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Thermogravimetry, coupled with a mass spectrometer (TG-MS) was used to investigate the catalytic effect potassium carbonate (K2CO3) and potassium chloride (KCl), on the char conversion and the product gas composition of chars derived from a South African inertinite-rich bituminous coal. Sequential leaching of the coal with HCl-HF-HCl was performed to reduce the mineral matter present in the coal. This was done in order to reduce possible undesirable interactions between the minerals and inorganic compounds in the coal during heat treatments. The leaching process substantially reduced the ash content from 21.5% to less than 3%. K2CO3 and KCl [0.5, 1, 3, 5 K-wt %] were loaded to the demineralized coal, raw coal and demineralized coal with added mineral mixture prior to charring. The mineral mixture was made up of kaolinite, quartz, pyrite, siderite, calcite, anastase and hydromagnesite. The ‘doped’ coal samples were then subjected to heat treatments in a CO2 atmosphere up to 1200 °C. The results obtained showed that both K2CO3 and KCl exhibit a catalytic effect on the char conversion during heat treatments in CO2 atmosphere and the char conversion was increased with increasing loadings up to 5 K-wt% of K2CO3 and KCl. The temperature ranges at which conversion occurred were found to be lower for K2CO3 than for KCl. Subsequently, char conversion occurred over a relatively narrower temperature range for K2CO3 than observed for KCl. The catalytic behaviour of K2CO3 and KCl was confirmed by the results obtained. The results also indicated that the catalytic influence of K2CO3 is greater than that of KCl and that KCl is more susceptible to deactivation by minerals and inorganic compounds present in the coal than K2CO3. Different analytical techniques (XRF and XRD) were used to determine the extent of interaction of the catalysts used with the char material in the 5 K-wt% ‘doped’ coal samples. From the XRF results, it was observed that the K2O content was reduced after heat treatments in CO2, however, no potassium crystalline phases were observed in the XRD results after heat treatments in CO2. The reduced K2O content may be attributed to the potassium been taken up in other mineral matter during char reaction with CO2, forming new amorphous inorganic complex compounds. Thus the potassium retained in the sample after heat treatment, indicated by the XRF results, may be in an amorphous phase. Mass spectrometry (MS) indicated that temperatures at which the maximum rate of evolution of gaseous species occurred were relatively lower for K2CO3 loaded char samples iv than observed for KCl loaded samples. In addition, no mass-to-charge ratio (m/z) peak at 39 atomic mass unit (amu) from the MS results was observed, indicating that no potassium was detected in the gaseous phases for all the char samples. The undetected potassium in the gaseous phase may be due to the detection limit of the MS equipment. The MS results also indicated that addition of the catalyst facilitates the evolution of H2 from the coal char samples. Addition of the catalysts to the samples lowered the temperature at which maximum H2 was given off. The shift to lower temperatures was observed with increased catalyst loadings for both K2CO3 and KCl loaded samples. / Thesis (MSc (Chemistry))--North-West University, Potchefstroom Campus, 201

Thermogravimetry, coupled with a mass spectrometer (TG-MS) was used to investigate the catalytic effect potassium carbonate (K2CO3) and potassium chloride (KCl), on the char conversion and the product gas composition of chars derived from a South African inertinite-rich bituminous coal. Sequential leaching of the coal with HCl-HF-HCl was performed to reduce the mineral matter present in the coal. This was done in order to reduce possible undesirable interactions between the minerals and inorganic compounds in the coal during heat treatments. The leaching process substantially reduced the ash content from 21.5% to less than 3%. K2CO3 and KCl [0.5, 1, 3, 5 K-wt %] were loaded to the demineralized coal, raw coal and demineralized coal with added mineral mixture prior to charring. The mineral mixture was made up of kaolinite, quartz, pyrite, siderite, calcite, anastase and hydromagnesite. The ‘doped’ coal samples were then subjected to heat treatments in a CO2 atmosphere up to 1200 °C. The results obtained showed that both K2CO3 and KCl exhibit a catalytic effect on the char conversion during heat treatments in CO2 atmosphere and the char conversion was increased with increasing loadings up to 5 K-wt% of K2CO3 and KCl. The temperature ranges at which conversion occurred were found to be lower for K2CO3 than for KCl. Subsequently, char conversion occurred over a relatively narrower temperature range for K2CO3 than observed for KCl. The catalytic behaviour of K2CO3 and KCl was confirmed by the results obtained. The results also indicated that the catalytic influence of K2CO3 is greater than that of KCl and that KCl is more susceptible to deactivation by minerals and inorganic compounds present in the coal than K2CO3. Different analytical techniques (XRF and XRD) were used to determine the extent of interaction of the catalysts used with the char material in the 5 K-wt% ‘doped’ coal samples. From the XRF results, it was observed that the K2O content was reduced after heat treatments in CO2, however, no potassium crystalline phases were observed in the XRD results after heat treatments in CO2. The reduced K2O content may be attributed to the potassium been taken up in other mineral matter during char reaction with CO2, forming new amorphous inorganic complex compounds. Thus the potassium retained in the sample after heat treatment, indicated by the XRF results, may be in an amorphous phase. Mass spectrometry (MS) indicated that temperatures at which the maximum rate of evolution of gaseous species occurred were relatively lower for K2CO3 loaded char samples iv than observed for KCl loaded samples. In addition, no mass-to-charge ratio (m/z) peak at 39 atomic mass unit (amu) from the MS results was observed, indicating that no potassium was detected in the gaseous phases for all the char samples. The undetected potassium in the gaseous phase may be due to the detection limit of the MS equipment. The MS results also indicated that addition of the catalyst facilitates the evolution of H2 from the coal char samples. Addition of the catalysts to the samples lowered the temperature at which maximum H2 was given off. The shift to lower temperatures was observed with increased catalyst loadings for both K2CO3 and KCl loaded samples. / Thesis (MSc (Chemistry))--North-West University, Potchefstroom Campus, 201

This thesis describes studies into Group 5 and Group 6 transition metal imido complexes, with particular emphasis on the development of complexes which can be applied to catalytic processes. Chapter 1 highlights the electronic and structural aspects of the imido and alkylidene ligands. The isolobal analogy between Group 4 bent metallocene. Group 5 half-sandwich imido and Group 6 bis(imido) metal fragments is outlined. In addition, Ziegler-Natta type a-olefin polymerisation and Ring Opening Metathesis Polymerisation (ROMP) are briefly reviewed. Chapter 2 describes initial screening of half-sandwich vanadium imido and chromium bis((^t)butylimido) dichloride complexes as catalyst precursors. Synthesis of the chromium bis(imido) dialkyl complex Cr(N(^t)Bu)(_2)(CH(_2)Ph)(_2) (1) is described, its conversion to a cationic alkyl species is probed and the polymerisation activity associated with the resultant compound is addressed. Finally this chapter details the synthesis and characterisation of a range of bis(adamantylimido) chromium complexes. Chapter 3 presents a synthetic entry point into the bis(arylimido) chemistry of chromium. The complex Cr(NAr)(_2)(NH(^t)Bu)Cl (12) is described (Ar = 2,6-(^i)Pr(_2)C(_6)H(_3)) and its conversion to the dichloride complex Cr(NAr)(_2)Cl(_2) (14) is examined. 14 forms the stable monoadduct with pyridine, the X-ray crystallographic study of which reveals a distorted square based pyramidal geometry about the chromium atom. The inclusion of the arylimido ligand at the metal centre allows stabilisation of the chromium bis- phosphine complexes Cr(NAr)(_2)(PMe(_3))(_2) (18) and Cr(NAr)(_2)(PMe(_2)Ph)(_2) (19). The reactivity of 18 towards unsaturated hydrocarbon substrates is briefly investigated. Chapter 4 focuses on the organometallic chemistry of the [Cr(NAr)(_2)] moiety. A range of dialkyl derivatives are isolated and the molecular structures of a selection are solved. The generation of the nascent species [Cr(NAr)(_2)(=CHCMe(_3))] is investigated and the conversion of Cr(NAr)(_2)(CH(_2)CMe(_3))(_2) (24) to Cr(NAr)(-2)(CHDCMe(_3))(C(_6)D(_5)) (25) is the subject of a kinetic study. In chapter 5, the ROMP of a series of amino acid derived norbomene monomers is studied. The resultant polymers are fully characterised and a brief molecular modelling study is carried out on representative polymers chain lengths. Chapter 6 contains experimental details to chapters 2-5.

Low temperature (165°C) Wet Oxidation (WO) and Catalytic Wet Oxidation (CWO) of 12 organic compounds has been studied in highly alkaline, high ionic strength solution (simulating that encountered in the Bayer process used to refine alumina) for the first time. Most (11 out of 12) of the 12 organic compounds studied (formic, acetic, propionic, butyric, oxalic, malonic, succinic, glutaric, citric, lactic, malic and tartaric acids) have been identified in various worldwide Bayer liquors. The various aspects of WO and CWO studied for each of the above-mentioned compounds were as follows; -Extent of complete oxidation to carbonate (i.e. extent of removal of organic compound) -Extent of overall oxidation (i.e. extent of complete oxidation and partial oxidation to stable products) -The product(s) formed from partial (incomplete) oxidation -The reaction mechanism occurring -Why certain compounds undergo low temperature WO and/or CWO in highly alkaline, high ionic strength solution -The ability of various transition metal oxides to catalyse the WO of the selected organic compounds Of the 12 organic compounds studied only six (formic, malonic, citric, lactic, malic and tartaric acids) underwent appreciable (>2% overall oxidation) WO in isolation under the reaction conditions used (4.4 -7.0 M NaOH, 165°C, 500 kPa Po₂, 2 hours). Each of these six compounds underwent some complete oxidation and therefore can be partly removed from highly alkaline, high ionic strength solution using low temperature WO. The order of extent of complete oxidation determined was as follows tartaric> citric> malonic> formic> lactic> malic. All of these compounds also underwent some partial oxidation under the reaction conditions used, excluding formic acid, which only underwent complete oxidation. Oxalic acid was a major product of partial oxidation of all of the above-mentioned compounds (excluding formic acid), while acetic acid was a major product of partial oxidation of citric, lactic, malic and tartaric acids. The WO of formic, malonic, citric, lactic, malic and tartaric acids varied considerably with NaOH concentration over the NaOH concentration range studied (4.4 - 7.0 M). The extent of overall oxidation undergone by each of these compounds increased significantly with increasing NaOH concentration. All of the compounds that underwent appreciable WO under the reaction conditions studied contained hydrogen(s) significantly more acidic then the compounds that did not undergo appreciable WO, thus indicating that only organic compounds that contain acidic (albeit weakly acidic) hydrogens undergo low temperature (165°C) WO in highly alkaline, high ionic strength solution. Two different reaction mechanisms were identified to occur during low temperature WO in highly alkaline, high ionic strength solution. Malonic and formic acids underwent WO predominantly via a free radical based reaction mechanism, while citric, lactic, malic and tartaric acids underwent WO predominantly via an ionic based reaction mechanism. The six organic compounds that did not undergo appreciable WO in isolation (acetic, propionic, butyric, oxalic, succinic and glutaric acids) all underwent appreciable WO when in the presence of malonic acid undergoing low temperature WO. Hence, low temperature WO of all of the above-mentioned compounds can be initiated by free radical intermediates produced by malonic acid undergoing WO in highly alkaline, high ionic strength solution. The ability of several transition metal oxides to catalyse the WO of the chosen 12 organic compounds was investigated. Of the transition metal oxides studied CuO was clearly the most active. Five of the organic compounds studied (malonic, citric, lactic, malic and tartaric acids) were catalytically wet oxidised by CuO in highly alkaline, high ionic strength solution in isolation. The order of catalytic activity observed was malonic > tartaric> lactic> malic> citric. Two different catalytic reaction mechanisms were identified for CuO catalysed WO in highly alkaline solution for the organic compounds studied. CuO catalysed the WO of malonic acid predominantly by catalysing the formation of free radical intermediates. CuO catalysed the WO of citric, lactic, malic and tartaric acids predominantly via a complexation-based reaction mechanism.

The homotetrameric enzyme dihydrodipicolinate synthase (DHDPS, E.C. 4.2.1.52) from Escherichia coli was used as a model for probing oligomeric structure in enzymes. Dimeric mutants of this enzyme have been found in previous work to be largely inactive, due to the trapping of a covalent adduct. Partial restoration of catalytic activity has been achieved by incubation in the presence of the substrate pyruvate to displace the adduct. It was hypothesized that the buttressing of dimeric units against one another in the wildtype tetrameric form of DHDPS provides stability in the dimer interface, necessary to maintain optimum catalytic performance and substrate specificity. We hypothesized that buttressing a dimeric DHDPS mutant against a surface would result in restoration of catalytic activity by mimicking the buttressing proposed to occur in the tetrameric structure. To test this hypothesis, dimeric DHDPS mutants were immobilised against an agarose support and the immobilised enzymes characterised. Three DHDPS mutants were prepared, the double mutant DHDPS-C20S/L167C was produced by mutagenesis and a crystal structure obtained in collaboration with Dr Renwick Dobson. Two other mutants, DHDPS-Ll67C and DHDPS-Ll97Y were also over expressed and purified. The quaternary structures of the three mutants were characterised in solution, DHDPS-Ll67C was determined to be tetrameric, DHDPS-C20S-Ll67C was found to equilibrate between tetramer and dimer and DHDPS-Ll97Y was confirmed as a dimer, consistent with previous findings. Modification experiments indicated that the sulfhydryl groups of DHDPS-C20S/L167C were available for immobilisation. Activation experiments indicated that both DHDPS-Ll67C and DHDPS-Ll97Y activated. These results were in accord with those of others in indicating that the displacement of an a-ketoglutarate adduct from the active site was responsible for the activation of mutant DHDPS enzymes. Wild-type DHDPS and the mutants were immobilised through amine and sulfhydryl groups. The free and immobilised enzymes were rigorously characterised, with thermal stability, pH optima, kinetic and lysine inhibition properties determined and compared to wild-type DHDPS. Following immobilisation, substrate affinity was found to decrease for wild-type and mutant enzymes, wild-type KmPyr = 0.26 mM free, 0.8-1.2 mM immobilised, Km(S)-ASA = 0.10 mM free, 1.5-2.5 mM immobilised. Lysine inhibition was determined to be largely unaffected by immobilisation. The largest change in K, was an increase to double that of the free enzyme. Restoration of some catalytic activity was found following the immobilisation of dimeric DHDPS-Ll97Y, the immobilised enzyme was 31 ± 12% more active than free DHDPS-Ll97Y. DHDPS-C20S/L167C was also found to immobilise as a dimer. Comparison ofthe immobilised DHDPS-C20S/L167C dimer with a derivatised free dimeric form ofthis enzyme indicated that an increase from 3% to 9% of wild-type activity had resulted from immobilisation. These results supported the hypothesis that buttressing of a dimeric mutant of DHDPS against a support surface would increase catalytic activity and that buttressing across the dimerdimer interface is essential for optimal catalytic activity in DHDPS enzymes.

Thesis (Ph.D.)--Bowling Green State University, 2008. / Document formatted into pages; contains x, 126 p. : ill. Includes bibliographical references.

The research problem addressed in this study was to determine what the main factors are that contribute to the competitive advantage of the catalytic converter industry cluster in the Eastern Cape. To achieve this objective theoretical models of competitive advantage and literature of industry clustering were identified. For the models on competitive advantage, Porter’s diamond was used for national competitive advantage and Porter’s model on the competitive environment, which affects the competitive advantage of a region. Other theories on competitive advantage of cities and regions were identified, leading up to the theory on the cluster approach. The literature mentioned was broken down and analysed using literature, from knowledgeable people in the automotive industry in the Eastern Cape, identified during the study. A questionnaire was developed to test the degree to which the catalytic converter industry cluster in the Eastern Cape is in agreement with the literature study. The empirical study obtained a strong concurrence with the literature study on national competitive advantage and the theory of clusters. This resulted in a strategy for the catalytic converter industry cluster to sustain competitive advantage and remain globally competitive.

The calcination of calcium carbonate in a cement or a lime kiln uses approximately two to four times the theoretical quantity of energy predicted from thermodynamic calculation depending upon the type of the kiln used (1.4 x 10^6 Btu/ton theoretical to 6 x 10^6 Btu/ton actual). The objective of this research was to attempt to reduce the energy required for the calcination by 1. decreasing the calcination temperature of calcium carbonate, and/or 2. increasing the rate of calcination at a specific temperature. Assuming a catalytic enhancement of 20 percent in the industrial applications, an energy savings of 300 million dollars annually in the United States could be reached in the cement and lime industries. Three classes of compounds to date have shown a positive catalytic effect on the calcination of calcium carbonate. These include alkali halides, phospho- and silico-molybdate complexes, and the fused carbonates system.