L'éthanol est converti, à 350°C sous 30 bar et sur des zéolithes protoniques, en un mélange de paraffines légères et d'aromatiques ; produits incorporables dans le pool essence. Cependant, la transformation de EtOH sur zéolithes acides conduit à la formation du coke. Des techniques physiques avancées, en particulier les techniques MALDI et LDI-TOF MS, couplées à la méthode d'analyse qui consiste à récupérer dans un solvant les molécules carbonées après dissolution de la zéolithe dans HF, contribuent à caractériser finement le coke. Sa composition dépend du catalyseur : sur HBEA(11), zéolithe à larges pores, 17 familles ont été détectées contre 4 sur HZSM-5(40) de taille de pore intermédiaire. Sur cette dernière, le coke, composé de polyalkybenzènes / naphtalènes / phénalènes et pyrènes, est localisé à l'intersection des canaux et a une toxicité vis-à-vis des sites acides de Brønsted de 1. En dépit d'un empoisonnement total, cette zéolithe est toujours capable de convertir EtOH, comme MeOH, en hydrocarbures et qui plus est avec les mêmes sélectivités en produits. La transformation de ces deux alcools ne s'explique pas par un mécanisme classique de catalyse acide, mais par un mécanisme concerté radicalaire-acide. La présence d'un inhibiteur de radicaux dans la charge réactionnelle, l'hydroquinone, provoque une désactivation immédiate et une diminution de la concentration des radicaux. La transformation de EtOH et MeOH passe par un intermédiaire réactionnel commun, le carbène :CH2, dont l'oligomérisation radicalaire conduit à la formation d'oléfines. Ces oléfines légères (n-O3-n-O5) sont très réactives et se transforment par catalyse acide (oligomérisation / cyclisation / t / Ethanol is converted into light paraffins and aromatics mixture at 350°C under 30 bar over protonic zeolites. These products can be incorporated in the gasoline pool. Nevertheless, EtOH transformation over acid zeolites leads to the formation of the coke. Advanced physical techniques, in particular MALDI and LDI-TOF MS, were coupled to the coke analysis method. This method consists of the recovery of the carbonaceous molecules in a solvent after zeolite dissolution in hydrofluoric acid solution. This coupling allows characterizing the coke through an extensive way. The coke composition depends on the catalyst morphology: over HBEA(11) zeolite of large pores, 17 families were detected while 4 over HZSM-5(40) of intermediate pore size. Over this latter, the coke, composed of polyalkylbenzenes/naphtalenes/phenalenes and pyrenes, is located in the channels intersections and has toxicity of 1 towards Brønsted acid sites. In spite of a total poisoning, HZSM-5 zeolite is always able to convert EtOH, like MeOH, into hydrocarbons with the same products selectivity. The transformation of the two alcohols cannot be explained by a classical mechanism of acid catalysis, but by a cooperative radical-acid mechanism. The presence of a radical inhibitor in the feed, the hydroquinone, causes an immediate deactivation and a decrease in the concentration of radicals. The transformation of EtOH and MeOH passed by the common reaction intermediate, the :CH2 carbene, which its radical oligomerization leads to the formation of olefins. Olefins (n-O3-n-O5) are very active and can be transformed through acid catalysis (oligomerization/cyclisation/Hydrogen transfer) into aromatics or undergo isomer

In this thesis, graphene (i.e. monolayer carbon film) and carbon clusters supported on a transition metal surface are systematically studied by local probe techniques, with respect to their structures, electronic properties and formation mechanisms. The main tools used are low-temperature scanning tunnelling microscopy and spectroscopy (STM and STS), which are introduced in Chapter 2. The mechanism of the resonance tunnelling at electron energies higher than the work function of the surface is discussed in detail, and a qualitative explanation of the Gundlach oscillations in the corresponding spectroscopy is presented. Epitaxial graphene synthesised on the Rh(111) surface by ethylene dehydrogenation is investigated by STM in Chapter 4. Such carbon film exhibits a hexagonal Moiré pattern due to a lattice mismatch between graphene and the rhodium substrate. The periodicity and local registries of the graphene/Rh(111) superstructure are carefully analysed. Based on a thorough discussion about the “commensurate vs. incommensurate” nature of the Moiré pattern in surface science field, the graphene/Rh(111) system is identified to have a non-simple-commensurate superstructure. The surface electronic properties and geometric buckling of graphene/Rh(111) are investigated by resonance tunnelling spectroscopy (RTS) and density functional theory (DFT) calculations in Chapter 5. Spectroscopy measurements reveal a modulation of the electronic surface potential (or work function Φ) across the supercell of epitaxial graphene. Based on the microscopy/spectroscopy data and the extended DFT calculations, we examined the electronic coupling of the various local C-Rh registries, and identified both experimentally and theoretically the local atomic configurations of maximum and minimum chemical bonding between graphene and the rhodium substrate. We studied in Chapter 6 the growth mechanism of graphene on Rh(111) at elevated temperatures. This part starts by investigating the dehydrogenation of ethylene into ethylidyne. When the dehydrogenation process is complete, monodispersed carbon species, identified as 7C6, are found to dominate the cluster population on the rhodium terraces. A significant coalescence of the 7C6 clusters into graphene islands occurs at temperatures higher than 873 K. The structural and electronic properties of the 7C6 carbon clusters are examined by high-resolution STM and STS, and compared with coronene molecules, i.e. the hydrogenated analogues of 7C6. DFT calculations are further used to explain the stability of 7C6 supported on the Rh(111) surface, and also the structural characteristics of such magic-sized carbon clusters.

A utilização de briquetes de misturas de carvão fóssil e biomassa em substituição ao coque como agente redutor pode contribuir para a diminuição das emissões de CO2 à atmosfera no processo de redução de minério de ferro. O fenômeno do amolecimento e fluidificação do carvão fóssil durante o aquecimento permite que o mesmo absorva certa quantidade de materiais inertes à coqueificação durante o tratamento térmico. O objetivo deste trabalho é correlacionar o efeito das principais variáveis de processo de fabricação (temperatura e tempo de tratamento térmico, tamanho de partícula dos componentes, porosidade e proporção de carvão vegetal e carvão fóssil) sobre as propriedades obtidas (resistência mecânica e reatividade ao CO2) de briquetes compostos de misturas de carvão fóssil e carvão vegetal, para uso na indústria siderúrgica. Briquetes de dois formatos diferentes foram preparados em matriz cilíndrica e em maquina briquetadeira e tratados termicamente em forno vertical aquecido com resistência elétrica sob atmosfera de nitrogênio. A resistência à compressão dos briquetes foi analisada em função das seguintes variáveis: proporção de carvão fóssil e carvão vegetal, taxa de aquecimento do tratamento térmico e tamanho de partícula dos carvões. A reatividade ao CO2 dos briquetes tratados termicamente foi analisada em função das seguintes variáveis: temperatura de ensaio e vazão de CO2. Foram comparados os resultados obtidos de ambos os formatos de briquetes. Com o aumento da proporção de carvão vegetal nos briquetes cilíndricos de biocoque, a densidade aparente e a resistência à compressão após tratamento térmico aumentaram para as misturas contendo 5, 10 e 15% de carvão vegetal. A partir dessa composição (15% de carvão vegetal) tanto a densidade final quanto a resistência à compressão apresentaram diminuição. Encontrou-se que tanto os briquetes cilíndricos a verde quanto os briquetes tratados termicamente apresentam perda de resistência mecânica com o aumento do tamanho de partícula do carvão fóssil. Os melhores valores de resistência à compressão foram obtidos em briquetes feitos com carvão fóssil em mistura de 15% em peso de carvão vegetal, tamanho de partícula abaixo de 0,044 mm, tratados termicamente a 1100°C durante 8 horas. Com o aumento na adição de carvão vegetal nos briquetes compostos de carvão fóssil e carvão vegetal, observou-se um aumento da reatividade do biocoque ao CO2. As micrografias dos briquetes tratados termicamente mostraram que a textura dos briquetes tende a ser mais homogênea com aumento de carvão vegetal de madeira na mistura. Os briquetes de biocoque fabricados em briquetadeira permitiram a ampliação do processo de fabricação de briquetes a uma escala laboratorial maior e mostraram a viabilidade industrial na fabricação do biocoque. Encontrou-se que a adição de carvão vegetal de madeira na mistura influencia diretamente na resistência a compressão e a reatividade ao CO2, devido a diferentes fatores como a composição das cinzas da madeira, a diminuição da fluidez devido à ação do inerte na mistura a carbonizar, a formação de uma estrutura porosa dentro da matriz carbonosa. Não encontrou-se correlação entre o índice de alcalinidade dos briquetes e sua reatividade ao CO2. / The substitution of metallurgical coke by briquetted mixtures of coal and biomass as a reducing agent can lower the emissions of greenhouse gases (CO2) in the iron and steelmaking industry. The thermal plasticity of the coking coal can be used to absorb an amount of inert materials during heat treatment. The objective of this study is to correlate the effect of the main processes variables (heat treatment temperature and duration, particle size of the materials, porosity and coal and charcoal ratio) on the properties (compressive strength and CO2 reactivity) of briquetted mixtures of coal and charcoal. Two types of briquettes were produced, one in a cylindrical die and another in a laboratory briquetting machine. The briquettes were heat treated in a vertical electrical furnace under nitrogen atmosphere. The compressive strength of the briquettes was analyzed as a function of the following variables: coal and charcoal ratio, heating rate and particle size. The CO2 reactivity of the heat treated briquettes was analyzed as a function of the following variables: temperature and CO2 flow. For the cylindrical briquettes, the increase of charcoal (5, 10, 15 wt%) in the coal-charcoal mixtures caused an increase on the bulk density and on the compressive strength of the heat treated briquettes. Above 15 wt% of charcoal in the mixtures, the bulk density and the compressive strength decreased. It was found out that both green and heat treated briquettes had a decrease in compressive strength with the increase of the coal particle size. Optimum results of compressive strength were obtained in the briquettes with 15 wt% of charcoal, particle size <0.044 mm, heat treatment temperature of 1100°C for 8 hours. The increase in charcoal proportion caused an increase in the CO2 reactivity of the briquettes. The SEM micrographs of the heat treated briquettes showed that the texture of the briquettes tend to be more homogeneous with the increase of charcoal in the mixture. The properties of the briquettes produced in the laboratorial briquetting machine showed that a large scale production could be viable. Also, it was found out that the addition of wood charcoal in the mixture directly affects the compressive strength and the CO2 reactivity of the briquettes due to factors such as: the ashes composition, the decrease in fluidity because of the inert material in the mixture, the formation of a porous structure inside the carbon matrix. It was not found a relation between the alkalinity index and the CO2 reactivity in the briquettes.

Cette thèse s'inscrit dans le domaine de la catalyse hétérogène pour des applications en raffinage et enpétrochimie. Comme objet d'étude, nous avons ciblé les catalyseurs d'hydrotraitement qui permettentd'éliminer les impuretés contenues dans le pétrole comme le soufre. Ces catalyseurs d'hydrotraitementsont constitués de sulfures de molybdène supportés sur alumine et généralement promus par du nickelou du cobalt.L'enjeu de la thèse porte sur la compréhension des phénomènes mis en jeu au cours de la sulfuration etde la stabilisation (cokage, passivation, évolution de la phase sulfure) des catalyseurs pour la réactiond'hydrodésulfuration des gazoles visant à réduire sa teneur en soufre. Néanmoins, à l'heure actuelleaucune technique ne permet de caractériser le catalyseur lors de la sulfuration en phase liquide (avecou sans DMDS) et du test dans les conditions de température et de pression industrielles.La présente thèse vise le développement d'une « caractérisation operando » de ce type de réaction ens'appuyant sur la spectroscopie Raman, une des seules technique de laboratoire permettant d'effectuerdes analyses avec les contraintes précédemment citées. Une unité, composée d'un réacteur cylindriquetransparent, a donc été conçue et mise au point pour suivre par spectroscopie Raman les phases solideet liquide au cours de la sulfuration et de la réaction d'HDS. Parallèlement, une méthodologie decaractérisation et de focalisation a été développée. Ce montage et cette méthodologie ont permisd'accéder pour la première fois à des profils spatiaux et temporels sur la phase solide dans lesconditions d'activation et de réaction d'hydrotraitement des gazoles en condition d'hydrodésulfuration(30 bar, 350 °C).Malgré un signal de fluorescence probablement liée à la décomposition radicalaire du précurseur desoufre (DMDS) entre 200 et 260°C, il a été possible de suivre au cours du temps à des positions fixesla disparition de la phase oxyde, l'évolution de la phase sulfure et du coke . Ces résultats ontnotamment permis d'étudier l'impact de la charge sur la cinétique de sulfuration .Le suivi spatial, lelong du réacteur par exemple, s'avère plus délicat et nécessitera de développer des méthodes pourcompenser les variations d'intensité du signal Raman induites par le positionnement aléatoire desgrains ainsi que l'écoulement. Concernant la phase liquide, une approche multivariée utilisant desoutils chimiométriques a été appliquée afin de relier l'émission de fluorescence intrinsèque à denombreux diesels à certaines de leurs propriétés (teneur en soufre et en aromatiques, densité…). Lesmodèles ont été développés à partir de spectres acquis à température ambiante et à pressionatmosphérique, mais leurs performances satisfaisantes encouragent à étendre l'approche auxconditions réactionnelles d'HDS qui reste une perspective de ce travail / This thesis is in the field of heterogeneous catalysis for the applications in refining and petrochemistry. As an aim of this study, we have focused on the hydrotreatment catalysts that are applied to remove some of the impurities from crude oils, like sulfur. Such hydrotreatment catalysts consist of alumina supported molybdenum sulfides, being generally promoted by nickel or cobalt.The aim of this work have consisted on the understanding of the phenomena occurring during the stabilization phase (coking, passivation, evolution of the sulfide phase) during the catalysts sulfidation and under the reaction of hydrodesulfurization, HDS, aiming to reduce the diesels sulfur content. A better understanding of these phenomena would ease the development of new generations of more efficient catalysts. This thesis aims at extending the operando characterization methods to allow a spatial and temporal follow-up of liquid and catalyst during this type of reactions. A unit was designed and built to follow the solid and liquid phases during the catalysts sulfidation and under HDS reaction. The operando follow-up was done using Raman spectroscopy through a cylindrical transparent reactor. In parallel, a methodology has been developed to focus and acquire good quality spectra through the reactor..With these reactor and methodology , we were able to access for the first time to time-space resolved profiles of the solid phase during the sulfidation and the diesel hydrodesulfurization (under 350 °C and 30 bar). Temporal profiles concerns the oxide phase disappearance, sulfide phase growth and coke formation. Spatial profiles are more challenging and will require a methodology more robust to signal changes induced by the random position of pellets and flow pattern. With respect to the liquid phase, a multivariate approach based on chemometrics has gave properties of diesels at room temperature and atmospheric pressure. The good results are encouraging enough to propose to extend the approach to HDS conditions that constitutes one of the perspectives of the work

A utilização de briquetes de misturas de carvão fóssil e biomassa em substituição ao coque como agente redutor pode contribuir para a diminuição das emissões de CO2 à atmosfera no processo de redução de minério de ferro. O fenômeno do amolecimento e fluidificação do carvão fóssil durante o aquecimento permite que o mesmo absorva certa quantidade de materiais inertes à coqueificação durante o tratamento térmico. O objetivo deste trabalho é correlacionar o efeito das principais variáveis de processo de fabricação (temperatura e tempo de tratamento térmico, tamanho de partícula dos componentes, porosidade e proporção de carvão vegetal e carvão fóssil) sobre as propriedades obtidas (resistência mecânica e reatividade ao CO2) de briquetes compostos de misturas de carvão fóssil e carvão vegetal, para uso na indústria siderúrgica. Briquetes de dois formatos diferentes foram preparados em matriz cilíndrica e em maquina briquetadeira e tratados termicamente em forno vertical aquecido com resistência elétrica sob atmosfera de nitrogênio. A resistência à compressão dos briquetes foi analisada em função das seguintes variáveis: proporção de carvão fóssil e carvão vegetal, taxa de aquecimento do tratamento térmico e tamanho de partícula dos carvões. A reatividade ao CO2 dos briquetes tratados termicamente foi analisada em função das seguintes variáveis: temperatura de ensaio e vazão de CO2. Foram comparados os resultados obtidos de ambos os formatos de briquetes. Com o aumento da proporção de carvão vegetal nos briquetes cilíndricos de biocoque, a densidade aparente e a resistência à compressão após tratamento térmico aumentaram para as misturas contendo 5, 10 e 15% de carvão vegetal. A partir dessa composição (15% de carvão vegetal) tanto a densidade final quanto a resistência à compressão apresentaram diminuição. Encontrou-se que tanto os briquetes cilíndricos a verde quanto os briquetes tratados termicamente apresentam perda de resistência mecânica com o aumento do tamanho de partícula do carvão fóssil. Os melhores valores de resistência à compressão foram obtidos em briquetes feitos com carvão fóssil em mistura de 15% em peso de carvão vegetal, tamanho de partícula abaixo de 0,044 mm, tratados termicamente a 1100°C durante 8 horas. Com o aumento na adição de carvão vegetal nos briquetes compostos de carvão fóssil e carvão vegetal, observou-se um aumento da reatividade do biocoque ao CO2. As micrografias dos briquetes tratados termicamente mostraram que a textura dos briquetes tende a ser mais homogênea com aumento de carvão vegetal de madeira na mistura. Os briquetes de biocoque fabricados em briquetadeira permitiram a ampliação do processo de fabricação de briquetes a uma escala laboratorial maior e mostraram a viabilidade industrial na fabricação do biocoque. Encontrou-se que a adição de carvão vegetal de madeira na mistura influencia diretamente na resistência a compressão e a reatividade ao CO2, devido a diferentes fatores como a composição das cinzas da madeira, a diminuição da fluidez devido à ação do inerte na mistura a carbonizar, a formação de uma estrutura porosa dentro da matriz carbonosa. Não encontrou-se correlação entre o índice de alcalinidade dos briquetes e sua reatividade ao CO2. / The substitution of metallurgical coke by briquetted mixtures of coal and biomass as a reducing agent can lower the emissions of greenhouse gases (CO2) in the iron and steelmaking industry. The thermal plasticity of the coking coal can be used to absorb an amount of inert materials during heat treatment. The objective of this study is to correlate the effect of the main processes variables (heat treatment temperature and duration, particle size of the materials, porosity and coal and charcoal ratio) on the properties (compressive strength and CO2 reactivity) of briquetted mixtures of coal and charcoal. Two types of briquettes were produced, one in a cylindrical die and another in a laboratory briquetting machine. The briquettes were heat treated in a vertical electrical furnace under nitrogen atmosphere. The compressive strength of the briquettes was analyzed as a function of the following variables: coal and charcoal ratio, heating rate and particle size. The CO2 reactivity of the heat treated briquettes was analyzed as a function of the following variables: temperature and CO2 flow. For the cylindrical briquettes, the increase of charcoal (5, 10, 15 wt%) in the coal-charcoal mixtures caused an increase on the bulk density and on the compressive strength of the heat treated briquettes. Above 15 wt% of charcoal in the mixtures, the bulk density and the compressive strength decreased. It was found out that both green and heat treated briquettes had a decrease in compressive strength with the increase of the coal particle size. Optimum results of compressive strength were obtained in the briquettes with 15 wt% of charcoal, particle size <0.044 mm, heat treatment temperature of 1100°C for 8 hours. The increase in charcoal proportion caused an increase in the CO2 reactivity of the briquettes. The SEM micrographs of the heat treated briquettes showed that the texture of the briquettes tend to be more homogeneous with the increase of charcoal in the mixture. The properties of the briquettes produced in the laboratorial briquetting machine showed that a large scale production could be viable. Also, it was found out that the addition of wood charcoal in the mixture directly affects the compressive strength and the CO2 reactivity of the briquettes due to factors such as: the ashes composition, the decrease in fluidity because of the inert material in the mixture, the formation of a porous structure inside the carbon matrix. It was not found a relation between the alkalinity index and the CO2 reactivity in the briquettes.

La méthode à privilégier pour améliorer dans les zéolithes la diffusion des réactifs, des intermédiaires réactionnels et des produits est de raccourcir la longueur du chemin diffusionnel, c'est-à-dire de diminuer la taille des cristaux. La croissance des cristallites est fonction de la composition du gel de synthèse, du temps de cristallisation, de la température, etc. La maîtrise de cette croissance permet d'obtenir un large éventail de taille pouvant aller de plusieurs micromètres à seulement quelques dizaines de nanomètres. Dorénavant, il est possible de limiter le chemin diffusionnel à seulement 3 mailles élémentaires en inhibant lors de la synthèse hydrothermale la croissance des cristaux dans une direction privilégiée. Pour cela l'utilisation d'agent structurant organique très particulier de type géminé s'avère indispensable et donne dans le cas de la zéolithe de type *BEA un matériau hiérarchisé avec des cristaux zéolithiques de 4 nm d'épaisseur séparés par des mésopores structurés et réguliers. La morphologie de ce matériau ressemble à une éponge de mer.<br>Deux réactions modèles, hydroisomérisation du n-héxadécane et transformation de l'éthanol en hydrocarbures, démontrent que la diffusion des réactifs et des produits sont optimisées dans les nanoéponges de bêta. La stabilité et la sélectivité du catalyseur se trouvent alors améliorées au détriment, étonnamment, de l'activité. Cela vient du fait que l'extrême diminution de l'épaisseur des cristallites conduit à une augmentation du nombre d'aluminium en bouche de pores qui sont, bien que très accessibles, incapables de catalyser les réactions d'isomérisation et de craquage. Les aluminium proche de la surface externe, contrairement à ceux situés au cœur du cristal ne bénéficient pas des effets longues distances ce qui les rend moins forts. / The method to ameliorate the diffusion of reactants, reaction intermediates, and products inside the zeolite is by shortening the diffusion path length, i.e., crystals size. The growth of the crystals is a function of gel composition synthesis, crystallization time, temperature, etc. The mastering of this growth allows to obtain a wide range of the size which ranges from several micrometers to a few tens of nanometers. It is possible now to limit the diffusion path to only three unit cells by inhibiting the crystals' growth in one direction during the hydrothermal synthesis. For that, the use of a peculiar organic surfactant geminate is indispensable, it gives a hierarchical material with zeolitic crystals of 4 nm thickness separated by structured and regular mesopores in the case of *BEA type zeolite. The morphology of this material resembles a sea sponge.<br>Two reaction models, n-hexadecane hydroisomerization and ethanol transformation to hydrocarbons, demonstrate that the reactants and the products diffusion was optimized in the beta nanosponges. Surprisingly the catalyst stability and selectivity were improved instead of activity. In fact this is due to the extreme reducing of the zeolite crystals’ thickness that leads to increase the aluminum number in the pore mouth, which although very accessible, but incapable to catalyze the isomerization and cracking reactions. The aluminums near the external surface, in contrary to those in the crystal heart, do not benefit from the long distance effects, which makes them weaker.

This thesis investigates the use of the Stagnation-Point Reverse-Flow (SPRF) combustor geometry for burning low-grade solid fuels that are attractive for specific industrial applications because of their low cost and on-site availability. These fuels are in general, hard to burn, either because of high moisture and impurity-content, e.g. biomass, or their low-volatiles content, e.g., petroleum-coke. This results in various challenges to the combustor designer, for example reduced flame stability and poor combustion efficiency. Conventional solutions include preheating the incoming flow as well as co-firing with high-grade fuels. The SPRF combustor geometry has been chosen because it was demonstrated to operate stably on standard gaseous and liquid-fuels corresponding to ultra fuel-lean conditions and power densities at atmospheric-pressure around 20-25 MW/m3. Previous studies on the SPRF combustor have proven that the unique, reverse flow-geometry allows entrainment of near-adiabatic products into the incoming reactants, thereby enhancing the reactivity of the mixture. Further, the presence of the stagnation-end created a region of low mean velocities and high levels of unsteadiness and mixing-rates that supported the reaction-zones. In this study, we examine the performance of the SPRF geometry on a specific low grade solid fuel, petroleum coke. There are three main goals of this thesis. The first goal is the design of a SPRF combustor to operate on solid-fuels based on a design-scaling methodology, as well as demonstration of successful operation corresponding to a baseline condition. The second goal involves understanding the mode of operation of the SPRF combustor on solid-fuels based on visualization studies. The third goal of this thesis is developing and using reduced-order models to better understand and predict the ignition and quasi-steady burning behavior of dispersed-phase particles in the SPRF combustor. The SPRF combustor has been demonstrated to operate stably on pure-oxygen and a slurry made from water and petroleum-coke, both at the baseline conditions (125 kW, 18 g/s, ~25 µm particles) and higher power-densities and powder sizes. For an overall combustor length less than a meter, combustion is not complete (global combustion efficiency less than 70%). Luminance imaging results indicate the incoming reactant jet ignites and exhibits intense burning at the mid-combustor region, around 15 jet diameters downstream of the inlet, most likely due to enhanced mixing as a result of the highly unsteady velocity field. This roughly corresponds to the location of the reaction zones in the previous SPRF combustors operating on gas and liquid fuels. Planar laser visualization of the reacting flow-field using particle-scattering reveals that ignition of a significant amount of the reactants occurs only after the incoming jet has broken into reactant packets. Post-ignition, these burning packets burn out slowly as they reverse direction and exit the combustor on either side of the central injector. This is unlike the behavior in liquid and gas-fueled operation where the incoming reactants burned across a highly corrugated, thin-flame front. Based on these findings, as well as the results of previous SPRF studies, an idealized model of combustor operation based on a plug flow reactor has been developed. The predictions suggest that fuel-conversion efficiency is enhanced by the combustor operating pressure and lowered by the heat-losses. Overall, this effort has shown the SPRF geometry is a promising compact-combustor concept for self-sustained operation on low-grade solid-fuels for typical high-pressure applications such as direct steam-generation. Based on these findings, it is recommended that future designs for the specific application previously mentioned have a shorter base-combustor with lower heat-losses and a longer steam-generation section for injection of water.

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.

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.

This work investigates the interactions of carbonaceous materials (metallurgical coke, natural graphite and HDPE/coke blends) with three EAF slags [FeO: 24% to 32%]. Experiments were conducted using the sessile drop technique (1500??C-1600??C) with off-gases (CO, CO2) measured using an IR analyzer; the wetting behaviour was determined from contact angle measurements. Estimation of slag foaming behaviour was determined from the droplet volume changes calculated using specialized software. At 1550??C, all slags were non-wetting with coke due to increased surface tension due to sulphur. At 1550??C, slag 1 was initially non-wetting on natural graphite due to gas entrapment in the slag droplet; the wetting improved after that. Other slags showed comparatively better wetting. At 1600??C, all slags were non-wetting with coke. Slags showed a shift from non-wetting to wetting behaviour with natural graphite. Slag/coke reactions produced high off-gases levels causing extensive FeO reduction; gas entrapment in the slag was poor (small volume droplets). Slag/natural graphite interactions revealed both slow gas generation rates and FeO reduction, and excellent gas entrapment (higher droplet volumes) with minor changes in slag properties due to low ash levels. The iron oxide reduction rates were determined to be 1.54x10-5 and 4.2x10-6 mol.cm-2/sec (Slag 1, 1550??C) for metallurgical coke and natural graphite respectively. Slag interactions with coke/HDPE blends showed increasing off-gas levels with increasing HDPE levels. Blend#3 produced the highest off-gas levels, extensive FeO reduction and displayed significantly higher slag foaming and better wetting compared to coke. Our line on trends compared well for slag/carbon interactions and resulted in deceased specific energy consumption and carbon usage and increased productivity. These findings have enhanced the possibility of utilizing polymeric wastes in blends with coke in EAF steelmaking for slag/carbon interactions.