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By Edgar Peek

Lixiviant regeneration is by definition a precondition for any hydrometallurgical process. In chloride hydrometallurgy either HCl or Cl2 has to be regenerated in order to establish an economically viable metallurgical process. One such regeneration process is widely used with steel pickling where HC1 is regenerated through the thermal decomposition of ferrous chloride in either spray roasters or fluid bed pyrohydrolyzers. This standard HC1 regeneration process deserves to be considered as a potential separation process, since thermodynamic calculations show that a fluid bed pyrohydrolyzer can function as a ferrous-nonferrous separator. Several nonferrous,metals such as zinc, lead and cadmium can be volatilized as a chloride under ferrous chloride pyrohydrolysis conditions. If such a nonferrous metal volatilization could be achieved in the case of slurry feeding of "contaminated" iron oxides, then this would increase the Fe/H2O ratio of the (process) feed and thus save on fuel per ton of iron, while yielding a marketable iron oxide product. Previous test work on synthetic materials revealed that the near-complete separation of zinc, lead and cadmium from iron oxide was possible in a pyrohydrolytic atmosphere, even if zinc was present as zinc ferrite (more than 99.5%). This investigation, which was carried out in a tube furnace at 1100 K has now been extended to treat synthetic zinc minerals and also franklinite ore. For the latter, it was found that 85% zinc volatilization could be achieved in 4 hours at 1300 K. It is postulated that complete zinc volatilization could not be attained due to the formation and/or presence of gahnite and hardystonite, which might be stable in HCl/H2O atmospheres at 1100 K. The effect of adding small amounts of calcium chloride to react with gahnite and hardystonite to give zinc chloride and both calcium aluminates and silicates is being discussed. Test work on slurry feeding of this complex ore in a recently constructed 4-inch diameter fluid bed pilot unit has been planned for the near future.

Jan 1, 1995

By C. A. Silva

Ladle change-over, during continuous casting of steel, initiates transient flow in the tundish which influences the inclusion content and degree of mixing between two consecutive batches of steel. The mixing behavior in the tundish during this period is determined by the casting rate and the ratios of: inflow to outflow during the refilling period; and, the low liquid level relative to the nominal level in the tundish during the transiency. A 3:10 scale water-model of a typical one strand slab caster was operated in conjunction with a tracer technique to characterize the velocity fields for several combinations of these parameters. Steady operation, a limiting case of the transiency, provided a basis for comparison. High-order moments -- skewness and kurtosis -- of the residence time density function have been utilized as signature elements associated with a particular residence-time distribution for the system. A simple mathematical model incorporating the above parameters as well as a characteristic Peclet Number was successful in simulating the features of the transient period.

Jan 1, 1993

By Lauri Holappa

Copper converting is mostly performed in Peirce-Smith converters. The process is still very similar to the original one developed in the early 20th century. It is a batch process in a horizontal cylindrical reactor with air blowing via tuyeres along the length of the reactor side. The Peirce-Smith converter has its roots in Bessemer's inventions in the 1850's as he tested both horizontal and vertical vessels for steel converting. However, for steel making a vertical pear-shaped converter with air bottom-blowing was established. In the course of time, there was a distinct necessity for oxygen usage instead of air due to harmful effects of nitrogen to steel properties and its cooling effect. In-bath blowing of oxygen did not succeed, however, and top-blown oxygen converter with oxygen lance (LD or BOF) was first developed in he 1950's and emerged rapidly to a dominating position. Somewhat later oxygen bottom-blowing via special shrouded tuyeres was developed (OBM or Q-BOP) but has attained only fractional share. Bottom-blowing technique had, however, impact on the current combined blown converters which adopted the benefits of both top and bottom blowing. In copper converting Peirce-Smith type converters have kept their position until today although new processes have been introduced and at least few of them seem to be emerging. In one respect copper converting has a clear leading position i.e. in the progress of continuous converting processes (Mitsubishi, Ausmelt). These processes utilise top-blowing lances instead of in-bath blowing tuyeres. A different principle for continuous converting is flash converting by Kennecott Outokumpu, which makes smelting and converting independent of each others. Solid ground matte is used as a feed for flash converting in a reactor shaft similar to Outokumpu matte flash smelting. A comparable process has been presented by Inco too. The paper discusses principal physico-chemical and process technical similarities and differences in copper and steel converting. Although these processes are metallurgically quite different it seems that during the modem history of ferrous and non-ferrous metallurgy, starting from the 1850's, the exchange of knowledge between these disciplines has been quite intensive. In long-term perspective, many similarities in the development can be found but also divergences due to different ambient circumstances.

Jan 1, 2003

By Veena Sahajwalla

The cupola furnace is a coke-fueled shaft furnace used as a primary melting unit in iron foundries. Control of chemical composition of the iron tapped from the cupola is a key factor in productivity and quality control. In an effort to develop a control model for the cupola, a fundamental approach based on physical and chemical principles has been taken to describe the melting process. The behavior of oxidation of the solid charge in the stack of the cupola has been studied. Sulfidation of the charge materials by sulfur-bearing components released to the furnace gases from the coke has been described. Carburization of metal droplets of iron and of steel in separate molten streams has been characterized. Finally, reactions with alloying elements in the hearth (well) of the furnace have been defined. These reactions have been described in a computer-implemented model developed to predict the composition of the iron tapped from the cupola. The model has utilized the thermodynamics and kinetics of the oxidation, sulfidation, and carburization reactions, including temperature and physical aspects, in the various zones of the melting unit. The model predictions have been compared favorably with operating results.

Jan 1, 1992

By Robert D. Rogers

The demand for phosphate will continue into the future, because phosphate is currently irreplaceable as a plant nutrient and in many chemical applications. Phosphate is not recycled, so the supply must be replenished through a process of mining and purification. Numerous microbial isolates. obtained from the environment were screened find those which demonstrated the greatest promise of solubilizing PO4 from the ore of interest. Screening was accomplished in a step wise manner an agar plate bioassay, shake flask studies, and semi continuous growth conditions. It was found that with the proper conditions of nutrient supply and solution pH; the bacteria and. fungus used in the semicontinuous process were able to solubilize in excess of 80% of an Idaho rock phosphate ore (RP) within nine days. A significant amount of solubilization occurred within the first six days. There was a 'reasonable correlation between the occurrence of soluble Ca and PO.4 during the processing of the RP thus providing evidence that the RP was being disintegrated by the organisms. In all cases, HPLC analysis of the solutions in which PO4 had been. extracted from RP showed that organic acids, which have been implicated as the mechanism of solubilization, were present.

Jan 1, 1991

By N. Menad

Thermal treatments of five different types of non-ferrous metallurgical wastes, under controlled atmosphere, were carried out at temperatures lower than 800 °C. The aim of these treatments was to reduce the toxic elements content and to increase that of valuable metals in the residue. <Best results were obtained by their treatments in air or hydrogen or successively both of them. Simple treatments using air or hydrogen of three samples allowed the elimination of more than? 95 % of their toxic elements and&apos; almost doubled their valuable metals&apos; concentration. For the rest two samples, combined treatment was necessary for their efficient decontamination and the concentration of valuable metals, in the treatments residue, to a reasonable value. Most of the solids issued from these treatments can be recycled in .the current non-ferrous metallurgical processes.

Jan 1, 1995

By Liming Wang

One of the steps in the extractive metallurgy of lead is a refining process called drossing. Hot dross is mixture of impurity compounds that form on the surface during the cooling of lead blast furnace bullion, and in Missouri, the main impurities are copper and sulfur. The slow cooling of bullion throws out of solution all other minor impurity elements (or their compounds) which are much less soluble at lower temperatures (mainly nickel, arsenic, iron, and zinc). The transfer of bullion from the blast furnace to the refinery and the subsequent hot drossing step cause fugitive emission of lead-containing fume and dust, which creates a plant hygiene problem. One cause of the emissions is the high vapor pressure of lead and its compounds during transmission of = 1000 °C bullion to the drossing kettle. Another cause is the lifting of dross dust during manual skimming of dross. The environmental problems associated with the traditional hot drossing process provided an incentive to investigate a new drossing process that avoids contact between plant air and hot bullion or dross. A key aspect of the process development was a detailed mineralogical examination of dross from two different bullions. The bullion samples were cooled at different rates, and the dross filtered out and examined. The morphology, phase identification, and composition of the dross was examined by optical and SEM microscopy. The principal dross phases were copper and cuprous sulfide, galena, a complex sulfide containing copper, nickel and lead, and speiss (containing nickel, cobalt, iron, copper, lead, and arsenic compounds). The copper was acicular, with nickel and arsenic in solid solution. The cuprous sulfide was largely digenite in a granular or dendritic form. A substantial part of the dross was solidified matte with a eutectic microstructure, consisting mainly of CU2S and PbS. Small particles (some of which had a eutectic microstructure) never floated to the surface of the lead during the slowest cooling rate, thus indicating that flotation of tiny matte droplets and dross crystals is exceedingly slow. The success in separating dross and lead by centrifugal filtration suggests its application in industry as a replacement for traditional hot drossing.

Jan 1, 1995

By Mahesh C. Meyer Jha

AMAX has developed a chloride refining process to produce pure nickel and cobalt metals from mixed sulfide .precipitates, Metal chloride solutions, generated in a hydrochloric acid leaching step and purified in a solvent extraction circuit, are converted to metal oxides .and HCI gas by pyrohydrolysis. A pilot plant consisting of a 30-inch diameter fluidized bed reactor and other ancillary units was designed, constructed, and operated for over one year. Process design was aimed at minimizing energy consumption, maximizing conversion efficiency, and achieving simplicity of operation and control. The operation provided valuable information on process scale up parameters, process control strategies, and materials of construction., Several process variables such as bed temperature, solution composition, solution feeding system, bed particle size distribution, and fines recycle system were investigated to determine their effects on process efficiency and the physical and chemical characteristics of the product.

Jan 1, 1985

By N. A. Barcza

DC plasma-arc technology using a hollow graphite electrode (cathode) has been successfully implemented in the primary metallurgical industry in South Africa up to the 30 MW scale. Mintek has applied its expertise base, established over the past fifteen years, to testing the treatment of metallurgical wastes such as carbon- and stainless-steel plant dusts, lead- and zinc-containing slags, and residues from the base-metal industry. Favourable results have been achieved, and disposable products were produced. The evaluation of numerous wastes indicates that recovery of zinc as metal gives the best economic return from these sources. Direct recovery via a splash condenser or electrolytic zinc extraction from fume are the two preferred alternatives under review. In both instances dehalogenation is an important issue, but can be achieved by suitable treatment processes. The Enviroplas technology provides a flexible, commercially viable approach to the treatment of a wide variety of wastes. Mintek, together with its associate Pyromet CC, are installing a plasma- arc pilot-plant facility with both an ISP lead-splash condenser of about 5 t/d condensed zinc capacity and a combustion chamber to burn zinc vapour to zinc oxide. This will demonstrate the suitability of the Enviroplas technology for treating specific metallurgical wastes, so that customized industrial plants can be engineered based on large-scale testwork.

Jan 1, 1994

By I. Gaballah

Spent hydrorefining catalysts may contain 4 to 6 % of COO and/or NiO, 8 to 16 % of Moo3 and up to 10 % V205 generally supported by alumina. Raw samples are roasted in order to eliminate carbon, sulfur and hydrocarbons contained in the spent catalysts. The roasting optimum temperature and time are 500 "C and 7 hours. Selective chlorination of roasted samples with Cl2 + air, Cl2 + N2 and Cl2 + CO is investigated in order to recover the valuable metals. Depending on the chlorination it is possible to recover more than 80 % of the Ni and Co about 95 % of the Mo and up to 80 % of vanadium compounds. Cobalt and nickel chlorides are obtained by leaching the chlorination residues&apos; by acidified water. Molybdenum and vanadium chlorides and/or oxychlorides are obtained by selective condensation from the vapor phase. The chlorination of the catalyst support, Al2O3, can be limited to less than about 5 %. Besides the reaction temperature and time, the oxygen partial pressure of the chlorinating gas mixture appears to be the key factor for the reactions&apos; selectivity.

Jan 1, 1993

By P. Heald-Wetlaufer

Doubly polished sections (i.e., sections polished on both sides) allow insights into complex paragenetic relationships, the interpretation of which is essential to understanding ore-forming processes. Alternate viewing of these optically superior sections in transmitted and. reflected light facilitates the recognition and definition of growth zones in ore and gangue minerals and the interpretation of postdepositional changes, such as hydrothermal leaching and replacement. Many such observations would escape detection by conventional petrographic methods. Our procedure for preparing doubly polished sections has evolved during the past 20 years and incorporates many standard procedures. Studies from such diverse districts as Creede, Colorado, Hokuroku, Japan, and the Upper Mississippi Valley zinc-lead district, southwestern Wisconsin, demonstrate the value of observations from doubly polished sections in constructing genetic models. The advent of doubly polished sections represents a major advance in the study of ore deposits and they should be a standard tool in every ore petrology laboratory.

Jan 1, 1982

By Kirsi M. Riihilahti

The oxidation characteristics of solid copper matte particles under simulated Kennecott-Outokumpu Flash Converting conditions are presented. This project is concerned with the determination of the effects of operating variables on the reaction of the particles. Experiments were carried out in a large laboratory-scale flash furnace with 72 wt-% Cu matte by varying initial particle size, temperature, oxygen partial pressure, oxygen-to-matte mass ratio and residence time. Chemical analysis was used to study the oxidation extent and copper volatilization. Particle fragmentation was examined. Fractional conversion and sulfur removal slightly decreased with initial particle size, while a higher oxygen-to-matte mass ratio mainly resulted in higher fractional conversion and more efficient sulfur removal. The fractional conversion values represented the overall extent of oxidation more closely than degree of sulfur removal.

Jan 1, 1997

By J. Brent Hiskey

Recently basic concepts of semiconductor electrochemistry and solid-state electronic structure theory have been applied to the dissolution of mineral electrodes. In this paper, fundamental aspects of semiconductor electro- chemistry and interfacial charge-transfer processes are reviewed. Information regarding the electronic and semiconductor properties of chalcopyrite is summarized. The electrochemical response of chalcopyrite in acidic solution is analyzed in terms of initial dissolution processes. The initial charge- transfer reaction involves the consumption of holes. It has been shorn that Fermi level pinning is consistent with observed electrochemical and dissolution behavior. Semiconductor electrochemistry has proved helpful in explaining the formation of intermediate surface films produced during the initial stages of chalcopyrite dissolution

Jan 1, 1993

By O. Barbosa F.

The thermochemistry of the systems SCN-H2O, Au-SCN-H2O and Ag-SCN-H2O is discussed. Potential-pH diagrams at 25°C are drawn for each system considering several sets of concentrations of the species involved. The information provided by the potential-pH diagrams is.complemented by distribution curves for each series of gold and silver complexes with thiocyanate. The analysis includes comparisons between the thiocyanate systems and the analogous cyanide systems, pointing out analogies and differences between the leaching of gold and silver with thiocyanate and with cyanide. The possibility of using soluble oxidizing agents such as ferric ions, hydrogen peroxide and Caro&apos;s acid is evaluated. The thermodynamic data used in the calculations and the chemical reactions represented in the Pourbaix diagrams are all reported in three Appendices. The overall results indicate the thermodynamic conditions for gold and silver leaching by thiocyanate.

Jan 1, 1989

By Thomas P. Battle

Ilmenite (iron titanate) is the source of over 90% of all the titanium produced in the world today. At some point during production of titanium dioxide or titanium metal the iron impurity must be removed. Too often it becomes a waste instead of a product. DuPont and MINPRO have developed a solid-state process which separates the iron and titanium components of ilmenite into different high-purity powders, which can be separated using conventional mineral processing techniques. The main reactor in this process is a unique high-temperature ball mill, where the iron segregates from the ilmenite lattice with the assistance of catalytic quantities of He\. The results of lab, pilot plant, theoretical, and scale-up studies are presented and discussed.

Jan 1, 1996

By T. T. Chen

Hydrometallurgical products are difficult to characterize because of their fine grain sizes, heterogeneity, often amorphous structures and water soluble or hydrated constituents. Such products are advantageously studied using complementary mineralogical techniques including >50, ore microscopy, SEM-EDX, electron microprobe analysis, selective leaching and wet chemical analysis to determine the phases and their morphologies, to identify specific element carriers, and to elucidate the chemical reactions occurring during the metallurgical process. Sample preparation is an important consideration for these materials. For extremely fine-grained particles, or soft and brittle products such as elemental sulphur, the study of loose powder mounts provides information not available from the examination of polished sections. To demonstrate the application of the various mineralogical techniques, commercial zinc roaster calcines and leach residues, copper refinery anodes and anode slimes, and laboratory bornite leach residues were examined in detail. The various sample preparation and mineralogical methods are presented, and the use of these complementary and practical mineralogical techniques to improve the understanding of a particular hydrometallurgical system is discussed.

Jan 1, 1989

By James C. Barker

Near Rainbow Mountain in the east-central Alaska Range an ultramafic complex forms a sill-like intrusion composed of dismembered bodies exposed along the south side of the Denali Fault and Broxson Gulch Thrust. The complex comprises dunite and peridotite with lesser gabbro, which together exhibit poorly defined, steeply-dipping compositional layering. The complex hosts four types of copper-nickel occurrences which have characteristic platinum-group elements (PGE), gold, and cobalt distributions. Three of the occurrence-types are considered to have formed as a result of primary mineral segregations which developed during intrusion of the complex. The fourth type of copper-nickel occurrence formed as a result of post-magmatic hydrothermal fluids at intrusive contacts. Scanning electron microscope examination indicates that PGE occur as micron-size telluride and arsenide minerals.

Jan 1, 1987

By T. R. A. Davey

The technologies of lead, zinc and tin extraction have made varying degrees of progress over the past twenty years. Producers of all metals have faced increasing demands for reduction of pollution and environmental degradation, and the level of public concern is rising rather than abating. New processing techniques must therefore be not only economically feasible, but politically acceptable, even when the demands of "conservationists" and ?environmentalists? are unreasonable. A new generation of processing techniques has come into being, which do not rely on an expensive sintering stage, nor use metallurgical coke, which is difficult to make without serious pollution. They utilise intense reactors, conveying materials from one stage to the next preferably within an enclosed space, obviating fume emissions, and avoiding heat losses as far as possible. The acceptability of the new techniques? is increased if lowgrade or complex materials can be treated, along with a variety of returns and wastes. In addition, a good selling and servicing organisation seems to be as important as good process technology in determining the spread of the new processes. In the field of pyrometallurgical refining the need is for more general application of several recently developed techniques rather than a search for alternatives to the existing process technologies. However, there is a need for fundamental work investigating the phenomenon of oxygen anode overvoltage in the electrolytic zinc process, in order to make progress in the further reduction of energy consumption. There is also scope for further development and application of vacuum distillation to up-grade thermally produced zinc. This paper presents a personal view of processes which should be developed to overcome existing problems, as we approach the turn of the century,

Jan 1, 1990

By T. T. Chen

Kidd Creek continuously-cast copper anodes are characterized by high levels of Se, Pb and Ag; the anode slimes constituents and their morphologies are controlled by both the anode composition and the casting process. Hollow Cu2Se spheroids and tube-like structures, enveloping Cu-Pb-As oxide and/or Cu2O, are present in the as-cast copper. During electrolysis, the selenides are liberated from the copper and accumulate in the slimes layer; the Cu2O and Cu-Pb-As oxide react rapidly with the electrolyte to form soluble species and PbSO4. Silver, which is present mostly as a solid solution in the anode copper, is also liberated during electrolysis and reacts with the Cu2Se to form (Cu,Ag)2Se. The ultimate composition of the selenides in the slimes layer depends mostly on the Ag and Se contents, but various other elements, including Au and Te, are also structurally incorporated. Although the selenides are the major Ag carrier, metallic silver also is present. A thin layer of Cu2O crystals sometimes forms at the copper surface, and may affect anode passivation. Copper sulphate is a common constituent and serves to agglomerate the slimes. Copper sulphate is present on both passivated and non-passivated anodes, but that observed on the passivated metal is present as a thick compact layer. Copper powder is associated with CuSO4.5H2O only on passivated surfaces.

Jan 1, 1987

By Richard D. Hagni

The techniques of reflected light microscopy and cathodoluminescence microscopy are uniquely suited to the study of the products from many important industrial problems. Ref1 ected 1 ight microscopy provides the means to rapidly identify the mineralogy of an industrial sample, determine the abundance of each phase, and examine the mineral intergrowths or textures. Cathodoluminescence microscopy is a relatively new instrument that provides the means to cause many minerals to cathodoluminescence under the microscopy. The cathodoluminescence of a mineral allows it to be readily distinguished from other phases that differ in cathodoluminescence but are similar in optical properties. Cathodoluminescence microscopy is especially useful to detect cathodoluminescence minerals that are present in only small quantities. Reflected 1ight microscopy and cathodoluminescence microscopy have been successfully applied in studies of beneficiation products, prediction of beneficiation and leaching problems, phosphatic iron ores and mill products, pyrometallurgical products, roasted refractory gold-bearing sulfides, ceramic build-ups, electric arc furnace and smelter dusts, and other industrial products.

Jan 1, 1993