M.Tech. / In this study, ethylene vinyl acetate-fly ash (EVA-FA) composites were explored for the removal of phenols from water. The composites were prepared from EVA and untreated and acid treated fly ash via the melt-mixing technique using a rheomixer. The fly ash was characterised by X-ray fluorescence (XRF), X-ray diffraction (XRD) scanning electron microscopy (SEM) and Brunauer, Emmett and Teller (BET) surface area measurement. Fly ash is composed mainly of SiO2, Al2O3, CaO and Fe2O3. Modified fly ash gave a better specific surface area of 0.4180 m2/g, while 0.0710 m2/g was obtained for unmodified fly-ash due to the disintegration of the outer layer which resulted in smaller particles, hence a larger surface area. EVA-FA composites were prepared from fly ash loadings of 3 to 20% and further characterised by XRD, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and SEM. XRD showed successful incorporation of fly ash into the EVA matrix through the appearance of fly ash diffraction peaks on the EVA-FA composite diffraction pattern. The incorporation of fly ash into the EVA matrix resulted in an improvement in the thermal stability of EVA, but did not have an effect on the melting temperature of the composites. However, a decrease in crystallisation temperature was observed. SEM micrographs revealed uniform dispersion of fly ash particles in the polymer matrix. Adsorption studies were performed using p-chlorophenol (PCP), 2,4,6-trichlorophenol (TCP) and p-nitrophenol (PNP) as model pollutants. An increase in adsorption efficiency of EVA-FA composites was observed as fly ash loading was increased from 3 to 10%. Between 10 and 20% fly-ash loading the removal efficiencies remained constant. The effect of contact time, pH and initial concentration was investigated. Polymer composites prepared from unmodified fly ash resulted in a higher adsorption capacity of phenols. The maximum uptake of PCP was 0.18 mg/g and that for TCP was 0.19 mg/g over a pH range of pH 3 to 5 and after contact time of 8 h. However, the adsorption capacity of 0.30 mg/g for PNP was achieved at pH 5 after a period of 10 h. Equilibrium adsorption data were evaluated using Langmuir and Freundlich adsorption isotherm models. There was no significant difference in the correlation coefficients (R2) from both models for the adsorption of PCP and TCP. However, the equilibrium adsorption data for PNP were better described by the Langmuir adsorption isotherm model. The kinetics data were analysed by pseudo-first-order and pseudo-second-order kinetic models. The pseudo-second-order kinetics model gave better correlation coefficients (> 0.9) for the adsorption of the phenols and the amount adsorbed at equilibrium was comparable to that calculated from the pseudo-second-order equation. Desorption studies were performed using NaOH solution with varying concentrations (0.1 to 0.3 M) and the studies revealed that PNP was the most difficult to be desorbed. Approximately 75% of PNP was recovered while 82% of PCP and 84% of TCP were recovered.

Magister Scientiae - MSc / This study evaluated SO4 2- removal from circumneutral mine water (CMW) collected from Middleburg coal mine using coal FA collected from Hendrina power station. The following parameters were investigated: the effect of the amount of FA, the effect of the final pH achieved during treatment, the effect of the initial pH of the mine water and the effect of Fe and Al on SO4 2- removal from mine water. The precipitation of ettringite at alkaline pH was evaluated to further reduce the SO4 2- concentration to below the DWAF limit for potable water. Removal of SO4 2- from mine water was found to be dependent on: the final pH achieved during treatment, the amount of FA used to treat the mine water and the presence of Fe and Al in the mine water. Treatment of CMW using different CMW:FA ratios; 5:1, 4:1, 3:1, and 2:1 resulted in 55, 60, 70 and 71 % SO4 2- removal respectively. Treatment of CMW to pH 8.98, 9.88, 10.21, 10.96, 11.77 and 12.35 resulted in 6, 19, 37, 45, 63 and 71 % SO4 2- removal respectively. When the CMW was modified by adding Fe and Al by mixing with Navigation coal mine AMD and treated to pH 10, 93 % SO4 2- removal was observed. Further studies were done to evaluate the effects of Fe and Al separately. Treatment of simulated Fe containing AMD (Fe-AMD) to pH 9.54, 10.2, 11.8, and 12.1 resulted in 47, 52, 65, and 68 % SO4 2- removal respectively. When Al containing AMD was treated to pH 9.46, 10.3, 11.5 and 12 percentage SO4 2- removal of 39, 51, 55 and 67 % was observed respectively. / South Africa

Magister Scientiae - MSc / It was hypothesized that South African FA and brine could sequester CO2 through mineral carbonation. A statistical approach was undertaken to optimize the % CaCO3 formed from FA/brine/CO2 interaction with input parameters of temperature, pressure, particle size and solid/liquid ratio (S/L) being varied. The ranges adopted for the input parameters were: temperature of 30 ºC or 90 ºC; pressure of 1 Mpa or 4 Mpa; four particle sizes namely bulk ash, > 150 μm, < 20 μm and 20 μm- 150 μm particle size range; S/L ratios of 0.1, 0.5 or 1. The FA/ brine dispersions were carbonated in a high pressure reactor varying the above mentioned input parameters. The fresh Secunda FA of various size fractions was characterized morphologically using scanning electron microscopy, chemically using X-ray fluorescence and mineralogically using qualitative X-ray diffraction. The carbonated solid residues on the other hand were characterized using quantitative X-ray diffraction, scanning electron microscopy, thermal gravimetic analysis and Chittick tests. The raw brine from Tutuka together with the carbonation leachates were characterized using inductively coupled mass spectrometry and ion chromatography. Total acid digestion was carried out to evaluate the differences in the total elemental content in both the fresh ash and the carbonated solid residues. The results suggested that South African FA from Secunda belongs to class F based on the CaO content as well as the total alumina, silica and ferric oxide content, while the RO brine from Tutuka were classified as NaSO4 waters. / South Africa

Philosophiae Doctor - PhD / The production of biodiesel (methyl esters) from vegetable oils represents analternative means of producing liquid fuels from biomass, and one which is growing rapidly in commercial importance and relevance due to increase in petroleum prices and the environmental advantages the process offers. Commercially, biodiesel is produced from vegetable oils, as well as from waste cooking oils and animal fats. These oils are typically composed of C14-C20 fatty acid triglycerides. In order to produce a fuel that is suitable for use in diesel engines, these triglycerides are usually converted into the respective mono alkyl esters by base-catalyzed transesterification with short chain alcohol, usually methanol. In the first part of this study, the transesterification reactions of three different vegetable oils; sunflower (SFO), soybean (SBO) and waste cooking oil (WCO) with methanol was studied using potassium hydroxide as catalyst in a conventional batch process. The production of biodiesel from waste cooking oil was also studied via continuous operation systems (employing the use of low frequency ultrasonic technology and the jet loop reactor). The characterisation of the feedstock used and the methyl ester products were determined by different analytical techniques such as gas chromatography (GC), high performance liquid chromatography (HPLC) and thin layer chromatography (TLC). The effects of different reaction parameters (catalyst amount, methanol to oil ratio, reaction temperature, reaction time) on methyl ester/FAME yield were studied and the optimum reaction conditions of the different process systems were determined. The optimum reaction conditions for production of methyl esters via the batch process with the fresh oil samples (SFO and SBO) were established as follows: a reaction time of 60 min at 60 ºC with a methanol: oil ratio of 6:1 and 1.0 KOH % wt/wt of oil; while the optimum reaction conditions for the used oil (WCO) was observed at a reaction time of 90 min at 60 ºC, methanol: oil ratio of 6:1 and 1.5% KOH wt/wt of oil. The optimum reaction conditions for the transesterification of the WCO via ultrasound technology applied in a continuous system in this study were: a reaction time of 30 min, 30 ºC, 6:1 methanol/oil ratio and a 0.75 wt% (KOH) catalyst concentration. The ultrasound assisted transesterification reactions performed at optimum conditions on the different oil samples led to higher yields of methyl esters (96.8, 98.32 and 97.65 % for WCO, SFO and SBO respectively) compared to methyl esters yields (90, 95 and 96 % for WCO, SFO and SBO respectively) obtained when using conventional batch procedures. A considerable increase in yields of the methyl esters in the ultrasound assisted reaction process were obtained at room temperature, in a remarkably short time span (completed in 30 min) and with a lower amount of catalyst (0.75 wt % KOH) while the results from the continuous jet loop process system showed even better results, at an optimum reaction condition of 25 min of reaction, a methanol: oil ratio of 4:1 and a catalyst amount of 0.5 wt%. This new jet loop process allowed an added advantage of intense agitation for an efficient separation and adequate purification of the methyl esters phase at a reduced time of 30 min. The use of homogeneous catalysts in conventional processes poses many disadvantages; heterogeneous catalysts on the other hand are attractive on the basis that their use could enable the biodiesel production to be more readily performed as a continuous process resulting in low production costs. Consequently, a solid base catalyst (KNO3/FA) prepared from fly ash (obtained from Arnot coal power station, South Africa) and a new zeolite, FA/Na-X synthesized from the same fly ash were used as solid base catalysts in the transesterification reactions in the conversion of a variety of oil feedstock with methanol to methyl esters. Since fly ash is a waste product generated from the combustion of coal for power generation, its utilization in this manner would allow for its beneficiation (as a catalytic support material and raw material for zeolite synthesis) in an environmentally friendly way aimed at making the transesterification process reasonably viable. Arnot fly ash (AFA) was loaded with potassium (using potassium nitrate as precursor) via a wet impregnation method while the synthesized zeolite FA/Na-X was ion exchanged with potassium (using potassium acetate as precursor) to obtain the KNO3/FA and FA/K-X catalysts respectively. Several analytical techniques were applied for characterization purposes. The results of the XRD and XRF showed that the AFA predominantly contained some mineral phases such as quartz, mullite, calcite and lime. The high concentration of CaO in AFA was apparent to be beneficial for the use of fresh fly ash as a support material in the heterogeneous catalysed transesterification reactions. XRD characterisation of KNO3/FA results indicated that the structure of KNO3/FA gradually changed with the increase in KNO3 loading. The catalyst function was retained until the loading of KNO3 was over 10 %. IR spectra showed that the KNO3 was decomposed to K2O on the fly ash support during preparation at a calcination temperature of 500 ºC. The CO2-TPD of the KNO3/FA catalysts showed that two basic catalytic sites were generated which were responsible for high catalytic abilities observed in the transesterification reactions of sunflower oil to methyl esters. On the other hand, XRD results for the as- received zeolite synthesized from AFA showed typical diffraction peaks of zeolite NaX. SEM images of the FA /NaX showed nano platelets unique morphology different from well known pyramidal octahedral shaped crystal formation of faujasite zeolites and the morphology of the FA /KX zeolite did not show any significant difference after ion exchange. The fly ash derived zeolite NaX (FA /NaX) exhibited a high surface area of 320 m2/g. The application of the KNO3/FA catalysts in the conversion reactions to produce methyl esters (biodiesel) via transesterification reactions revealed methyl ester yield of 87.5 % with 10 wt% KNO3 at optimum reaction conditions of methanol: oil ratio of 15:1, 5 h reaction time, catalyst amount of 15 g and reaction temperature 160 °C, while with the use of the zeolite FA/K-X catalyst, a FAME yield of 83.53 % was obtained for 8 h using the ion exchanged Arnot fly ash zeolite NaX catalyst (FA/KX) at reaction conditions of methanol: oil ratio of 6:1, catalyst amount of 3 % wt/wt of oil and reaction temperature of 65 ºC. Several studies have been carried out on the production of biodiesel using different heterogeneous catalysts but this study has been able to uniquely demonstrate the utilization of South African Class F AFA both as a catalyst support and as a raw material for zeolite synthesis; these catalyst materials subsequently applied sucessfully as solid base catalysts in the production of biodiesel. / South Africa

Philosophiae Doctor - PhD / In South Africa, almost 90 % of the country’s electricity is generated from coal combustion. This reliance on coal for energy production is projected to continue in the near and medium term due to the increasing demand for industrial and domestic energy. During coal combustion, a large quantity of fly ash is produced as the main waste product and in South Africa approximately 36 - 37 million tons of fly ash is produced on a yearly basis. The management of huge quantities of fly ash has been and still is a continuing challenge that requires urgent intervention. In this regard, there exists an urgent need to maximize fly ash beneficiation, thus forming the motivation for this research. The overall objectives of this thesis was to synthesize high pure phase zeolites A and X from South African fly ash, study their formation mechanism, and explore the potential of mine waters during the synthesis process as well as developing new and efficient zeolite synthetic protocols by the use of ultrasound. In order to address these objectives, the research was designed in a sequential manner so that the preceding results could act as a platform for the attainment of the next objective. In this case, the identification and optimization of synthesis conditions for producing zeolite A and X acted as a basis for understanding the influence of use of mine waters as a substitute for pure water. This further laid the foundation for the in-situ ultrasonic monitoring of the formation process of zeolite A and X from fly ash. The final stages of the study involved use of ultrasonic energy as an ageing tool to improve the conditions obtained during the hydrothermal synthesis of zeolite A as well as investigate the potential to synthesize zeolites directly by use of ultrasound without the need for the fusion, aging or conventional hydrothermal treatment step. The result of the optimized synthesis conditions for producing zeolite A starting either from clear extract of fused fly ash or unseparated, fused South African class F fly ash slurry were molar regimes of 1 Al2O3 : 30.84 Na2O : 4 SiO2 : 414.42 H2O or 1 Al2O3 : 5.39 Na2O : 2.75 SiO2 : 111.82 H2O respectively and at a hydrothermal synthesis temperature of 100 °C for 2 hours. The optimized procedure was simple, efficient and resulted in a considerable improvement of the quality and phase purity of the zeolite A product when the clear extract of fused fly ash was used instead of starting from unseparated, fused fly ash slurry. On the other hand, the optimized synthesis conditions for preparing the typical octahedral shaped zeolite X from South African fly ash was found to be a molar regime of 1 Al2O3 : 4.90 Na2O : 3.63 SiO2 : 115.92 H2O at a hydrothermal synthesis temperature of 80 ºC for hours.

Please read the abstract in the section 00front of this document / Dissertation (M Eng (Mechanical Engineering))--University of Pretoria, 2007. / Mechanical and Aeronautical Engineering / unrestricted

An increasing demand for electricity in modem society has resulted in the burning of large quantities of coal and ultimately the production of large quantities of fly ash. The petrochemical industry, if based on coal in a country such as South Africa, also produce large quantities of fly ash. In a semi-arid country like South Africa, there is a need to recover water. Processes currently in use for the recovery of wastewater produce large quantities of brines. These brines are stored in waste dams, which are not only expensive to maintain, but also pose a potential threat to the environment. The process of geosynthesis led to the development of a new type of material, namely geopolymers. Geopolymers can best be viewed as a polymeric silicon-oxygen¬aluminium framework with alternating silicon and aluminium tetrahedra joined together in three directions by sharing all the oxygen atoms. Cations such as Na+, K+, Ca2+ and H3O+ must be present in the framework cavities to balance the negative charge generated by the Al3+ in IV-fold co-ordination. It was attempted in this study to manufacture a geopolymeric binder, supplying most of the ingredients through waste materials. In the first set of experiments, matrices containing different amounts of fly ash, kaolinite, sodium hydroxide, sodium silicate and brine or water were synthesised by mixing and heating at 50°C for 24 hours. Compressive strength measurements showed a maximum strength of 4.05 MPa after 28 days. Leaching tests indicated that sodium was the best stabilised showing a stabilisation of between 30 and 40% (70 to 60% of the sodium initially added leached out again). The anions were stabilised to a lesser extent. Infrared spectra obtained confirmed an aluminosilicate structure. The second set of experiments was done to obtain the optimum curing conditions. Matrices containing the same amounts of fly ash, kaolinite, sodium hydroxide, sodium silicate and brine or water were cured at different temperatures and for different time periods. The matrices containing water showed a maximum compressive strength of 7.25 MPa after 28 days when cured at 60°C for 48 hours, while their brine-containing counterparts showed a maximum compressive strength of 7.76 MPa after 28 days when cured at 70°C for 72 hours. Infrared spectra obtained confirmed an aluminosilicate structure while X-ray diffraction patterns obtained indicated a largely amorphous product. In the third set of experiments matrices containing different amounts of fly ash, metakaolinite, sodium hydroxide, sodium silicate and brine or water were synthesised by mixing and heating at the optimum conditions determined previously. Compressive strength measurements indicated a maximum strength of 1.45 MPa after 28 days. Leaching tests indicated a higher stabilisation of the cations than in the first set of experiments. Potassium was the best stabilised, showing a stabilisation of above 80%. The anions were again stabilised to a lesser extent. Infrared spectra obtained confirmed an aluminosilicate structure while X-ray diffraction patterns obtained indicated a largely amorphous material. / Dissertation (MSc (Chemistry))--University of Pretoria, 2007. / Chemistry / unrestricted

Please read the abstract in the section 00front of this document / Dissertation (MSc Agric (Pasture Science))--University of Pretoria, 2005. / Plant Production and Soil Science / unrestricted

Please read the abstract in the section 00front of this document. / Thesis (PhD (Chemistry))--University of Pretoria, 2008. / Chemistry / unrestricted

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