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By Du Sichen, K. Mukai, S. Seetharaman

Viscosities of slags constitute an important physical property needed for an understanding of the mass transfer phenomena in metallurgical processes. Viscosity is also the key that leads to a better understanding of the structure of slags. It is well known that the viscosities of silicate slags decrease with the addition of basic oxides due to the breaking of the silicate network. The measurements of slag viscosities often pose experimental challenges, especially to the choice of materials. The keynote lecture takes up the experimental problems and the various techniques adopted. Dynamic viscosity measurement, as a powerful tool towards an understanding of the kinetics of some high temperature reactions, is brought out. A number of semi-empirical models have been developed to estimate the slag viscosities in the case of multi component slags. A critical survey of these models is presented in the lecture. Earlier models by Riboud et al., Urbain et al. and Mills et al. have been developed further into a new generation of models. Some of the current important models are (1) Model by Iida et al. (2)CSIRO model (3) Pyro research Model (4) Model by Tanaka et al. (5) Model approach by Reddy et al. and (6) KTH-model. The predictions and capabilities of the various models are compared. Estimations of viscosities from thermodynamic data and prediction of liquidus temperatures from viscosities are presented. The concept of surface viscosities with reference to slags and viscosities of two-phase mixtures are also taken up in the presentation.

Jan 1, 2004

By A. Kondratiev

A structurally-based viscosity model for fully liquid silicate slags has been developed and applied to the Al2O3-CaO-‘FeO’-SiO2system at metallic iron saturation. The model links the slag viscosity to the internal structure of melts through second nearest neighbour bonds concentrations taken from the quasi-chemical thermodynamic model. This viscosity model describes experimental data over the whole temperature and composition ranges within the Al2O3-CaO-‘FeO’-SiO2system at metallic iron saturation and can now be applied to other industrial slag systems.

Jan 1, 2004

By L. Jeffrey

The Waterberg Coalfield has vast potential to become a significantmining and industrial centre in South Africa. Its future developmenthinges on a number of critical decisions that must be made jointly by government, power utilities and industry, and on some technical and economic challenges that must initially be overcome. Sufficient water is the primary key to enabling exploitation, together with an adequate market for the large volumes of low-grade coal. As the most likely consumer of this coal will be either a power station or a petrochemical complex, the need for additional energy will be a driving force in the development of this coalfield. Conventional mining methods can exploit the shallow coal resources in both the Grootegeluk and the Vryheid formations, but alternative technologies such as coalbed methane extraction and underground coal gasification are the only currently known technologies that may be able to exploit the deep Grootegeluk Formation resources. However, extensive research is still required into these procedures, particularly with respect to the Waterberg coals. Transport infrastructure to the region is currently not sufficiently well developed to support large-scale exploitation of the region?s coal resources. In particular, the railway line would have to be extensively upgraded to allow the increased export of coal. Alternative transport methods such as pipelines would also have to be pursued to serve a large Sasol-type petrochemical complex or coal gas extraction. The road network would also require improvement, as only the roads between the main commercial centres are currently tarred. Dr Con Fauconnier, Kumba CEO, concluded his presentation to the Investing in African Mining Conference 2004 with the words: Again, it?s all about infrastructure? when it?s there, it enables the development of bulk mining projects which attract the resultant economic benefits for the region and country as a whole. These words aptly sum up one of the stumbling blocks to the future development of the Waterberg Coalfield.

Jan 1, 2005

By O. F. Oxtoby, J. E. Olsen, M. W. Erwee, Q. G. Reynolds

"The extraction of molten products and wastes through smelting furnace tap-holes during the tapping process is a complex procedure involving many coupled thermophysical effects. Insight into the fluid flow behaviour in such systems can be gained by using computational mechanics tools to build highfidelity models of the fluid flow and other relevant physics. Previous work using such models indicates that the nature of the flow in the tap-hole, as well as operational parameters such as the tapping flow rate, depends strongly on the properties of the material being tapped and the geometry of the tap-hole channel. Additional complications arise when multiple fluid phases (for example, slag and metal) are present simultaneously, when porous coke beds hinder flow to the tap-hole entrance, and when the geometry of the tap-hole changes over time due to cycles of wear and repair. In the present work, challenges with the coupling of phenomena such as multiphase flow and porosity into computational fluid dynamics methods for tap-hole modelling are discussed in the context of electric furnaces used for ferromanganese production. Qualitative and quantitative results of computational models of flow through tap-holes are presented and compared as a function of material parameters to determine sensitivity effects, and in response to operational parameters to determine typical process behaviour over the duration of a tap. IntroductionPyrometallurgical production using electric furnaces accounts for substantial portion of the world supply of ferroalloys and other strategic materials (Degel et al., 2015). A range of different furnace designs may be used depending on the metallurgical process, with circular three-electrode submerged arc furnaces (SAFs) powered by alternating current being the most common for commodities such as ferromanganese and silicomanganese (Olsen, Tangstad, and Lindstad, 2007).As shown in Figure 1, manganese furnaces typically operate with a deep charge consisting of an upper layer of loose burden (onto the upper surface of which is fed solid raw material), a molten slag layer partially or completely filled with unreacted carbonaceous reductant (generally metallurgical coke), and a molten metal layer which settles to the bottom of the furnace due to its high density. The solid particles present in the slag and burden layers form porous beds which hinder the fluid flow of molten process material and gases inside the furnace (Olsen, Tangstad, and Lindstad, 2007).In order to remove material from the furnace during normal operations, a single tap-hole is built into the sidewall of the vessel near to the level of the hearth. Tapping involves removing both slag and metal phases through the same tap-hole channel, which makes tap-hole design, operation, and maintenance particularly complex. In the case of processes such as ferromanganese, which operate with no external gas injection or open arcs present at the furnace electrodes, flow of material out of the tap-hole is driven primarily by the hydrostatic pressure generated by the weight of the solid and liquid phases above the tap-hole."

Jun 1, 2019

By M. Görnerup, A. Kapilashrami, Seetharaman. S., A. K. Lahiri

Simultaneous reduction and foaming of chromium-rich slag have been studied in a laboratory furnace equipped with X-ray image analysis. Reduction of the metal oxides by graphite generated CO, which caused the melt to foam. The slag composition continuously changed due to reactions and dissolution of lining. Gas generation rate, foam height, and gas bubble size were studied and correlated to slag composition. Viscosity increased significantly during the experiments due to a change in slag composition. Bubble sizes varied little during the progress of reactions but differed considerably for different slags. Bubble sizes were largest for V2O5 containing slag, which is contrary to the general understanding that the presence of strong surface active agents reduces the bubble size. The foaming index did not follow expected trends for bubble size and viscosity, suggesting that foaming index is not a suitable parameter for discussion of foams under dynamic conditions. Keywords: slag, foaming, dynamic conditions

Jan 1, 2004

By T. Markus, K. Hilpert

Discharge vessels of advanced light sources are made of translucent polycrystalline Al2O3(PCA).These tubes contain salt mixtures, which essentially consist of metal halides. The salt mixture is present as a melt at the coldest spot of the vessel under operating conditions and vaporizes partly. The temperatures of the coldest spot range between 1200 K and 1300 K, depending on the lamp performance. The maximum wall temperatures range up to 1500 K and for special purposes up to1700 K. Important constituents of the melt are alkali halides AX (A = Na, Cs, X= Br, I) and rare earth metal halides LnX3(Ln = Dy, Ho, Tm). Severe corrosion attack on the wall material is observed in the PCA discharge vessels. The aim of this work is to elucidate the corrosion mechanism. Annealing experiments under well defined temperatures were carried out in order to understand the complex chemical corrosion processes. Two different annealing vessels were used, one for experiments under isothermal conditions with a temperature of 1473 K and one for experiments with a linear temperature gradient from 1450 K to 1600 K. The vessels were filled with salt mixtures of different compositions and annealed for 1000 h. The corrosion attack was characterised by XRD, analytical electron microscopy, high temperature mass spectrometry, and chemical analysis of the salt melts. The results of our investigations show that the corrosion attack is caused by vapour species and by the salt melt. The most severe corrosion is observed in vessels filled with mixtures of alkali halides and rare earth metal halides. No corrosion of the alumina is practically observed if pure alkali halides or pure rare earth metal halides are present in the annealing vessel. Keywords: thermodynamic, corrosion, lamps, metal halide salt

Jan 1, 2004

By T. Tamura

It is known that the CaO-FetO-P2O5slag system has a wide liquid miscibility gap at steelmaking temperatures and this two-liquid slag phase has many advantages such as high activities of both FetO and CaO and high amount of P2O5. The phosphorus distribution ratio between the two-liquid slag and molten steel was confirmed to be higher than that between CaOsat.-FetO-P2O5slag and molten steel. The two-liquid slag may be useful for dephosphorization of molten steel and reduction of slag volume. Furthermore, the phase equilibrium of two-liquid CaO-FetO-P2O5slagsaturated with MgO was measured to determine the applicability of the two-liquid slag to dephosphorization in steelmaking process. Keywords: slag, refractories, solid solution, two-liquid phase, dephosphorization, steelmaking, phase equilibrium.

Jan 1, 2004

By Z. Zhang, R. G. Reddy

Experimental and thermodynamic modelling studies on the structure of alkali borate melts and properties are discussed. A thermodynamic structure model for alkali borate melts is developed to describe the distribution of structural groups in the alkali borate melts as a function of composition. A qualitative interpretation for the boron anomaly in viscosity has been proposed, which regards the boron anomaly as a manifestation of the various antithetical effects caused by the introduction of alkali oxide into boric oxide. It has been found that the viscosity of alkali borate melts increases or decreases according to the changes in rigidity and spatial connectivity of the glass network structure, which is the function of temperature and composition. These concepts with some key examples are discussed in relation to their usefulness and practicality in industrial slags. Keywords: alkali borate melts; structural model; activities; structural groups; viscosity;

Jan 1, 2004

"For effective steel refining in the ladle (secondary steelmaking) the amount of steelmaking slag that is transferred from primary steelmaking must be limited, because the steelmaking slag contains iron oxide, manganese oxide, and phosphorus oxide. Adverse effects of slag carry-over include increased consumption of deoxidizers, phosphorus pick-up by the steel, and increased ladle refractory wear. Infrared imaging at longer wavelengths is an effective non-contact method to detect slag in the tapping stream. Various devices are used to shut off the tapping stream rapidly. These include slag darts, pneumatic slag stoppers, and slide gates for steelmaking converters, and eccentric bottom tapping for electric arc furnaces. IntroductionOxygen converters and electric arc furnaces are used for primary steelmaking. For both process types, the product (liquid crude steel) has a similar composition: largely liquid iron, with around 800–1000 parts per million (ppm, by mass) dissolved oxygen and low but significant concentrations of carbon, nitrogen, and phosphorus. The steel is tapped into a ladle, which serves as the refining vessel to adjust the final steel composition and temperature before casting.Some steelmaking slag is inevitably tapped with the liquid steel. The mass of steelmaking slag tapped with the steel is termed ‘slag carry-over’. Controlling and limiting slag carry-over from steelmaking is a primary requirement for clean steel production (Fandrich, Lüngen, and Wuppermann, 2008). Steel cleanliness refers to limiting the concentrations of dissolved impurities (such as nitrogen, oxygen, phosphorus, and sulphur) and of nonmetallic inclusions (oxides, sulphides, and nitrides) in liquid steel and in the final solid steel product. Of these, the strongest effect of slag carry-over is on the content of dissolved phosphorus in the liquid steel"

Jun 1, 2019

In ilmenite smelting, the FeO content of the feed material (nominally FeO.TiO2) is decreased by reduction with carbon. In a parallel reaction, a significant amount of the TiO2is reduced to Ti2O3.One of the striking features of these reactions is a consistent relationship between the extents of FeO and TiO2reduction; this relationship is independent of furnace size. It was recently proposed that this relationship follows from the solidification behaviour of the slag, where the final slag composition corresponds to the minimum melting point (?eutectic groove?) in the FeO-TiO2-Ti2O3phase system; the hypothesis is that solidification equilibrium with the freeze lining stabilizes the slag composition. If this is the case, the system of slag and freeze lining must be capable of correcting two types of disturbances: thermal and compositional. Thermal disturbances result from incorrect power input, for the feed rates of ilmenite and reductant. For example, excessive power input will tend to overheat the slag, causing the freeze lining to melt partially, establishing a new steady-state heat loss from the furnace. Compositional disturbances result from an incorrect reductant input for the given power and ilmenite input. In this work, the dynamic response of the slag and freeze lining to different inputs (flow rates of ilmenite and reductant, and power input) is modelled. The model is based on solidification equilibria, and quantified heat loss through the freeze lining. The conclusion is that the solidification equilibrium cannot constrain the composition to the eutectic groove for typical operating conditions. Keywords: ilmenite smelting, freeze lining, solidification, high-titanium slag

Jan 1, 2004

By V. Coetzee

In 1992, a paper was compiled highlighting a common-sense approach to electric smelting at Impala Platinum. Since then, the smelter complex has undergone considerable changes. Mineral economics, UG2 exploitation, and changing environmental legislation have enforced numerous process upgrades, yet a common-sense approach has always been adopted. This document details the major changes in the smelter complex at Mineral Processes (Minpro) over the past 15 years, and provides the rationale for the changes. Keywords: Pyrometallurgy, furnace, PGM, platinum, nickel, copper, electric smelting, six-in-line, Peirce-Smith, Impala Platinum.

Jan 1, 2006

The effect of composition on electrical conductivity (resistivity), viscosity and liquidus temperature of the slags encountered in electric smelting of PGM containing suphide concentrates is reviewed, along with the relationsip between slag composition, slag-matte separation and metal losses to slag. Optimization of slag composition at furnace temperature is attempted on the basis of opposite and parabolic trends of the viscosity-conductivity relationships of the slags. The importance of surface tension of slags is emphasized using available and estimated information which are grouped into a useful correlation. These values are coupled with or incorporated into slag viscosity plots to illustrate the correlation between the two factors, which influence slag-matte separation as well as refractory attack. The electrode in the slag-resistance furnace is the central factor in the design and operation of the furnace by its role of conveying the smelting power. The obvious parameters are the size and positioning in the slag bath, which are defined by slag resistively, furnace resistance, cell constant and power input. The flow of heat generated by the electrode current determines the energy distribution and furnace dimensions creating viscosity profiles, which in turn affect flow conditions. Thus the flow of slag and matte are discussed in conjunction with the furnace geometry, stirring action of the electrodes, buoyancy and electromagnetic effects. The action of the electric furnace as a settler is discussed. The rectangular furnace is considered as a channel reactor in this analysis, and the action of the electrodes is described to indicate a balanced settling rate in the area of electrode action. Discussion of the design and production capacity of the electric furnace, with reference too perating current, power input, furnace dimensions and electrode size, are based on considerations derived mainly from slag properties such as its resistively, viscosity and liquidus temperature.

Jan 1, 2004

By S. H. Yi, J. R. Kim, Y. S. Lee

The viscosities of CaO-SiO2-Al2O3-MgO-FeO slags were measured under conditions ofCaO/SiO2=1.15–1.6, 10–13 percent Al2O3, 5–10 percent MgO and 5–20 percent FeO. Slag viscosity decreased with increasing FeO content at a fixed basicity (CaO/SiO2) of slag. Slag viscosity at low FeO (<7.5 percent FeO) exhibited a minimum value by increasing MgO content in slag. Viscosity decreased with increasing slag basicity up to 1.3 while it increased as slag basicity increased from 1.3 to 1.5. Thus, it was proposed that the driving force for the decreases of slag viscosity would be an increase in depolymerization of silicate network at C/S=1.3, while the viscous behaviour at C/S>1.3 would be increased with increasing the chemical potential of primary solid phase e.g. dicalcium silicate. A thermodynamic approach for the activity of primary solid phase in molten slags resulted in a reasonable relationship between viscosity and slag components. Therefore, it was confirmed that slag viscosity in basic slags system (C/S>1.3) could be determined by the chemical potential of dicalcium silicate. Keywords: viscosity, basicity, bosh slag, blast furnace, slag structure, FT-IR

Jan 1, 2004

By M. Magnelöv, Du Sichen, U. Sjöström

An experimental study has been performed to investigate the behaviour and separation of inclusions at the interface between steel and slag. The study has been limited to liquid inclusions because they can be a potential problem in transient situations such as ladle changes in continuous casting of steel. Model experiments with water and silicon oils have been carried out to study the kinetics of separation of simulated inclusions at an interface. The properties of the inclusions and the slags have been varied by using different oils with different viscosities, densities and surface tensions. The effect of temperature of the liquids has also been examined. Measurements of the terminal velocity, rest time and the behaviour of the liquid inclusions at the interface have been recorded using a video camera. It has been found that the inclusions reach their terminal velocity early in the vessel and the experimental velocities differ somewhat from the values evaluated using ?intermediate law?. The results from the experiments have shown that the size of the inclusions has no appreciable influence on the rest time. Droplets of AK50 oil have been found to have considerably long rest time. A water film surrounding the droplet has been expected to be the main reason for the long rest time. The present study has also shown that the viscosity of the oil has certain effect on the rest time, but only to some extent, since viscosity has double functions. A higher viscosity provides higher resistance to the droplet entering the oil phase leading to longer rest time and at the same time damps the lateral movement of the droplet along the interface, leading to easier stabilization and shorter rest time. On the other hand, a high viscosity of the oil phase results in slow dissolution process. It has been concluded that a meaningful model of inclusion separation at the metal-slag interface must take the interfacial phenomena into consideration. Keywords: Inclusions, terminal velocity, rest time, dissolution.

Jan 1, 2004

By A. D. Pelton, Y. -B. Kang, S. A. Decterov

Computerized thermodynamic databases for solid and liquid metal, slag and solid oxide phases in the Al2O3-CaO-CoO-CrO-Cr2O3-FeO-Fe2O3-MgO-MnO-NiO-SiO2-S system have been developed by critical evaluation/optimization of all available phase equilibrium and thermodynamic data. The databases contain parameters of models specifically developed for molten slags, liquid steel and solid oxide solutions such as spinels, pyroxenes, olivine, monoxide (wustite, periclase, lime), corundum, etc. By means of the optimization process, model parameters are found which reproduce all thermodynamic and phase equilibrium data within experimental error limits. Furthermore, the models permit extrapolation into regions of temperature and composition where data are not available. The databases are automatically accessed by user-friendly software that calculates complex equilibria involving simultaneously slag, metal, refractories and gases, for systems with many components, over wide ranges of temperature, oxygen potential and pressure. A short review of the available databases is presented. The critical evaluation/optimization procedure is outlined using the Al2O3-CaO-FeO-Fe2O3-SiO2and Al2O3-CaO-MnO-SiO2systemsas examples. Several applications of the databases to deoxidation of iron and to inclusion control in steel are discussed. Keywords: thermodynamics, phase equilibrium, phase diagrams, databases, ferrous metallurgy, steelmaking, inclusion control, slags, oxide systems.

Jan 1, 2004

By H. Hamma, R. Fehrmann, M. Gaune-Escard, G. Hatem, S. B. Rasmussen, K. M. Eriksen

The molten salts M2S2O7and MHSO4, the binary molten salt systems M2S2O7-MHSO4and the molten salt-gas systems M2S2O7-V2O5and M2S2O7-M2SO4-V2O5(M = Na, K, Rb, Cs) in O2, SO2and Ar atmospheres have been investigated by thermal methods like calorimetry, Differential Enthalpic Analysis (DEA) and Differential Scanning Calorimetry (DSC). Fundamental thermodynamic data like temperatures and molar heats of solid-solid transition and fusion, phase diagrams, heat capacities of solids and liquids, heat of mixing, and heats of complex formation have been obtained and are reviewed here. Also EPR spectroscopic evidence of V(IV) complexes and their structure are reported and the results are discussed in relation to the mechanism of SO2oxidation by V2O5based industrial catalysts. Keywords: Alkali pyrosulfates, alkali hydrogen sulfates, vanadium pentoxide, EPR spectroscopy, complex formation

Jan 1, 2004

By Hao Li, Allan Moss, Richard K. Brummer

At the Palabora Mine, the transition to caving 400 m below the bottom of the 800 m deep pit resulted in a slope failure of the North wall that began in 2003, and is still mobile. This failure can be explained by the daylighting into the cave zone of a prominent joint set. The failure was modelled by the 3-dimensional code 3DEC, which is capable of modelling the nonlinear behaviour of discontinuum materials with large displacement.

Jan 1, 2006

By G. Westcott

Impala Platinum, the second largest platinum producer in the world, is embarking on a major expansion strategy to increase its platinum output from 1.95 moz to 2.8 moz by the year 2008. The smelter complex, situated in Rustenburg, will undergo substantial modifications, and will require a solution to the capture and treatment of the smelter off-gases and dust produced during smelting and converting operations. One of the solutions explored was an integrated approach, where all the off-gases from both the primary smelting electric furnaces and the converter operations are routed to a large central gas cleaning and double catalysis, double absorption acid plant. In-line sulphur burning, utilizing a highly flexible LURO1spin cup burner with a turn down ratio of 50%, ensures that the acid plant operates independently of operating conditions at the smelter complex.

Jan 1, 2007

By H. Krogerus, P. Niemelä, P. Oikarinen

High carbon ferrochromium is produced by carbon reduction. No replacement for carbon as reductant has yet been developed. The reduction creates a considerable amount of CO-gas. In open and semi-closed furnaces the gas is burned when leaving the burden. In closed furnaces the formed gas is sucked out by a fan, washed and utilised as fuel. The formation of carbon monoxide is presented briefly starting from thermodynamic considerations up to solid and liquid state reduction. The volume, composition and energy content of the furnace gas are discussed, focusing on the raw materials and pre-treatment processes of the furnace feed as well as on the process equipment and control. Outokumpu has been using closed and sealed furnaces and utilising the CO-gas in its Tornio Ferrochrome Works since 1968. Today in Tornio with an annual ferrochromium production of 260 000 t CO-gas production is 186 million m3, representing 68 MWh an hour. At the same time the furnace power input is 95MW. About 98 % of the CO-gas is utilised, whereof 30% in the ferrochrome production itself. This paper focuses on the characteristics and utilisation of CO-gas. CO-gas is secondary energy, which on one hand saves primary electric and fossil fuel energy in ferrochromium production and, on the other, replaces other fossil fuels at the adjacent steel works. The characteristics of the fuel, requirements for utilisation as well as health and safety aspects are discussed. Utilisation of the gas has a high impact on the total dust and gaseous emissions and on the energy optimisation at the ferrochromium and steel works.

Jan 1, 2004

Experimental studies on viscosity of titanium bearing slags have been reviewed and the assessed data were used in extending the capability of the structurally related viscosity model for silicate melts, developed by the present authors. Experimental data on ternary and higher order systems containing CaO, MgO, MnO, FeO, Al2O3, TiO2, Ti2O3, SiO2were assessed and used. The newly extended viscosity model represented the viscosity behaviour over broad temperature and composition ranges. The structural role played by TiO2and Ti2O3in silicate network structure is discussed with respect to their effect on viscosity of melts. Keywords: viscosity model, TiOx containing silicate melts, silicate network structure.

Jan 1, 2004