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M.Tech. (Chemical Engineering) / Please refer to full text to view abstract

Thesis (PhD (Process Engineering))--University of Stellenbosch, 2006. / In the smelting of copper waste slags to recover cobalt and copper, the prediction of the metal liquidus temperature and the associated superheat for liquid metal handling for subsequent treatments cannot be done with certainty, making the management of furnace integrity very difficult. By studying the phase equilibria and solution thermodynamics in liquid ferrocobalt new experimental data on the liquidus temperature and phase equilibria of the quaternary system can contribute to the improvement of existing copper slag smelting processes. This will alleviate the operational uncertainties and difficulties associated with ferrocobalt production in electric arc furnaces. There is no specific literature available that describes the physicochemical and thermochemical properties of the ferrocobalt produced from smelting of waste copper slags. Therefore, the quaternary system Fe-Co-Cu-Si has been characterised by studying and reviewing the binary and ternary subsystems with respect to the high temperature phase equilibria. The ferrocobalt metal has been modelled on the Fe-Co-Cu-Si quaternary system. The liquidus temperatures and phase equilibria in the Fe-Co-Cu-Si system, within the composition and temperature regimes pertinent to smelting of slag, were investigated by differential thermal analysis and metallography. Drop-quench techniques coupled with scanning electron microscopy were used to study the phase equilibria. The activity of silicon in liquid Fe-Co-Cu-Si at 1450 °C was calculated from gas-alloy-silica equilibrium experiments conducted in controlled oxygen partial pressure atmospheres at 10-13 P, 10P -14 P, and 10P -15 atmosphere (absolute) corresponding to the conditions found in the industrial application. The liquidus temperature of the quaternary Fe-Co-Cu-Si is influenced by the content of silicon in the system. When silicon is added to the Fe-Co-Cu ternary the liquidus temperature is lowered in the new system (Fe-Co-Cu-Si). In the range of silicon content studied (0 0.1) < XSi ≤ , the liquidus temperature decreased by over 70 °C. The liquidus temperature profiles of the subsystems of the quaternary Fe-Co-Cu-Si, show large composition dependence too, except in the Fe-Co system. In the ternary Fe-Co-Cu, the liquidus temperature decreases with increasing copper content and is characteristic of the profiles of the liquidus lines in the binary subsystems Fe-Cu and Co-Cu.In the dilute concentrations of silicon, it is shown that the phase equilibria in the quaternary system have attributes of the Fe-Si and Fe-Cu-Si systems. Silicon is associated more with the iron rich phase than it is with the copper rich phase. It stabilises the metastable liquid immiscibility when added to the Fe-Cu, Co-Cu, and Fe-Co-Cu in the corresponding ternary systems Fe-Cu-Si, Co-Cu-Si and quaternary Fe-Co-Cu-Si system. The activity of silicon in liquid Fe-Co-Cu-Si at 1450 °C, in the composition range 1 to 5 wt. %Si exhibits a negative deviation from ideal liquid solution behaviour. The activity coefficient approaches a constant value of 0.2×10P -3 P, with pure liquid silicon as reference state, as the silicon concentration approaches zero implying a Henrian solution behaviour. This information should be useful in the thermodynamic modelling of the system.

Thesis (PhD)--University of Stellenbosch, 2004. / 388 leaves printed on single pages, preliminary pages i- xv and numbered pages 1-371. Includes bibliography, list of tables and figures. / Digitized at 330 dpi black and white and 330 dpi color PDF format (OCR), using KODAK i 1220 PLUS scanner. / ENGLISH ABSTRACT: Bath type furnaces have become an established technology for the intensive smelting, converting and refining of primary and secondary raw materials. Since these furnaces normally have large inventories, long time constants and complex metallurgies, a dynamic model-based prediction strategy is the only feasible approach to operator decision support and process control. This dissertation presents a semi-empirical approach to the stochastic modelling of bath-type pyrometallurgical reactors, which leads to a generic model type called the Equilib-ARMAX model. The modelling approach is applied to three case studies: • A nickel-copper matte converting operation using a submerged lance injection reactor • A chromite smelting operation to produce high carbon ferrochrome using a direct current (DC) plasma smelting furnace • An ilmenite smelting operation to produce high titania slag and pig iron, using a direct current (DC) plasma smelting furnace. In each case, the industrial operations were analysed with regard to the practical and technological constraints which influence the type and quality of the process data. The fundamental process phenomena associated with each operation have been analysed to ascertain which fundamental variables should be included within the overall semi-empirical approach, without sacrificing model transparency, simplicity, accuracy and calculation time. It was considered that an overly complex model would be inappropriate given that data from industrial smelting operations show significant random variance. The thermochemistry and phase equilibria associated with each operation are discussed in detail, as they become the fundamental backbone of the semi-empirical models. The equilibria have been modelled with software that uses non-ideal solutions models and Gibbs free energy minimisation to predict the phase and chemical equilibria that could be expected for a given feed recipe and operating temperature. As the thermodynamic modelling software is not stable within an industrial environment, an artificial intelligent mapping technique has been developed to map process inputs to equilibrium outputs. A multi-layer perceptron neural network has been used as the convenient mapping method to represent equilibrium. The neural networks were trained using tens of thousands of feed recipes, where the feed component ratios were varied based on a 3N factorial design. The amounts and chemistries of all equilibrium phases could be calculated with high accuracies (R2 > 0.95) in all cases. Further stochastic analysis and modelling require additional information about the property distributions associated with each measurement. The homogeneities of the furnace products (slag, alloy and flue dust) critically influence the level of confidence that one can associate with plant measurements. The homogeneities were characterised for the DC plasma arc furnaces and they were benchmarked against a submerged arc furnace. It was found that the homogeneity varied per element, with silicon and sulphur tending to show highest variations in the alloy melts. The observation that the variation in these two elements are both high can partially be attributed to the fact that SiS evaporates from the bath surface, especially in regions close to the arc attachment zone. A significant negative correlation was found between the relative standard deviation per tap (using silicon) and the degree of superheat / subcooling of the alloy, indicating that the homogeneity can be strongly influenced by the changes in rheology due to subcooling below the liquidus (which leads to the precipitation of solid phases and increases the observed melt viscosity). Mixedness or homogeneity and data uncertainty are therefore inseparably linked. The relative standard deviations associated with the homogeneity characterisation, as well as known sampling and assaying variances were used to develop reconciled material balances based on measured plant data. Material balance closure was therefore obtained within the inherent uncertainties of the plant data. Biases in the plant data were identified simultaneously with data reconciliation. Moreover, it was shown using Fast Fourier Power Spectra and statespace analysis that the data reconciliation was a good low-pass filter, as it extracted the major process trends components in the noisy data and it also improved the overall dynamic behaviour characteristics of the data. Finally systems identification techniques were used to develop dynamic transfer function models that were linear in the parameters to be estimated. These systems models were based on the reconciled plant data and equilibrium predictions. The final systems models are therefore equilibrium-autoregressive-moving-average models with exogenous variables (Equilib-ARMAX). The model parameters can be estimated recursively using a simple least squares method. The final models could dynamically predict the metallurgy of the subsequent tap 4-6 hours in advance, based on a given suite of set-points, within the inherent accuracy of the data. These models may be used to suggest the optimal operating conditions through an operator guidance system, or more simply, the models are simple enough to be used in a spreadsheet on a manager's desk. / AFRIKAANSE OPSOMMING: Bad-tipe oonde is reeds 'n gevestigde tegnologie wat algemeen gebruik word vir die intensiewe smelting, omsetting en raffinering van primere en sekondere roumateriale. Aangesien hierdie oonde normaalweg groot inventarisse, lang tydkonstantes en komplekse metallurgiee het, is dinamiese, modelgebaseerde voorspelling die enigste uitvoerbare benadering tot operateur besluitnemingsteunstelsels en prosesbeheer. Hierdie proefskrif stel 'n nuwe generiese, semi-empiriese benadering voor om die bad-tipe oonde stogasties te modelleer en lei tot die sogenaamde Equilib-ARMAX model. Die modelleringsbenadering word geevalueer deur drie gevallestudies: • 'n Nikkel-koper swawelsteen omsettingsproses in 'n dompel-Ians inspuit reaktor • 'n Chromiet smeltingsproses om hoe-koolstof ferrochroom te produseer in 'n gelykstroom (GS) plasmaboogoond • 'n Ilmeniet smeltingsproses om hoe titania slak en ruyster te produseer in 'n gelykstroom (GS) plasmaboogoond. In elke geval is die industriele prosesse ontleed met betrekking tot die praktiese en tegnologiese beperkings wat die tipe en die gehalte van die prosesdata beinvloed. Die fundamentele prosesgedrag van elke proses is ontleed om te bepaal welke fundamentele veranderlikes ingesluit moet word in die semi-empiriese benadering, sonder om model deursigtigheid, eenvoud, akkuraatheid en berekeningstyd in te boet. Die ontwikkeling van oor-komplekse modelle is beskou as ongepas, gegewe dat die data van industriele smeltingsprosesse beduidende onsekerhede toon. Die termochemiese en fase-ewewigte geassosieer met elke proses word breedvoerig bespreek, aangesien dit die fundamente1e grondslag van die semi-empiriese modelle verskaf. Die ewewigte is gemodelleer met rekenaar simulasie-programmatuur wat nie-ideale oplossingsmodelle en Gibbs vrye-energie minimering gebruik om die fase en chemiese ewewigte, wat verwag kan word vir 'n gegewe toevoerresep en bedryfstemperatuur, te voorspel. Aangesien termodinamiese modelleringsprogrammatuur normaalweg nie stabiele gedrag toon in 'n intydse industriele omgewing nie, word kunsmatig intelligente projeksietegnieke gebruik om prosesinsette te projekteer na die ekwavilente ewewigsvoorspellings. 'n Multilaag perseptron neurale netwerk is gebruik as 'n eenvoudige metode om hierdie ewewigsprojeksies voor te stel. Die neurale netwerke is afgerig deur van tienduisende toevoer resepte gebruik te maak. Die verhoudings van die komponente in die voer is gewissel gebaseer op 'n 3N faktoriaalontwerp. Die hoeveelhede en samestelling van al die ewewigsfases kon in alle gevalle bereken word met hoe akkuraatheid (R2 > 0.95). Verdere stogastiese analise en modellering is slegs moontlik met kennis oor die eienskapsverspreidings geassosieer met elke komponent. Die homogeniteite van die oondprodukte (slak, legering en vlieg-as) bepaal, tot 'n groot mate, die betroubaarheidsvlak van die aanlegmetings. Homogeniteite is gekarakteriseer vir die GS-plasmaboogoonde en is vergelyk met die homogeniteite wat in dompelboogoonde gevind word. Die homogeniteite het gevarieer per komponent. Silikon en swawel neig om die grootste ruimtelike variasies te toon in die legerings wat bestudeer is. 'n Beduidende negatiewe korrelasie is gevind tussen die relatiewe standaardafwyking per tap (gebaseer op silikon) en die graad van superverhitting / onderverkoeling van die legering. Dit dui aan dat die homogeniteit sterk beinvloed word deur veranderinge in die smelt reologie. Vermenging, reologie, homogeniteit en data onsekerheid (integriteit) is daarom ten nouste gekoppel. Die relatiewe standaardafwykings geassosieer met die homogeniteitsbepaling, asook die monsternemings- en ontledingsvariansies, is gebruik om die aanlegdata te rekonsilieer onderhewig aan die behoud van die komponent en totale stroom massabalanse. Die massabalanse is dus gesluit deur aanpassings aan die metings te maak binne die inherente onsekerhede in die data. Sistematiese foute in die data is gelyktydig met die rekonsiliasie geidentifiseer. Verder is deur diskrete Fourier energiespektra en toestand-ruimte analises getoon dat massabalans-rekonsiliasie dien as 'n goeie seinfilter om hoe-frekwensie geraas te verminder en tergelykertyd die dinamiese gedragseienskappe van die data te verbeter. Stelsel-identifikasietegnieke is gebruik om dinamiese oordragsfunksiemodelle te ontwikkel wat linieer is met betrekking tot die modelparameters. Hierdie stelselmodelle is gebaseer op gerekonsilieerde data, eksogene prosesdata en ewewigsberekeninge, en word vervolgens ewewigs-autoregressiewe-lopende-gemiddelde modelle met eksogene veranderlikes (Equilib ARMAX) genoem. Die modelparameters kan deur gewone kleinste-kwadrate metodes beraam word. Die finale modelle kan die metallurgie van toekomstige tappe 4-6 uur voortydig voorspel, gebaseer op beskikbare stelpunte en binne die inherente presisie van die data. Hierdie modelle kan gebruik word om optimale bedryfskondisies vir prosesbeheer te identifiseer, en is eenvoudig genoeg om in sigbladformaat op 'n aanlegbetuurder se rekenaar gebruik te kan word.

Thesis (MScEng.)--University of Stellenbosch, 2001. / ENGLISH ABSTRACT: Slag cleaning has become a common practice at many smelters in the nonferrous industry to maximize recovery of valuable metals. However, during the carbothermic reduction of nonferrous slag to recover cobalt, in particular, iron is recovered predominantly. High iron levels present a problem for the subsequent treatment of the alloy as it may increase the solids loading to the filter and lead to increased reagent consumption during leaching. Finding an appropriate slag modifier that would selectively improve the recovery of cobalt against that of iron to the metallic alloy can solve this problem. In the present study the effects of lime (CaO), rutile (Ti02), and fluorspar (CaF2) on the recovery of cobalt from waste nonferrous slag have been investigated under reducing conditions at 1500°C. The selective recovery of cobalt compared to the recovery of iron at different levels of flux additions is discussed in this study, to show the selectivity of these fluxes. It is also shown in the study that the recovery of cobalt does not only depend on the oxygen partial pressure and temperature but on the slag composition as well. The slags used in the experiments were a) synthetic slag prepared from chemically pure reagents and its composition was derived from that of the industrial nonferrous slag composition typical of reverbaratory furnace and b) actual slag obtained from an old slag dump situated on the Zambian Copperbelt region. The investigation has shown that Ti02 addition leads to the most selective cobalt recoveries in all cases. On the other hand, both CaO and CaF2 lead to higher overall cobalt recoveries. The effect of Ti02 on the slag chemistry leads to the formation of iron titanate compounds in the slag unlike CaO, which displaces "FeO" from the fayalitic slag and thus increases the activity of FeO in the molten slag, which in tum affects the iron recoveries to the alloy product. CaF2 on the other hand, affects the fluidity of the slag leading to improved recoveries by improved settling of metals through the slag to the alloy product. A 44V/I100A DC-plasma arc furnace was used to reduce slag to recover cobalt at about 13.5kV A power input. The major part of the study was conducted in a tube furnace and the findings were applied to the extraction of cobalt from slag using the plasma-arc furnace. It was found that the synthetic slag experiments could be used as a guide to understand the behaviour of cobalt during the carbothermic recovery of cobalt from silica saturated fayalitic slags. Cobalt recoveries were higher in the DC furnace than the corresponding reduction experiments carried out in the tube furnace. However, significant amounts of silicon and carbon were detected in the metallic alloy product of the DC plasma-arc furnace. / AFRIKAANSE OPSOMMING: Slak suiwering is besig om standaard praktyk te word by vele smelters om die herwinning van waardevolle metale uit slak te maksimeer. Tydens die karbotermiese reduksie van slakke vanaf kopersmelters om kobalt te herwin, word beduidende hoeveelhede yster ook herwin. Hoë ystervlakke in die herwinde legering veroorsaak probleme met die stroom-af verwerking van die legering aangesien dit lei tot verhoogde reagensgebruik tydens loging en 'n verhoogde vastestof las of die filterstelsel. Die identifisering van 'n geskikte slak modifiseerder, wat die selektiwiteit van herwinning van kobalt relatief tot yster verhoog, sal hierdie probleem verminder. In hierdie tesis word die rol van kalk (CaO), rutiel (Ti02) en vloeispaat (CaF2) toevoeging tot die selektiewe herwinning van kobalt uit afvalslakke ondersoek. Die karbotermiese reduksie van die slak vind by 1500 °C plaas. Dit word getoon dat bo-en-behalwe die suurstofpotensiaal en die bedryfstemperatuur, die slakchemie 'n beduidende rol speel. Die slakke gebruik in hierdie studie is: a) 'n sintetiese slak gemaak van chemies-suiwer rou-materiale (waarvan die samestelling afgelei is van die samestelling van tipiese reverbereeroond slakke), en b) monsters van die ware slak verkry vanaf 'n slakhoop van die Zambiese Kopergordel. Die studie het getoon dat Ti02 toevoeging gelei het tot die hoogste selektiwiteit in alle gevalle. Daarteenoor het CaF2 en CaO gelei tot hoër algehele herwinnings van kobalt. Ti02 toevoeging lei tot die vorming van ystertitanaat komplekse in die slak, teenoor CaO wat die "FeO" uit die fajaliet struktuur verplaas en die aktiwiteit van FeO in die slak verhoog en dus gevolglik herwinning van yster tot die legering beïnvloed. CaF2 verhoog egter die vloeibaarheid van die slak wat lei tot verhoogde herwinning deurdat die legering druppels makliker uitsak deur die slak. 'n 44VIII OOAGelykstroom-plasmaboogoond is gebruik om die kobalt te herwin uit die slak teen ongeveer 13.5 kVA Die grootste gedeelte van die studie is gedoen in 'n buisoond en die bevindings was dan toegepas op die ekstraksie van kobalt uit slak in die plasmaboogoond. Dit was gevind dat die sintetiese slak eksperimente gebruik kan word as 'n voorlopige gids om die gedrag van kobalt in silika-versadigde slakke tydens karbotermiese reduksie te verstaan. Kobalt herwinnings was oor die algemeen hoër il) die plasmaboogoond as vir die ooreenstemmende reaksies in die buisoond. Daar het egter beduidende hoeveelhede silikon en koolstof In die legering opgelos tydens die plasmaboogoond eksperimente.

Thesis (MScEng)--University of Stellenbosch, 2002. / ENGLISH ABSTRACT: Slag foaming occurs in several pyrometallurgical processes. These processes include steelmaking in basic oxygen steelmaking furnaces and electric arc furnaces (EAF) as well as various non-ferrous operations like sulphide smelting/converting and base metal slag cleaning. Although slag foaming in steelmaking processes has been extensively researched, little attention has been given to slag foaming in non-ferrous operations. Slag foaming phenomena are complex because often the system consists of three or more phases. The objectives of this study is to review the published work on slag foaming, to obtain through physical modelling an understanding of the principles governing foaming and to investigate slag foaming phenomena through pyrometallurgical experiments. To obtain these objectives, experiments were carried out with aqueous mixtures at different column sizes, different pore sizes for gas injection and varying liquid depths, and also for high temperature metallurgical slags with varying composition and at different temperatures. Through gas injection, foaming conditions were simulated and the equilibrium foam height was measured for different gas velocities. The following conclusions were drawn: 1. For physical modelling of slag foaming in 3-phase systems the average foam index increases with increasing amounts of solids present in the system. The effect of additional solids in the system is independent of the system geometry. 2. The following conclusions were reached by determining coefficients for an empirical dimensional model fitted to aqueous mixtures: Higher liquid density leads to lower foam index values. The influence of the liquid viscosity is dependent on the system investigated and may have a positive or negative result on foaming. The empirical model should only be applied to the property range and geometric set-up for which it was derived, as coefficients may vary greatly for different systems. 3. Influence of solid precipitates on slag foaming can be summarised by noting that small amounts of magnetite stabilise slag foaming, while precipitates of wollastonite and anorthite decreased foaming. The influence of solid precipitates is thought to be related to the density, morphology and degree of surface activity of the solid precipitates. 4. The foam index decreases with increasing basicity due to the lowering of the slag viscosity. This continues until the precipitation of solids starts and the foam index once again increases. 5. For increasing "FeO" concentration the foam index will decrease due to lower viscosity, but higher surface tension depression may lead to increased foam index values at high "FeO" concentrations. 6. Higher foam index values were obtained for slags with lower densities. The _1 empirical relationship observed is L IX: P 3 . 7. Higher foam index values were obtained for slags with higher viscosity. The empirical relationship observed is L IX: f1 . 8. Higher foam index values were obtained for slags with lower surface tensions. The empirical relationship observed is L IX: U-I. 9. Models derived for the foaming of basic steelmaking slags does not satisfactorily describe the foaming behaviour of acidic slags. 10. The physical properties of the slag influence the foam stabilisation mechanism. / AFRIKAANSE OPSOMMING: Slak skuiming kom in verskeie pirometallurgiese prosesse voor. Hierdie prosesse sluit die maak van staal in basiese staalmaakoonde en elektriese boogoonde in, sowel as verskeie nie-yster prosesse soos sulfied smelting/omsetting en die skoonmaak van basis metaal slakke. Alhoewel slak skuiming in staalmaak slakke reeds intensief nagevors is, is min aandag gegee aan slak skuiming in nie-yster prosesse. Slak skuiming verskynsels is kompleks, want dikwels betaan die sisteem uit drie of meer fases. Die doelwitte van hierdie studie is om werk wat reeds oor slakskuiming gepubliseer is te hersien, om deur fisiese modellering 'n begrip van die prinsiepe waarop skuiming berus te bekom en om slak skuiming verskynsels na te vors deur piromettallurgiese eksperimente te beplan en uit te voer. Ten einde hierdie doelwitte te bereik, is eksperimente uitgevoer met water mengsels in verskillende kolom groottes, verskillende porie groottes vir gas inspuiting en by verskillende vloeistof hoogtes, en ook vir hoë temperatuur metallurgiese slakke met variërende samestelling en by verskillende temperature. Skuimingskondisies is deur gas inspuiting gesimuleer en die ewewig skuimhoogte is gemeet by verskillende gas snelhede. Die volgende gevolgtrekkings is bereik: 1. Tydens fisiese (koue) modellering van slak skuiming in 3-fase sisteme styg die gemiddelde skuim indeks met toenemende hoeveelhede vastestof in die sisteem. Die uitwerking van addisionele vastestof in die sisteem is onafhanklik van die sisteem geometrie. 2. Die volgende gevolgtrekkings is gemaak deur die koëffisiente vir 'n empiriese dimensionale model te pas op waterige mengsels. Hoër vloeistof digtheid lei na laer skuim indeks waardes. Die invloed van die vloeistof viskositeit is afhanklik van die sisteem ondersoek en mag 'n positiewe of 'n negatiewe resultaat op skuiming hê. Die empiriese model moet slegs toegepas word op die eienskap omvang en geometriese opstelling waarvoor dit bepaal is, omdat koëffisiënte grootliks kan varieer vir verskillende sisteme. 3. Die invloed van vastestof partikels op slak skuiming kan opgesom word deur die waarneming dat klein hoeveelhede magnetiet slakskuiming stabiliseer terwyl neerslag van wollastoniet en anhortiet skuiming verminder. Die invloed van vastestof neerslag hou vermoedelik verband met die digtheid, vorm en graad van oppervlak aktiviteit van die vastestof partikels. 4. Die skuim indeks verminder met toenemende basisiteit as gevolg van die afname in die slak viskositeit. Dit geld tot die neerslag van vastestof begin en die skuim indeks weereens toeneem. 5. Vir toenemende 'FeO' konsentrasie sal die skuim indeks afneem as gevolg van laer viskositeit, maar hoër oppervlakspanning onderdrukking kan lei na hoër skuim indeks waardes by hoër 'FeO' konsentrasies. 6. Hoër skuim indeks waardes is verkry vir slakke met laer digthede. Die empiriese _1 verhouding is bepaal as L cx: p 3 . 7. Hoër skuim indeks waardes is verkry vir slakke met hoër viskositeit. Die empiriese verhouding is bepaal as L cx: Jl . 8. Hoër skuim indeks waardes is verkry vir slakke met laer oppervlakspannings. Die empiriese verhouding is bepaal as L cx: 0--1 • 9. Modelle afgelei vir die skuiming van basiese staalmaak slakke beskryf nie die skuimings gedrag van suur slakke bevredigend nie. 10. Die fisiese eienskappe van die slak beïnvloed die skuim stabiliseerings meganisme.

Thesis (MScEng (Process Engineering))--University of Stellenbosch, 2009. / ENGLISH ABSTRACT: A project was initially commenced for optimising the production output at a specific high-carbon ferromanganese furnace. Since operational difficulties were experienced in this furnace and with a lack of reliable data for the year 2007, it was decided that data from a more stable high-carbon ferromanganese furnace should be analysed instead. Three key performance indicators (KPI’s) were selected to give an indication of overall process performance. These were: (1) the total tonnes of high-carbon ferromanganese produced per tonne of feed material, (2) the percentage recovery of manganese to the alloy product, and (3) the alloy:slag ratio. Maximisation of each of these would contribute to the overall improvement of the process. To achieve the objectives of the project, a hybrid model was developed to characterise the production behaviour of the furnace and to optimise the proposed KPI’s. The hybrid model consisted of two modelling branches, viz. equilibrium and dynamic modelling. An equilibrium sub-model was created and the output results were then used as inputs into a dynamic sub-model, which not only considered the effects of thermo-equilibrium interactions, but also the faster-changing electrical dynamics of furnace control. The final modelling step involved genetic optimisation, whereby model variables were manipulated to optimise the proposed KPI’s. In other words, operating conditions were established to improve furnace performance. It was determined that significant improvement in the values of the KPI’s may be expected if the optimised setpoints are implemented on-site. The existing setpoints for electrical operation should be maintained while the power expended per tonne of alloy should be altered (by tapping more regularly). Specific adjustments to the proportions of the feed recipe should also be made. / AFRIKAANSE OPSOMMING: ‘n Projek is aanvanklik begin om die produksieproses by ‘n spesifieke hoëkoolstof ferromangaanoond te optimiseer. Sedert operasionele probleme ondervind is in die oond en daar ‘n tekort is aan vertroubare data vir die jaar 2007, is daar besluit om data van ‘n meer stabiele hoëkoolstof ferromangaanoond te annaliseer. Drie sleutelverrigtingsaanwysers (SVA’s) is geselekteer om die algehele prosesverrigting aan te dui. Hulle is: (1) Die totale tonnemaat hoëkoolstof ferromangaan geproduseer per tonnemaat van voermateriaal, (2) die persentasie herwinning van mangaan tot die allooiproduk, en (3) die allooi:slak verhouding. Die verhoging van elk van die bogenoemde sal bydra tot die algehele bevordering van die proses. Om die doelwitte van die projek na te kom, is ‘n Kombinasiemodel ontwikkel om die produksie gedrag van die oond te karakteriseer en om die voorgestelde SVA’s te optimiseer. Die Kombinasiemodel het bestaan uit twee modelleringsvertakkings, nl. termodinamiese ewewig en dinamiese modellering. ‘n Termodinamiese ewewig submodel is geskep en die uitset resultate is gevolglik gebruik as invoerdata na ‘n dinamiese sub-model, wat nie slegs die uitwerking van termo-ewewiginteraksies in ag neem nie, maar ook die vinnigveranderende elektriese dinamika van die oond. Die finale modelleringstap het genetiese optimisering behels, waarby model veranderlikes gemanipuleer is om die voorgestelde SVA’s te optimiseer. Met ander woorde, operasionele kondisies is vasgestel om oond produksie te bevorder. Dit is bepaal dat kenmerkende verbetering in die waardes van die SVA’s verwag kan word as die ge-optimiseerde setpunte toegepas is op die oond. Die oorspronklike setpunte vir elektriese beheer hoort gehandhaaf te word terwyl die krag verbruik per ton allooi verander moet word (deur om meer gereeld te tap). Spesifieke verstellings op die proporsies van die voerresep moet ook gemaak word.

Batteries have found wide use in many household and industrial applications and since the 1990s, they have continued to rapidly shape the economy and social landscape of humans. Lithium ion batteries, a type of rechargeable batteries, have experienced a leap-frog development at technology and market share due to their prominent performance and environmental advantages and therefore, different forecasts have been made on the future trend for the lithium ion batteries in-terms of their use. The steady growth of energy demand for consumer electronics (CE) and electric vehicles (EV) have resulted in the increase of battery consumption and the electric vehicle (EV) market is the most promising market as it will consume a large amount of the lithium ion batteries and research in this area has reached advanced stages. This will consequently be resulting in an increase of metal-containing hazardous waste. Thus, to help prevent environmental and raw materials consumption, the recycling and recovery of the major valuable components of the spent lithium ion batteries appears to be beneficial. In this thesis, it was attempted to recover lithium from a synthetic slag produced using pyrometallurgy processing and later treated using hydrometallurgy. The entire work was done in the laboratory to mimic a base metal smelting slag. The samples used were smelted in a Tamman furnace under inert atmosphere until 1250oC was reached and then maintained at this temperature for two hours. The furnace was then switched off to cool for four hours and the temperature gradient during cooling was from 1250oC to 50oC. Lime was added as one of the sample materials to change the properties of the slag and eventually ease the possibility of selectively leaching lithium from the slag. It was observed after smelting that the slag samples had a colour ranging from dark grey to whitish grey among the samples.The X - ray diffractions done on the slag samples revealed that the main phases identified included fayalite (Fe2SiO4), magnetite (Fe3O4), ferrobustamine (CaFeO6Si2), Kilchoanite (Ca3Si2O7), iron oxide (Fe0.974O) and quartz (SiO2). The addition of lime created new compound in the slag with the calcium replacing the iron. The new phases formed included hedenbergite (Ca0.5Fe1.5Si2O6), ferrobustamine (CaFeO6Si2), Kilchoanite (Ca3Si2O7) while the addition of lithium carbonate created lithium iron (II) silicate (FeLi2O4Si) and dilithium iron silicate (FeLi2O4Si) phases.The Scanning Electron Microscopy (SEM) micrographs of the slag consisted mainly of Fe, Si and O while the Ca was minor. Elemental compositions obtained after analysis was used to identify the different phases in all the slag samples. The main phases identified were the same as those identified by the XRD analysis above except no phase with lithium was identified. No lithium was detected by SEM due to the design of the equipment as it uses beryllium planchets which prevent the detection of lithium.Leaching experiments were done on three slag samples (4, 5 and 6) that had lithium carbonate additions. Leaching was done for four hours using water, 1 molar HCl and 1 molar H2SO4 as leaching reagents at room temperature. Mixing was done using a magnetic stirrer. The recoveries obtained after leaching with water gave a lithium recovery of 0.4%. Leaching with HCl gave a recovery of 8.3% while a recovery of 9.4% was obtained after leaching with H2SO4.It can be concluded that the percentage of lithium recovered in this study was very low and therefore it would not be economically feasible. It can also be said that the recovery of lithium from the slag system studied in this work is very difficult because of the low recoveries obtained. It is recommended that test works be done on spent lithium ion batteries so as to get a better understanding of the possibilities of lithium recovery as spent lithium ion batteries contain other compounds unlike the ones investigated in this study.

The sulphation and sulphate decomposition occurring during the oxidation of nickel concentrates were studied by thermal analysis. Samples of industrial nickel concentrates were heated in inert gas to temperatures between 400°C and 850°C and oxidized isothermally in air or in a 4%O2-96%N2 mixture. During isothermal oxidation of the concentrates, SO2 evolved from the roasting reactions led to partial formation of metal sulphates. Following the oxidation and sulphation of the sample, the decomposition of the formed sulphates was studied. This was completed either by heating the sulphated sample to 950°C to thermally decompose the sulphates, or by lowering the partial pressure of oxygen while holding the sample at the isothermal oxidation temperature. The sulphation of the sample was found to follow the parabolic rate law, implying diffusion as the rate controlling-step. The thermal decomposition of the sulphates occurred at a near constant rate, implying zero-order kinetics.

The sulphation and sulphate decomposition occurring during the oxidation of nickel concentrates were studied by thermal analysis. Samples of industrial nickel concentrates were heated in inert gas to temperatures between 400°C and 850°C and oxidized isothermally in air or in a 4%O2-96%N2 mixture. During isothermal oxidation of the concentrates, SO2 evolved from the roasting reactions led to partial formation of metal sulphates. Following the oxidation and sulphation of the sample, the decomposition of the formed sulphates was studied. This was completed either by heating the sulphated sample to 950°C to thermally decompose the sulphates, or by lowering the partial pressure of oxygen while holding the sample at the isothermal oxidation temperature. The sulphation of the sample was found to follow the parabolic rate law, implying diffusion as the rate controlling-step. The thermal decomposition of the sulphates occurred at a near constant rate, implying zero-order kinetics.