School of Chemical and Metallurgical Engineering (ETDs)
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Item Wear Reduction and Media Density Optimization for the Single Stage Pipe Densifier at Sishen Iron Ore’s Beneficiation Plants(University of the Witwatersrand, Johannesburg, 0202-02) Botha, Simone; Kabezya, KitungwaThe depleting high-grade iron ore mining supply at Sishen Mine in the Northern Cape, South Africa, has given rise to its beneficiation plants operating at higher media densities to upgrade lower-grade ore. In this study, densification was numerically modelled using an MPPIC model and experimentally tested using a 200-mm diameter centrifugal densifier from two local suppliers – Multotec and HMA. Shear stress, wear rate, separation efficiency and media losses were measured at increasing operating densities and differing vortex finder sizes. Optimum operating conditions were established. It was found that a feed density of 3.60 t/m3 and a shear stress of 9.70 e-3 N/m3 at the inlet using a vortex finder diameter size of 30 mm exhibited favourable performance in terms of media densification and downstream recovery. The practical significance of this is proven in terms of wear rate and its predictability to provide a consistent overflow of below 1.20 t/m3 media to the recovery circuit. Furthermore, information about ideal operating conditions in terms of inlet pressure and controls to identify premature failures were established.Item Experimental heat transfer coefficients for the cooling of oil in horizontal internal forced convective transitional flow(University of the Witwatersrand, Johannesburg, 1981) Rogers, Douglas Gordon; Van der Merwe, D.F.Item Co-gasification of Coal and Solid Waste to Hydrogen Enriched-Syngas in a Fixed Bed Gasifier(University of the Witwatersrand, Johannesburg, 2020-10) Ozonoh, Maxwell; Daramola, Michael O.; Oboirien, Bilainu O.The economic growth of every nation around the globe is centred on energy. Energy can be harnessed from different sources using different conversion systems, but such systems should be sustainable. Liquid fuels such as petroleum and solid fuels (e.g. coal & biomass) are largely used for energy production. Energy recovery from these fuels is usually carried out using thermal chemical processes such as combustion, pyrolysis, and gasification systems. Out of the three technologies, gasification is considered the most attractive based on its efficiency and other qualities. In the gasification process, syngas is produced. It is necessary to produce syngas of high quality such as hydrogen-enriched syngas. Hydrogen-enriched syngas can be used in fuel cells, gas turbines and engines for electricity production. This type of gas burns with little gaseous emissions to the atmosphere, but its production is dependent on the type of fuel and process conditions, and energy conversion system employed. In South Africa, around 95 % of electric power production comes from coal, and the current reserve is projected to last not more than a century [8]. Secondly, the coal is fast depleting and generates a lot of gaseous emissions (e.g. CO2, NOX & SOX) that pose a huge threat to the environment. The emission of the aforementioned gases is a very serious issue in South Africa. Presently, some Carbon Capture and Storage (CCS) projects are on-going in the country, although the CCS is not the fuse of this study. The gasification of biomass waste and coal could assist in gaseous emission reduction. Similarly, large amounts of agricultural wastes (e.g. sugarcane bagasse, corn cob & pine saw dust) and other solid waste such as tyre are in abundance in SA. It is detailed in chapter 2. Majority of the wastes are disposed indiscriminately, hence resulting in environmental pollution. Importantly, the solitary gasification of biomass is very expensive considering the prices of biomass. Besides that, biomass produces large amount of tar hence, resulting in operational difficulties in the gasifier and end user facilities. In this study, co-gasification of coal and solid wastes is considered as a crucial alternative to addressing the aforementioned problems. Particularly, the feedstocks used for this study were coal, biomass (corn cob (CC), pine sawdust (PSD), sugarcane bagasse (SCB)) and waste tyre (WT) and were pre-treated by drying, milling, sieving, and torrefaction (coal was not torrefied). The fuel samples were blended with coal at different ratios as detailed in the thesis and used for the study. For the torrefaction process, the most viable torrefaction process conditions and feedstock were determined, while the torrefaction process model for the feedstocks were developed, using Response Surface Methodology (RSM) and Artificial Neural Network (ANN), respectively. The Performance efficiency of gasification systems was evaluated using experimental data obtained from a few gasifiers (e.g. entrained, fluidised, and fixed bed) operated at varied experimental conditions using blends of feedstocks (e.g. biomass, coal, waste tyre etc.). A backpropagation Levenberg Marquardt (L-M) and Bayesian Regularisation (BR) algorithms of ANN model with Multiple Input- Multiple Output (MIMO) and Multiple Input-Single Output (MISO) layer networks were considered. The results of the MIMO and MISO layer networks obtained from the L-M algorithm were better than that of BR algorithm which is in affirmation with some of the results found in the literature. For model result improvement, Input Variables Representation Technique-by-Visual Inspection Method (IVRT-VIM) and Output Variables Representation Technique-by-Visual Inspection Method (OVRT-VIM) were developed from the study. Estimation of the gaseous emissions and profits from biomass, tyre, and coal fired co-gasification CHP Plant using Artificial Neural Network (ANN) was carried out for 20-year investment period using South Africa (SA) and Nigeria as cases studies via Artificial Neural Network (ANN). Higher profits were obtained from South African feedstocks than that of Nigerian feedstocks due to cheaper price of SA coal WFO and WOFC, but the gaseous emissions (CO, NOX, & SO2) from the Nigerian fuels were lower than that of SA because of differences in compositions of the fuels. The potentials of biomass torrefaction in terms of profitability in a co-gasification CHP plant for a 20-year-investment period was carried out using blends of Coal + SCB, Coal + CC, and Coal + PSD with coal-to-biomass ratio of 50:50, 71:29, and 80:20, respectively. The two financial cases mentioned earlier were considered. Four investment terms including: (A) 1st–5th, (B) 5th– 10th, (C) 10th– 15th & (D) 15th– 20th and two operational cost models; with feedstock costing (WFC) and without feedstock costing (WOFC) were employed. An estimated profit of between USD5.9 million - USD6.5 million and USD7.8 - USD7.9 million was earned at the end of investment plan using WFC and WOFC, respectively. The Internal Rate of Return (IRR) was 5 ± 1 %/yr. and 7 ± 4 %/yr. based on South African electricity price of 0.14 $/c kWh, respectively. The parametric effect of process variables during torrefaction of coal/biomass/waste tyre blends using ANN and RSM models were studied. The variables considered were Higher Heating Value (HHV), Enhancement Factor (EF), and Sold Yield (SY). The most effective operating process conditions (in terms of blending ratio, temperature and torrefaction time: input variables) is of the order: 50:50 at 300 OC and 45 min > 50:50 at 250 OC and 30 min >50:50 at 200 OC and 45 min. Similarly, the most viable fuel follows the order of Coal + Torrefied PSD > Coal + Torrefied SCB > Coal + Torrefied CC and > Coal + Torrefied WT. Coal + Torrefied PSD has HHV of 28.27 % and an EF of 1.41. This corresponded to around 10 % increase in the HHV of the torrefied fuel when compared to the raw fuel and about 25.23% higher than the EF of Coal + Torrefied WT of 1.03. Based on the result of the EF of Coal +Torrefied waste tyre, upgrading of the fuel quality via torrefaction is not recommended. Furthermore, a comprehensive study on tar treatment techniques was carried out using tars produced from biomass and blends of biomass and coal employing biochar based and Ni-biochar based catalysts. Box Behnken Design of Experiment (DoE) method was used. A full quadratic regression model was used to develop a mathematical model for tar treatment based on the feedstocks studied. The Pine Sawdust-Biochar Catalyst (PSD-BC) and Nickel Pine Sawdust-Biochar Catalyst (Ni-PSD-BC) were the most effective in terms of tar treatment and with an average percentage amount of tar conversion of 89.76 and 96.73%, respectively. Ni-PSD-BC was more efficient for tar cracking than PSD-BC, but PSD-BC (waste base) may be more attractive if sustainability and cost effectiveness of precursors are considered. Co-gasification of coal and pine sawdust (PSD) to hydrogen enriched syngas in a fixed bed gasifier was carried out with catalyst (WCAT) at 900 OC and without catalyst (WOCAT), at 700, 800, and 900 OC, respectively. Coal-to-PSD ratio of 1:1 was used, while Nickel-pine sawdust-biochar (Ni-PSD-BC) and pine sawdust-biochar (PSD-BC) were employed as catalysts. The gases produced at 700, 800 & 900 OC using WOCAT cannot be used in fuel cells and gas turbines due to poor quality, while others produced at 900 OC WCAT, can be used in internal combustion engines and gas turbines, but unfortunately, have lower quality to be employed in fuel cells for electricity production. However, the study provides a method of beneficiation of the high ash content South African coal for energy production. The outcome of this study is also instrumental to energy security, efficiency and sustainability as well as waste management in South Africa, Nigeria and other parts of the globe. An assessment of the economic, energy and environmental viability of a 5 MW co- gasification power plant was carried out, using blends of coal and biomass, and two financial cases were considered namely: with feedstock costing (WFC) and without feedstock costing (WOFC). Feedstock profitability in the plant for energy production was evaluated. Equipment consisting was not considered. The power plant used 20,473,451.41 kg, 20,986,049.96 kg, 18,251,806.49 kg, and 15,276,277.85 kg of Coal + SCB, Coal + CC, Coal + PSD, and Coal + WT to produce the 5 MW and 5.56 MW electric and thermal power, annually. Coal + Torrefied PSD was the most profitable of the fuels studied. The use of Coal-to-PSD ratio of 4:1 for the power generation as against Coal-to-PSD blend ratio of 1:1 resulted to an annual loss of about ZAR6, 461,301.77 ($90,458,224.70) and ZAR123,782.47 ($1,732954.58) WFC and WOFC, respectively.Item Thermo-mechanical processing and testing of titanium alloys for potential dental applications(University of the Witwatersrand, Johannesburg, 2022-12) Nape, Kgetjepe Tlhologelo; Chown, Lesley H.; Cornish, LesleyNew titanium alloy compositions were identified for potential dental implants on the basis of having two-phase microstructures for good mechanical properties and by avoiding problematic elements to increase biocompatibility. The Thermo-Calc program with the TTTI3 (TT Ti-alloy) database was used to calculate new Ti compositions, without toxic Al and V as alloying elements. The aim was to mimic the α+β phase proportions in Ti-6Al-4V and Ti-10.1Ta-1.7Nb-1.6Zr (TTNZ) (an analogue for Ti-6Al-4V). Copper (Cu = 1, 3, 5 and 10 wt%) was varied to give the Ti2Cu phase, which gives good hardness and antibacterial properties. A cost analysis was done and the less expensive Ti-6Nb-4Zr-xCu and Ti-8Nb-4Zr-xCu (x = 0 and 5 wt%) compositions were selected for experimental work. The samples were made by arc-melting and prepared for microstructural studies to understand the influence of alloying elements, and to compare with the commercial Ti-6Al-4V and reported Ti-10.1Ta-1.7Nb-1.6Zr (TTNZ) alloys. Hot deformation of the as-received Ti-6Al-4V and TTNZ alloys was investigated, using a Gleeble 3500® Thermo-mechanical Simulation Facility, at 850°C and 950°C and strain rates of 0.1 s-1 and 10 s-1. The as-cast Ti-6Nb-4Zr-xCu and Ti-8Nb-4Zr-xCu (x = 0 and 5 wt%) alloys comprised αTi and βTi, with Ti2Cu once Cu was added, although EDX indicated some inhomogeneity. The XRD analyses identified αTi and small amounts of βTi with solid solution (shifted peaks), with some Ti2Cu. The Ti-8Nb-4Zr alloy (285 ± 7 HV) had similar hardness to Ti-6Nb-4Zr (280 ± 13 HV), and was considered the better alloy. Adding 5 wt% Cu increased the hardness due to Ti2Cu. With the Gleeble, deformation at 950°C and 10 s-1 led to a finer Ti-6Al-4V microstructure, whereas finer Ti-10.1Ta-1.7Nb-1.6Zr (TTNZ) microstructures occurred at 850°C and 10 s-1. The XRD of all deformed Ti-6Al-4V and Ti-10.1Ta-1.7Nb-1.6Zr samples indicated αTi and βTi, with shifted βTi peaks. The Ti-6Al-4V (324 ± 9 HV) deformed at 850°C and 0.1 s-1 had higher hardness than both deformed TTNZ samples. Higher flow stress were obtained at higher strain rate (10 s-1) and lower temperature (850°C). The Ti-6Al-4V alloy had higher flow stress than the TTNZ alloy. Therefore, the TTNZ alloy was considered better, due to its lower flow stress, which indicated better formability. The new alloys had similar hardnesses to Ti-6Al-4V, and were higher than for TTNZ, suggesting that they might have similar properties to Ti-6Al-4V.Item Influence of copper on the corrosion and mechanical properties of Grade 4 titanium for biomedical applications(University of the Witwatersrand, Johannesburg, 2022-12) Hadebe, Nomsombuluko Dayanda Elizabeth; Cornish, Lesley; Chown, Lesley H.; Smit, Melanie; Mwamba, AlainThis study assessed the effect of Ti2Cu and its proportions on the corrosion resistance, and compared the results to Grade 4 commercially pure titanium. The Thermo-Calc program with the TTTI3 (Ti-alloy) database was used to predict the phases. Materials Studio software was used to model the crystal structures and XRD patterns of the phases of Ti-Cu alloys. Ti-Cu samples with 0, 5, 15, 25, 33, 40, 47 and 50 wt % Cu were produced. Composition, microstructures, phases, hardness and corrosion resistance were studied in the as-cast and annealed conditions (750° and 900°C water quenched). The CP Ti samples comprised basket-weave acicular microstructures. The Ti-5Cu samples comprised lamellar (αTi) and Ti2Cu phases. The Ti-15Cu, Ti-25Cu and Ti-33Cu alloys comprised (αTi) dendrites and sparse eutectic of Ti2Cu and (αTi). The ((βTi) dendrites decomposed to (αTi) and Ti2Cu, and could not be retained due to insufficient fast quenching. The Ti-40Cu and Ti-47Cu samples had minor titanium oxide dendrites which solidified first and then Ti2Cu nucleated on them and grew as dendrites, surrounded by the Ti2Cu + TiCu eutectic. In the Ti-50Cu sample, TiCu was the true primary phase and grew as needles, and was subsequently surrounded by a coarse TiCu + Ti2Cu eutectic. No Ti3Cu phase was observed. The microstructures of the as-cast alloys agreed with the Cu-Ti phase diagram of Ansara et al. (2021) and Dyal Ukabhai et al. (2022) with the congruent formation of Ti2Cu, as well as no Ti3Cu. The addition of copper to titanium increased the hardness, while annealing decreased the hardness of the Ti-Cu alloys. Addition of copper above 5 wt % Cu and annealing decreased the corrosion resistance of the samples, but since copper ions in liquid solutions promote the antimicrobial activity, some corrosion is necessary to allow the copper ions to be available. The corrosion tests showed that the corrosion rates obtained were very low, below 0.13 mm/y, which is an acceptable corrosion rate for biomaterial applications. Ti-5Cu showed the best corrosion resistance.Item Dynamic compartmentalised heat transfer modelling for systems with biological applications(University of the Witwatersrand, Johannesburg, 2023) Xu, Lan; Moodley, Prebantha; Hildebrandt, DianeProper thermal management is crucial to controlling the temperature of biological systems within an optimized operating range. A biological system is comprised of a multitude of interacting facets, where a system is often disrupted as a consequence of random events such as the change in ambient temperature. In contrast the design of most human engineered chemical systems or processes may assume steady state operation and as a result is relatively straightforward to design and optimise. Yet, often steady temperature ranges are required in unsteady conditions. This sort of unsteady state system requires consideration of the dynamic changes to the conditions and are often required to be within many applications. A narrow temperature band is essential for controlling the outcomes of how biological systems’ function—thermal denaturation of biological components depend on precise control of the transport of heat. Insulin—a hormone peptide drug—is temperature sensitive and undergoes thermal fibrillation when exposed to temperatures above manufacturers' recommendations. To maintain such medication within specific temperature bands is a challenge in the face of energy intermittency from the energy crisis that South Africa is currently facing. Within this dissertation, a medical device to contain thermosensitive biological compounds is designed and modelled as a system undergoing dynamic thermal conditions. This heat transfer modelling is used as a prototyping process for designing the medical device to protect temperature sensitive medication during power outages. The simulated device, when used correctly, is able to keep medication thermally stable under 8°C during Stage 4 load shedding (7.5 hours of power outages within a 24-hour period).Item A Life Cycle Assessment of Plastic vs Cardboard Packaging in the Fast-Moving Consumer Goods Market(University of the Witwatersrand, Johannesburg, 2024) Rivett, Stephanie Anne; Harding, KevinGlobally there is a movement to mitigate the need for single-use plastics as well as the utilization of plastic materials when alternative options are available. This movement comes in response to the extensive research that has demonstrated the long-term negative environmental impact that plastics pose to our existence when disposed of into landfills. A significant contributing factor to the mass of single-use plastics is the packaging industry. This study focused more specifically on the single use plastic packaging in the fast-moving consumer goods (FMCG) market which are used to shrink-wrap bottles together to be supplied into the trade such as Pick ‘n Pay and Checkers. South Africa is facing two main challenges pertaining to the FMCG market: namely the constrained supply of energy and the socio-economic pressure to reduce the environmental impact caused by unrecycled packaging waste. This research aimed to investigate the energy requirements and environmental impact of packaging configurations that included shrink-wrap plastic and cardboard cartons versus packaging configurations that utilized only cardboard cartons to ascertain which option provides the lowest possible energy requirements, and environmental impact. This study aimed to execute a cradle-to-grave life-cycle assessment (LCA) of the two different packaging configurations by utilizing the SimaPro software. The LCA was executed with respect to one reference product that is supplied into the FMCG market year-round known as Prewash Promo. Prewash Promo is a laundry pretreatment that aids in the removal of stains. The first of the two packaging configurations under analysis was the traditional packaging configuration of Prewash Promo that has always been used. This packaging configuration consisted of six bottles that were grouped into two sets of three using rubber bands. The two sets of three were then shrink-wrapped into a group of six. Two shrink-wrapped sixes were then placed into a box that was sealed using plastic packaging tape or sellotape. The second packaging configuration under analysis mitigated the use of shrink wrap plastic and associated materials (elastic bands) thus the second packaging configuration consisted of twelve bottles placed into the box that was then sealed using packaging tape. The main objective of this LCA was to ascertain the packaging material configuration that was the most energy-efficient and environmentally responsible choice to utilize in the Stephanie Anne Rivett A Life Cycle Assessment of Plastic vs Cardboard Packaging in the Fast-Moving Consumer Goods Market iv FMCG market. This LCA was conducted utilizing the data pertaining to the year 2022 and the functional unit of this study was one year’s worth of packaging used in the production of Prewash Promo. Prewash Promo was chosen as the reference product as it does not demonstrate seasonal or geographically specific use, and it was a viable option for the change in packaging configuration. A significant factor that influenced the impact of LCA results was the waste scenarios associated with the use of different materials. In this study, the exact quantities of material that were recycled versus sent to landfills could not be definitively known. It was for this reason that the published industry standard recycling rates for the year 2022 and knowledge of socioeconomic habits were used to formulate assumptions. It was assumed that the minor materials included in the packaging configurations such as packaging tape and elastic bands conformed with social habits and did not exhibit any recycling and went directly to landfill. The recycling rate of corrugated board for the year 2022 was reported to be 61.4% and the recycling rate of plastic for the year 2022 was reported to be 42.8% (Mpact Recycling, 2019a). These recycle rates were utilized to model the packaging configurations to facilitate the comparison between the two. The validity and influence of these assumptions were assessed by means of a sensitivity analysis after the main LCA was executed. The ecoinvent 3 database library available via the SimaPro software (version 9.4.0.3, 2022) and the ReCiPe Midpoint method were used to execute the impact assessment calculations. This method consisted of eighteen impact categories that assessed the impact of each of the packaging materials with respect to the impact they posed to human health, biodiversity, and resource scarcity. The full eighteen category impact assessment was condensed into five focus categories based on the target audience, the research objectives and geographical location of the study. These five focus categories were: global warming, stratospheric ozone depletion, fine particulate matter formation, freshwater ecotoxicity and water consumption. These five categories were chosen because they provide the best overview of the impact in a summarized form pertaining to factors contributing to environmental decline, changing weather conditions, reduction in air quality and the impact of freshwater resources. The LCA was first executed for each packaging configuration in isolation to ascertain the impact contributions of each of the individual factors involved in the construction of the Stephanie Anne Rivett A Life Cycle Assessment of Plastic vs Cardboard Packaging in the Fast-Moving Consumer Goods Market v packaging set-up. The analysis of each packaging configuration in isolation facilitated highlighting major contributing factors to consider replacing with alternatives or mitigating the use thereof. This assessment highlighted the drastic impact contribution that the use of electricity had on the impact score of the heat shrink-wrap plastic configuration. The full LCA comparison was then executed to compare the two packaging configurations. In each of the five focus impact categories the corrugated board only packaging configuration achieved an environmental impact score 83% lower than the heat shrink-wrap plastic packaging configuration. This drastic difference was only reduced to 79.6% when excluding long-term emissions. Upon the conclusion of the LCA comparative assessment the validity of the recycle rate assumptions for corrugated board and shrink-wrap plastic were assessed by executing sensitivity analyses. These analyses determined that the conclusion achieved at the end of the LCA comparison stage remained valid irrespective of the recycling rate of corrugated board or shrink-wrap plastic. The final objective investigated in this study was the uncertainty analysis to assess the accuracy and reliability of the data utilized in the LCA. The uncertainty analysis was executed in the SimaPro software by utilizing a Monté Carlo analysis with the ReCiPe 2016 midpoint (H) method which consisted of 1 000 fixed runs with a confidence interval of 95%. An uncertainty bar chart was generated that displays the error associated with each of the eighteen impact categories. The uncertainty analyses for both packaging configurations determined that the data for global warming, stratospheric ozone depletion, fine particulate matter formation and freshwater ecotoxicity demonstrated low error. The cardboard only configuration exhibited very low error values of between 8% and 61% as opposed to the plastic packaging configuration which exhibited errors between 16% and 214%. The water consumption data in contrast exhibited significant uncertainty for both configurations due to the difficulty in definitively determining accurate water consumption data for such extensive life cycles. Water was utilized extensively in the developmental stages of each of the materials (forestry, paper/pulp manufacturing and plastic polymer and plastic shrink manufacturing) and exhibited significant variation in volume of consumption due to high degrees of variation in plant technology and process equipment age. Stephanie Anne Rivett A Life Cycle Assessment of Plastic vs Cardboard Packaging in the Fast-Moving Consumer Goods Market vi The culmination of the results of each of the assessments executed concluded that the corrugated board only configuration is the packaging configuration that is the most environmentally friendly, and energy-efficient packaging option of the two that were considered.Item Extraction of gold from tailings using environmentally friendly reagents(University of the Witwatersrand, Johannesburg, 2024) Khuduwe, Marema JackThe depletion of high-grade gold ores, the high production costs associated with mining at lower depths, and the high demand for gold have caused the mining industry to search for alternative sources of gold. Additionally, the conventional cyanidation process raises health and environmental concerns. The treatment of waste generated by the cyanidation process to reduce the residual cyanide content before disposal also incurs additional costs. Therefore, this study focuses on the extraction of gold from tailings using environmentally benign reagents such as 1-butyl-3-methyl-imidazolium hydrogen sulfate (BmimHSO4) ionic liquid (IL), ethaline (mixture of choline chloride and ethylene glycol) deep eutectic solvent (DES), and thiosulfate. The gold tailings used in this work were obtained from DRD Gold Ergo Mining (Pty) Ltd operations in the Witwatersrand Basin, South Africa. Mineralogical analysis by X-ray diffraction (XRD) showed that the tailings material consisted of quartz (72.13%), muscovite (7.49%), chlorite (2.65%), pyrophyllite (1.50%), clinochlore (1.30%), and other trace minerals. The gold association by mineral liberation analysis (MLA) employing the Sparse Phase Liberation-Dual Zoom (SPL-DZ) method indicated that all the gold was locked in the iron oxide (FeO) matrix. Gold grade analysis by fire assay analysis (FAA) showed that the tailings had a head grade of 0.32 g/t Au. The leaching of the gold tailings was carried out by employing the use of the design of experiments (DOE) method to identify factors that significantly influence the gold extraction process. The central composite design (CCD) technique in conjunction with response surface methodology (RSM) was used to optimize the identified significant factors to obtain optimum conditions for optimal gold extraction. The effect of particle size and the co-dissolution of Ag, Cu, Fe, and Ni with Au was investigated. Furthermore, the recovery of Au by activated carbon (AC) from leach solutions of the investigated reagents was also investigated The results from the IL studies indicated that the reagent concentration had a positive and significant influence on the gold extraction process, suggesting that to achieve optimal gold extraction, IL concentration must be kept at a high level. The interaction of temperature, concentration, and pulp density also significantly influenced the gold extraction process in the IL solution. The theoretical optimum conditions established from the statistically-based optimization model were 75 C leaching temperature, 1.0 M (25% aqueous BmimHSO4 Extraction of gold from tailings using environmentally friendly reagents Marema J Khuduwe 4 mixture ) IL concentration, and 10 %w/v pulp density, giving a maximum Au extraction of 45.3%. This low Au extraction is attributed to the inefficiency of ILs in dissolving metals from their solid oxide form, thus unable to liberate the gold for dissolution locked in the metal iron oxide. On the other hand, leaching studies focusing on the use of DES found that pulp density and leaching time had a significant and positive influence on the gold extraction process. This suggests that to achieve maximum gold extraction, pulp density and leaching time must be kept at high levels. The optimum conditions were found to be 30 %w/v pulp density and 7 hrs leaching time. A maximum Au extraction of 76.4% was achieved. This high gold extraction is attributed to the high FeO destruction observed in the study, suggesting that the gold was liberated and amenable to leaching. Lastly, thiosulfate leaching studies identified temperature, time, pulp density, the interaction of temperature and concentration, the interaction of concentration and pulp density, and the interaction of temperature and time as the parameters significantly influencing gold extraction. A maximum Au extraction of 47% was achieved. This low gold extraction is attributed to the low efficiency of thiosulfate in dissolving metal iron oxide and the reagent consumption through silica dissolution, thus reducing the amount of thiosulfate available for gold dissolution. The results of the effect of tailings particle size results revealed that the IL leaching of bulk tailings (-300 m, P80 = 75 m) gave Au extraction of 21.9% while the leaching of smaller particle size tailings (-38 m) increased Au extraction to 45.3%. The high gold extraction at smaller particle sizes is attributed to the large surface area available for interaction with the leaching agent and the presence of a thin boundary, thus resulting in improved leaching efficiency. On the other hand, DES leaching of bulk tailings resulted in Au extraction of 71.9% and the leaching of smaller particle size tailings gave 76.4% Au extraction, indicating that reduction in particle size did not have a significant impact on gold dissolution. Lastly, thiosulfate leaching of bulk tailings gave a maximum Au extraction of 24% and the leaching of smaller particle size tailings resulted in an increased Au extraction of 47%, indicating that a reduction in particle size in this system had a significant effect. The study indicated that DES was more efficient in the dissolution of gold tailings compared to the use of IL and thiosulfate. Furthermore, DES gave higher Au extraction (71.6%) compared to cyanide solutions which gave Au extraction of 46.9%. However, cyanide gave a higher Au extraction compared to IL (21.9%) and thiosulfate (24%). These results indicate that ethaline DES is more efficient compared to 1-butyl-3-methyl-imidazolium hydrogen sulfate IL Extraction of gold from tailings using environmentally friendly reagents Marema J Khuduwe 5 and thiosulfate, and thus can be used in the processing of this kind of tailings as an alternative to cyanide. Moreover, the reagents dissolved more gold compared to other metals in the tailings except for IL which dissolved more Cu (50.4%) and Ni (61.9%) compared to Au (45.3%). Finally, the recovery of gold from the leach solution of the investigated reagents using activated carbon (AC) was found to be possible with the maximum Au adsorption of 84.6% achievable from IL leach solution in 2 hours at AC amount of 60 g/l and 4 hours at AC amount of 120 g/l. The maximum Au adsorption of 75% was achieved from DES leach solution in 4 hours at an AC amount of 120 g/l. The highest Au adsorption of 46.4% was achieved from thiosulfate leach solution in 6 hours. The recovery of Au by AC from leach solutions of IL and DES was high, however, they are not comparable to the 99% gold recovery by AC from cyanide solutions in the industry. This indicates that the recovery of gold from these solutions by alternative adsorbents should form a basis for further investigation.Item An Investigation into the Effect of Advanced Gravity Separation on Platinum Group Metals (PGM) Flotation Concentrates(University of the Witwatersrand, Johannesburg, 2024) Nair, Taurean Jevaldo; Sibanda, Vusumuzi“It's the gravity that shapes the large-scale structure of the universe, even though it is the weakest of four categories of forces” - Stephen Hawking Gravity concentration has been around since the dawn of mankind, and just as man has evolved so too has gravity concentration. The earliest records involved ancient cultures (Greeks, Romans, Mayans and Egyptians) using water to selectively separate precious metals from gangue. Gravity concentration has remained an integral part of many processes involving the recovery of native or alluvial precious metals and minerals which are amenable to this process. Developments in gravity concentration technology have led to the inception of advanced gravity separation devices. These advanced gravity separators can overcome the challenges associated with conventional gravity concentration as they are able to induce a high gravitational force that is capable of recovering fine and ultrafine heavy particles as well as particles with a complex mineralogy. Decreasing feed grades and falling metal prices are placing an exorbitant amount of pressure on the PGM industry. As a price-taker, the industry is at the mercy of the prevailing market conditions. This means that the only levers the industry can use are cost cutting or optimization of the process to produce more PGMs at a better quality from the current feed source. The premise of this research project is to essentially find a way to optimize the PGM beneficiation process by the use of gravity concentration. This research specifically targeted the high-grade flotation concentrate stream of a UG2 tailings plant to understand how effective advanced gravity concentration would be in recovering PGMs, upgrading the resulting concentrate as well as rejecting chromite and gangue. PGMs are associated with base-metal sulphides and are inherently complex. This complexity is further exacerbated by the fact that PGMs are in the fine to ultrafine particle size range which makes recovery of PGMs challenging. Gravity concentration is primarily a function of particle size, density and mineralogy. Separation of gangue and chromite from PGMs is another added complication as the gangue minerals are present in higher concentration than the PGMs, have a complex mineralogy and are also found in the fine and ultrafine particle sizes. Fire Assay/ICP- ii MS, XRF, XRD and SEM all confirmed the complexity of the ore being treated. This ‘entanglement of complexity’ makes processing these ores very challenging. A lab-scale Falcon gravity concentrator with an unfluidized (ultrafine) bowl was used in the main experimental work. The optimal parameters to run the gravity concentrator for PGMs was found to be a flow rate of 3 L/min, percent solids of 13.22% and a gravitational force of 300 G’s. These parameters were then applied to a multi-stage gravity concentration process. The feed to the gravity concentrator was found to have a grade of 131.02 g/t 4E PGM. The results indicated that a recovery of 48.90% and a final concentrate grade of 292.04 g/t 4E was achieved at a mass pull of 21.90%. The chromite in the final concentrate of the Falcon gravity concentrator was found to be 1.99% which did not exceed the maximum allowable chrome in concentrate of 3.00%. This proved that gravity concentration was indeed capable of recovering complex PGMs and rejecting chromite. The optimal parameters experiments indicated repeatability, and the assay results were validated by a statistical outlier test in the Minitab Software to ensure data integrity. The particle size analysis revealed that 97.07% of the feed to the Falcon was below 75μm and 66.29% below 25μm, thus confirming that the feed material was fine to ultrafine particles. The final gravity concentrate had a D90 of 42.24μm which was finer than the D90 for the feed, this demonstrates that fine and ultrafine heavy particles were more mineralized and recoverable by the Falcon. This analysis was further reinforced by the fractional analysis which confirmed that the majority of the PGMs were found in the fine to ultrafine fraction. The experiments were repeated using a fluidized bowl in the Falcon to see what the impact of fluidizing water would be. These experiments had lower overall recoveries and mass pulls than those done with an unfluidized bowl. The concentrate grade was, however, higher than the unfluidized bowl experiments possibly due to this bowl recovering PGMs in the coarser fraction. This research provides a steppingstone to understanding the effect of advanced gravity concentration on PGM flotation concentrates and indeed on PGMs in general as well as providing an alternative unique processing option for PGMs. Ultimately advanced gravity concentration has been shown to be an uncomplicated process that can be viable in the recovery of fine and ultrafine complex PGMs. It is environmentally friendly, has low capital and operational costs and has a relatively high efficiency.Item Carbon nanotubes application for lithium-ion battery anodes(University of the Witwatersrand, Johannesburg, 2024) Mhlanga, Nqobile; Raphulu, Mpfunzeni; Sibanda, VusumuziThe most commonly used anode material for lithium-ion batteries (LIBs) is graphite, however it has some shortcomings such as having a low reversible capacity and low diffusion rate which produce low-power density batteries. Thus, the purpose of this study was to examine the application of carbon nanotubes (CNTs) as an alternative LIB anode material. A bimetallic iron-cobalt catalyst supported on calcium carbonate (Fe-Co/CaCO3) was used for the synthesis of CNTs and it was prepared using the wet impregnation method. X-ray diffraction (XRD) analysis of the catalyst showed that it was highly crystalline. The specific surface area (SSA) which was determined using Brunauer-Emmett-Teller (BET) was found to be 11.3 m2/g. CNTs were prepared using the chemical vapour deposition (CVD) method at various test parameters i.e. temperature (650°C,700°C,750°C and 800°C), hydrocarbon flow rate (90 mL/min and 120 mL/min) and carbon source (acetylene and ethylene). High-resolution transmission electron microscopy (HRTEM) results for samples synthesised at 650°C and 700°C using acetylene at a flow rate of 90 mL/min (650°C-A90 and 700°C-A90) showed that CNTs which were multiwalled carbon nanotubes (MWCNTs) in nature were produced. The formation of what appeared to be non-tubular carbon and carbon nanofibers was observed when the synthesis temperature was increased from 700°C to 800°C. The average outer diameter (OD) of the tubes ranged from 20 to 89 nm. At a higher acetylene flowrate (120 mL/min), the quality of CNTs seemed to deteriorate for synthesis temperatures above 650°C. The formation of non-tubular carbon-like nanofibers was observed at synthesis temperatures above 650°C. The average OD of the tubes ranged from 22 to 81 nm. XRD analysis of all samples synthesised using acetylene showed a similar pattern with the most intense peak being that of carbon and minor peaks being of iron. The samples also contained some broad peaks which suggested that the samples contained amorphous carbon. The calculated crystallite size ranged from 3.4 to 6.4 nm for samples synthesised using acetylene at a flowrate of 90 mL/min. For samples synthesised using acetylene at a flowrate of 120 mL/min, the crystallite size ranged from 3.1 to 4.4 nm. Raman spectroscopy confirmed the successful synthesis of MWCNTs; however, the intensity ratio (ID/IG) was found to be above 0.7 for a majority of the samples which confirmed the presence of impurities in the samples. SSA studies revealed that an inversely proportional relationship existed between the SSA and the synthesis temperature. vi HRTEM results for samples synthesised at 650°C and 700°C using ethylene at a flow rate of 90 mL/min (650°C-E90 and 700°C-E90) revealed that CNTs which were MWCNTs in nature were formed. As the synthesis temperature increased from 700°C to 800°C, the formation of what appeared to be non-tubular carbon and carbon nanofibers was observed. The average OD of the tubes ranged from 21 to 84 nm. At a higher ethylene flowrate (120 mL/min), the quality of CNTs seemed to deteriorate for synthesis temperatures above 700°C. The formation of non-tubular carbon-like nanofibers was observed at synthesis temperatures above 700°C. The average OD of the tubes ranged from 11 to 79 nm. XRD analysis of all samples synthesised using ethylene showed a similar pattern with the most intense peak being that of carbon and minor peaks being of iron. However, the depicted minor peaks were broad which suggested that the samples contained amorphous carbon. The calculated crystallite size ranged from 3.7 to 5.7 nm for samples synthesised using ethylene at a flowrate of 90 mL/min. For samples synthesised using ethylene at a flowrate of 120 mL/min, the crystallite size ranged from 3.6 to 6.5 nm. Raman spectroscopy confirmed the successful synthesis of MWCNTs. SSA studies revealed that the SSA decreased with an increase in the synthesis temperature. Furthermore, to evaluate the electrochemical performance of the synthesised material, electrodes of selected samples were fabricated. Commercial graphite electrodes were also fabricated to compare the performance with the samples synthesised in this study. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were used for the electrochemical measurements. The CV tests were conducted at scan rates of 5 mV/s and 10 mV/s, An increase in the CV curve area was observed as the scan rate was increased. The calculated specific capacity of the samples compared well with that of the electrode fabricated with commercial graphite which reported an average of ~197 mAh/g after four cycles at a scan rate of 5 mV/s. The average specific capacity of the electrode fabricated with CNTs sample synthesised at 650°C using ethylene at a flowrate of 120 mL/min (650°C-E120) reported the highest value of 214 mAh/g after four cycles at a scan rate of 5 mV/s. Overall the variation between the samples of the EIS data was marginal. These EIS results also compared well with that of the electrode fabricated with commercial graphite. The findings of this work suggest that MWCNT electrodes have a good application potential and with doping, they may provide better electrochemical performance than graphite as a viable anode material for LIBs.Item Extraction of Alumina from South African calcined clays(University of the Witwatersrand, Johannesburg, 2024) Maria, Matome BatsalelwangThe growing need for high-purity alumina (HPA) is driven by its critical importance in sophisticated batteries and electronic applications. Typically produced from high- purity aluminum (Al) metal using the alkoxide method, HPA production is closely linked to the Bayer process, which relies on Al metal derived from alumina (Al2O3) extracted from bauxite ores. However, the scarcity of alumina-rich bauxite reserves has prompted interest in alternative local sources of alumina including kaolinitic clays, which are abundant and widespread. Although the Bayer process is not appropriate for treating kaolinitic clays owing to their high silica content, efforts have been made to explore alkaline and acidic processing methods for alumina extraction. In particular, the HCl acid leaching process has been extensively studied as a viable acidic processing route. South Africa possesses abundant kaolinitic clays despite the lack of bauxite reserves, making it necessary to investigate the potential for alumina extraction via HCl processing. This study investigated the dissolution of aluminum and iron species from thermally activated clay in a hydrochloric acid solution, emphasizing the selectivity of aluminum extraction over iron impurities. Furthermore, the effect of different calcination and acid leaching conditions on the dissolution of aluminum and impurity species in a hydrochloric acid solution was investigated. Three different kaolinitic clays sourced from South Africa, namely ball (BL), flint (FL), and fire (F) clays, were analyzed to ascertain their chemical and mineralogical properties. It was observed that the raw BL and FL clays utilized in this study shared similar mineralogical compositions, whereas the F clay contained additional clay minerals such as carbonates and smectite. However, mineralogical analysis revealed that BL and FL clays were predominantly rich in kaolinite (82.4% and 91.1%, respectively), whereas raw F clay exhibited a lower kaolinite content (16.5%) and a higher amount of quartz (44.7%). The calcination of kaolinitic clay was performed at temperature range of 600 to 800 °C (interval of 50 °C) for a period of 8 hours. Infrared spectroscopy and X-ray diffraction were employed to confirm the structural and mineralogical changes, iii revealing the transformation of kaolinite into amorphous metakaolinite. The research revealed that calcination temperature significantly influenced alumina extraction, with varying effects on iron content. The calcination temperatures necessary for the complete dehydroxylation of kaolinite into amorphous metakaolinite were uniform across all samples of raw BL, FL, and F clays at 600°C. At this temperature, BL clay demonstrated an Al extraction 79.4%, FL clay showed a recovery of 78.4%, and F clay exhibited an Al extraction of 36.7%. However, although the Al extraction from F clay increased with an increase in calcination temperature, it did not exceed 50 %. Conversely, an increase in the thermal decomposition temperature was accompanied by a decline in the amount of Al extracted from calcined BL clay. The incorporation of iron oxide species in calcined BL clay resulted in the formation of insoluble aluminum spinels at higher temperatures, particularly starting from 700°C until 800 °C. This process led to a decrease in the acid solubilities of both aluminum and iron. Interestingly, the extraction of aluminum from calcined FL clay exhibited a fluctuating pattern: it decreased at 650°C and 750°C but increased at 700°C (69.5%) and 800°C (71.8%). Both calcined BL and FL clays at 600°C demonstrated high aluminum extraction, although accompanied by high iron content (67.8% and 66%, respectively), whereas calcined FL clay at 800°C offered high aluminum extraction with moderate iron content (40.2%). In comparison with BL clay, the lower amount of iron oxides in FL clay did not present a clear trend for the formation of spinels. Statistical analysis showed that leaching time had a significant impact on aluminum extraction of BL clay. Meanwhile, the acid concentration (pertaining only to FL clay), leaching temperature, solid/liquid ratio, and leaching time and solid/liquid ratio interaction significantly affected aluminum extraction for FL and F clays. A higher iron content has ramifications in HPA production for subsequent processing of the leachate solution. However, the reduced energy requirement for achieving complete dehydroxylation, which is essential for aluminum dissolution, presents a significant advantage for aluminum recovery from both BL and FL clays. The choice between BL and FL clays would depend on either a lower energy requirement in the pre-treatment stage with the associated higher cost of processing leachate containing elevated iron content, or a higher energy demand in the iv pretreatment phase with a lower cost linked to processing leachate with moderate iron content. Notably, for FL clay, there was flexibility in assessing the three calcination temperatures that yielded high aluminum dissolution. The findings of this study hold considerable importance for utilizing South African kaolinitic clays as a cost-effective, locally sourced alumina resource for HPA production.Item Vapour Phase Extraction: A Re-Evaluation(University of the Witwatersrand, Johannesburg, 2024) Bailey, Douglas Gwyllm; Hoed, Paul den; Luckos, AdamResearch undertaken at the University of the Witwatersrand has pursued the recovery of valuable metals using vapour-phase extraction. VPE is a process in which an organic ligand reacts with an element of interest; the product, an organo-metallic complex, reports to the vapour/gas phase and so is separated from the bulk material. Contacting with the solid particulate material occurs in a fluidized bed. The stable organo-metallic complexes, being removed, are condensed and recovered. VPE seems a promising technology and so the use of acetylacetone (acac) to extract several metals from various sources was investigated at Wits. The extractions of (1) iron from iron ore fines and synthetic sources and (2) chromium and tantalum from synthetic samples were investigated; so, too, was (3) aluminium from fly ash and synthetic sources; (4) vanadium from depleted catalysts; and (5) gold from tailings. Gold and tantalum cannot be extracted by acac at all, yet it was thought that they could be. Ligands may also not react with—or react in the same way with—different structural states of the same compound; this was not considered in previous studies, which only mentioned that higher extractions were obtained from synthetic samples. The underlying causes were not adequately considered. Essential properties—such as phase and composition—were not identified, much less characterized. Other limitations include fractionation and fluidization. If the grade of the material is very low, there may not be sufficient metal recovered to isolate it by means of fractionation. This would require high selectivity, which precludes the use of acac. A lack of fluidization prevented reagents from reaching the target species, starving the reactions. Thus, the conditions needed to undertake kinetic studies were not met, invalidating previous tests and their findings. Previous work which reported success has been shown to be unreliable or misguided by experimental anomalies. However, the possibility of using such a process cannot be ruled out altogether. That is to say, alternative ligands can be considered, but only if they can be shown to react with a target species in the phase in which it occurs. The mechanisms involved in the process need to be properly understood and employed before a process can be conceived and developed.Item Characterization of a TW R260-60E1 Pearlite Rail Steel with a Weld Gap Size of 40 mm and 50 mm(University of the Witwatersrand, Johannesburg, 2024) Meyiwa, Lindani; Maledi, NthabisengThe continuous weld rails (CWR) tracks that are joined by thermite welding (TW) method are known to experience weld failures during their service life. In avoiding or mitigating these failures, a weld gap in joining two rail ends was introduced. The purpose of the weld gap was to accommodate rail expansion during elevated temperatures. Traditionally, a weld gap of 24 mm was created between two rail ends. However, these weld joints were observed to be experiencing challenges of not being able to withstand high contact loads during service life, leading to plastic deformation and eventual failures. This study was investigating the effect on microstructural characteristics, heat-affected zone (HAZ) dimensions, mechanical properties attributes, and wear resistance behaviour of TW R260-60E1 pearlitic rail steel when the weld gap was set to 40 mm and 50 mm. The results revealed that the TW R260-60E1 pearlitic rail microstructure had no martensitic, bainitic and intergranular Widmanstätten ferritic structures. Pearlitic grain sizes and interlamellar spacing on the weld zone of the web region were measured to be 3.6 % wider on the sample with 40 mm weld gap compared to those on the sample with 50 mm weld gap. Big surface area to volume ratio and fast cooling rate had an influence on the production of finer pearlite grain sizes and interlamellar spacing within the web region for both samples. The results further showed that the HAZ width was one of the attributors to the improvement on the mechanical and wear resistance properties. HAZ width varied from 29 mm – 35 mm for sample with 40 mm weld gap, and 27 mm – 33 mm for sample with 50 mm weld gap. The HAZ width on the sample with 50 mm weld gap was narrow than the HAZ width on the sample with 40 mm weld gap. Narrow HAZ width improves microstructural characteristics, mechanical properties and wear resistance behaviour compared to the wider HAZ width. The improvement on the microstructure characterisation, mechanical properties and wear resistance behaviour are expected to extend the service life of the rail and facilitate superior rail expansion capabilities. This, in turn, is projected to diminish the probabilitiy of rail-related incidents and mitigate the risks of human fatilies associated with rail transportationItem Development and experimental validation of an acid mine drainage prediction tool based on mineral particles(University of the Witwatersrand, Johannesburg, 2024) Ramatsoma, Mafeni SamuelAcid Mine Drainage (AMD) is an environmental hazard that is generated as a by-product of mining-related activities. It is an acidic metal-rich water formed when sulfide minerals react with oxygen and water. Due to different ore types at different mines, kinetic AMD models are often ‘calibrated’ with kinetic humidity tests done with the target mine site ore. However, most of these tests require several months to complete. This study aimed to investigate ways to reduce the time required to conduct kinetic humidity tests, and to develop a mineral particles-based kinetic AMD model. An Accelerated Humidity Cell (AHC) is proposed in this study. It was tested with two ore types and performed better (produced 24% more acidic-leachates) than normal humidity cells. The particles-based model was developed and tested with experimental data and gave promising results. It is recommended that the proposed model and AHC be further tested with other ore types.Item Design of an Industrial Process for Enzymatic Cannabidiol Conversion(University of the Witwatersrand, Johannesburg, 2024) Flavell, Erin Reece; Harding, Kevin; Rumbold, KarlThis work aims to model a theoretical enzymatic bioreactor and all the necessary surrounding processes required to facilitate the bioremediation of THC into CBD, to produce a CBD product with THC levels below the legal concentration limits (0.001%). The primary purpose is to explore whether further research into the potential biochemical remediation of THC into CBD would be worth pursuing in terms of both functionality and profitability within the CBD industry. Two primary process designs were modelled using SuperPro Designer, one producing a CBD isolate, and another producing a full spectrum CBD blend containing other cannabinoids beyond CBD, as well as other compounds like flavonoids and terpenes. The CBD isolate model is composed of four parts: the extraction of the crude oil (including the pre-extraction process); the upstream processing of the oil; the reaction of THC into CBD; and the downstream processing of the oil. The full spectrum CBD model is similarly structured but with a different fourth process stage (downstream processing). Cultivating one’s own cannabis was calculated to be more economical than purchasing it from a third-party supplier, and thus a drip-based irrigation system of 1.2108 hectares was used, requiring capital costs of $ 24 641.90 and a yearly cultivation cost of $ 7629.76. Both processes begin with milling to increase the surface area of the cannabis, followed by passing through two consecutive cold ethanol mixer-settler extraction units. Next, the oil-plant matter mixture passes through a plate-and-frame filtering system and then a decarboxylation oven, which will convert the cannabinoids into their neutral forms, producing CBD from CBDA and THC from THCA, and releasing CO2 as a co-product. The oil then passes into a PFR, where CLEAs catalyse the reaction of THC into CBD. Due to the theoretical nature of the as-yet-unknown enzyme, conversion was assumed to be 85 %, where 37.46 kg of the enzyme was calculated to be required per year, assuming replacement is required after seven days of operation. The possibility of either producing or purchasing the enzyme was considered, but producing the enzyme worked out more economically viable, at a yearly cost of $ 2.84. This is where the full spectrum process halts. In the isolate process, the oil is then mixed with an acetonitrile-TBME stream before entering the CPC, alongside a heptane stream. Most of the CBD passes into the heptane, which moves iv to a distillation column after exiting the CPC process, with CBD isolate emerging from the bottom stream. The acetonitrile-TBME stream exiting the CPC will contain other cannabinoids and remaining cannabis compounds and will flow into a separate distillation. The bottom stream of the distillation column provides other valuable cannabinoid isolates, forming ancillary products (CBG, CBN, and THC isolates). In the full spectrum CBD model, the oil flows directly into a series of three consecutive distillation columns upon exiting the PFR, designed to reduce the THC concentrations in the oil to acceptable levels. The CBD oil emerging from both processes must then be incorporated into an MCT carrier oil. CBD isolates were assumed to be sold for $ 39.00 per 30 ml, with each unit containing 600 mg of CBD. Full spectrum CBD oil was assumed to be sold for $ 40.00 per 30 ml, where every 30 ml contains 1500 mg of cannabis oil. Once the costs of the MCT oil were deducted from the theoretical revenue values, the net revenue values came to $ 64 089.93 per kilogram for CBD isolate and $ 26 302.64 per kilogram for the full spectrum CBD oil. Collectively, the ancillary cannabinoid products (CBG, CBN, and THC) yielded a net revenue value (less the cost of the required MCT oil) of $ 17749.48 /kg. CBD isolate was produced at a rate of 637 kg/year, at 99.47 % purity, with ancillary cannabinoid products being produced at 494 kg/year by the isolate process. The full spectrum CBD blend was produced at a rate of 656 kg/year and did not contain any solvent residues. The isolate process was found to have a gross margin of 83.86%, an ROI of 101.58%, a payback time of 0.98 years, and an NPV of $ 190 458 000. The full spectrum blend has a gross margin of 50.89%, an ROI of 21.75%, a payback time of 4.60 years, and an NPV of $ 14 199 000. Thus, the isolate process was deemed the more economically viable of the two processes. An additional CBD isolate design involving supercritical CO2 extraction was also modelled for comparison. In this variation, the cannabis buds undergo milling before passing through the supercritical CO2 extraction unit. The CO2-ethanol solvent feed enters a CO2 storage unit wherein is pressurised to achieve supercritical conditions before entering the extraction unit alongside the cannabis stream. The bottom stream from the extraction unit then passes into a plate-and-frame filtration system, which removes the plant matter from the stream; the recovered cannabis oil is then reunited with the top stream from the extraction unit. The combined oil stream then undergoes winterisation, in 24-hour cycles, before moving into a distillation column which removes any remaining solvent. The bottom stream from the column then enters the decarboxylation oven; the remainder of the process continues in the same manner as the original, cold ethanol extraction isolate process. The CO2 extraction process produced CBD isolate at a rate of 600.54 kg/year. CBD purity of 99.29 % was achieved. An economic analysis produced project indices of a gross margin of 84.07%, an ROI of 95.28%, a payback time of 1.05 years, and an NPV of $ 173 404 000. Thus, with gross margin being the sole exception, all project indices indicate the cold ethanol process being the process with greater potential profitability to produce CBD isolates. Because the isolate process proved the most profitable of the alternatives, its potential profitability when scaled up to industrial size was also assessed. The process feed rate was increased to 79 200 kg of cannabis buds per year, solvent input streams were proportionally scaled up, and several equipment units were multiplied as required. Additionally, the quantity of the enzyme required for catalysing the reaction was recalculated based on the increased plant material in the process, coming to a yearly mass of 576.25 kg, for $ 345 750. The scaled-up process produced a CBD isolate product with a purity of 99.47% and a production rate equivalent to 9800 kg per year and the ancillary cannabinoid product at a rate of 7587 kg per year. The NPV of the scaled-up process came to $ 3.99 billion and a gross margin of 99 % was achieved, with an ROI of 1340 % and a payback time of 0.07 years. Therefore, from the simulated model and the economic analyses, the production of CBD oils using THC-to-CBD bioremediation was found to be a potentially profitable, as-yet-untapped production method that would benefit from further research. It is worth noting, however, that the research is limited by its reliance on theoretical models and assumptions, which may not fully reflect real-world conditions, potentially affecting the generalisability of the findings. The lack of empirical validation and practical factors not captured by simulations, such as enzyme stability, further constrain the applicability. Future work should focus on empirical testing and exploring a wider range of parameters to improve the results' relevance and generalisability.Item Physico-chemical properties and treatment of scale formation in dust scrubber discharge lines at a PGM Smelter in South Africa(University of the Witwatersrand, Johannesburg, 2024) Fungene, Thandiwe; Ndlovu, SehliseloSeveral technologies in the field of flue-gas desulphurization (FGD) have been created to address the issue of sulphur dioxide (SO2) emission from gas streams. Among these, wet scrubbing, particularly the use of lime/ limestone (Ca(OH)2/ CaCO3) scrubbing, stands out as the primary method for reducing SO2 emissions from power plants. These methods are simple and cost-effective, making them suitable for various industrial facilities that emit SO2, including refineries and smelters. In Ca(OH)2 or CaCO3 scrubbing systems, calcium (Ca) compounds are introduced in the form of slurries into the scrubber liquid. However, this process leads to the undesired creation of solid Ca salts. Consequently, the solubility of Ca salts in the slurry restricts the efficiency of wet scrubbing techniques containing Ca. If the ion concentration in the water exceeds the solubility limit of Ca salts like calcium sulphate (CaSO4), it can result in the development of supersaturated CaSO4, which may lead to scale accumulation or deposition in the scrubber. This scaling issue, in turn, requires frequent plant shutdowns to open and remove scale from pipelines. The aim of this research is to propose a process for the prevention of hard water scale or its removal in FGD systems, particularly scrubbers commonly utilized in PGM smelters. To accomplish this goal, analyses were conducted to both physically and chemically characterize the scale or deposit, as well as all the feed materials within and around the variable throat scrubber (VTS) system at a local PGM smelter. By leveraging the physical and chemical properties of these materials, this study explores the application of traditional chemical "water softening" techniques like ion exchange and precipitation, as well as an emerging physical method known as magnetic water treatment (MWT), to combat scale formation in scrubbers. The water samples obtained from the Sibanye-Stillwater scrubbing circuit were characterized by extremely high levels of Ca and magnesium (Mg) hardness (1000—8000 mg/L CaCO3) and high levels of total dissolved solids (TDS) (3000—9000 mg/L). Both a strong acid cation exchange resin (SAC) and weak acid cation exchange resin (WAC) were employed in the treatment process. The WAC resin, commonly used for high TDS solutions, displayed better removal of Ca and Mg compared to SAC, effectively bringing the total hardness levels down to 120—180 mg/L CaCO3. Chemical precipitation using a lime and soda ash pre-treatment step prior to cation exchange resulted in residual hardness levels of 0—120 mg/L as CaCO3. Physico-chemical properties and treatment of scale formation in dust-scrubber discharge lines at a PGM smelter in South Africa Thandiwe Fungene VI The use of MWT remains a topic of debate as a non-chemical option for water softening due to concerns about its scientific validity. This research aims to investigate the potential of a magnetic field to reduce hard water scaling. Several factors, including pH, dissolved oxygen (DO), electrical conductivity (EC), calcium ion concentration ([Ca2+]), and scaling potential, were compared between treated and untreated water. The treated water displayed notable changes in these factors. Most significantly, the precipitation in treated water indicated a shift from calcite to aragonite formation, essentially inhibiting the overall scaling potential. These findings are substantiated by a mechanistic theory based on a comprehensive review of successful applications in the existing literature. This study holds significance in questioning the sustainability of chemical-based water treatment methods and explores the feasibility of non-chemical alternatives.Item Characterizing flotation processes of Platreef PGM ores: The applicability of models based on the Weibull and γ rate constant distributions(University of the Witwatersrand, Johannesburg, 2024) Ngema, Sithandokuhle Fortune; Safari, Mehdi; Sibanda, VusumuziThis dissertation delves into a comprehensive examination of the flotation behaviour of Platreef Platinum Group Metal ores, with a specific focus on the applicability of two widely used distribution models, the Weibull and Gamma distributions. The primary objective of this study was to demonstrate the effectiveness of these models in characterizing the flotation response of the ore under varying grind sizes, ranging from 80% passing 150 μm down to 38 μm, and under varying collector dosages. In this research, a series of meticulous experiments that involved the collection of samples from Platreef PGM ore were conducted. These samples were characterized based on their mineralogical composition, and their flotation behaviour across specified particle size distributions and varying collector dosages. The gathered data were then subjected to analysis using the Weibull and Gamma models. This allowed the assessment of the flotation performance of the ore and the description of the intricate flotation sub-processes involved to be possible. The parameters for both the Weibull and Gamma distributions were determined through a rigorous statistical method known as regression. This method involved fitting the experimental data to the models and iteratively adjusting the model parameters until convergence to their most accurate estimates was achieved. The results from the research reveal that both the Weibull and Gamma models demonstrate a commendable ability to describe the flotation process of Platreef PGM ores. However, the study also highlights certain limitations of these models, especially when dealing with coarser grind sizes, where the Weibull model shows a slight decrease in effectiveness. The investigation also points to the significant impact of liberation and grinding time on the accuracy of these models. These findings underscore the importance of understanding the nuances of particle interactions and liberation at different grind sizes in floatation processes. Furthermore, the effect of varying collector dosages on the performance of the models was explored. It was observed that the accuracy of the models diminishes with longer residence times, particularly when collector dosages are changed. This sensitivity to longer residence times and grind characteristics underscores the need for a holistic approach to model development. Another intriguing aspect of the study was the relationship between collector dosage and grind characteristics. It became apparent that increasing collector dosage has a more v pronounced positive effect on recoveries for both coarser and finer grinds, while the intermediate grinds exhibit a less substantial improvement. This discovery challenges the convention of a near-linear relationship between collector dosage and recovery. In conclusion, the research provides valuable insights into the complexities of the flotation process for Platreef PGM ores and underscores the significance of selecting the most appropriate distribution models based on specific ore characteristics and grind sizes. The dissertation also highlights the need for a nuanced approach to process optimization, acknowledging the interplay of factors such as liberation, grind characteristics, and collector dosage. This understanding can be applied to enhance recovery rates and efficiency in flotation processes, offering valuable contributions to the field of mineral processing and chemical engineering. Findings of this work shed light on the intricate nature of chemical processes, emphasizing the importance of a holistic approach to model development and practical applications.Item Modelling of the distribution of coal tar product qualities from a tar distillation plant(University of the Witwatersrand, Johannesburg, 2024) Mokoena, Lehlohonolo Christopher; Brooks, Kevin; Mulopo, JeanThis work presents the simulation modelling and optimisation of a coal tar distillation process to improve the product qualities and increase overall product revenue. The coal tar distillation process consists of three vacuum distillation units and a flash column. The system produces four distillate products: light oil, refined chemical oil (RCO), light creosote, and heavy oil, as well as the residue pitch used as a binder in the manufacturing of electrodes in the aluminium industry. The simulation model was developed in HYSYS using the actual plant mass balance and operating conditions for the production of a residue pitch product with a softening point of 115 – 118 Metller and associated distillates as reference. A mass balance reconciliation technique using an optimiser in HYSYS was applied to fit the plant quality and distillate rate data through adjustment of the Murphee tray efficiencies for each column. The simulation model was validated by simulating the manufacturing of a softer pitch product of softening point 68 – 73 Ring and ball using conditions specified for this particular product and its related distillate products. Through this process, the base conditions were established for the hard and soft pitch production processes. The resultant pitch yield of softening point 115 – 118 M was 42 %, with the light creosote distillate yield at 27 %, as for the softer pitch, the initial yield was estimated at 65 %, and the light creosote at 9,6 %. Following the model development and the establishment of base conditions, a sensitivity analysis focusing on product quality distribution was done to develop an operating philosophy of the process followed by an optimisation process carried out using HYSYS original optimiser to maximise the objective function defined as the sum of product revenue sales with constraints placed on product qualities and adjustable parameters selected as column reflux and boil up ratio as well as the top and bottom temperatures. From the optimisation results, the general adjustment on the first two columns was the drop-down of column top and bottom temperatures by increasing the reflux ratio and reducing the boil-up rate. The light oil product quality in the simulation of a 115 – 118 M pitch improved by decreasing the naphthalene content from 48 % to less than 8,0 % as required by standard operation, with the naphthalene recovery in the RCO stream increasing from 44 % to 67 %. The optimisation process had a large impact on the product yields, where the pitch product 115 – 118 M showed an increase in yield from 42 % to 49 %, which is close to the general yield of 50% mentioned in the literature and normally expected from a coal tar distillation process. and the light creosote distillate product had a positive yield increase of 14 % from the initial value. The overall revenue benefit for the production of a hard pitch improved by an estimated figure of 3,1 % per annum from the initial value (non-optimised condition). In the production of a softer pitch product, the total revenue benefit was 3,2 % higher per annum in comparison to the non-optimised condition.Item Quantification of benefits of digitalisation of process data of a craft distillery(University of the Witwatersrand, Johannesburg, 2024) Kankenga, Daniel Pembe; Higginson, AntonyCraft breweries and distilleries are frequently not digitalised, making them susceptible to regular production losses. Despite this, benefits of investing in digitalising process are often not easily measurable. The purpose of this research study is to develop a comprehensive framework to quantify the benefits of digitalising process data within the brewing process of a craft distillery. The study was based on historical data from Primal Spirit Distillery, located in Johannesburg, South Africa. The data underwent validation through the application of data visualisation techniques as well as a comprehensive statistical analysis. Mass balance calculations were conducted for the mash tun and fermentation processes, as well as an overall mass balance assessment to compare potential alcohol content with actual alcohol produced. Statistical tools, such as correlation analysis and the student t-test, were used to interpret the data and identify opportunities for digitalisation to enhance productivity. The study concluded with an economic analysis, assessing the financial implications and profitability of digitalising process data in the distillery. The conclusion of the research study highlighted the significant potential for improving productivity in craft distilleries and breweries through the digitalisation of process data. The developed framework proved effective in quantifying these benefits, encompassing steps such as historical data collection, visualisation, mass balance, statistical analysis, intervention planning, and economic feasibility assessment. The analysis revealed considerable sugar loss during mashing, with an average of 16.45%. Fermentation resulted in alcohol levels within the acceptable range in only 53.66% of instances, with an average alcohol deviation of 32.29%. The distillery, on average, operated at 67.71% of its potential alcohol production capacity. Correlation analysis and t-tests identified key variables requiring careful monitoring to reduce deviations and enhance productivity. While there are more economical alternatives, the optimal solution involves the use of affordable storage platform for process data, process control instrumentation devices, such as sensors and flow meters. The economic study indicates that a R 200,000 investment to digitalise the distillery's process data could boost productivity by 30%. The investment would be fully recovered in 4 months, with a 25.43% profit gain within 5 months. However, actual profitability may range between 10 to 20% due to potential unforeseen circumstances during production.Item A Process Systems Analysis Towards Hydrogen Pathways Optimisation(University of the Witwatersrand, Johannesburg, 2024) Kaitano, Caroline; Majozi, ThokozaniHydrogen is garnering increasing attention as a promising and eco-friendly energy carrier, holding the potential to address global energy and environmental challenges. The emergence of the hydrogen economy is a pivotal technological leap forward in future energy systems. Its central objective is to generate hydrogen primarily from abundant energy sources, thus mitigating our dependence on fossil fuels across industries, businesses, residences, and transportation sectors. At its core, the hydrogen economy encompasses essential facets, including the generation, dissemination, transformation, and retention of hydrogen gas and its diverse applications. Establishing efficient hydrogen production processes represents a critical stride toward the overarching global objective of constructing an economy that revolves around hydrogen as a principal energy carrier, capable of providing a substantial portion of our energy needs and services. The work in this dissertation comprehensively explores hydrogen production pathways by applying a superstructure approach, encompassing various options. A comprehensive database comprising 19 distinct hydrogen production pathways is established in this study. These pathways are subjected to a rigorous analysis, considering availability, environmental sustainability, and economic costs. The overarching goal is to discern the most feasible routes for hydrogen production. The framework devised in this research systematically narrows the initial 19 pathways to a final selection of three, achieving an impressive 84 % reduction in the search space. Among these, the pathway involving steam reforming with carbon capture at 1230 K and 10 bar emerges as the most promising option for hydrogen generation. Having identified the optimal reaction pathway, the focus of the study shifts beyond the framework towards the process design and optimisation of this specific route. After a thorough post-optimisation analysis, it is concluded that the steam reformer operates most favorably under a temperature of 908 K and a pressure of 10 bar. This optimised pathway boasts a remarkable 48 % conversion of methane, underscoring its exceptional environmental and economic advantages. iv This dissertation not only elucidates the systematic framework employed in synthesizing and evaluating the hydrogen pathways superstructure, leading to a significantly reduced search space, but also delves into the intricacies of process design and optimization for the most viable hydrogen production pathway. In doing so, it contributes valuable insights and a structured methodology to the field of hydrogen energy research, offering a blueprint for sustainable and efficient hydrogen production in the pursuit of a cleaner and more sustainable energy future.