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By S. R. Sankaranarayanan, T. Sowmya

Slags and fluxes used in metallurgical processes are typically made up of oxides (especially silicates), with additions of fluoride and carbonaceous matter. Despite the efforts made towards understanding the role of slags in various processes, little information is available on the structure of these slags. Tools such as X-ray diffraction, spectroscopy, and electron microscopy could be used for this purpose. This paper is based on an ongoing spectroscopic and structural investigation of slags and related materials. Spectroscopic studies of various commercial slags (predominantly ferrous), ores, glass and related materials, covering a wide range of compositions, have been carried out to understand the structure. The infrared spectra were recorded, predominantly, using FTIR spectrometer (Bruker IFS 66U) spanning 4000 to 100 cm-1using the KBr pellet method. The resolution was typically 4 cm-1. The spectral outputs have been compiled in terms of bands present (corresponding to different bonds) and then compared with the typical bands expected for such bonds. Efforts are in progress to identify the trends with respect to the chemical composition?for example, the effects of SiO2, Al2O3, and non-bridging oxygens. Data obtained so far indicate some trends such as (i) a shift in the Si-O band (969 to 1099 cm-1) towards a higher wave number with increasing silica content (almost 2 to 92 weight percentage) and (ii) further strong shifts as a function of the alumina content. These are being further investigated structurally and in terms of chemical composition/parameters. Keywords: slags, silicates, structure, spectroscopic analysis, shifting of bands

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. Pei

PZH (Pan Zhi Hua) Iron and Steel (Group) Corporation, the biggest steel company in southwest China, has been using titanium-vanadium-magnetite as the main raw materials for blast furnace iron making processing for over 30 years. One of the problems that has a negative affect on the blast furnace operation is slag foaming. Based on the chemical components of the blast furnace slag-bearing higher TiO2, the foaming properties were studied. The TiO2content, which is calculated according to the total titanium content in all the forms of titanium compound in the slag, in this research is 30% weight per cent. Different forms of titanium compounds have different actions on the slag foaming behaviour that depends on the reduction condition in the blast furnace. The relationships among slag foaming performance and the binary alkalinity of the slag, the content of CaF2, MnO in slag, and the amount of gas injected in slag are investigated. The results show CaF2 and MnO have a stronger anti-foaming affect on the slag, even in the lower percentage. The way to measure high TiO2slag foaming performance and how to eliminate foamy slag are also discussed. Keywords: blast furnace slag bearing TiO2, foamy slag, foaming performance

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 C. Righi, R. Carli

In modern steel continuous casting technologies mould fluxes are well-known to assure lubrication required by tribological system of mould-solidifying strand shell, and to provide crystalline phase solid film, contributing to control heat extraction between strand and mould wall. Actual cooling rates during normal continuous casting mould operations are far higher than critical cooling rate of the liquid slag. Indeed, DTA measurements point out that even relatively small cooling rates of 30?50 K/min are high enough to give exiguous formation of crystals. In this paper, contribution of devitrification in defining crystalline phase formation of industrial basic mould slag, used in continuous casting of crack-sensitive steel grades, has been investigated by means of non-isothermal experiments study. Devitrification has proved to play a major role in mould flux crystallization in a working environment explaining the higher amount of crystalline phase formed in plant sample in comparison with lab sample from DTA analysis with typical cooling rate of 5?20 K/min. The amount of crystalline phases formed ranks as follow: Cuspidine > Combeite > Gehlenite. Kinetic analysis of DTA non-isothermal experiments has provided kinetic parameters through Kissinger and Ozawa methods, as Avrami constant resulting to be n ?2 and activation energy of Cuspidine crystallization resulting to be EC= 315 kJ/mole. The effect of addition to the parent material of oxides as MnO, TiO2, ZrO2, Al2O3 and Fe2O3near to saturation point has proved to affect, in certain cases, crystallization behaviour of mold flux. In particular, MnO, TiO2, ZrO2oxides produce a relevant dump of crystallization of Combeite and Gehlenite phases, while Al2O3and Fe2O3do not appreciably affect crystallization. Key words: Mould flux, crystallization, devetrification, DTA non-isothermal analysis, Kissinger and Ozawa methods.

Jan 1, 2004

By K. Ding

The thermodynamic activity of MnO was measured in MnO-CaO-MgO-SiO2slags that are typically encountered in the production of manganese containing stainless steels. Gas equilibration-quenching technique was employed in measuring the activities. Activity of Mn in Pt-Mn alloys were redetermined at 1600°C which reconfirmed earlier results of strong negative deviations. MnO activities were then measured by equilibrating slags of various compositions based on a statistical experimental design procedure with Pt-Mn alloys under controlled partial pressure of oxygen in MnO saturated platinum crucibles at 1600°C. Activities of MnO were found to increase with increasing concentration of MnO, basicity and CaO to MgO ratio. Two multi-coefficient repression models were developed to predict the activities and activity coefficients of MnO in slags at 1600°C. Keywords: activity, MnO, slag.

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

By J. -Y. Jia, G. -B. Qiu, C. -G. Bai, D. -F. Chen

Due to the great importance of the smelting process, it is essential to establish a calculation model on the viscosity of the slag system containing titania. In this paper, the calculation models of mass action concentrations and viscosity for the CaO-SiO2-TiO2slag system have been established according to the coexistence theory of the slag structure, as well as the referenced viscosities ofCaO-SiO2-TiO2at different temperatures and TiO2compositions. With the two models, corresponding calculated programs are made by means of programming language Matlab5.3, and the curves of viscosity of the TiO2concentration (?TiO2/%) at 1400°C, (R=0.9~1.0) are plotted. The results show that mass action concentrations of TiO2increases with increasing percentage ofTiO2, while the viscosity of CaO-SiO2-TiO2system is decreased. The results show that the models are in good agreement with the experimental and referenced data. They also shows that the models are reasonable for the CaO-SiO2-TiO2slag system. Keywords: coexistence theory; CaO-SiO2-TiO2slag system; viscosity ; calculation models.

Jan 1, 2004

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 J. Hop, A. Støre, T. Foosnæs

The carbon cathode for aluminium electrolysis is also part of the container of the process. In order to understand the behaviour and possible failure of the cathode, detailed material properties under operating conditions are needed. The paper reports experimental studies of bath and sodium in filtration, graphitization with time, loss of strength due to sodium, sodium expansion as function of pressure, as well as creep due to the developed stresses. As an example, sodium and thermal expansion data are used to calculate strain-stress models of realistic cell designs, and possible design weakness can be pointed out. Keywords: carbon, cathodes, sodium expansion, strength, graphitization, creep

Jan 1, 2004

By K. M. Godiwalla, S. Ranganathan

The thermal state in submerged-arc furnaces (S.A.F.) producing ferro alloys is important for the conditions of both the grade of alloy produced as well as specific energy consumption. The temperature profile in the S.A.F. is affected by the endothermic chemical reactions and the rate of gas evolution. The gas evolution commences at about 900 C due to the reduction of iron in the ore. A first-principle-based 2-D model has been developed to predict the temperature profile in the furnace. In this study, four ores of different grades have been considered in order to simulate the thermal profile in the S.A.F. The influence of the composition of the ore on the thermal profile and its significance in rationalisation of charge distribution to optimise the process are discussed.

Jan 1, 2007

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 L. Andrews

Nickel is recovered as a by-product of the platinum-producing process operated by Anglo Platinum. The metal is mined mainly as sulphide minerals contained in platinum ores. These pass through the concentrating, smelting and converting process route and nickel is finally recovered by electrowinning. Smelting of the concentrated ore in the electric furnace produces a melt with a high slag to matte ratio. The resulting furnace slag is granulated and later milled and floated to recover matte. A project was initiated to investigate the distribution of nickel in the slag in order to improve recovery. Slag samples were examined using a combination of chemical and mineralogical techniques. The granulated slag was found to consist mainly of a silicate glass phase, which reflects the composition of the molten slag in the furnace. Nickel occurs as free matte granules, as matte phases locked inside the glass, and in the glass phase itself. Whereas nickel in the matte is as sulphide, most of the nickel in the glass phase appears to be oxide- bound(i.e. in solid solution). Milled slag as flotation feed showed recovery-limiting features such as free matte with oxidized surfaces and unliberated matte inclusions in the slag. The biggest nickel losses, assuming no tapping problems, are in the glass phase solid solution. Only around 40% of nickel would be recovered from the slag, even under ideal conditions. Spoon and pot slag samples were also examined to see if casting and crushing would improve recovery. Although larger and therefore more easily recovered matte phases formed, nickel partitioned into crystalline silicate phases, limiting the maximum theoretical nickel recovery to 70%.

Jan 1, 2004

By R. T. Jones

Slags have been produced as by-products from pyrometallurgical processes for thousands of years, and have generally been regarded as waste. Many of these slags are no longer seen as residues merely to be discarded, but as potential economic sources of metals, or as useful by-products in their own right. Slag cleaning can enhance the recovery of valuable metals in existing pyrometallurgical processes, or can produce economic value from recycling old slag dumps. For example, a process has been developed and implemented industrially for recovering cobalt from copper smelting slag in a DC arc furnace. The relatively non-leachable behaviour of glassy slags allows them to be used as a very safe means of disposal of metallurgical waste streams, including many that are classified as hazardous. The high temperatures, reducing conditions, and good mixing that can be achieved in a DC arc furnace enable the effective functioning of this environmentally beneficial means of disposal. Lead blast furnace slag can be rendered safe for disposal by treating it using the Enviroplas process, which strips most of the hazardous lead from the slag (and traps the rest in an insoluble glassy slag) and recovers economic quantities of zinc by absorbing (in a lead splash condenser)the zinc vapour that is fumed off in the furnace. Another example can be seen in the recovery of a chromium- and nickel-containing alloy from stainless steel plant dust, while producing a disposable residual slag. The examples presented here illustrate that it is possible to develop processes that are both economic and environmentally beneficial. Keywords: DC arc furnace, plasma, slag cleaning, cobalt recovery, zinc fuming, Enviroplas, jigging, re-melting fines, environmental, economic

Jan 1, 2004

By M. Karsten

Platinum mines in the Bushveld Complex are located in areas with a high geothermal gradient. This means that, compared to, for example, gold mines of the Witwatersrand region, high rock temperatures are encountered at relatively shallower depths. Thus air cooling and refrigeration need to be considered at early stages in mine development. Another factor that influences air cooling and ventilation requirements is the use of trackless diesel equipment for loading and hauling broken rock. At shallower depths it will be more cost-effective to locate the cooling and ventilation equipment on surface, whereas for deeper mines the more cost-effective option is to locate cooling equipment underground. For intermediate depths, trade-off studies need to be undertaken to determine the optimum mix between more cooling and less air or more air and less cooling, as well as the optimum location for this cooling equipment. Factors that are taken into account include power requirements, positional efficiency, and additional infrastructure requirements. Traditionally the approach has been to ventilate ?all of the mine all of the time?. However, with increasing power costs and growing pressure to ensure sustainability, this strategy must be modified to apply ventilation and cooling on demand. In other words, both cooling and ventilation equipment should be operated only when needed and should be adjusted to the demand at the time. Obviously there will be areas that will need to be ventilated (and cooled) continuously (for example, for dilution of flammable gases), but this can be built in to the overall strategy. In addition, in devising ventilation on demand (VoD) strategies, occupational criteria relating to exposure to gases, noise, and heat need to be taken into account. This paper discusses options available for implementing energy-efficient ventilation and cooling systems and suggests ways of changing traditional thinking in the overall ventilation and cooling of mines. Efficient ventilation and cooling designs can play a major role in improving sustainability and reducing energy costs and carbon footprint.

Jan 1, 2012

By Helge Rosenberg

Up to now, Topsøe WSA (Wet gas Sulphuric Acid) plants have been in operation for almost 30 years, and close to 80 plants have been sold. In spite of its unique features and ability to treat gases without any prior drying, the WSA technology has had certain restrictions with regards to SO2 concentration in the feed gas, and the overall conversion of SO2 by catalytic means has been limited to approx. 99.7%. In commercial scale sulphuric acid production on the basis of elemental sulphur and metallurgical off-gases, there is a demand for higher SO2 conversion and treatment of gases with a higher content of SO2. Therefore Topsoe has further developed its WSA technology to cope with these demands. This paper will explain more about the principles of such new development and leave the delegate with a better understanding of the potentials of the new generation of the WSA technology from Topsoe.

Jan 1, 2009

By Helge Rosenberg

Up to now, Topsøe WSA (Wet gas Sulphuric Acid) plants have been in operation for almost 30 years, and close to 80 plants have been sold. In spite of its unique features and ability to treat gases without any prior drying, the WSA technology has had certain restrictions with regards to SO2 concentration in the feed gas, and the overall conversion of SO2 by catalytic means has been limited to approx. 99.7%. In commercial scale sulphuric acid production on the basis of elemental sulphur and metallurgical off-gases, there is a demand for higher SO2 conversion and treatment of gases with a higher content of SO2. Therefore Topsoe has further developed its WSA technology to cope with these demands. This paper will explain more about the principles of such new development and leave the delegate with a better understanding of the potentials of the new generation of the WSA technology from Topsoe.

Jan 1, 2009

By Alan Bye, Megan Little

Geology, and the detailed understanding of its properties, are fundamental to the optimal design and successful operation of any mine. To that end extensive fieldwork has been conducted at Anglo Platinum?s PPRust operation to collect geotechnical information both from exploration boreholes and in-pit mining faces. Since 1998, geotechnical data has been collected from over 337 km of exploration core, 7 km of exposed mining faces and more than 15 600 field and laboratory tests, in order to define the complete set of geotechnical properties for each rock type in the mining area. The geotechnical information collected is stored in two databases, SABLE Warehouse and MineMapper3D before it is imported into the Datamine mining software package. The geotechnical parameters, mining rock mass rating system (MRMR), uniaxial compressive strength (UCS), fracture frequency per metre (FF) and rock quality designation (RQD), are modelled using geostatistics to generate a 3D geotechnical block model. Data is interpolated between exploration boreholes and exposed mining faces and modelling is constrained, using wireframes, by rock type and structural features. By having detailed geotechnical information available in a 3D model that can be readily accessed and interpreted, significant production optimisations, feasibility studies and planning initiatives can be implemented. From a slope design perspective the model is used to target data deficient zones and highlight potentially weak rock mass areas. As this can be viewed in 3D, the open pit slopes can then be designed to accommodate the poor quality area before it is excavated. It also follows that geotechnical zones can be readily identified and the slopes optimised accordingly. Rather than viewing the drill and blast department as an isolated cost centre and focussing on minimising drill and blast costs, the fragmentation requirements of the comminution and load and haul business areas are studied. It is well understood that chemical energy is the cheapest form of comminution and that major downstream benefits can be derived by increasing drill and blast expenditure. 238 blasts were assessed to determine the optimum fragmentation requirements for ore and waste. Based on the study a mean fragmentation target of 150 mm was set for delivery to the crushing circuit and a mean fragmentation of 230 mm was set for waste loading from the pit. Substantial benefits have been realised in the drill and blast department by developing empirical correlations that relate the MRMR values in the geotechnical model to a blastability index, fragmentation, required powder factor and costs. As the geotechnical model can predict changes in geotechnical conditions, the blasting

Jan 1, 2007

By L. Holappa

Ferroalloys like FeCr and FeMn are mostly produced in submerged electric arc furnaces. Typical for these processes is that the amount of slag is quite high. The role of slag for the process is thus very essential and specific chemical, physical and electrical properties are required. Slags in FeCr process are Al2O3-MgO-SiO2based with minor contents of CaO and CrOx. Slags in FeMn process are principally similar originating from silicate minerals but can have quite a large composition range depending on the manganese ore and its gangue minerals. Characteristic for FeMn process is that the slag is rich in manganese oxide up to above 30%. A common feature is that the ?ore oxides?, CrOx and MnOxin slag are not only divalent oxides but also containing some higher valent of Cr3+ and Mn3+, respectively. In FeMn production conditions the slag consists mainlyMn2+. This is a clear difference from CrOx containing slags in which both two and three valent coexists in slags in FeCr process conditions. Oxidation state of the slag depends on the ambient oxygen partial pressure and temperature in the examined process. Thermodynamics of slags in ferroalloys production are discussed in terms of phase diagrams, activities and oxidation state of chromium and manganese oxides. Further, slag properties influencing reduction kinetics and furnace operation i.e. viscosity and electrical resistivity are discussed. Keywords: review, slags, ferroalloys, ferrochromium, ferromanganese, thermodynamics, physical properties.

Jan 1, 2004

By R. Hope, C. van Heerden

In any process or organization inefficiencies are costly. In times of abundance this reality often does not receive much attention. During such times the focus is rather on increasing capacity to increase production. However, there is a growing awareness in the world of tougher economic, social as well as environmental conditions, and enterprises find themselves facing greater demands for accountability towards shareholders, the environment and the public, as well as growing competition for market share and limited global resources. This reality is no different in ensuring a sustainable mineral sands operation. In order to achieve this, any operation needs to be stripped of all process as well as operational inefficiencies. In this context it has become essential for any Mineral Separation Plant (MSP) to have the necessary process monitoring and control systems in place to continually monitor and optimize the production of on-spec products and maximize operational efficiency and consistency. The MSP Grade Control Solution developed by Crusader Systems and running on top of the CSense platform contributes towards these goals by improving the consistent production of on-grade product. This allows the process to operate closer to the maximum allowable product grade constraint, which in turn maximizes production.

Jan 1, 2003