept analysis data will be measured for a wider range of mineralogical textures. This could lead to a more comprehensive characterization of typical mineral ores that will be of considerable use in practical mineral processing.

Jan 1, 1991

By Norbert Patzeh

The demand for nickel is growing and will continue to do so for the foreseeable, future. This will make the construction of new leaching and smelting plants necessary. This paper described a number of possible alternative processes. The first projects with new technology are currently undergoing trials and feasibility studies. Experience from other industrial sectors and from existing plants is being incorporated into these investigations. The question is, to what extent the old nickel producing concepts will continue to be applied in the future. Keywords: Latcritc, rotary kiln, cyclonc rcactor, dust processing

Jan 1, 2004

By E. B. Freidina

We have investigated a new electrochemical process for preparing lead-calcium alloys. Calcium metal, reduced fiom a molten chloride mixture, forms an alloy with liquid lead cathode. The addition of calcium carbonate to conventional CaC12-NaCl electrolyte enables us to avoid chlorine production on the anode and replace it with oxygen and carbon dioxide. The ternary system CaClz-NaC1-CaCO3 has a range of melt compositions, where the electrolysis can be held below 650°C. In order to prevent the side reaction of carbon deposition on the cathode we have separated the anolyte from the catholyte with alumina diaphragm. The factors, which affect the level of impurities and the current efficiency of the process, are discussed.

Jan 1, 1999

By L. Becze, S. J. Hock, G. P. Demopoulos

"Regeneration of HCl from chloride solutions is commercially practiced by high temperature (800-900 °C) pyrohydrolysis associated with high energy consumption and capital cost. As an alternative to pyrohydrolysis a novel low temperature ( <200 °C) non-autoclave hydrolytic process has been studied in this research work, which comprises two steps. In the first step, ferrous chloride is oxidized by oxygen at 1;150 °C, followed by hydrolytic decomposition of ferric chloride to coarse hematite particles and superazeotropic hydrochloric acid (8-9M) operated at approximately 180 °C. This paper provides a summary of the laboratory results related to both oxidation and hydrolysis and presents a newly designed conceptual process flowsheet.IntroductionRecovery of base, noble and rare metals from ores and secondary materials (slags, dusts, residues) by chloride-based hydrometallurgical processes holds a lot of promise if a low cost HCl process becomes available. This is particularly so due to the high activity of HCl or more accurately activity of hydrogen ion [1] in concentrated chloride media and the formation of chlorocomplexes allowing for effective leaching under atmospheric leaching conditions and simultaneous ease of metal separation. However, during leaching significant amount of iron, which is associated with most of ores and secondary materials, goes into the solution. Hence, the obtained leach solution has to be treated to convert iron chlorides into easily filterable iron oxide and simultaneously produce concentrated hydrochloric acid. Apparently the critical operation of these processes is the regeneration of the lixiviant (HCl). Currently in the industry, its regeneration is accomplished by high capital and intensive pyrohydrolysis which operates at 700- 900 °C. Aimed at lowering the operational cost of pyrohydrolysis a process called PORI [2] was developed and tested in pilot plant scale in the 1970s for the purpose of treatment of pickle liquors without, however, resulting in industrial application."

Jan 1, 2011

By R. L. Nyirenda

The use of ammoniacal ammonium carbonate (AAC) leaching for the treatment of carbon steelmaking EAF dust has been investigated on a laboratory scale. The experiments have been conducted on dust samples obtained from three European steelmaking companies. As received, the dusts were found to be toxic when tested according to current EPA toxicity testing procedures. Toxicity was on account of the leachability of one or more of the following elements: Ag, Hg, Pb, and Cd. Leaching experiments with concentrated AAC solution at 40 " C showed that zinc oxide present in the three dust samples, 60-80% of the total contained zinc, was rapidly solubilized. Data on the dissolution characteristics of Cd, Fe, Pb, Mg, and Mn are also presented. Toxicity tests conducted on residues of the leaching experiments found these to have leachates below past and current EPA toxicity threshold limits.

Jan 1, 1993

By Zhongliang Tian, Yun Cheng, Yexiang Liu, Ming Jia, Yanqing Lai

"A fundamental electrochemical study of Si ions in Na3AlF6-LiF melts and electrolysis using liquid cathodes was conducted. Cyclic voltammograms (CVs) clearly showed the depolarization of silicon deposition on liquid cathode by forming chemical complexes with the liquid solvent metals. Besides, co-deposition of Al and Si is possible when Si ions are insufficient in the molten salt. Based on the electrochemical results, silicon diffusion into liquid cathode is modelled and evolution of Si activity with concentration is deduced by a mathematic approach. Electrochemical study using liquid metals as working electrodes, can be used as an alternative approach for the acquisition of basic data on alloy behavior. Galvanostatic electrolysis showed that liquid cathodes are appropriate to collect the deposited solid silicon and the highest collection efficiency is almost 85%.IntroductionRecent years have witnessed an increasing demand for solar-grade silicon (Si) by the photovoltaic industry [1-4]. The preparation of high-purity metals through electrolysis and electrorefining offer many advantages such as low cost, low-energy consumption, and environment-friendly process, and thus has been widely used worldwide. From the perspective of electrochemistry [5-7], by utilizing the electronegativity difference between the impurities and Si and controlling the relevant process parameters, it is possible in principle to electrodeposit monatomic Si from a Si4+-containing compound melt. Moreover, because the carbon content of the high-purity Si obtained through electrolysis can be effectively controlled and used as a very ideal raw material in the preparation of electronic-grade and solar-grade Si, the preparation of high-purity Si through electrolysis has received widespread attention [8,9]. Monnier et al. [9] used a graphite electrode to obtain high-purity Si (99.9 %-99.99 %) from Si02/Na3AlF6 system through electrolysis; however, because the Si was precipitated in a solid form and showed poor conductivity, the deposition rate was too slow. Olsen et al. [10] obtained high-purity Si films via electrodeposition in K2SiF6/KF-LiF system by selecting electrode materials with high surface quality (such as Ag and graphite). However, in order to ensure the film quality, the deposition current density must be relatively low (10-50 mA/cm2), resulting in a low current efficiency and low deposition rate, which are not conducive to reducing energy consumption and applying to practical use"

Jan 1, 2014

By J. Smuts

The mixed-valence iron silicate ISCORITE (Fe7Si010) was identified recently in a number of ironmakingmater1als, some of which were first produced more than a century ago. Although the existence of iscorite was not reported before 1967 and published phase diagrams do not make provision for it, the morphology of the phase in all the materials that were examined suggests that it is stable under a variety of conditions. It is shown that is-corite can accommodate various foreign cations in its lattice where they can replace Fe and/or Si. The morphology of is-corite in a number of materials of different origin is shown in relation to iron oxides and silicates in optical and SEM/BSE images.

Jan 1, 1991

By S. C. Flood, J. D. Hunt

"The columnar-equiaxed transition (CET) has been studied numerically under unsteady-state conditions using mathematical models that: (i) include a non-equilibrium undercooling at the columnar front;and(ii) describe the simultaneous evolution of the columnar and equiaxed zones.The results are discussed and compared with those produced by a steady-state analysis.IntroductionThe majority of the previous work on the columnar-equiaxed transition (CET) has concentrated on the production of equiaxed nuclei, regarding this as being the critical step in the formation of an equiaxed zone. Recently, the growth of equiaxed grains has been considered and this is not unreasonable because, for an equiaxed zone to be present, the grains must grow as well as nucleate. Since the growth rate of the grains will be determined by the thermal environment at and ahead of the columnar tips, it was decided to model the liberation and flow of heat during solidification to discover whether the various trends in the columnar range might be explained by their effect on the temperature profile throughout the casting. The models presented here for the solidification of a casting are the first to include the latent heat liberated ahead of the columnar front. Burden and Hunt (1) consider its effect only qualitatively, and although Lipton et al (2) adopt a criterion for the CET which is based on the thermal interaction of the columnar and equiaxed grains, they do not actually include the latent heat in their calculations.It can be argued that the latent heat liberated by the equiaxed grains in the bulk will retard the columnar dendrites in a casting: once the equiaxed grains are sufficiently well-established, the latent heat that they evolve could slow down the columnar growth to such an extent that the equi axed would dominate. Alternatively, the latent heat produced by the equiaxed grains might suppress further equiaxed solidification by raising the bulk temperature. The nature of the thermal interaction between columnar and equiaxed growth is not obvious, and because it is dependent on the material parameters and the dimensions of the system, it cannot be considered effectively in a qualitative way but has to be studied quantitatively: hence the need for the mathematical models discussed in the following pages. The results of the models are discussed in the light of a steady state analysis."

Jan 1, 1986

By G. A. Irons, D. Guo

"The average spout height and width produced by bottom gas injection in a water model of a steel ladle were measured with an image processing technique. It was revealed that the spout height could be described by a Gaussian curve. A combined SIMPLE -VOF model was developed to simulate the liquid surface and flow. The results showed that, though the model produced reasonable velocity distributions and free surface positions, the spout height due to the dynamic head of the rising liquid was substantially lower than observed, indicating that the bubble dynamics at the bath surface play an important role in spout height.IntroductionDue to the enormous importance of gas injection and stirring in metallurgical processes, there have been numerous publications on water and numerical modeling of such vessels. The free surface of the bath has received considerably less attention, despite its importance. At the free surface there are often important chemical phenomena occurring that require a good understanding of the fluid flow; these would include reoxidation of steel, metal splash and fume formation. Furthermore, to understand the details of slag-metal interactions such as slag entrainment, metal losses to slag and the transport phenomena associated with refining reactions, it is necessary to understand the plume and spout interactions first.There have been few experimental studies of the free surface of liquid in gas-injected ladles [1- 3], and even fewer on numerical modeling. Brimacombe and co-workers [1] studied the gas void fraction in the spout region, using a double-tip electrical resistance probe. This sensor cannot distinguish between gas in bubbles about to break and gas in the freeboard. Thus, it is a matter of judgement as to the position of the free surface. Schwerdtfeger and co-workers [2] used a single probe configuration with a wire and a counter electrode in the liquid, so that the height of the continuous liquid phase was unambiguously determined. Irons and co-workers [3] measured the spout height by ultrasonic and electrical capacitance techniques. These techniques were as reliable as the resistance techniques, but were restricted to low flow rates."

Jan 1, 2001

By James C. Foley, David K. Rehbein

"In-situ characterizations of green state part density and sintering state have long been desired in the powder metal community. Recent ·advances in non-contact electromagnetic acoustic transducer (EMAT) technology have enabled in-situ evaluations of the acoustic attenuation and velocity as sintering proceeds. Pure aluminum (99.999%) and aluminum alloy powders were prepared with high-pressure gas atomization (HPGA). The powders were pressed in a uniaxial die and examined with acoustic waves for changes in velocity and attenuation during sintering. The changes in acoustic properties were correlated with sample microstructures and mechanical properties. Evolution of the acoustic echo train during sintering is shown to provide information on the state of sintering as well as having the potential for detection of interior flaws.IntroductionThe versatility of powder metalallurgy (PIM) technology in the manufacture of complex shapes has enabled an increasing amount of wrought and casting production capacity to be converted to PIM technology. However, ultrasonic inspection of green components produced using PIM techniques remains a challenge and is not generally practiced [1]. Inspection of PIM components in the green state is highly desirable, because the green part can be reclaimed with only accepted components being subjected to further costly processing. Another potential benefit is characterization and greater understanding of the sintering process itself. An increased scientific understanding of the sintering process enables intelligent process control, greater reliability of the production process and a lower rate of rejection of the finished product. In order to realize these potential benefits, it is necessary therefore that accept/reject criterion be based on real time nondestructive evaluation of the green-state components and the sintering process.Most current nondestructive inspection techniques suffer from their inability to perform inspections below the near-surface region with the exception of X-ray and to some extent pulsed eddy current [2]. X-ray inspection requires extensive shielding of production personnel and expensive film and film processing. While development of pulsed eddy current techniques have lessened the impact of the well-known skin effect, the depth of penetration of the induced eddy currents remains somewhat of an issue [2]."

Jan 1, 2000

By T. Maruyama

The Tamano Smelter of Hibi Kyodo Smelting CO. ,Ltd. went into operation in 1972. The Flash Smelting Furnace that was originally adapted was equipped with electrodes that were attached to the settler substitute of the slag cleaning furnace. Later the development of our own original coke combustion technology was promoted and a new Tamano Type Flash Smelting Furnace (T-FSF), without electrodes, was put into operation in 1988. The technology of coke combustion and combustion the burner have continued to improve. As a result the copper losses in the slag have been reduced as well as a stable operation has been achieved. Furthermore, this has been accomplished while increasing the concentration feed and the matte grade The current objective is to continue to strive for high matte grade operation and to raise production efficiency while paying attention to the important subject of copper losses in the slag. In this report, the data related to the copper loss in the slag reduction are presented along with the influence of the thickness, settling time and coke. The recent operation conditions of the T- FSF are also presented.

Jan 1, 2003

By Cesar O. Gomez

A procedure has been developed for mounting at random particles of mineral samples to be characterized using image analysis. The procedure is based on the generation of a random distribution of sample particles in particles of a diluent material. and the embedding of this particle mixture in an epoxy resin without disturbing the initial distribution. Two materials with atomic number similar to that of the epoxy resin were successfully used as diluents: activated charcoal and graphite. The proportion of diluent material to be mixed with the sample to have a large number of mineral particles in the field of view while keeping the occurrence of touching particles at an acceptable level was determined empirically. The randomization achieved with the procedure developed in this work was tested using as samples known mixtures of silica and pyrite particles of the same sieve class. The agreement obtained between the mass ratio of minerals used in the preparation of a particular specimen and that resulting from image analysis demonstrates that the procedure developed is successful in producing a specimen where the embedded particles are randomly distributed.

Jan 1, 1988