Orientador: João Andrade de Carvalho / Resumo: Caldeiras de produção de vapor são utilizadas no setor siderúrgico para produzir e disponibilizar vapor para o processo de geração de energia e para os vários setores que necessitam de aquecimento durante a fabricação de seus produtos, como por exemplo, a vaporização de criogênicos para distribuição na planta. Portanto, caldeiras são equipamentos que necessitam ter confiabilidade. Atualmente, a CSN (siderúrgica brasileira de grande porte) possui duas caldeiras do início da década de 80 que somente partem e operam com uma chama piloto utilizando gás de coqueria, um gás que é subproduto da produção de coque em uma planta siderúrgica. Assim, para alcançar o objetivo de mais confiabilidade e flexibilidade na operação destas caldeiras, utilizou-se os métodos de índice Wobbe, corrigido pela pressão, e o método dos múltiplos índices de Weaver para avaliar a substituição do gás de coqueria pelo gás natural de modo que estas caldeiras possam operar com gás natural em caso de indisponibilidade de gás de coqueria. Mesmo que o aporte energético entre os gases seja diferente, este pode ser ajustado pela pressão do gás. A temperatura de chama adiabática não tem variação significativa, reduzindo-se apenas 1,4%. As emissões de fumaças e CO2 aumentam com a substituição, porém as emissões de NOx tem redução. A utilização do método dos múltiplos índices de Weaver para análise de intercambiabilidade demonstra que o gás natural não é um substituo para um queimador projetado para queimar gás de co... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Steam generators are used in the steel industry to produce and supply steam process for power generation and for other sectors that need heat to manufacture their products, such as the cryogenics vaporization for distribution in the facilities. Therefore, steam generators are equipment that need to have reliability. Currently, CSN (large Brazilian steelmaker) has two steam generators from the early 1980s that only startup and operate with a pilot flame using coke oven gas, a gas that is a byproduct of coke production at a steel plant. Thus, in order to achieve the working objective, reliability and flexibility in the operation of these steam generators, the Wobbe index method, with pressure-corrected, and the Weaver's multiple index method were used to verify the coke oven replacement for natural gas, and then, these steam generators can operate with natural gas in case of coke oven gas unavailability. Results shown in the same way that the energy increase between the gases are different can be adjusted in the pressure reduction. The flame temperature has insignificant variation, only 1.4%. Off gas and CO2 emissions increase with interchangeability. However, NOx emissions are reduced. The Weaver multiple index method for interchangeability analysis demonstrates that natural gas is not a gas to replace coke oven gas in a burner designed to burn coke oven gas, but if the burner is designed to natural gas, coke oven gas may be the substitute gas. Regarding the heat input and pri... (Complete abstract click electronic access below) / Mestre

As the largest source of iron in North America, and as the largest energy consumer in the modern integrated steel mill, the blast furnace is a critical part of modern ironmaking. Any improvements that can be made to the efficiency or emissions of the blast furnace can have far reaching environmental impacts as the production of one ton of steel results in 1.85 tons of carbon dioxide emissions. Given the concerted push to reduce greenhouse emissions, novel technologies are needed to improve efficiency. In this study the injection of preheated natural gas, precombusted syngas from a variety of feedstocks, and hydrogen injection were all modeled using computational fluid dynamics, from the tuyere through the shaft of the furnace. The impacts of these various operational changes were evaluated using CFD calculated analogs for Raceway adiabatic flame temperature (RAFT), top gas temperature (TGT), and coke rate (CR). Results indicate that a reduction of 3% to 12% in CO2 emissions is possible through the implementation of these technologies, with each possessing distinct benefits and drawbacks for industrial implementation.

The topic of this diploma thesis is to design the co-firing of blast furnace gas and coke-oven gas. First, the stoichiometric calculation for the gas mixture was made. It is followed with the determination of basic measures of heating surfaces and with their thermal calculation. The part of the work is also the drawing documentation of the boiler.

[pt] Este trabalho tem como objetivo analisar a importância da localidade da cultura na apropriação da comunicação publicitária global e a maneira com que se dá a recepção da mensagem à luz de novas referências culturais mundializadas. A abordagem ao tema é feita a partir de uma visão histórica do consumo e da análise da publicidade como ferramenta de afirmação dos valores culturais por meio da divulgação para aquisição, posse e uso dos bens. Para traçar este caminho, foram utilizados teóricos das ciências sociais e da comunicação que estudaram as mudanças nos padrões de consumo como um importante campo de reflexão sobre o indivíduo e suas práticas sociais na cultura contemporânea. Como estudo de caso, foi utilizada a campanha global Viva o Lado Coca-Cola da Vida. / [en] This work analyzes the importance of local culture in the appropriation of global advertising campaigns and the way message is received within new world cultural references. The topic is discussed within the framework of a historical view of consumption and the analysis of advertising as a tool to affirm cultural values by means of campaigns for acquisition, ownership and use of goods. In order to carry out the work, we focused on authors, in the field of social sciences and communication, who saw the changes on patterns of consumption as important to the understanding of people and his/her social practices in contemporary culture. The global campaign Live the Coca-Cola side of life was used as a case study.

There has recently been an increased interest in methane as a rocket propellant due to its physical properties as well as the possibility of in-situ resource utilization in places like Mars. As part of ESA’s Future Launcher Preparatory Program, KTH in cooperation with GKN Aerospace has started the MERiT program, which seeks to study the characteristics of methane under conditions found in rocket nozzle cooling channels. In particular, the current work examines the influence of different wall temperatures, fluid flow rates, and fluid residence times on methane pyrolysis due to the catalytic properties of nickel based metals. Pyrolysis is the thermo-catalytic decomposition of methane, which results in the creation of hydrogen and solid carbon in the cooling channels. This can affect the performance of the rocket engine, the cooling channels, as well as the lifespan of the engine, which makes the process important to quantify when designing highly reusable engines. A chemical kinetics computer model has been developed, which has been used to quantify the most important parameters for methane pyrolysis. Based on these results, a small-scale pyrolysis experimental setup has been developed and used to characterise methane pyrolysis for different material temperatures and gas flow rates. The experimental setup has been proven to work and consistently provide pyrolysis at temperatures between 600 ◦C to 700 ◦C, although more work on the data collection side, in particular with regards to a gas chromatograph and a scanning electron microscope, is required to quantify and compare different experiments.

[pt] A produção de coque metalúrgico em plantas do tipo heat recovery convertem todo o calor gerado da combustão de gases destilados durante a coqueificação em vapor e eletricidade, portanto eliminando a necessidade de processamento de sub-produtos químicos e rejeitos perigosos. Os gases, após a etapa de inertização no interior dos fornos, são direcionados à planta de dessulfuração denominada flue gas dessulfurization que utiliza lama de cal para abatimento de compostos SOx (SO2 e SO3) e filtros de mangas para remoção do resíduo gerado, cinzas de cal, precedente ao descarte para a atmosfera. Em virtude do alto custo da cal torna-se importante modelar o processo e avaliar quais são as principais variáveis que impactam no re-sultado, logo permitindo atuação no processo para torna-lo mais competitivo e am-bientalmente sustentável. A proposta deste trabalho foi elaborar um modelo matemático usando redes neurais artificiais para determinar as principais variáveis que impactam o consumo específico de cal no processo. A literatura existente revela que os principais parâmetros que impactam a eficiência de remoção de enxofre, logo a redução de consumo específico de cal, são temperatura de aproximação e relação Ca/S no processo. Este estudo indicou que o consumo está relacionado, principal-mente, aos parâmetros de temperatura dos gases na entrada e saída do SDA, além de concentração de oxigênio na chaminé principal e densidade da lama de cal utilizada de acordo com a análise de sensibilidade de rede neural feedfoward backpropagation com arquitetura MLP 14-19-2 e função de transferência tangente hiperbólica na ca-mada intermediária e logística na camada de saída. A avaliação reforçou o efeito do aumento da temperatura de saída dos gases no consumo específico de cal conforme literatura e adicionou parâmetros relevantes: temperatura de entrada dos gases, con-centração de O2(g) na chaminé e densidade da lama. / [en] The production of metallurgical coke in heat recovery coke production plants converts all heat generated from the combustion of distilled gases during coking pro-duction to steam and electricity, thus eliminating the need of processing hazardous by-products chemical substances. The gases, after inertization inside the ovens, are directed to the desulphurization plant called flue gas desulphurization (FGD) which uses lime slurry to remove SOx compounds (SO2 and SO3) and bag filters to remove the generated residue, lime ash. Due to the high cost of lime, it is important to model the process and evaluate which are the main variables that affects its result, thus allowing action in the process to make it more competitive and environmentally sus-tainable. The purpose of this work was to develop a mathematical model using arti-ficial neural networks to determine the main variables that affect lime consumption in the desulphurization process. Literature reveals that the main parameters that in-fluence sulfur removal efficiency, thus reducing specific lime consumption, are ap-proach to adiabatic saturation temperature and Ca/S ratio in the process. This study indicated that consumption is mainly related to the inlet and outlet SDA gas temper-atures, oxygen concentration in stack and lime slurry density according to the feed-foward backpropagation neural network sensitivity analysis. MLP 14-19-2 and hy-perbolic tangent transfer function in the intermediate layer and logistics in the output layer. Thus, the evaluation reinforced the effect of the increase of the gas outlet tem-perature on the specific lime consumption according to the literature, but also added new parameters: gas inlet temperature, O2 (g) concentration in the outlet of stack and lime slurry density.

Climate change and environmental degradation, in addition to the challenges of limited fossil fuel resources, have driven governments to pursue creative renewable energy sources. Natural gas and biofuels are limitless energy sources produced from both fossil fuels and biomass that is renewable. SOFCs (Solid Oxide Fuel Cells) are a type of renewable energy system that can convert biofuels into power and heat whenever needed. They often operate at high temperatures (> 850 °C), which allows for fuel flexibility; nevertheless, such high temperatures are associated by rapid material deterioration and performance loss, usually before 40,000 hours of operation. As a result, many recent studies and activities have concentrated on lowering the operating temperature of SOFCs. Lowering the temperature causes decreased ionic conductivity, decreased catalytic activity, and increased carbon deposition on the anode side catalysts. This project aimed at developing an innovative cathode-supported SOFC to be fed by biofuels and operating at low-intermediate temperatures. Colloidal processes and co-sintering were selected to fabricate the final SOFC owing to their flexibility in optimizing the final desired properties and saving more manufacturing costs. The first chapter of this thesis provides an introduction to the essential concepts as well as professional specifics and previous work. The cell design and component materials are defined, as are additional requirements for lowering the operating temperature in SOFCs. Commercialization challenges and recommended solutions are also discussed, which involve the development of both new anode materials and production procedures. The project's goal is detailed at the end of Chapter 1, along with the reasons why various approaches were chosen. Molybdenum was chosen as a suitable anodic material to be doped into LSCF, and tape casting was developed further to create the cathode. The cathode support layer should have a consistent thickness, balanced flexibility and mechanical strength, and better shrinkage qualities. The plasticizer is a high molecular weight polyethylene glycol (PEG 4000), which improves these characteristics. Chapter 2 covers the steps involved in creating the button SOFC, starting with powder synthesis and ending with cathode tape casting. SOFC performance and anode catalytic activity are investigated to assess SOFC durability while fed by biogas. In Chapter 3, the findings are presented and explored in various contexts. Meanwhile, the anode material performance and cathode design and structure receive the greatest attention. Molybdenum was doped into LSCF via auto-combustion, yielding a fine and porous powder form. X-ray diffraction patterns demonstrated that increasing the Mo dopant increases anodic stability. In parallel, flat and crack-free green cathodes with 47% solid loading can be obtained by adjusting the PEG 4000 to binder quantity ratio at 1.00 wt% and drying the tapes at 70% relative humidity. The tapes had an excellent mechanical strength to flexibility ratio, which allowed them to be readily handled and rolled. The tapes benefited from a strong balance of flexibility and mechanical strength, allowing them to be easily handled and rolled while also exhibiting very low residual stresses during subsequent lamination and co-sintering procedures. The final manufactured SOFC revealed a porous anode structure and a less porous cathode layer using electron microscopy. Whereas the electrolyte was dense enough to ensure gas tightness. There was no delamination throughout the cell. The cells were then electrochemically measured, and the reactivity of LSCFMo to various fuels and temperatures was investigated. LSCFMo performed best when fed by methanol at 700 °C, leaving no carbon traces after operation. The very low ohmic resistance of the electrodes indicates a very good design and manufacture technique. A conclusion is presented in the final section of this thesis to highlight the most significant achievements of this research.

Des anodes de haute densité et de qualité uniforme sont d'un grand intérêt dans la production d'aluminium primaire. La variation dans les propriétés des matières premières ainsi que le grand nombre de variables est reconnue comme étant un grand défi et conduit à des anodes de qualité très variable. Dans ce projet, une d'essai de comportement au compactage de la pâte d’anode a été développée. Le comportement au compactage de la pâte d'anode a été utilisé comme indice de qualité intermédiaire pour réduire le nombre de variables. Différentes combinaisons de temps et de températures de mélange ont été utilisées pour faire de la pâte d’anode afin de comprendre les effets des variables de mélange. Les pâtes ont été compactées, cuites et caractérisés par la suite. Le mélange effectué à 178 C pendant 10 minutes a été celui permettant d’obtenir la distribution la plus homogène de coke et de brai et la densité maximale des échantillons verts et cuits. Il est admis que le comportement à la déformation de la matrice liante (particules fines de coke+brai) contribue fortement au processus de compactage. Les mélanges des matrices liantes et des pâtes d’anodes, avec différents ratios de brai et de particules de coke, ont été compactés à des taux de déformation différentes. La compaction de la matrice liante et de la pâte d'anode, avec les compositions classiques utilisées dans ce projet, n’est pas significativement dépendante de la vitesse de mise en forme. L'effet de la forme et de la densité des particules sur la densité de la pâte compactée a été étudié. La densité apparente des particules, la densité apparente (Scott) et la densité apparente vibrée du lit de particules ont été mesurées pour différentes fractions de cinq sources de coke éponge. Des pâtes d’anode ont été produites à partir des cinq cokes et ensuite compactées. Il a été suggéré que la densité apparente vibrée n'est pas un facteur suffisant pour déterminer les propriétés de compaction et la densité de la pâte compactée et aussi que les facteurs de forme et la densité des particules sont des paramètres importants qui devraient être considérés.

La thèse s’intéresse au contrôle de la température d’un front de combustion propagé dans un milieu poreux contenant du carbone fixe et des carbonates (CaCO3). L’objectif principal est de réduire la température, in situ (récupération d’huile ou production de gaz à partir d’un schiste bitumineux) ou dans un procédé (combustion de semicoke), afin de limiter la décarbonatation du milieu et les émissions induites de CO2. Le milieu réactif retenu pour réaliser les expériences en laboratoire est un schiste bitumineux préalablement broyé (0.5 à 2 mm) et pré-pyrolysé, appelé semicoke. Le front est propagé en co-courant. La première technique testée expérimentalement est l’ajout au semicoke d’un matériaux inerte (sable) et/ou d’un matériaux réactif (CaCO3) afin de faire varier le taux de carbone fixe et le taux de CaCO3 et ceci indépendamment. Nous montrons que l’augmentation de CaCO3 permet de baisser la température à 800 °C, mais pas en dessous, ce qui ne permet pas d’éviter la décarbonatation. Faire chuter le contenu en carbone fixe permet de baisser la température du front, voire d’atteindre l’extinction. Aux températures de propagation les plus basses, la décarbonatation est fortement limitée. En revanche le front ralentit car il n’utilise plus tout l’oxygène alimenté. La deuxième technique originale consiste à ajouter du CO2 (20 %molaire) dans l’air de combustion. Nous montrons que dans le cas d’un front chaud, ceci permet de réduire le taux de décarbonatation de 100% à 70%, et d’augmenter en parallèle la production de CO résultant de l’oxydation du carbone fixe, ce qui augmente le PCI du gaz produit. Sur un front plus froid, la décarbonatation qui était de 20% est totalement évitée par l’ajout de CO2. Enfin, des expériences sont proposées dans le mode de combustion “reaction trailing”, très peu connu et mis en oeuvre. Ce mode a l’intérêt majeur d’éviter les réactions de “Lower Temperature Oxidation” préjudiciables au rendement en huile ou en gaz d’un process in situ. Des expériences stables et répétables sont réalisées avec différents pourcentages d’oxygène dans le gaz alimenté. La température du front est directement liée à ce paramètre ; la décarbonatation est clairement limitée dans ce mode de propagation. Deux types de modélisation sont proposés. Un bilan de matière et d’énergie basé sur des expressions analytiques simples permet d’évaluer la température du front et sa vitesse de propagation. Un modèle numérique développé par l’IMFT se base sur des équations de transfert convectif/diffusif de chaleur et de matière, couplées aux réactions d’oxydation du carbone (en CO et en CO2) et de décarbonatation de CaCO3. Il décrit de façon très satisfaisante les expériences en mode “reaction leading” avec variation de la composition du milieu (première technique). / This PhD thesis focuses on the control of the smoldering front propagating in a porous medium containing fixed carbon and carbonates (CaCO3). The main objective is to reduce the front temperature, in situ (oil recovery or gas production from oil shale) or in process (combustion of semicoke), in order to limit the medium decarbonation and the resulting CO2 emissions. The reactive porous medium retained to realize the laboratory experiments is a crushed (0.5 to 2 mm) and pre-pyrolyed oil shale, called semicoke. The front propagates in co-current. The first technique experimentally tested is the addition to the semicoke of an inert material (sand) and/or a reactive material (CaCO3) to vary the contents of fixed carbon and of CaCO3, independently. We show that the increase of the CaCO3 content enables to reduce the temperature to 800 °C, but not below; this does not allow to avoid decarbonation. Bringing down the fixed carbon content enables to reduce the front temperature, see even to reach extinction. In the lowest temperatures of propagation, the decarbonation is strongly limited. On the other hand, the front slows down because it does not use all of the fed oxygen. The second original technique consists in adding CO2 (20 mol.%) to the oxidizer air. We show that for a hot front, the decarbonated fraction is reduced from 100% down to 70%, and the CO production at fixed carbon oxidation is increased; this leads to increase the LCV of the produced gas. For a cold front, the decarbonation which was 20%, is totally avoided by adding CO2. Finely, experiments are proposed in the “reaction trailing” combustion mode, little known and implemented. This mode has the major interest to avoid the reactions of “Lower Temperature Oxidation” prejudicial for oil or gas yields in in situ process. Stable and repeatable experiments are realized with different oxygen fractions in feeding gas. The front temperature is directly linked to this parameter; the decarbonation is clearly limited in this mode of propagation. Two types of modeling are proposed. A mass and thermal balance based on simple analytical expressions enables to evaluate the front temperature and velocity. A numerical model developed by IMFT is based on convective/diffusive heat and mass transfer equations coupled with the oxidation reactions (into CO and CO2) and CaCO3 decarbonation is proposed. It describes in a very satisfactory way the experiments in the “reaction leading” mode with variation of the medium composition (first technique).

Dans les fours de raffinerie, l'efficacité du transfert énergétique vers le pétrole brut avant sa distillation est altérée par la formation d'un composé carboné dans les tubes, appelé coke. Cela conduit à l'augmentation des coûts de production et de maintenance, et exige une compréhension accrue ainsi qu'un meilleur contrôle de ce phénomène. Cet encrassement est de type chimique et induit par les fortes températures. Dans les fours de cette dimension, le transfert de chaleur s'effectue principalement par rayonnement des produits de combustion. Le flux radiatif net sur les surfaces d'échange des tubes dépend de la température de toutes les surfaces solides et a donc besoin d'être prédit avec une précision suffisante. La température sur les tubes est le résultat d'un équilibre entre le rayonnement thermique et la conduction. Le comportement thermique de l'ensemble du système est un problème de couplage entre le rayonnement et la conduction. Une méthodologie complète de couplage est exposée et validée de la manière suivante. Dans ce problème, la flamme est décrite par un modèle analytique axisymétrique avec chimie complexe. Le couplage avec la conduction dans les tubes est réalisé par l'utilisation d'une méthode aux ordonnées discrètes (DOM) avec un modèle spectral de type bandes étroites pour le rayonnement des gaz de combustion. Un bilan énergétique confirme que les transferts de chaleur sont dominés par le rayonnement thermique. Un bon accord avec les mesures disponibles sur un four réel montre que l'approche proposée est capable de prédire le rayonnement thermique. L'étape suivante consiste à coupler le calcul de la température du tube à une loi d'encrassement. Un modèle chimique simple est utilisé. Il est validé à l'aide d'une expérience de laboratoire. La comparaison entre les températures obtenues avec la simulation et celles mesurées par des sondes thermiques montre que la simulation est capable de capturer l'évolution de la température dans le tube avec précision. Enfin, un modèle d'encrassement pour la configuration réelle est trouvé puis appliqué dans une simulation couplée complète. Cette simulation montre un bon accord entre l'évolution de la température sur site et dans la simulation. Une analyse plus poussée est réalisée sur les profils de température, de flux radiatif et de dépôt de coke et montre l'impact de ce dépôt sur l'installation / In industrial refinery furnaces, the efficiency of the thermal transfer to heat crude oil before distillation is often altered by coke deposition inside the process pipes. This leads to increased production and maintenance costs, and requires better understanding and control. Crude oil fouling is a chemical reaction that is, at first order, thermally controlled. In such large furnaces, the predominant heat transfer process is thermal radiation by the hot combustion products, which directly heats the pipes. As radiation fluxes depend on temperature differences, the pipe surface temperature also plays an important role and needs to be predicted with sufficient accuracy. This temperature results from the energy balance between thermal radiation and conduction in the solid material of the pipe, meaning that the thermal behavior of the whole system is a coupled radiation-conduction problem. In this work, this problem is solved in a cylindrical furnace, using the Discrete Ordinate Method (DOM) with accurate spectral models for the radiation of combustion gases, described by a complex chemistry flame model, and coupled to heat conduction in the pipe to predict its wall temperature. An energy balance confirms that heat transfers are effectively dominated by thermal radiation. Good agreement with available measurements on a real furnace shows that the proposed approach is able to predict the heat transfer to the pipe. The method gives an accurate prediction of the radiative source term and temperature fields in the furnace and on the pipe surface, which are key parameters for liquid fouling inside the pipe. Although reasonably accurate results are obtained with simple models, they still can be easily improved by more sophisticated models for turbulence, combustion and radiation. The next step is to couple the calculation of the pipe temperature to a fouling law. Since exact composition of crude oil is not available, one needs to model coke deposition with simple fouling law. The idea is to model the deposition rate by a thermal resistance added to the heated pipe and allows to coupling the calculation of the pipe temperature to a fouling law. A simple chemical model is used, and validated against a labscale experiment, prior to apply it to a furnace configuration. Comparing the temperature obtained with the simulation to the temperature measured by thermal probes at selected locations shows that the simulation is able to capture the temperature variation at these points. It is shown that coking occurs when the temperature has remained high on both sides of the pipe for a sufficient length. We explain how to extract a fouling law in controlled condition when the deposit is induced by thermal stressing of the crude. Finally, the whole system, including radiation,conduction and deposition, is coupled. Results are compared to the real furnace and show relatively good agreement in terms of external skin pipe temperature prediction. This observation validates the methodology exposed in this script