M.Sc. (50/50) Research project submitted to School of Chemical and Metallurgical Engineering, Faculty of Engineering and the Built Environment, University of the Witwatersrand, Johannesburg, South Africa July 2017 / This study and the work done involves investigating the effects of different parameters on the decarburization process of high carbon ferrochromium melts to produce medium carbon ferrochrome, and takes into account the manipulation of the different parameters and thermodynamic models based on actual plant data. Process plant data was collected from a typical plant producing medium carbon ferrochrome alloys using AODs. The molten alloy was tapped from the EAF and charged into the AOD for decarburization using oxygen and nitrogen gas mixtures. The gases were blown into the converter through the bottom tuyeres. Metal and slag samples and temperature measurements were taken throughout the duration of each heat. The decarburization process was split into two main intervals namely first stage blow (where carbon content in the metal bath is between 2-8 wt. % C) and second stage blow (carbon mass% below 2 wt. %). The first and second blow stages were differentiated by the gas flow rates whereby the first stage was signified by gas flow ratio of 2:1 (O2:N2), whilst the stage blow had 1:1 ratio of oxygen and nitrogen respectively. The effect of Cr mass% on carbon activity and how it relates to rate of decarburization was investigated, and the results indicated that an increase in Cr 66.54 – 70.5 wt. % reduced carbon activity in the metal bath from 0.336 – 0.511 for the first blowing stage. For the second blowing stage, the increase in Cr mass % of 67.22 – 71.65 wt. % resulted in an increase in C activity from 0.336 – 0.57. The trend showed that an increase in chromium composition resulted in a decrease in carbon activity and the same increase in Cr mass% resulted in reduced carbon solubility. Based on the plant data, it was observed that the rate of decarburization was time dependent, that is, the longer the decarburization time interval, the better the carbon removal from the metal bath. An interesting observation was that the change in carbon mass percent from the initial composition to the final (Δ%C) decreased from 10.18 – 8.37 wt. % with the increase in Cr/C ratio from 8.37 – 10.18. This effect was attributed to the chromium affinity for carbon and the fact that an increase in chromium content in the bath was seen to reduce activity of carbon. It was also observed that the effect of the Cr/C ratio was more significant in the first stage of the blowing process compared to the second blowing stage. A mass and energy balance model was constructed for the process under study to predict composition of the metal bath at any time interval under specified plant conditions and parameters. The model was used to predict the outcome of the process by manipulating certain parameters to achieve a set target. By keeping the gas flow rates, blowing times, gas ratios and initial metal bath temperature unchanged, the effect of initial temperature on decarburization in the converter was investigated. The results showed that the carbon end point with these parameters fixed decreased with increasing initial temperature, and this was supported by literature. The partial pressure of oxygen was observed to increase with decrease in C mass % between the first and second blow stages. For the second stage blow the partial pressure changed from 5.52*10-12 – 2.1*10-10 and carbon mass % increased from 0.754 – 2.99 wt. %. A carbon mass % of 7.87 had an oxygen partial pressure of 4.51*10-13 whilst a lower carbon content of 1.53 wt. % had an oxygen partial pressure of 8.06*10-11. The CO partial pressure however increased with increase in carbon composition in the metal bath. When the oxygen flow rate increased, a corresponding increase in the carbon removed (Δ%C) was observed. For the first stage of the blowing process, an increase in oxygen flow rate from 388.67 – 666.5Nm3 resulted in an increase in carbon removed from 5.06 – 7.28 wt. %. The second blowing stage had lower oxygen flow rates because of the carbon levels remaining in the metal bath were around +/- 2 wt. %. In this stage oxygen flow rates increased from 125 – 286.67 Nm3 and carbon removed (Δ%C) from 0.16 – 2.093 wt. %. The slag showed that an increase in basicity resulted in an increase in Cr2O3 in the slag. As the basicity increased from 0.478 – 1.281, this resulted in an increase in Cr2O3 increase from 0.26 – 0.68. Nitrogen solubility in the metal bath was investigated and it was observed that it increased with increasing Cr mass %. The increase in nitrogen solubility with increasing Cr mass % was independent of the nitrogen partial pressures. / MT2018

It was been reported that untreated wastes from ferrochrome plants release heavy metals including lead, chromium, copper, cadmium, zinc and nickel in the environment. Some of these metals such as hexavalent chromium are potentially toxic and carcinogenic, and can cause a serious threat to human health. The contamination of terrestrial and aquatic ecosystems by hexavalent chromium is worldwide of major environmental concern, especially in South Africa which is the largest producer of chromite and ferrochrome. Therefore, the pre-treatment of these wastes before landfill is of great importance to prevent the contamination of the ecosystems. In the present study, vermiculite, a natural occurring mineral, has been tested for its adsorption effectiveness in removing Cr(VI) from ferrochrome dust leachate. Batch adsorption studies have been carried out to determine the effect of pH, contact time and adsorbent dose on the removal of Cr(VI). The process was found to be highly pH dependent. The optimum conditions for the removal were found to be at pH 1.5, contact time 2 hours and adsorbent dose 10 g.L-1. According to kinetic and isotherm studies, the process is best fitted by the pseudo-second order kinetic model, and to both Langmuir and Freundlich isotherms. The maximum adsorption capacity was found to be 23.25 mg.g-1. Thermodynamic parameters show the spontaneous and endothermic nature of Cr(VI) adsorption onto vermiculite. / Dissertation (MSc)--University of Pretoria, 2011. / Materials Science and Metallurgical Engineering / unrestricted

During ferrochrome (FeCr) production, three types of generic chromium (Cr) containing wastes are generated, i.e. slag, bag filter dust (BFD) and venturi sludge. The loss of these Cr units contributes significantly to the loss in revenue for FeCr producers. In this study, the liberation of Cr units was investigated utilising two case study waste materials, i.e. BFD from a semi-closed submerged arc furnace (SAF) operating on acid slag and the ultrafine fraction of slag (UFS) originating from a smelter operating with both open and closed SAFs on acid slag. A detailed material characterisation was conducted for both case study materials, which included particle size distribution, chemical composition, chemical surface composition and crystalline content. Cr liberation was achieved utilising two methods, i.e. aqueous ozonation and the advanced oxidation method. Various advanced oxidation processes could be applied. However, the advanced oxidation processes considered in this study was the use of gaseous ozone (O3) in combination with hydrogen peroxide (H2O2). Controlling parameters such as the influence of pH, ozonation contact time, waste material solid loading, gaseous O3 concentration and temperature on Cr liberation were investigated for the aqueous ozonation process. The influence of pH, volume H2O2 added and the method of H2O2 addition were considered for the advanced oxidation process. Results indicated that with aqueous ozonation, limited Cr liberation could be achieved. The maximum Cr liberation achieved was only 4.2% for BFD by varying the process controlling parameters. The Cr liberation for UFS was significantly lower than that of the BFD. The difference in the results for the two waste materials was attributed to the difference in characteristics of the materials. The Cr content in BFD was mostly related to chromite and/or altered chromite particles, while the Cr content of the UFS was mostly related to FeCr particles. It is possible that the Cr(III) present in the chromite and/or partially altered chromite might be more susceptible to oxidation to Cr(VI) than the metallic Cr(0) present in the FeCr. During ozonation, aqueous O3 spontaneously decomposes to form hydroxyl (OH•) radicals, which are very strong oxidants in water. The above-mentioned Cr liberation observed was related to the formation of the OH• radicals during the spontaneous decomposition of aqueous O3. This was indicated especially by enhanced Cr liberation at higher pH values, which was attributed to the acceleration of the spontaneous decomposition to OH• radicals at higher pH levels. The advanced oxidation method gave significantly higher Cr liberation results for both case study materials considered, achieving Cr liberations of more than 21%. The advance oxidation processes improve normal oxidation methods. In this study, the H2O2 used in combination with O3 enhanced the formation of the OH• radicals that are responsible for the oxidation of Cr. The Cr liberation levels achieved are possibly not high enough to be feasible for industrial purposes. However, a further investigation of the advanced oxidation process could optimise the process to yield even higher Cr liberation. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2014

During ferrochrome (FeCr) production, three types of generic chromium (Cr) containing wastes are generated, i.e. slag, bag filter dust (BFD) and venturi sludge. The loss of these Cr units contributes significantly to the loss in revenue for FeCr producers. In this study, the liberation of Cr units was investigated utilising two case study waste materials, i.e. BFD from a semi-closed submerged arc furnace (SAF) operating on acid slag and the ultrafine fraction of slag (UFS) originating from a smelter operating with both open and closed SAFs on acid slag. A detailed material characterisation was conducted for both case study materials, which included particle size distribution, chemical composition, chemical surface composition and crystalline content. Cr liberation was achieved utilising two methods, i.e. aqueous ozonation and the advanced oxidation method. Various advanced oxidation processes could be applied. However, the advanced oxidation processes considered in this study was the use of gaseous ozone (O3) in combination with hydrogen peroxide (H2O2). Controlling parameters such as the influence of pH, ozonation contact time, waste material solid loading, gaseous O3 concentration and temperature on Cr liberation were investigated for the aqueous ozonation process. The influence of pH, volume H2O2 added and the method of H2O2 addition were considered for the advanced oxidation process. Results indicated that with aqueous ozonation, limited Cr liberation could be achieved. The maximum Cr liberation achieved was only 4.2% for BFD by varying the process controlling parameters. The Cr liberation for UFS was significantly lower than that of the BFD. The difference in the results for the two waste materials was attributed to the difference in characteristics of the materials. The Cr content in BFD was mostly related to chromite and/or altered chromite particles, while the Cr content of the UFS was mostly related to FeCr particles. It is possible that the Cr(III) present in the chromite and/or partially altered chromite might be more susceptible to oxidation to Cr(VI) than the metallic Cr(0) present in the FeCr. During ozonation, aqueous O3 spontaneously decomposes to form hydroxyl (OH•) radicals, which are very strong oxidants in water. The above-mentioned Cr liberation observed was related to the formation of the OH• radicals during the spontaneous decomposition of aqueous O3. This was indicated especially by enhanced Cr liberation at higher pH values, which was attributed to the acceleration of the spontaneous decomposition to OH• radicals at higher pH levels. The advanced oxidation method gave significantly higher Cr liberation results for both case study materials considered, achieving Cr liberations of more than 21%. The advance oxidation processes improve normal oxidation methods. In this study, the H2O2 used in combination with O3 enhanced the formation of the OH• radicals that are responsible for the oxidation of Cr. The Cr liberation levels achieved are possibly not high enough to be feasible for industrial purposes. However, a further investigation of the advanced oxidation process could optimise the process to yield even higher Cr liberation. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2014

Ferrochrome slag is a by-product from the production of ferrochrome, an essential component in stainless steel. World wide it is known that ferrochrome slags are been used mainly in the road and civil construction industries, and in producing refractories. Slag management at ferrochrome producing companies has been influenced by the limited space available and financial cost implications of the siag dumps. In South Africa, according to the Department of Water Affairs and Forestry's minimum requirements, (DWAF, 1998), ferrochrome slag due to its quantity or volume on the disposal sites has been classified as hazardous, as it leaches Manganese (Mn) (33%) above the DWAF minimum environmental requirements acceptable levels. This rating of the slag has therefore put limitations on the use of slag commercially. This paper investigates the various slag uses proposed which can impact positively on the management of the slag i.e. that would reduce its dumping loads and consequently its impact on the surrounding environment. The uses proposed for are brick and concrete making and road building. The paper provides results for the proposed slag uses leaching potential, performs a risk assessment to determine its potential effect on the environment and human health as weli as discusses the method used to delist the slag through the South African delisting process. Comments on the process from the DEAT are also provided. / Thesis (M. Environmental Management)--North-West University, Potchefstroom Campus, 2009.

Ferrochrome slag is a by-product from the production of ferrochrome, an essential component in stainless steel. World wide it is known that ferrochrome slags are been used mainly in the road and civil construction industries, and in producing refractories. Slag management at ferrochrome producing companies has been influenced by the limited space available and financial cost implications of the siag dumps. In South Africa, according to the Department of Water Affairs and Forestry's minimum requirements, (DWAF, 1998), ferrochrome slag due to its quantity or volume on the disposal sites has been classified as hazardous, as it leaches Manganese (Mn) (33%) above the DWAF minimum environmental requirements acceptable levels. This rating of the slag has therefore put limitations on the use of slag commercially. This paper investigates the various slag uses proposed which can impact positively on the management of the slag i.e. that would reduce its dumping loads and consequently its impact on the surrounding environment. The uses proposed for are brick and concrete making and road building. The paper provides results for the proposed slag uses leaching potential, performs a risk assessment to determine its potential effect on the environment and human health as weli as discusses the method used to delist the slag through the South African delisting process. Comments on the process from the DEAT are also provided. / Thesis (M. Environmental Management)--North-West University, Potchefstroom Campus, 2009.

The production of ferrochrome (FeCr) from chromite ore is a reducing process, whereby the Cr(III) and Fe(II) in the ore are reduced to metallic chromium (Cr) and iron (Fe) in the final product. FeCr is mostly used for the production of stainless steel, which is a vital alloy in modern society. It is, however, impossible to exclude oxygen completely from all the high temperature steps during the production process and very small amounts of Cr(VI) are therefore formed, although not intended. The formed Cr(VI) is mostly associated with the off-gas of the high temperature processes, which are cleaned before it is released into the atmosphere by means of venturi scrubbers or bag filter systems. Certain Cr(VI) species are regarded as carcinogenic, with specifically airborne exposure to these Cr(VI) species being associated with cancer of the respiratory system. FeCr smelter facilities generate three main types of waste materials, i.e. slag, venturi sludge and bag filter dust (BFD). Most of the Cr in the waste materials consists mostly of Cr(III). However, BFD generated during the cleaning of the off-gas of open/semi-closed furnaces, could contain more significant levels of Cr(VI) than the slag and sludge. The aim of this study was to determine the solubility of different Cr(VI) species present in BFDs. This would allow that the Cr(VI) in BFD is categorised as water soluble Cr(VI), sparingly soluble and insoluble Cr(VI). These solubility categories can then be related to groups of Cr(VI) compounds, therefore taking the first step in better characterisation of Cr(VI) present in BFD. Four different BFD samples from FeCr producers in South Africa were characterised in detail. Analytical methods such as scanning electron microscope (SEM), SEM with energy-dispersive X-ray spectroscopy (SEM-EDS), particle size analysis, trace metal analysis with inductively coupled plasma with a mass spectrometer detector (ICP-MS) and Cr(VI) analysis with ion chromatography (IC) were utilised in order to characterise and categorise the samples. The results indicated that more Cr(VI) leached with an increase in pH. This was in contrast with the trend for most heavy metals. This was also an indication that not only soluble, but also sparingly- and insoluble Cr(VI) compounds occur in the BFD samples evaluated. Further analysis showed that approximately one third of the Cr(VI) species was insoluble and the remainder consisted of sparingly insoluble and soluble Cr(VI) compounds. The most significant finding was that the current leaching procedures applied by FeCr producers, prior to the chemical reduction of Cr(VI), do not effectively extract the sparingly water insoluble compounds. This results in Cr(VI) leaching from waste facilities at later stages, even if seemingly effective Cr(VI) treatment was applied. Therefore, it should be considered as an extremely important future perspective to develop economically feasible Cr(VI) extraction procedures that will ensure complete extraction of sparing water soluble Cr(VI) compounds together with the water soluble fraction, prior to chemical reduction of Cr(VI) and subsequent storage of the residue on a waste facility. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2015

The production of ferrochrome (FeCr) from chromite ore is a reducing process, whereby the Cr(III) and Fe(II) in the ore are reduced to metallic chromium (Cr) and iron (Fe) in the final product. FeCr is mostly used for the production of stainless steel, which is a vital alloy in modern society. It is, however, impossible to exclude oxygen completely from all the high temperature steps during the production process and very small amounts of Cr(VI) are therefore formed, although not intended. The formed Cr(VI) is mostly associated with the off-gas of the high temperature processes, which are cleaned before it is released into the atmosphere by means of venturi scrubbers or bag filter systems. Certain Cr(VI) species are regarded as carcinogenic, with specifically airborne exposure to these Cr(VI) species being associated with cancer of the respiratory system. FeCr smelter facilities generate three main types of waste materials, i.e. slag, venturi sludge and bag filter dust (BFD). Most of the Cr in the waste materials consists mostly of Cr(III). However, BFD generated during the cleaning of the off-gas of open/semi-closed furnaces, could contain more significant levels of Cr(VI) than the slag and sludge. The aim of this study was to determine the solubility of different Cr(VI) species present in BFDs. This would allow that the Cr(VI) in BFD is categorised as water soluble Cr(VI), sparingly soluble and insoluble Cr(VI). These solubility categories can then be related to groups of Cr(VI) compounds, therefore taking the first step in better characterisation of Cr(VI) present in BFD. Four different BFD samples from FeCr producers in South Africa were characterised in detail. Analytical methods such as scanning electron microscope (SEM), SEM with energy-dispersive X-ray spectroscopy (SEM-EDS), particle size analysis, trace metal analysis with inductively coupled plasma with a mass spectrometer detector (ICP-MS) and Cr(VI) analysis with ion chromatography (IC) were utilised in order to characterise and categorise the samples. The results indicated that more Cr(VI) leached with an increase in pH. This was in contrast with the trend for most heavy metals. This was also an indication that not only soluble, but also sparingly- and insoluble Cr(VI) compounds occur in the BFD samples evaluated. Further analysis showed that approximately one third of the Cr(VI) species was insoluble and the remainder consisted of sparingly insoluble and soluble Cr(VI) compounds. The most significant finding was that the current leaching procedures applied by FeCr producers, prior to the chemical reduction of Cr(VI), do not effectively extract the sparingly water insoluble compounds. This results in Cr(VI) leaching from waste facilities at later stages, even if seemingly effective Cr(VI) treatment was applied. Therefore, it should be considered as an extremely important future perspective to develop economically feasible Cr(VI) extraction procedures that will ensure complete extraction of sparing water soluble Cr(VI) compounds together with the water soluble fraction, prior to chemical reduction of Cr(VI) and subsequent storage of the residue on a waste facility. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2015

Tez (Doktora) - Süleyman Demirel Üniversitesi, Fen Bilimleri Enstitüsü, İnşaat Mühendisliği Anabilim Dalı, 2008. / Bibliyografya var.

In South Africa, the ferrochromium industry produces approximately 100,000 t bag house filter dust and slurry, while the stainless steel industry produces 24,000 t of dust annually [17,39]. The toxic substances in these wastes potentially pose a threat to the environment and human health, especially Cr (VI) due to its toxic, carcinogenic, highly soluble and strongly oxidizing properties. Therefore, the existence and treatment of wastes from stainless steel and ferrochrome production remain a challenge and an issue of concern. The increase of environmental legislation globally and the trend towards sustainable development are drives for alternatives to landfill. In the present thesis, the characteristics, formation mechanisms, leachability and stabilisation of the Cr (VI)-containing electric furnace dust and filter cake were investigated using various techniques such as XRD, XRF, TG/DTA, XPS, SEM-EDS, FT-IR, Raman spectrometer and UV/Vis spectrometer. The electric furnace dust and filter cake are very fine particles. Stainless steel dust forms by the entrainment of charge materials, evaporation or volatilisation of elements and ejection of slag and metal by spitting or the bursting of gas bubbles. It was found that ferrochrome dust is formed by the ejection of slag and metals droplets from the electrode hole, the entrainment of charge materials, vaporisation as well as the formation and precipitation of compounds from vaporised species in the off-gas duct. Filter cake contains crystal phases (CaF2 and CaSO4 ) and metal rich amorphous phases. It is formed due to super saturation and precipitation. Leaching experiments on the wastes showed that Cr (VI) rapidly leaches out by distilled water. Bricks were produced by mixing wastes (stainless steel plant dust, ferrochrome dust and filter cake) and clay. The optimum sinter parameter was found to be 1100oC and 5 hours for a 50wt% SPD-50wt% AS mixture in the brick. The leachability of Cr(VI) is strongly influenced by the mass%CaO/mass%SiO2 ratio and alkali metal oxides content in the wastes. The emission factors from the stabilised wastes (SPD, FCD1, FCD2 and FC) are similar to those reported for the cement industry. Semi-dynamic leaching tests indicated that the predominant leaching mechanisms of chromium species are initial surface wash-off followed by matrix diffusion. / Thesis (PhD (Metallurgical Engineering))--University of Pretoria, 2007. / Materials Science and Metallurgical Engineering / unrestricted