To assess strategies aimed at minimizing the release of trace elements and the impact of disposal of coal waste materials on the environment, two long-term leaching experiments of up to five months duration were performed using waste materials from two plants cleaning high and low sulfur bituminous coal. The tests evaluated the mobility of major trace elements under different disposal scenarios: (i) a static leaching test designed to simulate the quiescent conditions encountered by coal waste material stored under water in a stable impoundment, and (ii) a dynamic test to simulate waste materials exposed to the atmosphere, either in variable wet/dry storage conditions, or in unusual circumstances like those resulting from breaching of an impoundment containment wall. The results indicate that different refuse streams have different leaching characteristics due to difference in their mineralogy and the mobility of most elements is enhanced under highly alkaline or acidic conditions with a few being mobilized under both conditions, suggesting that the minimization of element mobility requires the pH value of the medium to be maintained around neutral. In addition, most of heavy metals were associated with the illite and pyrite minerals. Two strategies of treating coal refuse were evaluated: fly ash mixed with coarse refuse and co-disposal of coarse and fine refuse. Both methods were found to neutralize the pH conditions and thus reduce mobility of the trace elements in static leaching tests whereas the opposite was found from dynamic experiments. The results indicate that such controlled storage under water could retard acid generation and the mobility of trace elements.

In today’s society large quantities of waste is produced. In Sweden this is reused as fuel for incineration processes where electricity and district heating are generated. However, during this process two hazardous by-products are formed, namely slag and fly ash. These contain relatively high concentrations of heavy metals, which make them harmful to the environment if not taken care of, but also make them valuable resources if the metals could be extracted and reutilized. One possible way to extract metals from the waste products is to use electrochemical methods. In order to implement these techniques on an industrial scale, there are several parameters that have to be considered. One important parameter is the choice of material of the electrode, which needs to have a large surface area, a high chemical inertness and electrical conductivity, and preferably also a reasonable price. A material that fulfills these qualifications is reticulated vitreous carbon (RVC), and therefore the extraction efficiency of this porous material has been evaluated in this thesis. Studies were also performed to evaluate how several other parameters affected the extraction efficiency, since this does not rely on the choice of electrode material alone. The results showed that RVC is suitable as electrode material for efficient metal extraction from fly ash. The most efficient electrode combination was RVC with a pore size of 10 pores per linear inch as working electrode, stainless steel as counter electrode, and Ag/AgCl as reference electrode. Both the amperometric and galvanostatic experiments extracted equal amounts of copper within the same time interval, which means that the choice of using either controlled potential or controlled current for an efficient extraction of copper was not of significant importance. The mass transfer rate for copper was 0.12 mg·h-1·cm-2 in both methods, where an electrolyte of 200 ml was used with an initial copper concentration of 50 mg/l. Regarding stirring of the electrolyte, circulation in the solution is an advantage, but not critical for an efficient reduction. The extraction efficiency for one particular metal did not seem to be affected by the presence of other metals in the electrolyte. It was also shown that a selective extraction of metals was possible by applying different potentials. Lastly, an experiment with fly ash was performed, with the optimal conditions and electrode combination based on the previous experiments. This yielded a mass transfer rate of 0.59 mg·h-1·cm-2 for zinc using an electrolyte of 200 ml, which initially contained 595 mg/l of zinc.

The disposal of combustible wastes by incineration is a controversial issue that is strongly debated by both scientists and environmental activists due to the resulting emissions of noxious compounds, including (inter alia) polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), heavy metals and acid gases like sulfur dioxide. Currently available air pollution control devices are capable of effectively cleaning flue gases, and PCDD/F emissions to air from modern municipal solid waste (MSW) incinerators are low. However, the PCDD and PCDF end up in ash fractions that, in Sweden, are usually deposited in landfills. The European Union has recently set a maximum permitted total concentration of 15 µg TEQ/kg for PCDD/F species in waste. Fly ash from municipal solid waste (MSW) incineration containing PCDD/Fs at concentrations above this limit will have to be remediated to avoid disposing of them in landfills; an expensive and environmentally unfriendly option. Therefore, effective, reliable and cost-effective methods for degrading PCDD/F in fly ash are required, and a better understanding of the behavior of PCDDs and PCDFs during thermal treatment will be needed to develop them. In the studies this thesis is based upon both the formation and degradation of PCDDs and PCDFs in ashes from MSW incineration were studied. The main findings of the investigations regarding PCCD/F formation were: - The concentrations of PCDD and PCDF in fly ash increased with reductions in the temperature in the post-combustion zone. - The homologue profile in the ash changed when the temperature in the post-combustion zone changed. - The final amounts of PCDD and PCDF present were affected by their rates of both formation and degradation, and the mechanisms involved differ between PCDDs and PCDFs. The main findings from the degradation studies were: - The chemical composition of ash has a major impact on the degradation potential of PCDD and PCDF. - The presence of oxygen during thermal treatment can enhance the degradation of PCDD and PCDF. - Thermal treatment is a viable option for degrading PCDD and PCDF in ashes from MSW. - Shifts in chlorination degree occur during thermal treatment. - Rapid heat transfer into the ash is a key factor for ensuring fast degradation of PCDD and PCDF. - Degradation of other chlorinated organic compounds, e.g. PCB and HCB, also occurs during thermal treatment of ash. - Reductions in levels of PCDD and PCDF were not solely due to their desorption to the gas phase. - Differences between the behavior of 2378-substituted congeners of PCDD and PCDF and the other congeners during thermal treatment were observed. - Differences in isomer patterns of both PCDD and PCDF were observed between the ash and gas phases after thermal treatment at both 300 and 500 oC. Overall, the results show that the formation and degradation mechanisms of PCDDs differ substantially from those of PCDFs. Thus these groups of compounds should be separately considered in attempts to identify ways to reduce their concentrations.

Soil acidity is a major land degradation problem that limits crop production globally. The high cost of traditional liming materials (calcitic limestone, dolomite etc.) and the vast areas of land that require liming have led to the exploratory utilisation of alkaline industrial by- products such as fly ash and stainless steel slag. The liming potential and effects of liming with fly ash (from the Duvha power station) and processed stainless steel slag (Calmasil) on two acid soils were investigated in this study. The quality of fly ash and Calmasil as liming materials and their potential impacts on the soil quality and plant growth were investigated. The effects of liming with these materials on soil pH, EC, extractable Al, Mn, base cations and trace elements were investigated in an incubation experiment. A glasshouse trial was conducted to assess the effects of these materials on the growth of an acid intolerant crop, perennial rye grass. The incubation and glasshouse study were of a factorial design with two acid soils (the Avalon and Inanda soils), three materials (fly ash, Calmasil and lime); and five application rates of 0, 50, 100, 200 and 400% of the recommended optimum liming rate (OLR) for the growth of perennial rye grass. Characterization of fly ash showed that the major elements (>5%) present (Si > Al > Fe) are not comparable to lime (Ca > Si > Mg) and that it has a low liming potential (calcium carbonate equivalence (CCE) of 9.6%) in comparison to lime. The chemical composition of Calmasil is comparable to lime with Ca > Si > Mg as the major elements and it has a very high liming potential (CCE = 97%). The incubation experiment showed that adding fly ash and Calmasil increased the pH of both soils. However, at the optimum liming rate (100% OLR), only the treatment with Calmasil in the Avalon soil attained pH levels within the desired pH range. Extractable Al and Mn decreased with addition of fly ash and Calmasil to levels comparable to lime in the incubated soils. Addition of fly ash and Calmasil also increased the extractable base cations of both soils. The yield-response of perennial rye grass to treatments in both soils was in the following order: fly ash > Calmasil > lime. Application of fly ash at > 200% OLR in the Avalon soil caused injury of ryegrass. Application of fly ash and Calmasil at lower rates has great agronomic potential in ameliorating soil acidity. / Thesis (M.Sc.)-University of KwaZulu-Natal, Pietermaritzburg, 2008.

<p>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 &ordm / C or 90 &ordm / C / pressure of 1 Mpa or 4 Mpa / four particle sizes namely bulk ash, &gt / 150 &mu / m, &lt / 20 &mu / m and 20 &mu / m- 150 &mu / m 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...</p>

<p>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.</p>

<p>Fly ash and AMD samples were characterised by standard analytical methods for selection of the test materials. Active treatment by means of mixing fly ash with AMD in beakers and a large tank at pre-determined ratios have shown that fly ash is capable of neutralising AMD and increasing the pH beyond neutral values, which optimises the removal of heavy metals and ions. The trend was: the more fly ash added the quicker was the reaction time and higher the pH values achieved. Iron was reduced by as much 99 % in beaker scale experiments via Fe(OH)3 precipitation at pH values &gt / 4.0. A 99 % decrease in aluminium concentration was observed which was attributed to the precipitation of primarily gibbsite and various other mineral phases at pH values &gt / 5.5. As the pH increases, sulphate is adsorbed via Fe(OH)3 and gypsum precipitation at elevated pH. Sulphate attenuation with fly ash was excellent, achieving 98 % attenuation with beaker scale experiments and 1:1 fly ash:AMD ratio. Sulphate attenuation with fly ash was comparable to membrane and ion exchange systems and exceeded the performance of limestone treatment. Except for the larger volumes of fly ash needed to neutralise the AMD, fly ash proved to be a feasible and cost efficient alternative to limestone treatment. Fly ash produced competing results to limestone concerning acidity removal and sulphate attenuation. The comparison highlighted the advantages of utilising fly ash in comparison to limestone and demonstrated its cost effectiveness. The results of this study have shown that fly ash could be successfully applied for the neutralisation of acid mine drainage (AMD) and effectively attenuate the sulphate load in the treated water. The critical parameters to this technology are the variations of chemical composition and mineralogy of fly ash, which could influence the pH, contact time of the neutralisation reaction, and the same is true if the AMD quality varies.</p>

<p>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 &ordm / C 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 &ordm / C, 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 &ordm / C, 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 &ordm / C. 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 &deg / 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 &ordm / C. 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.</p>

The ever-increasing quantity of by-products generated from burning coal in the production of electricity has brought about the need for new areas of utilization. This study examined the use of FGD gypsum and fluidized bed combustion ash along with Class F fly ash in the production of low-energy, 100% by-product cement blends. The cement blends used the advantageous properties of the by-product materials to create cementing properties rather than energy intensive clinker used in ordinary portland cement. The FGD gypsum was converted to hemihydrate which rapidly hydrated to provide the cement with early strength gains, whilst the fluidized bed combustion ash reacted with the Class F fly ash to form pozzolanic cementitious phases which provided the longer-term compressive strength and possibly resistance to weathering. The rate of compressive strength gains and minimizing detrimental expansion were two properties of particular interest in the study. Chemical admixtures were used to improve the compressive strengths of the cement mortars and decrease their solubility.

Natural geomaterials exhibit a wide range in size, physical properties, chemical properties, and mechanical behaviors. Soils that are composed of mixtures of particles with different physical and chemical properties pose a challenge to characterization and quantification of the engineering properties. This study examined the behavior of particulate mixtures composed of differently sized silica particles, mixtures composed of aluminosilicate and organic carbon particles, and mixtures composed of particles with approximately three orders of magnitude difference in particle size. This experimental investigation used elastic, electromagnetic, and thermal waves to characterize and to quantify the small to intermediate strain behavior of the mixtures. The mechanical property of stiffness of mixed materials (e.g. binary mixtures of silica particles and fly ashes with various carbon and biomass contents) was evaluated through the stiffness of active grain contacts, and the stiffness of particles which carry applied load, using the physical concepts of intergranular void ratio and interfine void ratio. Additionally, the change in both contact mode/stiffness and electrical property due to the presence of nano-sized particles (i.e., iron oxides) on the surface of soil grains was evaluated according to applied stress, packing density, iron coating density, and substrate sand particle size. Finally, the biomass fraction and total organic carbon content of mixtures was used to quantify the electrical and thermal conductivities when particulate organic was mixed with aluminosilicate particles.