Refcoal is a refined carbon source obtained by extraction of coal with dimethylformamide (DMF). During the coking process, Refcoal goes through a mesophase (fluid) stage to form an anisotropic coke. In contrast, oxidised Refcoal does not undergo such a mesophase stage during the carbonisation process. Thus it does not yield an anisotropic coke, but forms an isotropic coke. The objective of this study is to produce an anisotropic coke from oxidised Refcoal. For this purpose, diabietic acid, a hydrogen donor, was considered as a suitable additive. Coking was performed in sealed glass capillary tubes as diabietic acid proved to be volatile at the carbonisation temperature of 500 °C. The resultant cokes were analysed using thermogravimetric analysis, Raman spectroscopy and optical microscopy. The results show that the degree of anisotropy increased with diabietic acid content (3, 5 and 10 mass %). / Dissertation (MSc (Chemistry))--University of Pretoria, 2008. / Chemistry / MSc / Unrestricted

Lors du procédé de cokéfaction, en raison de la faible largeur de la chambre de carbonisation des fours modernes, l’expansion horizontale de la pâte à coke génère une poussée sur les parois de chauffage. L’objectif de cette thèse, qui s’inscrit dans le cadre du projet européen « Swelling Pressure in a Coke Oven, Transmission on Oven walls », est de mieux comprendre le phénomène de poussée des charbons lors de la cokéfaction et de développer un modèle permettant d’anticiper ce phénomène. Pour cela, un modèle phénoménologique prenant en compte les phénomènes physico-chimiques en présence a été développé. Une mise en équation originale est proposée pour la cinétique de condensation des goudrons et le gonflement des grains de charbon lors de la pyrolyse. Le modèle proposé est le premier reproduisant simultanément la poussée sur les piédroits et la pression des gaz produits lors de la cokéfaction. Les résultats de simulation du cas particulier de la cokéfaction du charbon Blue Creek dans le four pilote du Centre de Pyrolyse de Marienau et les mesures de pression, de température et de poussée réalisées lors des essais présentent des écarts mais demeurent en bon accord. Ces écarts sont essentiellement dus à la méconnaissance des propriétés du charbon et de son comportement mécanique. L’hypothèse d’un comportement élastique linéaire entraîne une surestimation de la poussée. L’étude de sensibilité amène, entre autres, à la conclusion que la poussée ne dépend pas directement de la pression des gaz et que le gonflement des grains de charbon joue un rôle déterminant. / During the coking process, due to the small width of the carbonization chamber of modern ovens, horizontal expansion of coal generates a pressure on the oven walls. The objective of this thesis, which is part of European project « Swelling Pressure in a Coke Oven, Transmission on Oven walls », is to better understand the wall pressure phenomenon during coking process and to develop a model which can permit to anticipate this phenomenon. For this, a phenomenological model which takes into account the physical chemistry phenomena in presence is developed. An original implementation is proposed for the kinetic of tars condensation and the coal swelling during pyrolysis. The proposed model is the first which reproducing simultaneously the wall pressure and the gas pressure during coking process. The simulation results of coking process of the specific case of Blue Creek coal in the pilot oven of Centre de Pyrolyse de Marienau and the measurements of gas pressure, of temperature and of wall pressure performed during the tests have discrepancies but remain in good agreement. The discrepancies are mainly due to the ignorance of coal properties and its mechanical behavior. The assumption of linear elastic behavior leads to wall pressure overestimation. The sensitivity study permits to conclude that the wall pressure is not directly dependant to the gas pressure and that coal swelling play a causal role.

O controle de processo de uma planta de fabricação de coque depende de muitas variáveis particulares de cada planta. A busca de modelos de controle próprios torna-se necessário. O presente trabalho apresenta um projeto de experimentos, em forno piloto, para investigar a influência dos principais parâmetros de controle de fabricação do coque quanto à produção e consumo de calor e utilizá-los futuramente num modelo de automação do controle do processo dessa planta. O resultado do experimento apresentou significância estatística para os fatores temperatura e umidade da mistura enfornada e para as interações entre umidade e temperatura e entre umidade e granulometria com relação ao consumo de calor e também o fator temperatura com relação ao tempo líquido de coqueificação. Além do projeto de experimentos em forno piloto foi feito também um experimento em um forno industrial cuja metodologia mostrou-se adequada para um projeto em escala industrial. Com os dados dos experimentos obtiveram-se também equações matemáticas de previsão do consumo de calor e do tempo líquido de coqueificação. / The process control of a coke plant depends on a lot of particular parameters. This work describes an experimental design in a pilot oven aiming at getting the influence of the main control factors of a coke oven battery, relating these parameters with production and heat consumption for future process control automation. The result of the experiment showed statistic significance for the factors temperature and coal blend moisture and for the interactions between temperature and coal blend moisture and between moisture and coal size on the heat consumption and also for the factor temperature on the net coking time. Theses relations can be used to develop coking control at an industrial plant. In addition to the design of experiments in a pilot oven, it was also made an experiment in an industrial battery oven whose methodology showed to be appropriated to an industrial design of experiment. With the experimental data it was possible to write mathematical equations for estimation of heating and net coking time.

O controle de processo de uma planta de fabricação de coque depende de muitas variáveis particulares de cada planta. A busca de modelos de controle próprios torna-se necessário. O presente trabalho apresenta um projeto de experimentos, em forno piloto, para investigar a influência dos principais parâmetros de controle de fabricação do coque quanto à produção e consumo de calor e utilizá-los futuramente num modelo de automação do controle do processo dessa planta. O resultado do experimento apresentou significância estatística para os fatores temperatura e umidade da mistura enfornada e para as interações entre umidade e temperatura e entre umidade e granulometria com relação ao consumo de calor e também o fator temperatura com relação ao tempo líquido de coqueificação. Além do projeto de experimentos em forno piloto foi feito também um experimento em um forno industrial cuja metodologia mostrou-se adequada para um projeto em escala industrial. Com os dados dos experimentos obtiveram-se também equações matemáticas de previsão do consumo de calor e do tempo líquido de coqueificação. / The process control of a coke plant depends on a lot of particular parameters. This work describes an experimental design in a pilot oven aiming at getting the influence of the main control factors of a coke oven battery, relating these parameters with production and heat consumption for future process control automation. The result of the experiment showed statistic significance for the factors temperature and coal blend moisture and for the interactions between temperature and coal blend moisture and between moisture and coal size on the heat consumption and also for the factor temperature on the net coking time. Theses relations can be used to develop coking control at an industrial plant. In addition to the design of experiments in a pilot oven, it was also made an experiment in an industrial battery oven whose methodology showed to be appropriated to an industrial design of experiment. With the experimental data it was possible to write mathematical equations for estimation of heating and net coking time.