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By Du Sichen, S. Seetharaman, A. Jakobsson

"In the Present paper, the principles of oxygen potential measurements have been discussed along with the design details for oxygen sensors that are used in copper industry. A description of some of commercial probes is presented along with their salient features. The application of these sensors in flash smelting, converter and casting sections of copper production are discussed along with their implications on process optimization.I. IntroductionThe high temperature galvanic cells have come into prominence on account of their numerous applications in both fundamental as well as applied measurements. Since the inception of the oxygen-ion conducting electrolytes like ZrOrCaO·by Kiukkola and Wagner [1], the oxygen concentration cells have been extensively used in laboratories as well as in industries. In metal-production technology, these cells have been used to monitor the oxygen potentials in metallic, slag as well as gas phases and also to control and styr metallurgical processes. The pioneer among the various industrial users of such cells is the copper industry. To-day, high temperature solid electrolyte cells involving oxygen ion conducting electrolytes have become an integral part of copper pyro-refining and continuous casting. In the present paper some of the applications according to the industrial processes are described including the developments that are going on in the European scene."

Jan 1, 1997

By I. Gaballah

About forty percent of the SOx emissions are generated during the processing of metal sulfides of Cu, Pb, Zn, Ni, etc. Although new technologies for metal sulfide's smelting allow the production of H2S04 with a reasonable cost and decrease the emissions of sulfur oxides, the generated quantity of SOx is considered as a serious threat to environment. This paper suggests alternatives for low temperature processing of complex sulfide ores or concentrates 'CSO or CSC' under neutral, reducing and chlorinating atmospheres or their combination. At T > 400 "C, The neutral and reducing treatments allow the decomposition of pyrite and the partial recovery of sulfur as So and H2S. At 300 "C, the chlorinating treatment of CSC is fast, exothermic and allows the separation of FeC13 from the valuable elements' chlorides. It also generates SyCIx that can be either reduced by H2 or hydrolyzed in presence of sodium sulfide. The recovery rate of elemental sulfur with respect to the sulfur input exceeds 90 %.

Jan 1, 1999

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 I. Perus, M. Fazarinc, G. Kugler, M. Tercelj

"Ledeburitic tool steels are highly alloyed steels used for specific highly loaded applications but are characterized by low and variable hot workability. In this contribution the importance of selecting the right choice of some essential process parameters, i.e. casting temperature, solidification rate and soaking temperature, needed for improving the intrinsic hot deformability of ledeburitic tool steels, is studied. An inappropriate selection of casting temperature and cooling rate results in precipitation of unusual eutectic carbides that decreases the hot workability, whereas with the selection of appropriate soaking temperature the temperature range of safe hot working can be broadened. For each initial as-cast microstructure individually determined soaking temperature should be selected.IntroductionThe surface cracking during hot deformation of ledeburitic tool steels reduces mechanical properties and their industrial yield. These tool steels have high hardness, wear resistance and high tempering resistance on one hand, and high flow stresses and low hot deformability on the other. Decreased hot deformability of the tool steels is attributed to the type, size, shape, distribution, fraction of eutectic carbides and/or other phases, grain growth, etc. at upper limit while precipitation of secondary carbides and decreased recrystallization rate at lower limit of the safe hot deformation temperature range, [1-6].The occurrence of cracks on most exposed areas of workpiece are related to the areas where similar conditions related to upper and/or lower limit of temperature working range prevail, i.e. areas with accelerated cooling, areas with higher value of accumulated strains where also decreased recrystallization rate with simultaneously presence of higher tensile stresses takes place, furthermore areas of workpiece which are due to combustion conditions in furnace heated to higher temperatures, etc. Thus the areas, where combination of previously mentioned conditions prevails, are more exposed to cracking. This additionally requires that hot deformability of ledeburitic tool steel should be considered as a complex problem. Publications in the literature with regards to hot deformability of tool steels are predominately of a partial nature thus all reasons for unexpected occurrence of cracks are not sufficiently explained in available literature so far. Furthermore modern practice proves that previous processing parameters significantly influence the hot deformability and thus this cannot be considered as a constant value. During heating, soaking and hot deformation various processes take place: decay (decomposition) of carbides, formation of new carbides, dissolution of carbides and of alloying elements, etc. Thus depending on variation of process parameters and chemical composition, that consequently influences the processes related to carbides, shifting of decreased deformability at both limits of temperature working range to higher and/or to lower temperatures can occur, [1-14]."

Jan 1, 2012

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 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 D. Lui, B. G. Thomas, B. Ho

"Results from mathematical models and plant experiments are combined to quantify the effect of transverse depressions and oscillation marks on heat transfer in the continuous casting mold. A heat transfer model has been developed to calculate transient heat conduction within the solidifying steel, coupled with the steady-state heat conduction with the continuous casting mold wall. The model features a detailed treatment of the interfacial gap between the shell and mold, including mass and momentum balances on the solid and liquid powder layers. The model predicts the solidified shell thickness down the mold, temperature in the mold and shell, thickness of the resolidified and liquid powder layers, heat flux distribution down the mold, mold water temperature rise, ideal taper of the mold walls, and other related phenomena. The important effect of non-uniform distribution of superheat is incorporated using the results from previous 3-D turbulent fluid flow calculations within the liquid cavity. Results from plant experiments confirm that transverse surface depressions and oscillation marks form at the meniscus and move down the mold. Measurements of mold thermocouple temperatures and breakout shell thickness were used to calibrate the models. The results indicate that the surface depressions and oscillation marks are filled with mold flux, but still have a significant effect on decreasing heat transfer. The predicted mold temperature fluctuations are consistent with measurements. If the depressions become filled with air, their effect is greatly increased. These results should be useful in the difficult task of interpreting transient mold thermocouple signals for on-line quality monitoring.IntroductionMany different types of intermittent surface defects on steel slabs arise during initial solidification in the mold of the. continuous casting machine. These defects include deep oscillation marks, surface depressions, and cracks. They may lead to quality problems, such as slivers, in the final rolled product. In severe cases, breakouts may occur, where liquid steel bursts through a thin section of the shell and drains over the casting machine below the mold."

Jan 1, 1997

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 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 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'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 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 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 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 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 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 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 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 Anupam Madhukar

The essence of an atomistic unified kinetic model of strained thin film growth and defect initiation is presented along with a comparison of its consequences obtained from computer simulations with experiments. Within the competing kinetics of a strain dependent activated incorporation of atoms and an asymmetry between upwards and downwards inter-layer migration, the model provides a consistent description of 2D versus 3D morphology evolution accompanied by the appearance of surface vacancies and steps at no energy cost. The correlated migration of these precursor defects offers an atomistic mechanism for the emergence of surface half-loops from the growth front (thus accounting for configurational and thermal entropy) governed by activation energies closer to their correlated motion under the evolving strain fields and thus substantially less than those calculated with respect to the perfect crystal as the reference state. The essential mechano-chemical nature of the problem is compared and contrasted with the historical literature of such phenomenon as precipitation hardening and sintering in metallic and ceramic composites.

Jan 1, 1994

By Sepp Härkki

The energy crisis in Finland after World War I1 together with a sharp rise in the price of energy caused Outokumpu Oy to consider replacing the electric furnace smelting of copper concentrates by some other method. The flash smelting method developed under these circumstances offered a considerable saving of fuel through the utilization of the reaction heat of sulphides and yielded a high recovery of sulphur in the form of acid. The pilot plant testing of the new process was carried out in the years 1947 - 1948. The process was adopted for the smelting of copper concentrates (1) (2) (3) on a commercial scale in 1949 and applied successfullv to the smelting of -nickel concentrates' at the Harjavalta Works in 1959 (4) (5) (6). In 1962 Outokumpu adopted another type of flash smelting where elemental sulphur is recovered from the gases after the thermal decomposition of pyrite in the flash smelting furnace (7) (8): In recent years, the copper-nickel flash smelter and pyrite process have been combined to produce elemental sulphur instead of SO2 from the smelter gases (9) (10). The basic idea of the Outokumpu flash smelting process for sulphidic ores is that the conventional methods with separate roasting and smelting operations are replaced by a combined roasting, smelting and part-converting process carried out in one unit. The heat generated from the exothermic reactions can thus be used for smelting the ore so that only a small amount of additional fuel is needed. The characteristic of the method is also that the dried, fine-grained concentrate is smelted in suspension, which offers the best conditions for rapid reactions. The recovery of waste heat from the furnace off-gases had been considered already in the original flash smelting system. A

Jan 1, 1976