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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

Published experimental data on thermodynamic behaviour of cobalt-containing slags have been reviewed and used in validating a recently developed thermodynamic model. The results from the exercise show that the model provides a reasonably good description of behaviour of cobalt in multi-component slag systems. The models for cobalt containing slags, matte and oxide solid solution phases were incorporated into CSIRO?s multi-phase equilibrium (MPE) package, which was used to calculate the equilibrium distribution of cobalt between matte and slag phases under various conditions. The results agreed well with the experimental data. Furthermore, the good agreement between the calculation and the plant data indicates that the operating conditions of industrial smelting and converting processes are close to equilibrium. Two diagrams showing the effects of slag chemistry and SO2and O2partial pressures on the distribution of cobalt between phases were generated for conditions similar to smelting and converting processes. These diagrams provide some useful guidelines for developing new strategies to improve cobalt recovery.

Jan 1, 2004

By S. Rolseth, J. Thonstad

The traditional electrolyte for aluminium electrolysis is based on molten cryolite (Na3AlF6), acting as solvent for the raw material, alumina (Al2O3). Over the years there has been a trend to increase the content of excess aluminium fluoride (AlF3) to the cryolite-based electrolyte, in order to enhance the current efficiency of the process. In most cases one has ended up at 11?13 wt% excess AlF3because higher contents makes it difficult to control the heat balance of the process. This problem may be overcome if sensors are developed that will allow online control of electrolyte temperature and composition, and we may then see a surge towards still higher AlF3contents. In the development of new anode materials to replace the carbon anode with inert, oxygen-evolving anodes, focus is on anode corrosion, and a low electrolyte temperature is then highly desirable. While the conventional process operates at around 960°C, electrolyte temperatures as low as 750°C are being tested. This is achieved by having large excess contents of AlF3(40 wt%). The consequences of using such electrolyte compositions are discussed.

Jan 1, 2004

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 M. Somerville, S. Sun

The liquidus temperature and viscosity of a range of melter slags produced in South Africa were determined. Drop-quench experiments were carried out on the supplied plant samples to determine the liquidus temperature and phase relations at sub-liquidus temperatures. The temperature measurement range covered 1300°C to 1630°C. Results from these experiments show liquidus temperatures for the melter slags to be in excess of 1500ºC with the chromium containing spinel as the primary crystalline phase. At lower temperatures, an olivine or pyroxene phase co-existed with the spinel phase. The viscosity of the slags was determined over a temperature range of 1350 to 1550°C, under a controlled atmosphere. Results show two orders of magnitude variation in the viscosity (0.2 to 20Pa s) with strong effects of slag chemistry and temperature. Slags with lower SiO2and Cr2O3concentrations were more fluid. Slags with the lowest FeOx and highest SiO2concentrations were the most viscous. These observations are in accord with general behaviour of silicate slags. While the presence of a spinel phase may have an effect on the viscosity of the melter slags, results obtained to date indicate a much stronger effect due to the presence of an olivine or pyroxene phase at lower temperatures. Keywords: phase equilibria, liquidus, viscosity, slags, olivine, spinel, pyroxene

Jan 1, 2004

By S. Pal, A. K. Lahiri

Most of the compounds present in slag are surface active. This gives rise to foaminess of slag. The foam life and foaming index are normally determined by the draining rate of slag through the plateau border, so the foaming index is directly proportional to slag viscosity and inversely proportional to slag density and bubble diameter. When a small amount of a strong surface active compound like P2O5or Cr2O3is present in slag, however, the foam life increases significantly and the above relationship is not obeyed. The strong surface active compounds reduce the draining rate from the film between the adjacent bubbles so the film draining controls the life of the foam. The thickness of the film, Marangoni force, viscosity of the slag, and diffusion of surface active compounds determine the film draining rate. The interplay of these factors leads to very low or high film draining rates and affects the film and foam stability significantly. Keywords: slag, foam, foaming index, film draining

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 P. Lundman, L. Rosengren, T. Brandshaug

Tunnel 99’, the Swedish National Road Administration´s (SNRA) general technical specification for road tunnels requires that the load bearing system must be designed to withstand specified design explosion loads. This paper presents the results of an SNRA study to provide a perspective of design analyses tailored to comply with the new requirement. The paper provides an example of a design analysis for assumed tunnel conditions using a numerical model. Dynamic predictions of potential damage to the rock mass and ground support system (rock bolts and shotcrete) from the specified explosion loads are presented including the nonlinear response of the shotcrete. “Tunnel 99”, qui fixe les règles de l’Administration nationale suédoise des Routes (Vägverket) concernant la conception et la construction des tunnels routiers, requiert entre autres que la structure porteuse soit capable de résister à certaines contraintes spécifiques résultant d’explosions. Cette étude présente les résultats d’une étude effectuée par Vägverket en vue d’obtenir une perspective d’analyses de conception spécialement élaborées pour se conformer aux nouvelles règles. Il contient un exemple d’analyse en fonction de conditions déterminées, basée sur un modèle numérique. Des prévisions de’études dynamiques de dommages potentiels subis par la masse rocheuse et les systèmes de soutènement (boulons d’ancrage et béton projeté) du fait des contraintes libérées par la force d’explosion spécifiée sont également présentées, y compris dans le cas d’une réaction non linéaire du revêtement en béton. “Tunnel 99” - die Vorschriften für Strassentunnel der Nationalen Schwedischen Behörde für Straßenwesen - (Vägverket) - fordern vom Tragsystem eine Auslegung in der Form, dass es spezifischen Explosionsbelastungen standhält. Dieser Artikel präsentiert die Ergebnisse einer Studie der Behörde, um einen Ausblick über konstruktive Auslegungen zu geben, die geeignet sind, die neuen Vorschriften zu erfüllen. Der Artikel zeigt ein Beispiel einer konstruktive Auslegung für eine angenommene Tunnelsituation mit Hilfe eines numerischen Modells. Voraussagen unter Beachtung der vollständigen dynamischen Berechnung zu potentiellen Schädigungen des Gebirges und des Ausbaus (Anker und Spritzbetonauskleidung) durch die spezifizierten Explosionsbelastungen, einschließlich des nichtlinearen Verhaltens der Spritzbetonauskleidung, werden gezeigt.

Jan 1, 2003

A physical modelling study has been carried out to simulate the slag-metal dispersion induced by a high-strength bottom gas injection. Water and kerosene were utilized to simulate metal and slag respectively. A water model of CLU (Creusot-Loire Uddeholm) vessel was used with three different nozzle orientations, namely, off-centre, triangular off-centre and centre. The gas flow rates changed from 0.00599m3/sec to 0.01081m3/sec. Height of heavy and light phases was kept fixed at 0.23 m and 0.02 m respectively. The dispersed phase holdup was determined at various axial and radial distances, gas flow rates, and tuyere configurations. The observations revealed that at a fixed gas injection rate, as the vertical distance increased in the centerline, straight off-centre orientation resulted in greater dispersed phase hold up values than those of the centre configuration and the triangular off-centre orientation. The dispersed phase holdup was found to increase with gas injection rate and decreased with axial distance. The variation of the dispersed phase hold up with the dimensionless axial distance and the gas injection rate was correlated by using the Modified Froude Number. The experimental values of the dispersed phase holdup were found to be in good agreement with the correlated values obtained from the modelling equations. The findings of the present study may be utilized in the ferroalloy refining vessels in terms of designing tuyere locations for optimum processing conditions.

Jan 1, 2004

By M. Sanchez, C. Morales, J. Palacios

The slag produced in the Peirce Smith converters at the Ilo smelter of Southern Peru Copper Corporation has shown a wide range of magnetite content, which introduces an additional problem in the smelting units due to materials? recirculation. However, the operation data analysis and the application of thermodynamic concepts have made it possible to produce slag with magnetite content between 18 and 20%. The results have suggested that matte grade enhances magnetite formation while silica controls its precipitation, and they are also influenced by the increasing temperature of the slag. Thus, in order to obtain the required magnetite content in the slag, matte grade is gradually enriched in equilibrium with slag containing from 25 to 32% silica.

Jan 1, 2004

By G. Akdogan, Q. G. Reynolds, S. J. Baumgartner

A computational model of a submerged arc furnace (SAF) used in the production of ferrochrome is presented. The model‘s intended use is to investigate the extent to which intrinsic and extrinsic properties of the raw materials affect burden distribution and electrical resistance within the furnace. The model is built on the discrete element method and calculates the mechanical interactions of particle distributions resulting from the flow motion of typical raw materials used in the smelting of chromium ore. This model excludes the effects of thermodynamics, furnace chemistry, and heat transfer. It illustrates how the consumption of materials (chromite pellets, flux, and reductant) is affected by changes in electrode length, reductant fractions, and reductant sizing and density during the formation of a reductant bed. The resistance calculation algorithm developed by Mintek was applied to construct networks developed from particle contacts, which can quantitatively generate estimates of the electrode-to-electrode and electrode-to-bath electrical conduction conditions.

Apr 16, 2024

By T. Lindstad, S. Gaal, S. Hansen, S. Prytz

The SINTEF SiO-reactivity test, developed by Tuset and Raaness in the 1970?s, is a recognised method of characterising the ?reactivity? of carbonaceous reactants, used in the ferrosilicon and silicon metal industries. Recently, the test has been updated, which has resulted in the development of an extended and improved SINTEF SiO reactivity test. This has included updating the test reactor, control system, data-logging, handling and preparation of carbonaceous materials to be tested and measurement procedure. The scientific basis has been re-assessed, resulting in a new interpretation of the test results. The repeatability of the test has improved significantly, especially through system automation. In the ?old? test, the kinetics of the reaction: SiO(g) + 2C(s) = SiC(s) + CO(g) for a specific carbonaceous material was characterised solely by the ?R10? parameter, the volume of SiO(g) which passes un-reacted through the coke-bed as the concentration of CO in the outlet gas decreases from 18 to 10%. As both the kinetics and obtainable conversion of SiO to SiC for a reductant is of importance to the ferroalloy producer, the new SINTEF SiO reactivity test ranks carbon materials both according to degree of conversion and reaction rate. From research carried out on the test in the past couple of years at SINTEF and NTNU, it has also become clear that some of the reactions taking place in the test reactor are more complex than previously assumed. As an example, it was previously assumed that the condensation reaction of SiO gas in the condensation chamber of the test reactor can be described as: 2 SiO(g) = Si(l,s) + SiO2(s). However, it has been established that the side-reaction: CO(g) + 2Si(l) = SiC(s) + SiO(g) causes approximately 10% of the total volume of CO to react to SiC and SiO2 in the condensation chamber. This means that some back-reaction i.e., the reverse SiO-generator reaction 3SiO(g) + CO(g) = 2SiO2 + SiC also takes place in the condensation chamber. In the new SINTEF test, the %CO versus time curves are therefore corrected in order to describe the effect of the reaction between SiO(g) and C(s) studied i.e., SiO(g) + 2C(s) = SiC(s) + CO(g). A correction-formula for this purpose is presented.

Jan 1, 2007

By M Lipalile, A B. Tunono, A W. Naismith

Konkola No 3 shaft experienced severe mining induced stress and time related deterioration in ground conditions in an area where an over-cut and bench (OCB) mining method was used to extract a shallow dipping wide orebody. This caused an unacceptable risk for safe mining operations to sustain the required levels of production. After a review of the conditions it was decided to change the mining method to CASCADE to recover ore in the affected area and modify the OCB method and use a modified over-cut and bench method (MOCB) for new mining sections. This paper describes the geotechnical criteria included to derive the mining standards for the MOCB. The geotechnical risks are identified and taken into account to develop stope design parameters, stoping sequences and support requirements. A monitoring programme to assess conditions as mining progresses is also discussed.

Jan 1, 2005

By A. B. Fox, R. P. Thackray, K. C. Mills

The role of mould fluxes in continuous casting is reviewed. The main functions of the flux are described and the importance of the flux in providing lubrication and the right level of heat transfer between the shell and the mould is described. The major problems of longitudinal, transverse and star cracking, gas and slag entrapment and deep oscillation marks in the steel product and ?sticker breakouts? are analysed. The important physical properties of the flux in combating these various problems are identified. Physical property data for the fluxes are given.

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

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

By M. Shapiro, L. A. le Grange, B. Henning

Effective pyrometallurgical process vessel design requires accurate assessment of the heat fluxes through the walls of the furnace. This is particularly important for freeze lining operation which is designed to protect refractory materials exposed to chemically corrosive molten contents, or facilitate high temperature operation when the refractory materials are used at conditions close to their service limits. Numerical modelling of fluid flow and heat transfer in process vessels is often used to aid in the design of process vessels. Sophisticated models are used to analyse the three dimensional flow and heat transfer predicting the effects of electrical heating, magnetic stirring, buoyancy, shear forces, various cooling effects and ultimately heat fluxes at the walls of the furnace and refractory. Traditionally these models are applied to the separate single fluid systems in a vessel such as the freeboard region including the arc, the slag region and the metal bath. Boundary conditions such as shear forces and heat fluxes between connecting regions such as the slag and metal bath are either estimated or carried over from separate solutions. Shortcomings in these traditional approaches include the estimation of sometimes critical boundary conditions leading to unreliable heat flux calculations. Also when boundary conditions are carried over between solutions, the process is difficult to set up, time-consuming and finally not fully coupled. In this paper the definition and results of a fully integrated numerical model of a complete arc furnace are presented. The most important mechanisms acting in an arc furnace were considered, including the fields of electrical potential, current, magnetism, momentum, heat transfer and radiation. Temperature dependant properties included electrical conductivity, density, viscosity, and thermal conductivity. The geometry consists of the freeboard, the arc, slag, metal baths and different refractory regions. Although the combined model of air, slag and metal would be defined as a multi-phase problem it is not solved as such. Instead the different fluids are separated by sets of special solid baffles. These baffles allow the implicit transfer of current, magnetism, heat transfer and shear forces between the different fluids and disallow mixing of the separate fluids. The strengths of the integrated model are threefold: Firstly, it provides robustness in defining the geometry and boundary conditions for the overall model. Secondly, it provides the capability to switch on and off individual mechanisms such as buoyancy, magnetic stirring and shear forces in order to observe their individual importance. Finally, it provides a useful tool in the design process through its ability to obtain results of parameter changes in short time scales.

Jan 1, 2004

By Y. Rajpal

The Hedley and Grant pillar strength formula is widely used within the South African mining industry to calculate pillar strengths in bord and pillar mining layouts, and is currently being used at Bathopele Mine. Bathopele is an operation of Anglo American Platinum near Rustenburg, mining the UG2 reef at depths ranging from 40 m to 300 m below surface. The formula includes a parameter K, which is a downrated uniaxial compressive strength value of the rock, used to calculate the strength of a pillar. At Bathopele Mine, for the shallower areas Less than 150 m the value was 33 MPa, but this was increased to 44 MPa due to the fact that rock mass conditions improved and there were no incidence of failure in the shallower areas. Underground observations showed pillars to be stable with no signs of failure, and it was questioned whether the design was not still too conservative, resulting in sub-optimal extraction ratios and consequently a loss of revenue to the mine. A trial mining section was started at the mine where the pillars were reduced from 6 m x 6 m to 5 m x 5 m and the pillar behaviour was monitored for the onset of failure. Numerical modelling was conducted using the TEXAN code to back-analyse pillar stresses in order to find a more realistic value for K. Results from the trial section indicated that the pillar design was in fact too conservative, and the value for K was adjusted to 54 MPa for future designs. This paper details the findings from underground monitoring and numerical modelling results, and includes details for further calibration of the K value in order to further optimize the extraction of the orebody.

Jan 1, 2012

By T. Watanabe, S. Hayashi, M. Hayashi, K. Nagata, H. Fukuyama

Chemical states of fluorine in CaO-SiO2-CaF2glasses in a composition range of CaO/SiO2=0.5?1.3 and 5?25 mol%CaF2have been investigated by 19F solid-state NMR with and without MAS. The isotropic chemical shifts of the glasses are close to those of cuspidine crystal (59.4 and64.3 ppm with respect to C6F6) and CaF2crystal (58.6 ppm). The fluoride ions are coordinated with four or less than four calcium ions in this composition range. The chemical shifts move to the lower frequency with an increase in the CaF2content, whereas those are not affected by theCaO/SiO2ratio. The ionic distance between calcium and fluoride ions increases with an increase in the CaF2content. The chemical state of fluorine is not disturbed by the degree of polymerization of the silicate network. Comparing the MAS and static NMR spectra, the second moment attributed to 19F-19F dipole-dipole interaction has been estimated. The values of the glasses range over 3.1?7.3107Hz2andthose are larger than the calculated value of cuspidine crystal. This indicates that fluoride ions form Ca-F clusters in the glasses and that the size of clusters increases with increasing the CaF2content. Keywords: chemical state of fluoride ion, CaO-SiO2-CaF2glass, solid state 19F NMR spectroscopy

Jan 1, 2004

By J. E. Nesset

The bubble size, together with the gas rate, determines the bubble surface area flux in flotation machines and, therefore, impacts directly on the kinetics of flotation. Understanding the variables that influence bubble size is one of the keys to understanding flotation recovery. Surprisingly, these relationships are poorly understood, largely due to the difficulties associated with gas dispersion measurements in industrial environments. The McGill gas dispersion sensors (bubble size, gas rate, gas holdup) are capable of reliably making such measurements. This paper reports on a study, using the McGill sensors in a 0.8 m3 Metso RCSTM pilot cell, which investigated the effect on bubble size of frother type and concentration, gas rate, temperature and rotor speed. A Denver laboratory cell was used to investigate the effect of elevation above sea level. Frother concentration proved to have the predominant influence on bubble size, and the effect of frother type can be normalised as a function of the critical coalescence concentration (CCC). Measurements made at many plant sites worldwide are compared to the model developed using the Metso RCSTM unit.

Jan 1, 2007