As indústrias lançam diversos poluentes no meio ambiente. Dentre os poluentes destacam-se os elementos tóxicos presentes em efluentes líquidos por acarretarem alto risco potencial à saúde humana e ao meio ambiente. Os efluentes podem ser tratados por materiais adsorventes, os quais podem ser provindos de resíduos industriais. Uma forma de contribuir significativamente na sustentabilidade de uma indústria é a transformação de um de seus resíduos em sub-produto de valor agregado para aplicação no tratamento de seus efluentes líquidos como adsorvente de baixo custo. O objetivo deste trabalho foi sintetizar, e caracterizar zeólitas de cinzas de carvão e avaliar sua aplicação como material adsorvente no tratamento de efluente. Os materiais zeolíticos derivados de três tipos diferentes de cinzas de carvão (cinzas manga, cinzas ciclone e cinzas pesadas) geradas na usina termelétrica de Figueira-PR foram usados para tratar o lixiviado do aterro de cinzas de carvão da mesma usina. As seguintes características das zeólitas foram determinadas: composição mineralógica, composição química, teor de carbono total, análise morfológica, área superficial específica, capacidade de troca catiônica (CTC), perda ao fogo, pH, condutividade e densidade aparente. A fase zeolítica formada foi do tipo sodalita com as três amostras usadas como matéria prima após ativação hidrotérmica alcalina. O material zeolítico de cinzas manga apresentou a menor relação SiO2/Al2O3 (1,46), maior CTC (2,36 meq g-1) e área superficial específica (69,5 m2 g-1) e, consequentemente, maior capacidade de remoção dos íons do efluente. As concentrações de As e Cr estavam acima do padrão de lançamento de efluentes. As três amostras de materiais zeolíticos apresentaram uma remoção significativa de Ni, Cd, Zn e Co na dose de 10 g.L-1. Os materiais zeolíticos das cinzas manga e ciclone foram eficientes para reduzir a concentração de As abaixo do limite imposto pela legislação, enquanto a remoção do Cr não foi efetiva com nenhum dos materiais. Na segunda etapa do trabalho, as zeólitas foram modificadas com o surfactante brometo de hexadeciltrimetilamônio (HTDMA-Br) em concentrações de 1,8 e 20 mmol L-1. A modificação das zeólitas não melhorou a eficiência de remoção do As. A remoção do Cr usando a amostra de zeólita de cinzas manga modificada com HDTMA-Br 20 mmol L-1 resultou em uma concentração final muito próxima ao limite permitido pela legislação. / The industries release various types of pollutants into to the environment. Among these pollutants are the liquid effluents containing toxic elements, they carry a high potential risk to human health and the environment. Some effluents can be treated by adsorbent materials, which can be made from industrial waste. One way to contribute significantly to the sustainability of an industry is to transform one of its residues into a value-added by-product and use in the treatment of its own liquid effluents as a low cost adsorbent. The objective of this estudy was to synthesize and characterize coal ash zeolites and evaluate their application as adsorbent material in the treatment of effluent. Zeolite materials derived from three different types of coal ash (fly ashes, cyclone ashes and heavy ashes) generated at the Figueira-PR thermoelectric plant were used to treat leachate from the coal ash landfill of the same plant. The following zeolite characteristics were determined: mineralogical composition, chemical composition, total carbon content, morphological analysis, specific surface area, cation exchange capacity (CTC), fire loss, pH, conductivity and bulk density. The zeolite phase formed with the three samples used as raw material after alkaline hydrothermal activation was sodalite. The zeolite material from fly ash had the lowest SiO2/Al2O3 ratio (1.46), higher CTC (2.36 meq g-1) and specific surface area (69.5 m2 g-1) and, consequently, greater effluent removal capacity. The As and Cr concentrations were above the effluent discharge standard. The three samples of zeolitic materials showed a significant removal of Ni, Cd, Zn and Co in the dose of 10 g L-1. The zeolite materials from fly and cyclone ash were efficient to reduce As concentrations below the limit imposed by legislation, while removal of Cr was not effective with any of the materials. In the second stage of the study, the zeolites were modified with the surfactant hexadecyltrimethylammonium bromide (HTDMA-Br) in concentrations of 1.8 and 20 mmol.L-1. The zeolite removal efficiency of As did not improve after its modification. Removal of Cr using the 20 mmol.L-1 modified HDTMA-Br modified fly ash zeolite sample resulted in a final concentration very close to the limit allowed by the legislation.

Ga,Ge,As,Se and Sb in coal fly ash S and Pb in gasoline

In this research, it is aimed to remove toxic heavy metals in waste water with the help of fly ash from &Ccedil / ayirhan thermal power plant. The chemical and physical properties (size distribution, specific surface area, porosity, chemical composition, etc.) of fly ash were determined. The experiments were carried out in synthetic waste water containing lead, zinc and copper metals at different concentrations with the addition of fly ash. The effects of metal concentration, agitation time, particle size, ash amount, and pH in the metal removal were examined. With the addition of even very small amount of fly ash, heavy metal removal from waste water was attained at up to 99%. Fly ash particle size has no significant effect on removal of heavy metal ions from solutions. Higher solution pH and longer treatment time were resulted better metal removal. The results also indicated that the main mechanism for metal removal was precipitation due to alkaline characteristics of fly ash and more than 90 % of metals in solutions were removed by precipitation. The pH ranges for maximum metal precipitation were 10-11, 8-10, and 10-11 for copper, zinc, and lead respectively. Very small percentages of adsorbed metal was released during the desorption test.

No presente estudo obteve-se com sucesso o compósito zeólita:magnetita usando-se como material de partida sulfato ferroso para síntese da magnetita e cinzas leves de carvão para síntese da fase zeolítica. A zeólita foi sintetizada por tratamento hidrotérmico alcalino e as nanopartículas de magnetita foram obtidas pela precipitação de íons Fe2+ em uma solução alcalina. Uma reprodutibilidade foi alcançada na preparação de diferentes amostras do nanocompósito zeolítico. O material foi caracterizado pelas técnicas de espectrometria de Infravermelho, difratometria de raios-X de pó, fluorescência de raios-X, microscopia eletrônica de varredura com a técnica de EDS, massa especifícia e área específica e por outras propriedades físico-químicas. O compósito era constituído pelas fases zeolíticas hidroxisodalita e NaP1, magnetita, quartzo e mulita das cinzas remanescentes do tratamento alcalino e magnetita incorporada na sua estrutura. A capacidade de remoção de U(VI) de soluções aquosas sobre o compósito zeólita:magnetita foi avaliada pela técnica descontínua. Os efeitos do tempo de contato e da concentração inicial do adsorbato sobre a adsorção foram avaliados. Determinou-se o tempo de equilíbrio do sistema e foram avaliados os modelos cinéticos de pseudo-primeira ordem, pseudo-segunda ordem e o modelo de difusão intrapartícula. Um tempo de contato de 120 min foi suficiente para a adsorção do íon uranilo alcançar o equilíbrio. A velocidade de adsorção seguiu o modelo cinético de pseudo-segunda-ordem, sendo que a difusão intrapartícula não era a etapa determinante do processo. Dois modelos de isotermas de adsorção, os modelos de Langmuir e de Freundlich, também foram avaliados. O modelo de Langmuir foi o que melhor se ajustou aos dados experimentais. A partir do modelo cinético e da isoterma que melhor descreveram o comportamento do sistema foi possível calcular os valores teóricos para a capacidade máxima de adsorção do U(VI) sobre o compósito zeólita:magnetita. As capacidades máximas de remoção calculadas foram de 20,7 mg.g-1 pela isoterma de Langmuir e de 23,4 mg.g-1 pelo modelo cinético de pseudo-segunda ordem. O valor experimental obtido foi 23,3 mg.g-1. / Within this work, a magnetic-zeolite composite was successfully synthesized using ferrous sulfate as raw material for the magnetic part of the composite, magnetite, and coal fly ash as raw material for the zeolitic phase. The synthesis of the zeolitic phase was made by alkali hydrothermal treatment and the magnetite nanoparticles were obtained through Fe2+ precipitation on alkali medium. The synthetic process was repeated many times and showed good reproducibility comparing the zeolitic nanocomposite from different batches. The final product was characterized using infrared spectroscopy, powder X-ray difraction, X-ray fluorescence, scanning electron microscopy with coupled EDS. Specific mass, specific surface area and other physicochemical proprieties. The main crystaline phases found in the final product were magnetite, zeolites types NaP1 and hydroxysodalite, quartz and mulite, those last two remaing from the raw materials. Uranium removal capacity of the magnetic zeolite composite was tested using bathc techniques. The effects of contact time and initial concentration of the adsorbate over the adsorption process were evaluated. Equilibrium time was resolved and the following kinectics and difusion models were evaluated: pseudo-first order kinectic model, pseudo-second order kinectic model and intraparticule difusion model. A contact time of 120 min turned out to be enough to reach equilibrium of the adsorption process. The rate of adsorption followed the pseudo-second order model and the intraparticle diffusion didnt turned out to be a speed determinant step. Two adsorption isotherms models, the Langmuir model and the Freundlich model, were also evaluated. The Langmuir model was the best fit for the obtained experimental data. Using the best fitted adsorption isotherm and kinectic model, the theorical maximum adsorption capacity of uranium over the composite was determined for both models. The maximum removal capacity calculated was 20.7 mg.g-1 for the Langmuir isotherm and 23.4 mg.g-1 for the pseudo-second order model. The experimental value attained was 23,3 mg.g-1.

>Magister Scientiae - MSc / Most of the world's energy production is still mainly achieved by the combustion of coal in power stations. Coal fly ash is the inevitable waste product that accumulates to metric ton volumes each year. These vast volumes pose a problem in the disposal of the coal fly ash which conventionally is loaded onto ash dumps located near the coal power stations. Alternatives need to be investigated for the use of the coal fly ash in applications that would make the coal fly ash useful and thereby help to mitigate the environmental strain imposed by conventional ash dump disposal. This study focussed on investigating the extraction of Si and Al from CFA. The investigation into the removal of the magnetic iron oxide content and calcium content from coal fly ash was also carried out to enhance the extraction of the Si and Al from CFA e.g. the removal of calcium was attempted to promote the leaching of aluminium from the ash. The rationale for this process was that by removing and recovering these major constituent elements from the ash, it would be easier to concentrate and isolate the trace elements especially the rare earth elements that are present in the CFA. Coal fly ash sourced from Matla coal power station was characterised using x-ray diffraction to determine the mineral phases present in the raw coal fly ash and elemental composition determined by x-ray fluorescence and laser ablation ICP-MS. The main mineral phases in coal fly ash were determined to be quartz, mullite, magnetite and lime (CaO). Magnetic extraction was initially carried out on the coal fly ash to remove the iron rich magnetic material. Extraction tests were then performed on the coal fly ash using alkaline and acidic media namely; NaOH, HCl and H₂SO₄. The extraction tests were assessed and a sequential extraction experimental procedure developed to achieve the highest extraction yield for Si, Al, Fe, Ca, and Mg from the coal fly ash. Lastly the rare earth element content in coal fly ash was tracked from the beginning till the end of the sequential extraction procedure to ascertain whether the rare earth elements partitioned to the leachates or the solid residues. The total element recoveries for Al, Si, Ca Fe, Mg were 53.36 %, 39.96 %, 93.8 %, 25.6 % and 67.3 % respectively using the sequential extraction procedure developed in this study. The rare earth elements contents were not affected by the sequential extraction procedure and on the whole remained in the solid residues at the completion of the sequential extraction, resulting in a residue with enriched levels of recoverable or extractable REE content after the removal of the major oxides from the CFA. The lowest enrichment being approximately 5 % for Thulium and the highest being approximately 76 % for Erbium.

>Magister Scientiae - MSc / Coal is the main source of electricity in South Africa, the combustion of which produces a large amount of waste (coal fly ash) annually. The large-scale generation of coal fly ash places major strain on landfills and the material is toxic in nature. The high silicon and aluminium content in fly ash makes it a suitable starting material for zeolite synthesis. Utilisation of fly ash as a starting material for zeolite synthesis alleviates an environmental burden by converting a waste product to an industrially applicable material. In this study, hierarchical zeolite X was synthesised from coal fly ash via the fusion method. The clear fused fly ash (FFA) extract (with molar composition 0.12 Al·14.6 Na·1.00 Si·163 H₂O) served as the synthesis solution for hydrothermal treatment. The influence of synthesis parameters (such as Si/Al ratio, aluminium source, hydrothermal temperature and stirring) on hierarchical zeolite X formation was studied to determine the cause behind the formation of this material. Synthesised zeolites and starting materials (Arnot coal fly ash and fused fly ash) were characterised by various analytical techniques such as XRD and SEM-EDS to determine the phase purity, morphology and elemental composition (framework Si/Al ratio) of these materials. The synthesis of hierarchical zeolite X under hydrothermal conditions was found to be highly sensitive to the aluminium content of the synthesis solution. The hierarchical morphology of zeolite X was formed preferentially in relatively aluminium-deficient (i.e. high Si/Al ratio) synthesis environments under stirred hydrothermal conditions of 90 °C for 16 hours. In the case of sodium aluminate addition, octahedral shaped zeolite X crystals were formed in relatively low Si/Al ratio synthesis environments, which was attributed to the presence of excess sodium cation content in the synthesis solution. Selected hierarchical zeolites (D2 and E2) were characterised further to gain more insight into the properties of this material. HR-TEM and FTIR revealed that hierarchical zeolite D2 and E2 exhibited the typical structural features of zeolite X. Zeolite D2 and E2 contained both micropores and mesopores and had a high BET surface area of 338-362 m²/g. These zeolites also exhibited appreciable solid acidity (0.81-1.12 mmol H/g zeolite). These properties make hierarchical zeolite X a favourable material for application in catalysis or adsorption. Overall, the formation of zeolite X with hierarchical morphology was proposed to be linked to the presence of zeolite P1 structural units in the framework of the zeolite. / National Research Foundation

>Magister Scientiae - MSc / Fly ash is the major waste material produced by power plants in the combustion of coal to generate electricity. The main constituents of fly ash are Si, Al, Fe and Ca with smaller amount of S, Mn, Na, K, and traces of many other elements such as Co, Cd, As, Se, Zn, Mo, Pb, B, Cu and Ni. Fly ash is usually disposed either by dry or wet disposal methods. These disposal methods have raised major environmental concerns due to the potential leaching of chemical species from the ash heap by ingress of rainfall and brine used to transport the fly ash to the dam. This study focuses on the changes in chemical composition, morphology and mineral phases due to weathering, of coal fly ash co-disposed with brine over 20 years at Sasol Secunda ash dump in Mpumalanga Province, South Africa. The design and operation of the Secunda ash dump presupposes that the ash dump may act as a sink for the salts which originated from chemicals used for normal operation in the plants. The majority of these salts come from the brines generated during desalination and raw water regeneration. The aim of this study is to ascertain if the ash dump could serve as a sustainable salt sink.Samples were drawn along the depth of two drilled cores (S1 and S3) from the weathered Secunda ash dump and analysed in conjunction with the fresh (unweathered) Secunda fly ash taken from the fly ash hoppers for comparative analysis. Scanning electron microscopy (SEM), X-ray diffractive (XRD) and X-ray fluorescence (XRF) spectrometry were employed to obtain a detailed morphological, mineralogical and bulk chemical composition of all the samples. Pore water analysis was used to determine the pH, EC and moisture content of fly ash samples. A five step sequential chemical extraction procedure was used to establish the geochemical association of particular elements with various mineral phases. The total acid digestion test was also used to determine the total elemental compositions of the Secunda fly ash samples. The SEM results showed that the fly ashes consist of irregular and numerous spherically shaped particles. Changes (encrustations, etchings and corrosion) in the morphologies of the weathered ash particles were also observed. The XRD results revealed quartz, mullite, lime and calcite as the major mineral phases. Other minerals identified in very minor quantities in the drilled Secunda ash core that were dried prior to analysis were halite, kaolinite, nitratine, bassanite, microline. and hydrophitte. These phases may have formed during sample handling. XRF investigation revealed that the major oxides present in the dumped ash samples were SiO₂, A₂2O₃, CaO, Fe₂O₃, MgO, Na₂O, TiO₂ and the minor elements present were K₂O, P₂O₅, SO₃ and MnO. The sum of the mean values of the % composition of SiO₂, Al₂O₃, and Fe₂O₃ was 70.19 %, and 72.94 % for the two drilled ash core samples (S1 and S3) respectively, and 78.67 % for the fresh ash which shows the significant alteration of the Si, Al and Fe content in the ash matrix over time. The fly ash is classified as Class F using the ASTM C 618 standards. The loss on ignition (LOI) which is an indication of unburned carbon or organic content was 4.78 %, 13.45 % and 8.32 % for the fresh ash, drilled ash cores S1 and S3 respectively. The high LOI values for the drilled ash cores could indicate high hydrocarbon content in the ash dump because of co-disposal practises where hydrocarbon waste are included in the brine stream for disposal on the ash. While the ash samples from the surface appeared dry, moisture content (MC) analysis showed that there is considerable water entrained in the fly ash dump. The fresh ash MC was 1.8 % while core S1 ranged from 41.4 – 73.2 %; core S3 ranged from 21.7 – 76.4 %. The variations in the MC values can be attributed to uneven flow paths due to inconsistent placement conditions or variations in ambient weather conditions during placement. The fresh fly ash (n=3) had a pH of 12.38±0.15, EC value of 4.98±0.03 mS/cm and TDS value of 2.68±0.03 g/L, the pH of the drilled ash core S1 (n=35) was 10.04 ±0.50, the EC value was 1.08±0.14 mS/cm and the TDS value was 0.64 ±0.08 g/L. Core S3 (n=66) had pH of 11.04±0.09; EC was 0.99 ±0.03 and TDS was 0.57 ± 0.01. The changes in pH values can be attributed to the dissolution and flushing out from the dump basic alkaline oxides like CaO and MgO These variations in pH values shows that the fly ash is acidifying over time and metal mobility can be expected under these conditions. The large decrease of EC in the drilled ash cores S1 and S3 compared to the fresh ash indicated a major loss of ionic species over time in the ash dump. The sequential extraction scheme revealed that the elements Al, Si, Ca, Mg, Ba, Sr, Fe, Mn, Na, K, As, Pb, Cr, Mo, Cu, Ni and Zn are present in Secunda fresh and weathered fly ash and are partitioned between the water soluble, exchangeable, carbonate, iron and manganese, and residual fractions of the coal fly ash. It also showed that the trace elements As, Pb, Cr, Mo, Cu, Ni and Zn do not show permanent association with particular mineral phases as a continuous partitioning between different mineral phases was observed in the weathered drilled core. Generally, all the elements had the highest concentration in the residual fraction. But it was evident that the labile phase (water soluble, exchangeable and carbonate fractions) had fairly high concentrations of Si (± 6.5 %), Al (± 6.5 %), Ca (±10 %), Mg (± 5.5 %), Ba (± 7.5 %),Sr (± 7.5 %), Na (± 12 %) and K (± 12 %) for the Secunda drilled ash core (S1 and S3) and fresh fly ash samples. This indicates that these species can leach easily upon water ingress and could pose a danger to the environment. Na and K had the highest concentrations leached out in the labile phase in all the ash samples. The amount of Na leached out of the drilled Secunda ash core in the labile phase was 13.21 % of 18584.26 mg/kg in the five geochemical phases of core S1; and 9.59 % of 11600.17 mg/kg in the five geochemical phases of core S3 while the fresh Secunda fly ash leached out 11.28 % of 16306.30 mg/kg of Na in the five geochemical phases. This study provided significant insight into the pore water chemistry, morphology, mineralogy and chemical composition and the elemental distribution pattern of the major and trace elements in the Secunda fly ash and weathered drilled Secunda ashm core S1 and S3. Though results from XRF analysis and the sequential extraction scheme shows that Na, K, S, Ca and Mg were slightly captured from the co-disposed brine by the Secunda fly ash, these species were however released in the labile phase. Hence there was no significant retention of these species in the ash dump. The amount of these species retained in the weathered ash were (0.26 % and 0.55 %) for Na, (0.02 % and 0.34 %) for K, (0.08 % and 0.06 %) for S, (0.94 % and 0.01 %) for Ca and (0.37 % and 0.96 %) for Mg in drilled ash cores S1 and S3 respectively. This poor retention of Na K, S, Ca and Mg which are major components of Sasol Secunda brine in the drilled ash cores S1 and S3 clearly shows the unsustainability of the Secunda fly ash dump as a salt sink.

Philosophiae Doctor - PhD / The catalytic support materials used in the present study are zeolite HBEA and MCM-41. These high silica zeolites were synthesised from coal fly ash (CFA) waste via a novel approach that involved a fusion step, acid assisted silica extraction and removal of Al, Ca and Na from the silica by treatment with oxalic acid. The generated silica was converted to HBEA and MCM-41 via conventional hydrothermal treatment. The metal incorporation onto HBEA was done via two approaches namely; liquid phase ion exchange (LIE) and wet impregnation (WI) while the loading on MCM-41 was only done via WI since the material does not possess exchange sites. The metal solution precursors were AMD and Fe extracted from CFA (FeAsh) via acid leaching followed by pH regulation by concentrated NaOH. This is the first time these solutions were tested as possible metal precursors in catalyst synthesis. / 2021-08-30

Philosophiae Doctor - PhD / Power generation in South Africa depends majorly on the combustion of coal and the increasing demand for energy due to industrialisation and population growth signifies the continuous consumption of coal. During this process, a by-product known as coal fly ash (CFA) is generated which poses several environmental issues. The common management of the waste involves the disposal of CFA in landfills or the direct disposal to open uncultured lands, thus contaminating water bodies by the leaching of constituent CFA metals and salts that render arable land uncultivable.

This thesis studies a new more affordable way to build sidewalks in the U.S. Typical sidewalks are often impractical on many roads because of a steep runoff slope and/or close proximity to the drainage ditch. Also, if future road widening is required, the sidewalk must be removed. This thesis proposes a structure called a Lanwalk which is an elevated sidewalk made of precast units. A Lanwalk could simultaneously serve as a sidewalk and potentially as a guardrail. It can be placed over drainage areas if necessary without obstructing the flow of water. Lanwalks can be easily installed and relocated if necessary. This thesis examines the possibility of using high amounts of waste ash as an admixture during the construction of Lanwalks or sidewalks to lower cost and save landfill space. The two waste products examined are municipal solid waste incinerator bottom ash (IBA) and coal fly ash (CFA).