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

Die Arbeit beschreibt neuartige Isocyanat- und Initiierungsreaktionen von speziellen Basen mit dem Imin-Strukturinkrement. Gegenstand des ersten Teils ist die Synthese und Charakterisierung neuer Imidazolin-Isocyanat-Adduksysteme, welche genutzt werden um organische Netzwerke auf der Basis von 1-Ethylimidazolin und diversen Diisocyanaten aufzubauen. Ferner wurden die unterschiedlichen Adduktsysteme hinsichtlich ihrer Anwendbarkeit als blockierte Isocyanate untersucht. Hierzu wurden thermische Analysen wie DSC- und TG-MS-Messungen durchgeführt. Durch experimentelle Ergebnisse und quantenchemische Rechnungen konnte ein neuartiger Reaktionsmechanismus einer Adduktbildung gefunden werden. Die Imidazolin-Isocyanat-Adduktnetzwerke wurden als Macroinitiatoren für die radikalische Polymerisation von Methylmethacrylat (MMA) verwendet, wodurch Adduktnetzwerk-PMMA-Kompositmaterialien erhalten wurden. Gegenstand des zweiten Teils dieser Arbeit ist die Entwicklung eines neuartigen Initiatorsystems für die radikalische Polymerisation von MMA und Styrol, auf der Grundlage der Iminbase-(Meth-)Acrylat-induzierten Polymerisation (IBA-Polymerisation). Hierzu wurden unterschiedlich substituierte Isoxazolone synthetisiert und als Starter für die Polymerisation eingesetzt. Der radikalische Charakter der Polymerisation wurde mittels Copolymerisationsexperimenten belegt.:Abkürzungsverzeichnis 1. Einleitung und Zielsetzung 1.1. Einleitung 1.2. Zielsetzung und Motivation 2. Theoretische Grundlagen 2.1. Isocyanat-Imidazolin-Adduktsysteme als blockierte Isocyanate 2.1.1. Blockierte Isocyanate 2.1.2. Iminbasen-Isocyanat-Addukte 2.2. Radikalische Polymerisation 2.2.2. Autoinitiierung von Styrol und Methylmethacrylat 2.2.3. Definition der IBA- und IBI-Polymerisation 3. Ergebnisse und Diskussion 3.1. Isocyanat-Imidazolin-Adduktsysteme als blockierte Isocyanate 3.1.1. 3 : 1-Isocyanat-Imidazolin-Addukte basierend auf 1-Ethylimidazolin 3.1.2. Organische Netzwerke basierend auf 3 : 1-Isocyanat-Imidazolin-Addukten 3.1.3. 2 : 1-Isocyanat-Imidazolin-Addukte basierend auf 1-Ethyl-2-iso-propyl-imidazolin 3.1.4. 2 : 1-Isocyanat-Imidazolin-Addukte basierend auf 1-Ethyl-2-methyl-imidazolin 3.2. IBA-Polymerisation mittels Isoxazolonen 3.2.1. Tautormerie und thermische Analysen von Isoxazolonderivaten 3.2.2. Polymerisation von Acrylatmonomeren mit Isoxazolonen 3.2.3. Kinetik der IBA-Polymerisation mit Isoxazolonen 3.2.4. IBA-Polymerisation von Styrol mit 3-Phenyl-5-isoxazolon 3.2.5. Mechanistische Studien der IBA-Polymerisation initiiert durch Isoxazolone 4. Zusammenfassung und Ausblick 5. Experimenteller Teil 5.1. Geräte und Chemikalien 5.2. Synthese der Iminbasen 5.3. Synthese der Iminbase–Isocyanat–Addukte 5.4. Synthese der 3 : 1 Adduktnetzwerke 5.5. Synthese von Isoxazolonderivaten 5.6. Polymerisationen von MMA und Styrol mit Isoxazolonen 6. Literatur 7. Anhang Danksagung Lebenslauf Liste an Veröffentlichungen Selbstständigkeitserklärung