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Magister Philosophiae - MPhil / Due to an increasing demand for energy, alternative renewable energy sources are investigated globally. However fossil fuels are still one of the main energy sources. The combustion of these fuels produces by-products such as SOx, NOx and CO2, which have detrimental effects on the environment and human health. Therefore, effective methods are needed to minimize the pollution and affects that these by-products cause. Catalysts are commonly employed to convert these by-products to less harmful and/or resalable products. Ceria and ceria based materials are good candidates for the removal and conversion of SOx and NOx. Ceria and ceria related materials are most effective as catalysts when they are in the nano-form with good crystallinity and nanoparticles that are uniform. The growth of nanoparticles is preceded by a nucleation process which can occur by solid-state restructuring of a gel or precipitation from a saturated solution. The precipitation method was selected to synthesize Ceria nanoparticles. Synthesis conditions such as temperature, solution type and ageing time and their effect on the physical and chemical forms of the Ceria particles were investigated. The morphology and structural properties were investigated using Scanning Electron Microscopy, X-ray diffraction and Transmission Electron Microscopy. X-ray Photoelectron Spectroscopy was used to investigate the chemical properties. It was found that low temperatures, low base volume and a solvent with a small dielectric constant favor the formation of small crystallites with a relatively large concentration of defects. These defects are desirable since they enhance the catalytic activity of ceria.

>Magister Scientiae - MSc / With current climate change, growing population, and rapid industrialization of developing countries, water is increasingly becoming a scare resource. Within a power plant, processes that consume most water are demineralized water production (boiler make-up), heat rejection (cooling) and emission control (wet flue gas desulfurization). Eskom’s fleet of existing coal-fired power plants are not equipped with SO2 abatement technologies and therefore retrofitting of the plants will be required to meet the compliance levels for SO2 emissions.

Flue gas desulfurization (FGD) is utilized by the coal-powered generating industry to safely eliminate sulfur dioxide. A FGD vessel (scrubber) synthetically creates gypsum crystals by combining limestone (CaCO3), SO2 flue gas, water and oxygen resulting in crystalline gypsum (CaSO4 ∙ 2H2O), which can be sold for an economic return. Flat disk-like crystals, opposed to rod-like crystals, are hard to dewater, lowering economic return. The objectives were to investigate the cause of varying morphologies, understand the environment of precipitation, as well as identify correlations between operating conditions and resulting unfavorable gypsum crystal growth. Results show evidence supporting airborne impurities due to the onsite coal pile, the abundance and size of CaCO3 and high Ca:SO4 ratios within the scrubber as possible factors controlling gypsum crystal morphology. In conclusion, regularly purging the system and incorporating a filter on the air intake valve will provide an economic byproduct avoiding costly landfill deposits.

Magister Commercii - MCom / In order to comply with the Air Quality Act 2010, Eskom will have to install flue gas desulphurisation (FGD) plants for both new and old power stations. Wet-flue gas desulphurisation (wet-FGD) is adopted world-wide as an effective flue gas treatment technology and therefore will be adopted by Eskom. During the process of desulphurisation, the flue gas is stripped of SO2 but gains a substantial amount of water. Sustaining this process requires a continuous supply of fresh water, a scarce resource in many places where power stations are built. This research investigates the economic feasibility of technologies capable of recovering water from flue gas. The following technologies were considered to capture water vapour from flue gas taking Eskom’s Medupi Power Station as a case study; condensing heat exchanger technology, desiccant drying systems and membrane technology using membrane modules developed by other students in this project. The water vapour selective membrane technology turned out to be superior.

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Large scale biofuel production from microalgae is expected to be integrated with point source CO2 sources, such as coal fired power plants. Flue gas (CO2) integration represents a required nutrient source for accelerated growth while concurrently providing an environmental service. Heavy metals inherent in coal will ultimately be introduced into the culture system. The introduced heavy metals have the potential to bind to microalgae cells, impact growth due to toxicity, and negatively impact the quality of biofuel and other microalgal derived products. Heavy metals As, Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, Sb, Se, Sn, V and Zn, commonly present in coal, were introduced to the microalgae growth medium at a concentration expected from a 7 day growth period using coal flue gas. Experimentation was conducted with Nannochloropsis salina cultivated in photobioreactors at a light intensity of 1000 μmol m-2 s-1. Heavy metals negatively impacted the growth with the average productivity being 0.54 ± 0.28 g L-1 d-1, corresponding to a decrease of 52% in biomass yield compared to control growths. Heavy metal analysis showed significant binding of the majority of the heavy metals to the biomass. A lipid content analysis found a decrease in lipid content from 38.8 ± 0.62% to 31.58 ± 0.50% (percent dry biomass). Control and heavy metal contaminated biomass were processed into biofuel through one of two different in-situ transesterification techniques, either acid-catalyzed or supercritical methanol conversion. The acid-catalyzed conversion resulted in an average crude biofuel production decrease from 0.31 ± 0.03 grams biofuel/gram microalgae for the control algae to 0.28 ± 0.02 grams biofuel/gram microalgae for the heavy metal algae, representing a 9.7% reduction. Supercritical methanol conversion exhibited a similar trend corresponding to a 15.8% reduction. Compared to the control, the total production of biofuel from the contaminated system was decreased by 51% for the acid-catalyzed conversion and 55% for the supercritical methanol conversion. Heavy metal analyses were performed on the biofuel, lipid extracted algae, and other biofuel conversion byproducts. Biochemical methane potential testing was performed on the lipid extracted algae to determine the effect of heavy metals on the generation of biogas. The effects of heavy metals in combination with the effects of acid catalyzed transesterification were found to have a positive effect on the amount of methane produced with an average productivity of 105.89 mL g-COD-1 from the heavy metals contaminated LEA compared to the control microalgae biomass which produced 53.25 mL g-COD-1.

The hybrid Zero Valent Iron (hZVI) process is a novel chemical treatment platform that has shown great potential in our previous bench-scale tests for removing selenium, mercury and other pollutants from Flue Gas Desulfurization (FGD) wastewater. This integrated treatment system employs new iron chemistry to create highly reactive mixture of Fe^0, iron oxides (FeOx) and various forms of Fe (II) for the chemical transformation and mineralization of various heavy metals in water. To further evaluate and develop the hZVI technology, a pilot-scale demonstration had been conducted to continuously treat 1-2 gpm of the FGD wastewater for five months at Plant Wansley, a coal-fired power plant of Georgia Power. This demonstrated that the scaled-up system was capable of reducing the total selenium (of which most was selenate) in the FGD wastewater from over 2500 ppb to below 10 ppb and total mercury from over 100 ppb to below 0.01 ppb. This hZVI system reduced other toxic metals like Arsenic (III and V), Chromium (VI), Cadmium (II), Lead (II) and Copper (II) from ppm level to ppb level in a very short reaction time. The chemical consumption was estimated to be approximately 0.2-0.4 kg of ZVI per 1 m^3 of FGD water treated, which suggested the process economics could be very competitive. The success of the pilot test shows that the system is scalable for commercial application. The operational experience and knowledge gained from this field test could provide guidance to further improvement of technology for full scale applications. The hZVI technology can be commercialized to provide a cost-effective and reliable solution to the FGD wastewater and other metal-contaminated waste streams in various industries. This technology has the potential to help industries meet the most stringent environmental regulations for heavy metals and nutrients in wastewater treatment.