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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 S. E. Olsen, M. Tangstad, G. Tranell, K. Berg, S. Gaal

In this study, the reduction behaviours of MnO and SiO2containing slags by solid carbonaceous materials was investigated in both small and larger-scale laboratory experiments. Five types of carbonaceous material were investigated: 2 graphites, industrial coke, anthracite and eucalyptus charcoal. The effects of the reductant type/properties on the reduction kinetics, metal composition and metal yield, have been quantified. Results show that the reduction rate is highly dependant on the type of carbon used. It was found that the reductant type significantly influenced the SiO2reduction while it did not seem to have a large effect on the MnO reduction. This may be due to the different CO2and SiO reactivities of the materials.

Jan 1, 2004

By P. J. D. Lloyd

The widely employed IPCC models for the release of methane from underground coalmining operations are reviewed, and put in the context of the South African National Communication on greenhouse gas emissions. Then attempts to calibrate the model via measurements on South African coalmines are described. These attempts failed because it rapidly became clear that the IPCC model, involving methane adsorbed by the coal and released (a) by the depressurization of the strata caused by mining, (b) from the broken coal and (c) from coal remaining in roof, floor, pillars or goaf after mining, was not valid. Instead, measurements showed that the methane release was very variable, sporadically falling to zero. Carbon dioxide concentrations were monitored at the same time as methane, and followed methane concentrations. An alternative model was developed, in which methane was largely displaced from the coal and held in fissures, cleats and pores, which, when intersected by mining, released methane into the ventilation stream. In a key test of this hypothesis, methane concentrations around a continuous miner were monitored both during operation and after shutdown. Even during operation, methane became undetectable. It is hypothesized that heating of the South African coal-seams during the emplacement of the igneous dykes that cut so many of the seams caused displacement of the methane from the coal into the pores. This fissure-held methane, or free methane, is released rapidly once a pathway through the coal into the mine atmosphere is established. In contrast, methane adsorbed in the coal, and measured as the seam gas, desorbs relatively slowly. Measurements suggest that on average about 50%of the adsorbed methane is lost one day after mining. By that time, the coal will have left the mine, so that the remaining seam gas will be released to the atmosphere outside the mine. Attempts to measure methane emissions from surface coal-mining operations showed very little detectable methane. Coal from surface operations, which was milled and exposed to atmosphere, adsorbed gas from the air. It is concluded that methane release from surface operations is probably less than 3Gg/a. It is estimated that the total methane release from the coalmining industry amounts to about 72 Gg/a, as opposed to the National Communication estimates of 323 Gg/a in 1990 and 317 Gg/a in 1994. However, there are large errors associated with these estimates, and it is recommended that the methodology outlined in this report be extended to as many mines as possible to reduce the errors that are inherent in the physical processes underlying the release of methane from South African coalmines.

Jan 1, 2005

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 E. Kapilashrami, S. Seetharaman

Refractory/metal interactions and associated reactions are significant during casting as they can lead to inclusion formation. High-temperature interactions between aluminosilicate refractories and molten steel were studied in the present investigation using the sessile drop method. The changes in the contact angles between molten iron with well-defined oxygen levels and substrates of silica, mullite (3Al2O3?2SiO2) as well as commercial refractories were measured in the dynamic mode. In all cases, the reaction led to slag formation. The experiments were performed under isothermal conditions at 1823 and 1873 K. A known and constant oxygen partial pressure was imposed above the iron drop, through appropriate CO-CO2-Ar mixtures. For all substrates, the contact angles started decreasing due to the lowering of the surface tension of iron, as oxygen was imposed on to the system. When a critical level of oxygen was reached, slag started forming at the drop/substrate interface and at this stage, the contact angle dropped suddenly. Subsequent behaviour of silica and mullite was observed to be different, with SiO2showing a non-wetting behaviour. In the case of SiO2substrate, there were also deep erosions along the periphery of the drops and there was slag accumulation at the sides of the metal drop, probably due to Marangoni flow and/or SiO(g) formation. SEM and EDS analysis of the substrates revealed that the formed slag was fayalite. The thermodynamic criteria for slag formation and possible mechanisms of the reaction are discussed in the light of the experiments. Key words: silica, mullite, fayalite, corundum, slag formation, sessile drop.

Jan 1, 2004

By J. Little

It is common practice for underground mine plans to be created sequentially, where results from one planning process form the input data for another. While this is practical for manual methods, computerized optimization techniques should consider an integrated approach to creating the global mine plan. This is because optimizing an individual mine planning process, such as stope layouts, introduces a likelihood of increasing costs or decreasing revenues associated with other areas, such as production scheduling, as harmful decisions must be balanced. Considering the interaction and influence that individual underground mine planning processes have on each other during optimization will provide more profitable results than if these are ignored. Optimization techniques for stope layouts and production scheduling are reviewed. An integer programming model is proposed that allows for either integrated or isolated optimization. Both approaches are separately applied to a block model. The results demonstrate the model?s ability to produce optimal long-term sublevel stoping mine plans and the benefits of using an integrated approach. Keywords underground mine optimization, stope layouts, underground production scheduling, integer programming, mathematical programming application.

Oct 1, 2013

Publications on hard rock tunnel support design in the South African mining industry have originated primarily from the goldmines during the past 50 years. Little has been published to date on the platinum and chrome mines of the Bushveld Complex. This paper covers the search for a suitable design methodology for off-reef tunnels at Impala Platinum Mine, situated on the Western Lobe of the Bushveld Complex. The fall of ground accident statistics for off-reef excavations of the mine are presented and the available rock mass quality evaluation systems are reviewed. The Q-Tunnelling Quality Index (or Q-Index) is selected because it assesses the important driving factors behind falls of ground at Impala. Two off-reef excavations are evaluated using the Q-Index, and it is shown that minor modifications are required for implementation at Impala. It will take some time before support design throughout the mine is based on the outcome of proper geotechnical investigations based on the Q-Index. Widespread implementation of such support designs should help to solve the fall of ground problem in off-reef excavations while at the same time reducing support costs.

Jan 1, 2002

By C. F. Vos, J. D. Miller, J. C. Davidtz

Small replacements of C12-trithiocarbonate (C12-TTC) for dithiocarbonate (DTC)/dithiophosphate(DTP) in a reagent suite for the flotation of platinum group metals (PGM) have significantly improved the rejection of gangue. Coupled to this is an improvement in kinetics, grade and recovery of PGMs. In a pilot-plant trial, after a 5 mole per cent replacement of the current DTC/DTP collector combination by C12-TTC, large opaque bubbles were replaced by small clear ones. In addition, a similar flotation response was realized with one-third of the current depressant dosage. During a preliminary plant trial on underground UG2 ore, the initial rougher concentrates were characterized by higher PGM concentrate grades and this was in part due to improved chromite rejection. The concentrate produced from the TTC trial also exhibited a much finer particle size distribution. The overall circuit performance, which included secondary regrind and flotation, showed an increase in concentrate grade of approximately 44% while the tailings grade remained unchanged

Jan 1, 2006

By J. P. W. Bennie, A. de Jong, G. M. Denton

Mintek together with Middelburg Steel & Alloys, developed the DC arc furnace process for the production of ferroalloys with the expressed objective of smelting ore fines (<1mm) without the need for agglomeration. In the case of ferrochrome production, the DC arc furnace, being a semi-open bath operation, loses radiant energy directly from the bath to the furnace roof and sidewalls above the melt. This energy loss is reflected in a higher electrical energy usage per ton of alloy than for a submerged-arc operation smelting lumpy ores or sintered pellets. The difference increases still further when pre-heated sintered pellet feed is used in a submerged-arc operation. This shortcoming of the DC arc furnace can however be overcome by preheating the feed to the furnace in a fluidized bed or flash reactor fuelled by cold furnace off-gas. In addition to fluidization and preheating testwork, various preheating flowsheets with associated mass and energy balances have been developed and compared from a techno-economic viewpoint. The three major advantages identified were: a) fluidized beds can preheat ores and fluxes up to 950°C without sticking and defluidizing, b) the open bath DC arc furnace does not require expensive coke or char to maintain the burden porosity and, c) the capital cost associated with the milling, pelletising and sintering plant falls away since ore fines are used directly.

Jan 1, 2004

By J. J. Bezuidenhout

The waste-heat boiler is used within the Sulphide flash smelting process as the main dust and energy recovery unit. The large volume of off-gas discharged from the flash smelter is at a very high temperature (1350°C) and contains a significant dust load that subjects the downstream waste-heat boiler to tough and demanding conditions. The boiler cavity is especially prone to dust accretions, fouling, and corrosion caused by accumulation of molten particles and precipitation of sulphuric acid. Computational fluid dynamics (CFD) is applied within a qualitative study to model the flow and heat transfer distribution throughout the waste-heat boiler. The commercial CFD package, Fluent 6.2.16, was applied to a modified waste-heat boiler (23 m ×11 m ×5.4 m) within the Outokumpu flash smelting process. This investigation focuses on the geometric modifications to the typical boiler design, which includes elevation of the ceiling, placement of flow-obstructing baffles and radiation plates parallel within the flow path. Also investigated were various boiler operating conditions such as the circulation of process off-gas, air leakage from the dust discharging hoppers and variation in inlet gas composition. The geometric modifications had the desired effect of increasing the volumetric utilization and therefore enhancing heat transfer between the boiler surface and the gas stream and dust segregation. Introducing circulated off-gas at a rate of 20 m/s and at a 45° angle to the front of the waste boiler further enhanced cooling while reducing the high impact of the furnace-uptake gas-stream on the boiler ceiling. The placement of radiation plates was found to be very effective in enhancing the heat transfer surface and distributing gas flow within the boiler. These results present recommendations towards an improved waste-heat boiler design. Keywords: flash smelting, waste-heat boiler, CFD simulation, off-gas cooling.

Jan 1, 2008

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 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. Urata, K. Ishii

To determine the effect of F ions in the molten alkali silicate systems on their structures, quenched Na2O-SiO2-NaF systems were investigated by Raman spectroscopy and molecular dynamics simulation. The systematic increase of 1100 cm-1band intensity in the Raman spectra of the silicate melts accompanying the replacement of F for O provides the evidence for concomitant polymerization of melts. From the molecular dynamics simulation, it was confirmed that most of substituted F was mainly coordinated to Na+ ions but not Si4+ions. These results were consistent with the mechanism in which F associated with otherwise network-modifying Na rather than with network-forming Si. Since F was associated to Na+ ions, the replace of O ion by two F ions promote the polymerization of silicate melts. Keywords: fluorine; molten flux; slag structure; molecular dynamics simulation; Raman spectroscopy.

Jan 1, 2004

By D. G. Krige

For the purpose of determining confidence limits for ore grade estimates, an extensive simulated data base was used, which included 1728 ore blocks with ‘actual’ grades and the corresponding estimates based on ordinary and simple kriging. The practical results show that conditional unbiasedness is essential and that acceptable confidence limits can then be set using Normal theory for the simulated error distribution based on the logarithms of the ratios of ‘actuals’/estimates with a variance related to the kriging variance. The mean of the data used to prepare the variogram and the estimated block grade are to be used properly in this approach. A practical analysis was also done of the actual point and block data from a very large mined out Carbon Leader area. The distributions of the actual grades for two levels of block sizes with different levels of variability were fitted using three models, ie. 2-. 3- and compound-lognormal. The trends of tonnages, grades and relative profits for a range of pay limits, as well as the usual tonnage-grade curves, show a practical insensitivity for the choice between the three lognormal models considered.

Jan 1, 2003

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 David Norval

The increased tendency to use hydrometallurgy as an extraction step towards final refining following a pyrometallurgical smelting process requires melts which have to be cast and or comminuted which can then be taken up into solution or leached. To generate surface area for optimal leaching, a common process is to granulate and in many cases mill, which is a general practice with friable material with properties associated with higher sulphur, carbon and silicon levels. However, in the case of metallic melts milling can be unfeasible due to the ductility of the granulated particles. Water solidification is capable of producing either fine particles by means of granulation or atomisation. Atomisation however, can produce particles as fine as 40 microns without a milling circuit.

Jan 1, 2005

We present a novel hybrid algorithm for quantifying the ore grade variability that has central importance in ore reserve estimation. The proposed algorithm has three stages: (1) fuzzy clustering, (2) similarity measure, and (3) grade estimation. The method first considers data clustering, and then uses the clustering information for quantifying the ore grades by means of a cumulative point semimadogram function. The method provides a measure of similarity and gives an indication of the regional heterogeneity. In addition, grade estimations can be obtained at different levels of similarity using a weighting function, which is the standard regional dependence function (SRDF). Keywords: Grade, fuzzy clustering, similarity measure, point madogram, weighting function.

Jan 1, 2008

By J. Eriksson

Slag from stainless steelmaking is known to disintegrate, which is an environmental problem and prevents the cooled slag from being utilized. This disintegration is due to the transformation from the ßto the ? polymorph of di-calcium silicate. The transformation is accompanied by an increase in volume of about 11% and a total disintegration of the slag. AOD slag from stainless steelmaking was re-melted in a laboratory induction furnace, together with olivine and calcinated dolomite, to investigate the prevention of disintegration by increased MgO content of the slag with small changes in CaO to SiO2ratio. The modified slag was examined with X-ray diffraction and scanning electron microscopy. The trials showed that an increased MgO content can change the mineral composition towards formation of more Merwinite and Bredigite, which prevents disintegration of the slag. Keywords: slag, disintegration, di-calcium silicate

Jan 1, 2004

By X. Pan

Slag-metal equilibrium experiments were conducted at 1500ºC and 1580ºC under 0.03 atm, 0.05atm and 0.83 atm CO partial pressures using silica and Cr-oxide crucibles. The complex slags belonged to SiO2-CaO-Al2O3-MgO-FeOx-CrOxand the metal phase to the Cr-Fe-C-Si-(S)systems. The carbon saturation of the metal phase was avoided using oxide crucibles and thus the results are pertinent to ferrochromium refining slags and processes. From equilibrium data and thermodynamic calculations the CrO /(CrO+Cr2O3) ratio in the slag was determined as 0.75, 0.80and 0.86 under 0.83 atm and 0.05 atm of CO pressure at 1500ºC and 0.03 atm and CO pressure at1580ºC respectively. The results clearly demonstrated that a higher chromium content of the metal results in higher Cr in the slag, and chromium in slag decreases with increasing SiO2. The results were also sensitive to the crucibles used as these oxide crucibles saturated the slag either with respect to SiO2or Cr-oxides. It was also demonstrated that the relative amount of CrO in the slag was higher when SiO2crucibles were used in accord with thermodynamic calculations. Iso-concentration curves for carbon and chromium of the metal phase in equilibrium with the slag were drawn on pseudo ternary SiO2–(AI2O3+CaO+MgO)–(Cr2O3+Fe2O3) diagram. The activity coefficients and activities of carbon and chromium of the metal phase were also calculated from the experimental data and available thermodynamics information and were plotted as iso-activity curves in the same pseudo ternary diagram. Keywords: Chromium, slag, equilibrium

Jan 1, 2004

By J. M. Richards

For most of the 20th century optical petrography has been the primary petrological and mineralogical tool used to characterize coal. The development of quantitative SEM-based techniques, e.g. QEMSCAN®, for coal began only about a decade ago. The application of these techniques for coal lagged behind other commodities, but they are currently being developed with the aim to provide ?one complete analysis? for coal. Quantitative SEM-based techniques are supplemented by quantitative X-ray diffraction (XRD). Recent indications are that these more modern techniques cannot replace the ?standard? petrographic and chemical evaluations, but rather complement them where and when required. The great advantage of quantitative SEM-based techniques is that they are very rapid, with the result that large volumes of samples can be processed on a routine basis. This is ideal for coal type identification, since the results can be used in the creation of ?intelligent? composites. This can lead to the more speedy evaluation of coal deposits by reducing the number of samples on which detailed metallurgical and characterization test work is required, without an increase in the overall statistical error of the resource model. Coal petrography, however, remains important for the prediction of the coking characteristics of certain coals and coal products. As a consequence it is therefore important that any coal laboratory be able to produce data with confidence. This requires strict quality control and assurance protocols that adhere to international standards. Keywords coal petrography, coking strength, scanning electron microscopy, QEMSCAN®.

Nov 1, 2013