Of all coke properties the influence of the catalytic mineral matter on reactivity of metallurgical cokes is least understood. There is limited information about the form of minerals in the metallurgical cokes and no information about their relative concentration. A comprehensive study was undertaken for characterisation of mineral matter in coke (qualitative and quantitative), which enabled quantification of the effect of catalytic minerals on the reaction rate, and establishment of the effect of gasification on the mineral phases. Also, the relative importance of coke properties on the gasification reaction rate was determined. The reactivity experiments were performed at approximately 900??C using 100% CO2 under chemically controlled conditions. The mineralogical composition of the investigated cokes was found to vary greatly as did the levels of catalytic mineral phases. These were identified to be metallic iron, iron sulfides and iron oxides. The gasification reaction rate at the initial stages was strongly influenced by the content of catalytic mineral phases and also by the particle size of the catalytic mineral matter. The reaction rate increased as the contact surface between catalyst and carbon matrix increased. Catalytic mineral phases showed a strong influence on the reaction rate at early stages of reaction. But their influence diminished during gasification. At later stages of reaction the influence of micropore surface area became more important. The influence of the catalytic mineral phases diminished during gasification because the catalyst was inactivated to some degree and the contact surface between the catalyst and carbon matrix diminished due to the strong gasification of the carbon around the catalyst particles. The partial inactivation of the catalytic mineral phases occurred because metallic iron and pyrrhotite were oxidised by CO2 to iron oxide, and in turn iron oxide reacted with other mineral phases, which it is associated with, to form minerals that are not catalysts. It is noteworthy that a significant percentage of the mineral matter present in the investigated cokes was amorphous (44 - 75%). The iron, potassium and sodium present in the amorphous phase did not appear to catalyse gasification, but their potential contribution to gasification could not be completely excluded.

Thesis (Ph.D.)--University of Wollongong, 2009. / Typescript. Includes bibliographical references: leaf 248-256.

Of all coke properties the influence of the catalytic mineral matter on reactivity of metallurgical cokes is least understood. There is limited information about the form of minerals in the metallurgical cokes and no information about their relative concentration. A comprehensive study was undertaken for characterisation of mineral matter in coke (qualitative and quantitative), which enabled quantification of the effect of catalytic minerals on the reaction rate, and establishment of the effect of gasification on the mineral phases. Also, the relative importance of coke properties on the gasification reaction rate was determined. The reactivity experiments were performed at approximately 900??C using 100% CO2 under chemically controlled conditions. The mineralogical composition of the investigated cokes was found to vary greatly as did the levels of catalytic mineral phases. These were identified to be metallic iron, iron sulfides and iron oxides. The gasification reaction rate at the initial stages was strongly influenced by the content of catalytic mineral phases and also by the particle size of the catalytic mineral matter. The reaction rate increased as the contact surface between catalyst and carbon matrix increased. Catalytic mineral phases showed a strong influence on the reaction rate at early stages of reaction. But their influence diminished during gasification. At later stages of reaction the influence of micropore surface area became more important. The influence of the catalytic mineral phases diminished during gasification because the catalyst was inactivated to some degree and the contact surface between the catalyst and carbon matrix diminished due to the strong gasification of the carbon around the catalyst particles. The partial inactivation of the catalytic mineral phases occurred because metallic iron and pyrrhotite were oxidised by CO2 to iron oxide, and in turn iron oxide reacted with other mineral phases, which it is associated with, to form minerals that are not catalysts. It is noteworthy that a significant percentage of the mineral matter present in the investigated cokes was amorphous (44 - 75%). The iron, potassium and sodium present in the amorphous phase did not appear to catalyse gasification, but their potential contribution to gasification could not be completely excluded.

A reutilização de resíduos e sua destinação são desafios seguidamente enfrentados na indústria. Por ser extensa e empregar uma grande variedade de processos, matérias-primas e insumos, a cadeia do aço se beneficia por ter ampla flexibilidade e diversas possibilidades de reintrodução de compostos em sua rota de fabricação. Resíduos carbonosos, por exemplo, podem ser parcialmente usados em misturas de carvões no processo de coqueificação dependendo do tamanho e da composição química. Este trabalho, teve como objetivo, avaliar a influência da adição de moinha de carvão vegetal em uma mistura de carvões para a produção de coques em forno piloto de coqueificação e determinar os teores máximos de incorporação suportados pela mistura, avaliando parâmetros de qualidade do coque. Para isso, a moinha de carvão vegetal de eucalipto foi introduzida em duas frações granulométricas distintas, uma composta por partículas mais grosseiras (fração G) e outra composta por partículas mais finas (fração F), e caracterizado juntamente com a mistura utilizada. Posteriormente, os coques produzidos em forno piloto também foram caracterizados através de diversas análises: imediata, elementar, área superficial, porosidade, textura óptica, reatividade em termobalança, CRI/CSR e DI150/15. Os resultados atingidos mostraram que inserção da fração G de moinha comprometeu menos os parâmetros de qualidade dos coques com carvão vegetal. Teores de até 3% de moinha foram suportados para essa distribuição de tamanho de partícula enquanto que para a fração F, somente 1%. Outro fator observado foi que os coques produzidos com adição de moinha de carvão vegetal não tiveram queda significativa no teor de enxofre, a exceção da amostra contendo 10% de carvão vegetal na fração G. Em todas as amostras com moinha de carvão vegetal também foi possível notar o aumento da área superficial em relação ao coque de referência. Os testes termogravimétricos dinâmicos também trouxeram informações relevantes a respeito das temperaturas e taxas aparentes de reações dos coques feitos com moinha de carvão vegetal. / The reuse of waste materials and its destination are challenges continuously faced for industry. For being far-flung and apply a huge variety of process, raw materials and inputs, the steel supply chain benefits from having a high flexibility and many possibilities of reintroducing compounds in its manufacturing route. For example, carbonaceous materials can be used partially in coal blends for cokemaking process depending on particle size and chemical composition. The current work aimed to evaluate the influence of adding fine charcoal to a coal blend for coke production in a pilot oven and to determine the maximum content tolerated for the blend, assessing coke quality parameters. For this, a eucalyptus charcoal residue was introduced in two different size distributions, one composed of coarser particles (fraction G) and another of finer (fraction F), and characterized together with the coal blend used. Afterwards, the cokes produced in pilot oven were also characterized through several analyzes: proximate, ultimate, surface area, porosity, optical texture, reactivity on thermobalance, CRI/CSR e DI150/15. The results achieved showed that the insertion of charcoal on fraction G compromised less the quality parameters of cokes with charcoal. Contents up to 3% of charcoal were tolerated for this particle size distribution while for fraction F, only 1%. Another point noticed was that the coke produced with charcoal addition had no significant drop on sulfur content, with the exception of the coke sample with 10% of charcoal and fraction G. In all samples with charcoal it was also possible to see an increase on surface area in relation to the reference coke. The dynamic thermogravimetric tests also provided relevant information regarding to the temperatures and apparent reaction rates of cokes made with charcoal.

A reutilização de resíduos e sua destinação são desafios seguidamente enfrentados na indústria. Por ser extensa e empregar uma grande variedade de processos, matérias-primas e insumos, a cadeia do aço se beneficia por ter ampla flexibilidade e diversas possibilidades de reintrodução de compostos em sua rota de fabricação. Resíduos carbonosos, por exemplo, podem ser parcialmente usados em misturas de carvões no processo de coqueificação dependendo do tamanho e da composição química. Este trabalho, teve como objetivo, avaliar a influência da adição de moinha de carvão vegetal em uma mistura de carvões para a produção de coques em forno piloto de coqueificação e determinar os teores máximos de incorporação suportados pela mistura, avaliando parâmetros de qualidade do coque. Para isso, a moinha de carvão vegetal de eucalipto foi introduzida em duas frações granulométricas distintas, uma composta por partículas mais grosseiras (fração G) e outra composta por partículas mais finas (fração F), e caracterizado juntamente com a mistura utilizada. Posteriormente, os coques produzidos em forno piloto também foram caracterizados através de diversas análises: imediata, elementar, área superficial, porosidade, textura óptica, reatividade em termobalança, CRI/CSR e DI150/15. Os resultados atingidos mostraram que inserção da fração G de moinha comprometeu menos os parâmetros de qualidade dos coques com carvão vegetal. Teores de até 3% de moinha foram suportados para essa distribuição de tamanho de partícula enquanto que para a fração F, somente 1%. Outro fator observado foi que os coques produzidos com adição de moinha de carvão vegetal não tiveram queda significativa no teor de enxofre, a exceção da amostra contendo 10% de carvão vegetal na fração G. Em todas as amostras com moinha de carvão vegetal também foi possível notar o aumento da área superficial em relação ao coque de referência. Os testes termogravimétricos dinâmicos também trouxeram informações relevantes a respeito das temperaturas e taxas aparentes de reações dos coques feitos com moinha de carvão vegetal. / The reuse of waste materials and its destination are challenges continuously faced for industry. For being far-flung and apply a huge variety of process, raw materials and inputs, the steel supply chain benefits from having a high flexibility and many possibilities of reintroducing compounds in its manufacturing route. For example, carbonaceous materials can be used partially in coal blends for cokemaking process depending on particle size and chemical composition. The current work aimed to evaluate the influence of adding fine charcoal to a coal blend for coke production in a pilot oven and to determine the maximum content tolerated for the blend, assessing coke quality parameters. For this, a eucalyptus charcoal residue was introduced in two different size distributions, one composed of coarser particles (fraction G) and another of finer (fraction F), and characterized together with the coal blend used. Afterwards, the cokes produced in pilot oven were also characterized through several analyzes: proximate, ultimate, surface area, porosity, optical texture, reactivity on thermobalance, CRI/CSR e DI150/15. The results achieved showed that the insertion of charcoal on fraction G compromised less the quality parameters of cokes with charcoal. Contents up to 3% of charcoal were tolerated for this particle size distribution while for fraction F, only 1%. Another point noticed was that the coke produced with charcoal addition had no significant drop on sulfur content, with the exception of the coke sample with 10% of charcoal and fraction G. In all samples with charcoal it was also possible to see an increase on surface area in relation to the reference coke. The dynamic thermogravimetric tests also provided relevant information regarding to the temperatures and apparent reaction rates of cokes made with charcoal.

A reutilização de resíduos e sua destinação são desafios seguidamente enfrentados na indústria. Por ser extensa e empregar uma grande variedade de processos, matérias-primas e insumos, a cadeia do aço se beneficia por ter ampla flexibilidade e diversas possibilidades de reintrodução de compostos em sua rota de fabricação. Resíduos carbonosos, por exemplo, podem ser parcialmente usados em misturas de carvões no processo de coqueificação dependendo do tamanho e da composição química. Este trabalho, teve como objetivo, avaliar a influência da adição de moinha de carvão vegetal em uma mistura de carvões para a produção de coques em forno piloto de coqueificação e determinar os teores máximos de incorporação suportados pela mistura, avaliando parâmetros de qualidade do coque. Para isso, a moinha de carvão vegetal de eucalipto foi introduzida em duas frações granulométricas distintas, uma composta por partículas mais grosseiras (fração G) e outra composta por partículas mais finas (fração F), e caracterizado juntamente com a mistura utilizada. Posteriormente, os coques produzidos em forno piloto também foram caracterizados através de diversas análises: imediata, elementar, área superficial, porosidade, textura óptica, reatividade em termobalança, CRI/CSR e DI150/15. Os resultados atingidos mostraram que inserção da fração G de moinha comprometeu menos os parâmetros de qualidade dos coques com carvão vegetal. Teores de até 3% de moinha foram suportados para essa distribuição de tamanho de partícula enquanto que para a fração F, somente 1%. Outro fator observado foi que os coques produzidos com adição de moinha de carvão vegetal não tiveram queda significativa no teor de enxofre, a exceção da amostra contendo 10% de carvão vegetal na fração G. Em todas as amostras com moinha de carvão vegetal também foi possível notar o aumento da área superficial em relação ao coque de referência. Os testes termogravimétricos dinâmicos também trouxeram informações relevantes a respeito das temperaturas e taxas aparentes de reações dos coques feitos com moinha de carvão vegetal. / The reuse of waste materials and its destination are challenges continuously faced for industry. For being far-flung and apply a huge variety of process, raw materials and inputs, the steel supply chain benefits from having a high flexibility and many possibilities of reintroducing compounds in its manufacturing route. For example, carbonaceous materials can be used partially in coal blends for cokemaking process depending on particle size and chemical composition. The current work aimed to evaluate the influence of adding fine charcoal to a coal blend for coke production in a pilot oven and to determine the maximum content tolerated for the blend, assessing coke quality parameters. For this, a eucalyptus charcoal residue was introduced in two different size distributions, one composed of coarser particles (fraction G) and another of finer (fraction F), and characterized together with the coal blend used. Afterwards, the cokes produced in pilot oven were also characterized through several analyzes: proximate, ultimate, surface area, porosity, optical texture, reactivity on thermobalance, CRI/CSR e DI150/15. The results achieved showed that the insertion of charcoal on fraction G compromised less the quality parameters of cokes with charcoal. Contents up to 3% of charcoal were tolerated for this particle size distribution while for fraction F, only 1%. Another point noticed was that the coke produced with charcoal addition had no significant drop on sulfur content, with the exception of the coke sample with 10% of charcoal and fraction G. In all samples with charcoal it was also possible to see an increase on surface area in relation to the reference coke. The dynamic thermogravimetric tests also provided relevant information regarding to the temperatures and apparent reaction rates of cokes made with charcoal.

Notre travail est consacré à l’étude des matériaux carbonés utilisés comme réducteurs pour la production des alliages de manganèse dans le four électrique à arc immergé. Le choix du réducteur est important pour l’optimisation du procédé métallurgique et sa réactivité au CO2 est le paramètre le plus important utilisé par les producteurs de ferroalliages pour évaluer sa qualité. Les objectifs de notre travail sont : ? d’établir les critères de sélection du coke métallurgique ou réducteur de remplacement, utilisés pour la production des alliages de manganèse dans le four électrique, en utilisant la réactivité au CO2 comme le principal paramètre pour évaluer sa qualité ; ? d’un point de vue plus fondamental, apporter une meilleure compréhension des réactions du carbone dans le réacteur industriel. Dans l’optique d’une modélisation globale du four électrique, notre travail fournit des paramètres cinétiques d’une des réactions les plus importantes du procédé : la réaction de Boudouard. L’étude de la réductibilité des oxydes de manganèse pourrait donc être une nouvelle étape vers la construction d’un modèle global du réacteur industriel. Un troisième volet d’expériences utile à la modélisation serait l’étude de l’influence de la nature et du calibre du réducteur sur la résistivité électrique de la charge. / The main aims of our work have been to establish criteria useful for reductant selection, using coke reactivity to CO2 as the main parameter for reductant quality assessment and, from a fundamental point of view, to develop a better understanding of carbon reactions inside the industrial reactor. Therefore, Boudouard reaction has been studied on three increasing scales: intrinsic chemical reaction, coke lump, and coke bed scales. Several different types of carbonaceous materials have been studied. They represent the variety of reductants commonly used in the production of manganese ferroalloys in the electric furnace. It has been shown that this extended range of reductants introduces large differences between their characteristics, mainly between their reactivity to CO2. Regarding the coke lump gasification kinetics, the Langmuir-Hinshelwood model has been used to represent the intrinsic rate of the Boudouard reaction. A good correlation has been found between the initial gasification rates of the coke beds and the single coke lumps. The difference between these rates increases with increasing reductant reactivity. It is possible to determine coke gasification regime inside the industrial electric arc furnace using single particle and coke bed gasification models. The overall rate at which coke reacts with CO2 inside the industrial reactor is probably limited by the intrinsic chemical reaction. Therefore, a reactivity index, based on the initial gasification rate of the reductant, measured in the chemical-kinetics controlled regime, seems to be adapted to the reductant quality assessment. An additional technique could be the microtextural analysis.