Refcoal is a carbon precursor obtained by alkali-mediated extraction of coal with aprotic solvents such as DMF. Refcoal can be converted into a graphitic material through appropriate heat treatment. Graphitisable materials require the development of an intermediate liquid crystalline mesophase. Thus formation of a mesophase during the carbonisation of Refcoal is essential for obtaining highly graphitisable anisotropic cokes suitable for nuclear graphite applications. Anisotropic carbons are even more important in other commercial and industrial application because of their distinctive properties. The formation of anisotropic carbon depends on the nature of the parent precursor, temperature and carbonisation conditions, especially the molecular mobility during the mesophase stage. High-temperature extraction of coal produces Refcoal that yield cokes with a low level of anisotropy. Good control of the mesophase stage during carbonisation may lead to the development of anisotropic cokes. Hydrogen donor additives increase the molecular mobility in the liquid phase by stabilising the free radicals formed by thermal decomposition of coal. Hydrogen donor additives also increase the temperature range over which fluidity occurs, thereby allowing the formation of large sized mosaic structures. Mittal pitches (CTP) and tetralin were examined for their effectiveness as hydrogen donor additives. Refcoal blends containing 10 to 50% by mass additive were prepared by mixing and carbonisation conducted at temperatures ranging form 400 to 1000 °C. Samples were analysed using thermogravimetric analysis (TGA), diffuse reflectance infrared Fourier transform (DRIFT), optical microscope techniques, scanning electron microscopy (SEM), Raman spectroscopy and X-ray diffraction (XRD). It was found that addition of at least 10% tetralin improves the optical texture of Refcoal cokes and also increases the carbon yield. In both tetralin and pitch addition, 20% additive gave coarse circular anisotropic cokes after carbonisation at 650°C. However the carbon yield was reduced for the Refcoal coke treated with Mittal pitch. In fact the yield roughly decreases with an increase in pitch content. Although the cokes from pitch treated Refcoals showed a low ratio of d/g (where d indicates the degree of disordering and g the degree of ordering), Raman and XRD results indicate little further improvement in crystallinity but SEM showed development of a smooth morphology with increasing pitch content. Previous literature results suggest that this indicates that the material must have passed through a mesophase stage. Surprisingly, the addition of tetralin yielded cokes with high ratio of d/g, but improved the carbon yield and optical anisotropy. Increasing tetralin content in the carbonising system increased the size of anisotropic textures but the SEM micrographs show rough morphology with compounds that appear to inhibit mesophase spheres coalescence. / Dissertation (MSc)--University of Pretoria, 2009. / Chemistry / unrestricted

A decomposição térmica dos asfaltenos é a principal responsável pela formação de coque no processamento de petróleos. O fenômeno não é claramente entendido, pelas dificuldades ainda existentes na caracterização de tais componentes pesados do óleo. Este trabalho apresenta informações sobre os produtos da decomposição térmica dos asfaltenos isolados de um petróleo da Bacia de Campos, maior bacia produtora de petróleo no Brasil. A abordagem envolveu: 1) estudos da decomposição térmica dos asfaltenos por termogravimetria (TG) em condições controladas; 2) caracterização dos produtos voláteis dessa decomposição por termogravimetria acoplada à cromatografia gasosa e espectrometria de massas (TG/DTA-CG-EM) e 3) caracterização dos produtos sólidos obtidos em diferentes temperaturas pela reação de oxidação catalisada pelo íon rutênio (RICO) que converte seletivamente alquil aromáticos em ácidos alcanóicos. A decomposição térmica dos asfaltenos foi estudada por termogravimetria. Os asfaltenos se decompõem drasticamente entre 320 e 650ºC produzindo 54% de produtos voláteis e 46% de coque. O material volátil liberado dos asfaltenos a 700°C foi analisado por TG/DTA acoplado a CG-EM. Foi identificada uma série de alcanos contendo de C3 a C10. Esse resultado causou grande surpresa, pois na análise da pirólise de diferentes asfaltenos são observados alcanos com maior número de átomos de carbono. Outro experimento foi realizado, agora em duas etapas: coleta do material volátil e injeção desta no sistema GC-EM. Desta vez foi possível identificar a série homóloga de alcanos de C11 até C33. Para o maior conhecimento da decomposição térmica dos asfaltenos, foram obtidos, em escala preparativa, produtos sólidos de decomposição térmica destes nas temperaturas de 320, 380, 400, 440, 480, 550 e 580°C. As análises realizadas nesses produtos - elementar, espectroscopia na região do infravermelho, ressonância magnética nuclear de carbono 13 no estado sólido - indicaram que quanto maior a temperatura de obtenção dos produtos sólidos, menor é o conteúdo de hidrogênio e carbono alifático. Os asfaltenos e os seus produtos de pirólise foram submetidos a reação de oxidação seletiva. Os ácidos gerados foram metilados para análise por CG-EM. Nos asfaltenos e nos produtos obtidos a 320, 380, 400 e 440°C foram identificados ésteres metílicos lineares que indicaram a presença de hidrocarbonetos alifáticos contendo de 5 a 25 átomos de carbono, ésteres metílicos de ácidos dicarboxílicos que indicaram a presença de pontes alquilicas entre os grupamentos aromáticos contendo de 3 a 15 átomos de carbono e alguns ésteres metílicos de ácidos benzenodicarboxílicos. Comparando-se o teor total desses ésteres metílicos presentes em cada produto de reação, foi verificado que a concentração dos ésteres metílicos lineares diminui lentamente a 320, 380, 400ºC, e drasticamente a partir de 400ºC. O mesmo ocorrendo com os ésteres dos ácidos dicarboxílicos e benzeno dicarboxílicos, em menor concentração que os ésteres metílicos lineares. / The thermal decomposition of asphaltenes is mainly responsible for the formation of coke in petroleum processing. The phenomena involved are not clearly understood, due to the difficulties in characterizing such heavy components. This research reports the application of thermal analysis techniques to study the thermal behavior of asphaltenes from Brazilian oil (Campos Basin). The approach involves: 1) studies of the thermal decomposition of asphaltenes under controlled conditions by thermogravimetry (TG); 2) characterization of volatile fractions by thermogravimetry and differential thermal analysis coupled with gas chromatography and mass spectrometry (TG/DT-GC-MS); 3) solid products from the thermal decomposition of asfaltenes where subjected to ruthenium (VIII) ion catalyzed oxidation reaction (RICO) that converts selectively and efficiently, alkyl aromatics to alkanoic acids. Thermogravimetry was used to study the asphaltenes thermal decomposition. The asphaltenes drastically decomposes from 320 to 650ºC to produce 54% of volatile products and 46% of coke. The volatile products of the asphaltenes at 700ºC were done by TG/DTA coupled to GC-MS. The volatile material was identified as a series of straight chain of normal alkyl ranging from C3 to C10. This result indicated limitations of the apparatus employed n-alkyl chains longer than these were expected. However, it worked well for lighter components. Another experiment, in which gaseous products from pyrolysis procedure were recovered by bubbling in CH2Cl2, accounted for the heavier components. The solution obtained this time can be analyzed by syringe injection in a CG-MS. The majority of the volatile material is constituted of straight chain alkanes ranging from C13 to C33. Knowing more about the thermal decomposition conversion of asphaltenes, the solid pyrolysis products of them were obtained in larger quantities at 320, 380, 400, 440, 480, 550 e 580ºC. They were characterized by elemental analysis and solid state 13C nuclear magnetic resonance. It was observed that at higher pyrolysis temperatures, lower the hydrogen and aliphatic carbon contents were obtained for the solid products. So, to improve knowledge on these systems, asphaltenes and their solid products from thermal decomposition were oxidized with ruthenium (VIII) ion. The acids formed were mixed with excess of ethereal diazomethane and submitted to GC-MS in order to identify the correspondent methyl esters. It was observed three homologous series: methyl esters of linear carboxylic acids ranging from C6 to C27, corresponding to chain alkyl length from C5 to C26 substituent on aromatic carbon; small amounts of dimethyl esters were also present in a homologous series, ranging from C5 to C17 indicating bridge polymethylenes between aromatics from C3 to C15 and benzene dicarboxilic acids from C10 to C12. The total content of methyl ester of each reaction products was compared. It was observed that the linear esters content decreased slowly at a 320, 380, 400°C and drastically up to 400ºC. The same occurred with the dimethyl aliphatic esters and dimethyl benzyl esters.

A decomposição térmica dos asfaltenos é a principal responsável pela formação de coque no processamento de petróleos. O fenômeno não é claramente entendido, pelas dificuldades ainda existentes na caracterização de tais componentes pesados do óleo. Este trabalho apresenta informações sobre os produtos da decomposição térmica dos asfaltenos isolados de um petróleo da Bacia de Campos, maior bacia produtora de petróleo no Brasil. A abordagem envolveu: 1) estudos da decomposição térmica dos asfaltenos por termogravimetria (TG) em condições controladas; 2) caracterização dos produtos voláteis dessa decomposição por termogravimetria acoplada à cromatografia gasosa e espectrometria de massas (TG/DTA-CG-EM) e 3) caracterização dos produtos sólidos obtidos em diferentes temperaturas pela reação de oxidação catalisada pelo íon rutênio (RICO) que converte seletivamente alquil aromáticos em ácidos alcanóicos. A decomposição térmica dos asfaltenos foi estudada por termogravimetria. Os asfaltenos se decompõem drasticamente entre 320 e 650ºC produzindo 54% de produtos voláteis e 46% de coque. O material volátil liberado dos asfaltenos a 700°C foi analisado por TG/DTA acoplado a CG-EM. Foi identificada uma série de alcanos contendo de C3 a C10. Esse resultado causou grande surpresa, pois na análise da pirólise de diferentes asfaltenos são observados alcanos com maior número de átomos de carbono. Outro experimento foi realizado, agora em duas etapas: coleta do material volátil e injeção desta no sistema GC-EM. Desta vez foi possível identificar a série homóloga de alcanos de C11 até C33. Para o maior conhecimento da decomposição térmica dos asfaltenos, foram obtidos, em escala preparativa, produtos sólidos de decomposição térmica destes nas temperaturas de 320, 380, 400, 440, 480, 550 e 580°C. As análises realizadas nesses produtos - elementar, espectroscopia na região do infravermelho, ressonância magnética nuclear de carbono 13 no estado sólido - indicaram que quanto maior a temperatura de obtenção dos produtos sólidos, menor é o conteúdo de hidrogênio e carbono alifático. Os asfaltenos e os seus produtos de pirólise foram submetidos a reação de oxidação seletiva. Os ácidos gerados foram metilados para análise por CG-EM. Nos asfaltenos e nos produtos obtidos a 320, 380, 400 e 440°C foram identificados ésteres metílicos lineares que indicaram a presença de hidrocarbonetos alifáticos contendo de 5 a 25 átomos de carbono, ésteres metílicos de ácidos dicarboxílicos que indicaram a presença de pontes alquilicas entre os grupamentos aromáticos contendo de 3 a 15 átomos de carbono e alguns ésteres metílicos de ácidos benzenodicarboxílicos. Comparando-se o teor total desses ésteres metílicos presentes em cada produto de reação, foi verificado que a concentração dos ésteres metílicos lineares diminui lentamente a 320, 380, 400ºC, e drasticamente a partir de 400ºC. O mesmo ocorrendo com os ésteres dos ácidos dicarboxílicos e benzeno dicarboxílicos, em menor concentração que os ésteres metílicos lineares. / The thermal decomposition of asphaltenes is mainly responsible for the formation of coke in petroleum processing. The phenomena involved are not clearly understood, due to the difficulties in characterizing such heavy components. This research reports the application of thermal analysis techniques to study the thermal behavior of asphaltenes from Brazilian oil (Campos Basin). The approach involves: 1) studies of the thermal decomposition of asphaltenes under controlled conditions by thermogravimetry (TG); 2) characterization of volatile fractions by thermogravimetry and differential thermal analysis coupled with gas chromatography and mass spectrometry (TG/DT-GC-MS); 3) solid products from the thermal decomposition of asfaltenes where subjected to ruthenium (VIII) ion catalyzed oxidation reaction (RICO) that converts selectively and efficiently, alkyl aromatics to alkanoic acids. Thermogravimetry was used to study the asphaltenes thermal decomposition. The asphaltenes drastically decomposes from 320 to 650ºC to produce 54% of volatile products and 46% of coke. The volatile products of the asphaltenes at 700ºC were done by TG/DTA coupled to GC-MS. The volatile material was identified as a series of straight chain of normal alkyl ranging from C3 to C10. This result indicated limitations of the apparatus employed n-alkyl chains longer than these were expected. However, it worked well for lighter components. Another experiment, in which gaseous products from pyrolysis procedure were recovered by bubbling in CH2Cl2, accounted for the heavier components. The solution obtained this time can be analyzed by syringe injection in a CG-MS. The majority of the volatile material is constituted of straight chain alkanes ranging from C13 to C33. Knowing more about the thermal decomposition conversion of asphaltenes, the solid pyrolysis products of them were obtained in larger quantities at 320, 380, 400, 440, 480, 550 e 580ºC. They were characterized by elemental analysis and solid state 13C nuclear magnetic resonance. It was observed that at higher pyrolysis temperatures, lower the hydrogen and aliphatic carbon contents were obtained for the solid products. So, to improve knowledge on these systems, asphaltenes and their solid products from thermal decomposition were oxidized with ruthenium (VIII) ion. The acids formed were mixed with excess of ethereal diazomethane and submitted to GC-MS in order to identify the correspondent methyl esters. It was observed three homologous series: methyl esters of linear carboxylic acids ranging from C6 to C27, corresponding to chain alkyl length from C5 to C26 substituent on aromatic carbon; small amounts of dimethyl esters were also present in a homologous series, ranging from C5 to C17 indicating bridge polymethylenes between aromatics from C3 to C15 and benzene dicarboxilic acids from C10 to C12. The total content of methyl ester of each reaction products was compared. It was observed that the linear esters content decreased slowly at a 320, 380, 400°C and drastically up to 400ºC. The same occurred with the dimethyl aliphatic esters and dimethyl benzyl esters.