Due to large amount of solid wastes produced each year, thermal treatment in conjunction with the resource utilization has become attractive in the future. Treatment by pyrolysis can recover the gaseous products for fuels and solid residuals, thus it has potential for R&D and market development.

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A series of experiments was conducted to investigate the potential influence of pre- and post adding of catalysts to a demineralized coal char. The catalysts were chosen according to yield better catalytic activity and be inexpensive. CO2 gasification was conducted on the samples in a temperature range of 500 °C to 900 °C. The coal chosen was a high-inertinite, high-ash, Highveld bituminous coal. The catalysts chosen were sodium carbonate, potassium carbonate, and a mixture of the two catalysts. Different methods were used to investigate the factors influencing the reactivity of the demineralized coal char, and the extent of the influence from the catalysts. Proximate analysis, ultimate analysis and ash yields were conducted on the starting material to determine the change the demineralization had on the coal. Ash fusion temperatures of the samples were also obtained. The results indicated that demineralization lowered the ash content, as well as the ash fusion temperatures, but the ultimate analysis showed consistency in both sets of samples. Mass losses obtained during the thermal treatment experiments under CO2 atmosphere showed an increase in mass loss in the order of samples without addition of catalysts to the smallest amount of addition. Potassium carbonate showed the largest increase in mass loss during CO2 thermal treatment, together with the mixture of the two catalysts. Samples with pre-added catalysts also had a larger mass loss than samples with post-added catalysts. According to the XRD and QEMSCAN results, some potassium species are retained in the ash, which is confirmed by XRF results. The XRF results also showed that the amount of alkali species retained is quite large. / Thesis (M.Sc. (Chemistry))--North-West University, Potchefstroom Campus, 2011

Single-site catalysts revolutionized the polyolefin manufacturing industry and research with their ability to make polymers with uniform microstructural properties. Several of these catalysts are currently used commercially to produce commodity and differentiated-commodity resins. The key to their rapid success and industrial implementation resides in the fact that they can be used without major modifications in the polymerization reactors that previously used heterogeneous Ziegler-Natta and Phillips catalysts. Since most of these industrial processes use slurry or gas-phase reactors, soluble single-site catalysts must be supported on adequate carriers that ensure not only high activity, but also the formation of polymer particles with the proper morphology and bulk densities. Metallocene catalysts have been supported on a variety of carriers, but supporting late transition metal catalysts has not been investigated in detail, despite their very interesting properties such as tolerance to polar comonomers and impurities, activity in the absence of MAO, and the formation of short chain branches by the chain walking mechanism. The research work of this PhD thesis intends to fill this gap, by developing supported late transition metal catalysts with high catalyst activities towards ethylene polymerization and good polymer particle morphology. The effects of catalyst structure and polymerization conditions on silica-supported nickel diimine catalysts are discussed in Chapter 3. Compared with the equivalent homogeneous catalysts, the covalently-attached supported catalysts had high activities, produced spherical polyethylene particles with good morphologies, and polyethylene with higher melting temperatures, higher molecular weight averages, and broader molecular weight distributions. Borates used as internal activators during the synthesis of these supported catalysts successfully activated the nickel diimine complexes. In Chapter 4, MgCl2/alcohol adducts are recrystallized with alkylaluminum compounds and used as catalysts supports for nickel diimine complexes functionalized with amine groups. Polymerization results were compared with those of the equivalent SiO2-supported nickel diimine catalysts. MgCl2-based supported nickel diimine catalysts had high catalyst activity without the use of activators, and it was possible to control polymer molecular weight averages by changing the support composition. Although linear low density polyethylene made with metallocenes offers superior mechanical properties such as excellent toughness, impact strength and clarity, it suffers from poor processability. To overcome some of these disadvantages, Chapter 5 introduces methods to produce bimodal polyethylene resins using supported hybrid early and late transition metal catalyst systems. The presence of short chain branches in the higher molecular weight component is attributable to the incorporation of alpha-olefin molecules by the metallocene sites, while the nickel diimine catalyst sites produce chains with a distribution of short chain branch sizes through the chain walking mechanism. Finally, in Chapter 6 supporting a nickel diimine catalyst onto organo-modified montmorillonite (MMT) to prepare polyethylene/clay nanocomposites through in-situ polymerization is described. The thermal properties and crystallinity of the nanocomposites could be controlled by varying the fraction of MMT in the nanocomposite, and the dispersion of the MMT layers in the polymer matrix were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM).

Polymer electrolyte membrane (PEM) fuel cells have been viewed as promising power source candidates for transport, stationary, and portable applications due to their high efficiency and low emissions. The platinum is the most commonly used catalyst material for the oxygen reduction reaction (ORR) at the cathode of PEM fuel cells; however, the limited abundance and high cost of platinum hinder the large-scale commercialization of fuel cells. To overcome this limitation, it is necessary to enhance the catalyst utilization in order to improve the catalytic activity while decreasing or eliminating the use of platinum. The material on which the catalyst is supported is important for the high dispersion and narrow distribution of Pt nanoparticles as well as other non-precious metal active sites, and these characteristics are closely related to electrocatalytic activity of the catalysts. The support materials can influence the catalytic activity by interplaying with catalytic metals, and the durability of the catalyst is also greatly dependent on its support. A variety of support materials like carbons, oxides, carbides, and nitrides have been employed as supports materials for fuel cell catalysts, and much effort has been devoted to the synthesis of the novel carbon supports with large surface area and/or pore volume, including nanostructured carbons such as carbon nanotubes (CNTs), carbon nanofibers, and mesoporous carbon. These novel nanostructured carbon materials have achieved promising performance in terms of catalytic activity and durability. However, there is still enormous demand and potential for the catalysts to improve. In the first study, non-precious metal catalysts (NPMC) for the oxygen reduction reaction were synthesized by deposition of Fe/Co-Nx composite onto nanoporous carbon black with ethylenediamine (EDA) as nitrogen precursor. Two different nanoporous carbon supports, Ketjen Black EC300J (KJ300) and EC600JD (KJ600), were used as catalyst support for the non-precious catalysts. The results obtained from the optimized FeCo/EDA-carbon catalyst, using KJ600 as the support, showed improved onset, half-wave potentials and superior selectivity than that of the KJ300. Similarly, the catalyst showed good performance in the hydrogen-oxygen PEM fuel cell. At a cell voltage of 0.6 V the fuel cell managed to produce 0.37 A/cm2 with a maximum power density of 0.44 W/cm2. Fuel cell life test at a constant voltage of 0.40 V demonstrated promising stability up to 100 h. The X-ray photoelectron spectroscopy study indicated that pyridinic type nitrogen of the non-precious metal catalysts is critical for ORR catalytic activity and selectivity. These results suggest higher pore volume and surface area of carbon support could lead to higher nitrogen content providing more active sites for ORR and this type of catalyst has great potential used as a non-precious PEM fuel cell catalyst. In the second study, we report the development of a novel NPMC in acid electrolyte using pyrimidine-2,4,5,6-tetramine sulfuric acid hydrate (PTAm) as a nitrogen precursor and graphene nanosheets as catalyst supports. Graphene, consisting of a two-dimensional (2D) monolayer of graphitic carbon atoms, has been viewed as a promising candidate for the fuel cell catalyst support, due to its many intriguing properties such as high aspect ratios, large surface areas, rich electronic states, good electron transport, thermal/chemical stability and good mechanical properties. We investigate the effect of different pyrolysis temperatures on the catalysts’ ORR activity along with detailed surface analysis to provide insight regarding the nature of the ORR active surface moieties. This novel NPMC demonstrates promising electrocatalyst activity and durability superior to that of commercial catalyst for the ORR, rendering graphene nanosheets as a suitable replacement to traditional nanostructured carbon support materials. In the final study, we have developed Pt catalyst by combining the precious metal with nitrogen-doped activated graphene (N-AG) as the support. A transmission electron microscopy (TEM) image of the catalyst shows uniform size and distribution of platinum nanoparticles on a graphene layer. This novel catalyst demonstrates superior electrocatalyst activity and durability over Pt/XC72 catalyst for ORR under the studied conditions, rendering graphene as an ideal replacement to traditional nanostructured carbon support materials. In summary, several catalyst samples were made using novel nanostructured support materials to improve the ORR performance. Several recommendations for future work were suggested in the last section of this work to further apply the knowledge and understanding of nanostructured support materials to design a highly active, durable, and low-cost NPMCs and platinum catalysts.

Monodisperse Pd nanocubes of 20 nm rib length and Pd nanospheres of 3 nm diameter deposited on corundum were used as efficient tool to reveal structure sensitivity of three-phase hydrogenations of unsaturated alcohols. For an olefin alcohol hydrogenation in the kinetic regime, surface (100) atoms of the cubes displayed lower activity than other surface atoms of the spheres. Apparent activation energies of 23 kJ/mol for the cubes and 17 kJ/mol for the spheres confirmed the reaction structure sensitivity. In an acetylenic alcohol hydrogenation, the cubes showed higher selectivity to an olefinic product than the spheres. Apparent activation energy was found as 38 kJ/mol for the cubes and 24 kJ/mol for the spheres. The apparent structure sensitivity in this case was attributed to liquid-solid mass transfer limitations governing the sphere-catalyzed reactions. The study shows the applicability and limitations of the use of nanoparticles for structure sensitivity studies in catalysis. / Chemical Engineering

Hydrotreating is the response to the necessity of a cleaner feed for downstream processes and reduced pollution. Hydrotreating catalysts are vital in this process; hence catalyst deactivation is a key issue. The principal objective of this research was the experimental study of hydrotreating catalyst deactivation due to arsenic compounds. The hydrotreating of light gas oil, in the presence and absence of an arsenic compound over a commercial NiMoS catalyst, was investigated in a trickle bed reactor (temperature 315-360˚C, space velocity = 1-3 h-1, pressure = 3MPa). Kinetics of first order for nitrogen and sulphur were found and activation energies values of 32 kj/mol and 76 kj/mol respectively. Studies of activity changes, suggested that arsenic mainly affects the conversion of sulfur compounds; which might indicate that arsenic prefers mainly the S edge of the catalysts. Activation energy values decreased after arsenic introduction, which may suggest pore plugging of the catalyst. / Chemical Engineering