Orientador: Rubens Maciel Filho / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-14T20:26:29Z (GMT). No. of bitstreams: 1 RamirezHernandez_MonicaRocio_M.pdf: 1944205 bytes, checksum: 84f7c13a59eeccf1f35ecf94dc3a2b79 (MD5) Previous issue date: 2009 / Resumo: A necessidade que a indústria do petróleo tem de suprir a demanda de produtos leves do mercado embora esteja ocorrendo uma diminuição nas reservas de óleos leves e o fato de que a rentabilidade do processo de refino esteja representada na capacidade de obtenção destes derivados leves, faz com que sejam aplicadas tecnologias de "upgrading" dos óleos crus. Diante deste contexto torna-se necessário desenvolver metodologias que permitam simular os fenômenos que ocorrem nestes processos, para deste modo poder avaliar o comportamento das cargas na unidade e desenvolver, a partir destas predições, políticas operacionais com o objetivo de evitar impactos desfavoráveis nos produtos finais, nas unidades de processo e na rentabilidade. Entre as tecnologias de "upgrading" encontram-se desasfaltação com solventes, hidrotratamento, hidroconversão, viscorredução, coqueamento retardado entre outras. No entanto, existe grande preferência na utilização destas duas últimas tecnologias, sendo as mais econômicas e que requerem menor investimento. Com a finalidade de prever situações operacionais foi desenvolvido um simulador, dos processos de coqueamento retardado e viscorredução, que permite predizer os rendimentos de leves gerados no forno tanto em escala piloto como em escala industrial, em função das características da carga e conversão. Além disso, o simulador possibilita o cálculo das constantes cinéticas que descrevem a formação dos destilados, do intermediário (etapa pré-coque), e do coque. A importância de desenvolver estes simuladores para este equipamento se deve ao fato de que os mesmos são encarregados de fornecer as temperaturas necessárias para atingir as reações de craqueamento térmico. Neste processo de aquecimento ocorre a deposição dos asfaltenos, os precursores do coque, os quais ao longo da operação da unidade vão-se depositando sobre os tubos do forno. Com o intuito de controlar o pressionamento gerado pela deposição do coque e a diminuição na transferência de calor é necessário realizar reduções na temperatura de operação, ocasionando menores conversões. Deste modo, é importante definir políticas operacionais que possibilitem bons rendimentos, rentabilidade e tempo de operação da unidade os maiores possíveis. Com os resultados obtidos com os simuladores desenvolvidos pode-se predizer o comportamento das unidades com relação a temperatura de operação, pressionamentos, temperatura de parede, conversão, constantes cinéticas e parâmetros da equação de Arrhenius. Isto possibilita a análise operacional destas unidades de craqueamento quando for alterada a carga e condições operacionais do forno. / Abstract: The obligation that petroleum industry has to supply the market demand for light products, although exists a decrease in light oil reserves and the fact that the refining process profitability is represented by the ability to obtain these lighter products. Against this context is necessary the application of crude oil "upgranding" technologies and methodologies development to simulate the phenomena occurring in these processes, in order to evaluate the feed behavior at the unit and based on predictions, set operational politics with the objective to avoid negative impacts in the final products, unit processes and its profitability. Among the "upgranding" technologies are solvent deasphalting, hydrotreating, hydroconversion, visbreaking, delayed coking and others, however, there is a strong preference in using the last two technologies, being the most economical and requires less investment. With the aim to anticipate operational situations was developed a simulator that can predict the light products yields generated at the furnace, at pilot and industrial units of delayed coking and visbreaking, depending on the feed characteristics and conversion, it also calculates the kinetic constants that describes the rate formation of distillates, intermediate (pre-coke stage), and coke. The importance of developing such simulators for this equipment lies that this is the responsible of providing the temperature necessary to achieve the thermal cracking reactions. In the heating process occurs the asphaltene deposition, the coke precursors, which along the unit operation will be deposited on the furnace tubes. In order to control the pressing generated by the coke and the decrease in heat transfer is needed reductions in operating temperature, causing lower conversions. Thus, is important define operational politics that allows good yields, profitability and run lengths the greatest possible. With the obtained results through the simulators, can be known in advanced the unit behavior as operation temperature, drop pressure, wall temperature, conversion, kinetic constants and parameters of Arrhenius equation, which will facilitate the operational analysis of thermal cracking units when is change for example, feed and operational variables . / Mestrado / Desenvolvimento de Processos Químicos / Mestre em Engenharia Química

Em nível microscópico, as rochas apresentam microdefeitos que agem como concentradores locais de tensão, favorecendo a ocorrência de ruptura frágil. O entendimento desse processo requer análises experimentais em rochas submetidas a tensões de tração. O ensaio de compressão diametral é uma alternativa apropriada, pois não apresenta as dificuldades envolvidas no ensaio de tração direta. A propagação de microfissuramento em materiais frágeis produz liberação de energia na forma de ondas elásticas chamadas de emissões acústicas (EA). O monitoramento com EA permite acompanhar a propagação de dano no corpo de prova (CP), sem perturbá-lo. Nesta pesquisa, CPs de mármore e monzogranito são submetidos a ensaios de compressão diametral com deslocamentos monotônicos e cíclicos, com controle de deslocamento. Aplica-se a técnica de EA, em conjunto com análises petrográficas, análises das curvas de força versus deslocamento e exame visual, para caracterizar o seu processo de microfissuramento. A localização tridimensional das fontes de EA foi realizada inicialmente utilizando-se o software AEwin® da PASA. Foi desenvolvido um programa de localização aprimorado que incorpora o cálculo da velocidade de propagação das ondas (vp) média para cada instante em que uma fonte é localizada. O novo programa (Crack Location by Acoustic emission with P Wave Velocity determination, CLAPWaVe) mostra um claro decréscimo da velocidade de propagação com o aumento do dano. O programa desenvolvido (CLAPWaVe) mostrou melhor ajuste e maior coerência com a literatura e com a condição final rompida dos CPs do que o software AEwin. Em mármore e monzogranito o microfissuramento se inicia a 25-30% e 75-85% do carregamento de pico, respectivamente, e localiza-se na vizinhança do centro do CP. Em ambas as rochas se acumulou, também, dano na região dos apoios do CP, associado à transferência de carregamento do berço ao CP. Antes do pico de carregamento, o microfissuramento tornou-se mais denso e localizado no centro e nos apoios do CP, embora a região central ainda concentre a maior parte. Após o pico, o microfissuramento acumulou-se em uma das faces do CP, progredindo até a outra face. O monzogranito apresentou ruptura progressiva do CP, enquanto que no mármore a maior parte da superfície de ruptura já está desenvolvida imediatamente após o pico. Durante o ensaio em ambas as rochas, no núcleo central foram registradas as menores velocidades vp do CP. Na região dos apoios, embora tenha havido microfissuramento, registraram-se as maiores velocidades vp no CP, pois o confinamento produzido pelo contato com o berço aumentou localmente a rigidez do CP. A distribuição não homogênea de vp no CP revelou que a consideração desse parâmetro como constante e igual à condição intacta ao longo do ensaio, como comumente encontrado na literatura, não representa a condição real do CP danificado. O microfissuramento no monzogranito se propaga principalmente através dos cristais de quartzo, seguindo um caminho tortuoso subparalelo à direção de carregamento e liberando altos níveis de energia absoluta. No mármore, a propagação segue os planos de clivagem da calcita, liberando níveis baixos de energia absoluta. Os histogramas da distribuição espacial da resistência em ambas as rochas mostraram bom ajuste a uma distribuição de Weibull, porém o monzogranito mostrou melhor ajuste e menor variabilidade que o mármore. As análises dos sinais no domínio das frequências mostraram que o microfissuramento é caracterizado por emissões de banda larga. / At microscopic level, rocks exhibit microflaws, which act as local stress concentrators, favoring the occurrence of brittle failure. The understanding of this process requires experimental analyses of rock specimens under tensile stresses. The diametral compression test is an adequate alternative for such a studies, because it does not present the difficulties of direct tension tests. Crack propagation in brittle materials releases energy as transient elastic waves known as acoustic emission (AE). Monitoring with AE enables an insight into the cracking process without affecting the integrity of the sample. In this work, marble and monzogranite specimens were subjected to monotonic and cyclic displacementcontrolled diametral compression tests. The AE monitoring technique was applied in conjunction with petrographic analyses, interpretation of the load versus displacement curves and visual examination of the samples for the characterization of their cracking process. The three-dimensional localization of the AE sources was initially carried out by using the software AEwin® from PASA. An improved localization software, which considers the P-wave velocity variation along the damage process (vp) for each AE source was developed. The developed software (Crack Location by Acoustic emission with P Wave Velocity determination, CLAPWaVe) has shown greater consistency with literature and the final cracked samples and better accuracy than AEwin. Microcracking in monzogranite and marble initiated at 25-30% and 75-80% of the peak load, respectively, and is located at the center of the specimen. In addition, both rocks showed concentrated microcracking close to the region of contact between the specimen and the loading platens, related to the loading transference along the loading edge. Before peak load, microcracking becomes denser and localized at the center and the contact region of the specimen, although, the central region still concentrates the main portion of the damage. After the peak load, new microcracks were first concentrated on one of the faces at the center of the specimen and then propagated through its thickness all the way to the other face. The progressive failure in monzogranite extended through to the end of the test, while in marble the main portion of the failure surface of the specimen developed just after peak. During the whole test in both rocks, the lowest velocities (vp) of the specimen were recorded in the central core. Although microcracking was induced at the contact region, the highest velocities vp of the specimen were registered there, because of the confinement effect produced by the platens, which lead to a local increase in the stiffness of the specimen. The non-homogeneous distribution of vp in the specimen has revealed that the utilization of this parameter as a constant and equal to the value measured in the specimen before testing (as usually adopted in the literature), does not represent the real condition of the damaged specimen. In monzogranite, microcracks propagate mainly through quartz crystals, following a tortuous path subparallel to the loading direction, by releasing high-level of absolute energy, while in marble the propagation of microcracks follows the cleavage planes of calcite, by releasing low-level of absolute energy. The histograms of spatial strength distribution in both rocks have shown good adjustment to a Weibull distribution, but monzogranite exhibited a more accurate adjustment with lower variability than marble. The analysis of signals in the frequency domain showed that the microcracking is characterized by wide band emissions.

Pour améliorer l'efficacité des procédés thermiques de craquages et réduire les phénomènes de cokage liés à la température de paroi trop élevée, l'utilisation de tubes nervurés est une technique potentiellement car elle permet d'améliorer le mélange et d'augmenter les transferts de chaleur. Cependant, la perte de charge est significativement augmentée. En raison de la complexité de l'écoulement turbulent, du système chimique et du couplage turbulencechimie, il est difficile d'estimer a priori la perte réelle en termes de sélectivité des tubes nervurés. Les expériences représentatives de laboratoire combinant turbulence, transferts de chaleur et chimie sont très rares et trop coûteuses à l'échelle industrielle. Dans ce travail, l'approche simulation aux grandes échelles résolue à la paroi (WRLES) est utilisée pour étudier écoulement non-réactif puis réactif dans des tubes à la fois lisses et nervurés, pour quantifier leur impact sur la turbulence et sur la chimie. Le code AVBP, qui résout les équations de Navier-Stokes compressibles pour les écoulements turbulents, est utilisé avec des schémas chimique réduites du craquage de l'éthane puis du butane. L'écoulement à la paroi est analysé en détail et comparé pour les deux géométries, fournissant des informations utiles pour le développement ultérieur de modèles de parois pour ce type de rugosité. L'impact de la résolution du maillage et du schéma numérique est également discuté, pour trouver le meilleur compromis entre coût et précision de calcul pour une application industrielle. L'impact des structures d'écoulement turbulent ainsi que leurs effets sur le transfert thermique et le mélange sur les réactions chimique sont étudiés à la fois pour les tubes lisses et les tubes nervurés. Perte de pression, transfert de chaleur et conversion chimique sont finalement comparés. / To improve the efficiency of thermal-cracking processes, and to reduce the coking phenomena due to high wall temperature, the use of ribbed tubes is an interesting technique as it allows better mixing and heat transfer. However it also induces significant increase in pressure loss. The complexity of the turbulent flow, the chemical system, and the chemistry-turbulence interaction makes it difficult to estimate a priori the real loss of ribbed tubes in terms of selectivity. Experiments combining turbulence, heat transfer and chemistry are very rare in laboratories and too costly at the industrial scale. In this work, Wall-Resolved Large Eddy Simulation (WRLES) is used to study non-reacting and reacting flows in both smooth and ribbed tubes, to show the impact of the ribs on turbulence and chemistry. Simulations were performed with the code AVBP, which solves the compressible Navier-Stokes equations for turbulent flows, using reduced chemistry scheme of ethane and butane cracking for reacting cases. Special effort was devoted to the wall flow, which is analyzed in detail and compared for both geometries, providing useful information for further development of roughness-type wall models. The impact of grid resolution and numerical scheme is also discussed, to find the best trade-off between computational cost and accuracy for industrial application. Results investigate and analyze the turbulent flow structures, as well as the effect of heat transfer efficiency and mixing on the chemical process in both smooth and ribbed tubes. Pressure loss, heat transfer and chemical conversion are finally compared.

Em nível microscópico, as rochas apresentam microdefeitos que agem como concentradores locais de tensão, favorecendo a ocorrência de ruptura frágil. O entendimento desse processo requer análises experimentais em rochas submetidas a tensões de tração. O ensaio de compressão diametral é uma alternativa apropriada, pois não apresenta as dificuldades envolvidas no ensaio de tração direta. A propagação de microfissuramento em materiais frágeis produz liberação de energia na forma de ondas elásticas chamadas de emissões acústicas (EA). O monitoramento com EA permite acompanhar a propagação de dano no corpo de prova (CP), sem perturbá-lo. Nesta pesquisa, CPs de mármore e monzogranito são submetidos a ensaios de compressão diametral com deslocamentos monotônicos e cíclicos, com controle de deslocamento. Aplica-se a técnica de EA, em conjunto com análises petrográficas, análises das curvas de força versus deslocamento e exame visual, para caracterizar o seu processo de microfissuramento. A localização tridimensional das fontes de EA foi realizada inicialmente utilizando-se o software AEwin® da PASA. Foi desenvolvido um programa de localização aprimorado que incorpora o cálculo da velocidade de propagação das ondas (vp) média para cada instante em que uma fonte é localizada. O novo programa (Crack Location by Acoustic emission with P Wave Velocity determination, CLAPWaVe) mostra um claro decréscimo da velocidade de propagação com o aumento do dano. O programa desenvolvido (CLAPWaVe) mostrou melhor ajuste e maior coerência com a literatura e com a condição final rompida dos CPs do que o software AEwin. Em mármore e monzogranito o microfissuramento se inicia a 25-30% e 75-85% do carregamento de pico, respectivamente, e localiza-se na vizinhança do centro do CP. Em ambas as rochas se acumulou, também, dano na região dos apoios do CP, associado à transferência de carregamento do berço ao CP. Antes do pico de carregamento, o microfissuramento tornou-se mais denso e localizado no centro e nos apoios do CP, embora a região central ainda concentre a maior parte. Após o pico, o microfissuramento acumulou-se em uma das faces do CP, progredindo até a outra face. O monzogranito apresentou ruptura progressiva do CP, enquanto que no mármore a maior parte da superfície de ruptura já está desenvolvida imediatamente após o pico. Durante o ensaio em ambas as rochas, no núcleo central foram registradas as menores velocidades vp do CP. Na região dos apoios, embora tenha havido microfissuramento, registraram-se as maiores velocidades vp no CP, pois o confinamento produzido pelo contato com o berço aumentou localmente a rigidez do CP. A distribuição não homogênea de vp no CP revelou que a consideração desse parâmetro como constante e igual à condição intacta ao longo do ensaio, como comumente encontrado na literatura, não representa a condição real do CP danificado. O microfissuramento no monzogranito se propaga principalmente através dos cristais de quartzo, seguindo um caminho tortuoso subparalelo à direção de carregamento e liberando altos níveis de energia absoluta. No mármore, a propagação segue os planos de clivagem da calcita, liberando níveis baixos de energia absoluta. Os histogramas da distribuição espacial da resistência em ambas as rochas mostraram bom ajuste a uma distribuição de Weibull, porém o monzogranito mostrou melhor ajuste e menor variabilidade que o mármore. As análises dos sinais no domínio das frequências mostraram que o microfissuramento é caracterizado por emissões de banda larga. / At microscopic level, rocks exhibit microflaws, which act as local stress concentrators, favoring the occurrence of brittle failure. The understanding of this process requires experimental analyses of rock specimens under tensile stresses. The diametral compression test is an adequate alternative for such a studies, because it does not present the difficulties of direct tension tests. Crack propagation in brittle materials releases energy as transient elastic waves known as acoustic emission (AE). Monitoring with AE enables an insight into the cracking process without affecting the integrity of the sample. In this work, marble and monzogranite specimens were subjected to monotonic and cyclic displacementcontrolled diametral compression tests. The AE monitoring technique was applied in conjunction with petrographic analyses, interpretation of the load versus displacement curves and visual examination of the samples for the characterization of their cracking process. The three-dimensional localization of the AE sources was initially carried out by using the software AEwin® from PASA. An improved localization software, which considers the P-wave velocity variation along the damage process (vp) for each AE source was developed. The developed software (Crack Location by Acoustic emission with P Wave Velocity determination, CLAPWaVe) has shown greater consistency with literature and the final cracked samples and better accuracy than AEwin. Microcracking in monzogranite and marble initiated at 25-30% and 75-80% of the peak load, respectively, and is located at the center of the specimen. In addition, both rocks showed concentrated microcracking close to the region of contact between the specimen and the loading platens, related to the loading transference along the loading edge. Before peak load, microcracking becomes denser and localized at the center and the contact region of the specimen, although, the central region still concentrates the main portion of the damage. After the peak load, new microcracks were first concentrated on one of the faces at the center of the specimen and then propagated through its thickness all the way to the other face. The progressive failure in monzogranite extended through to the end of the test, while in marble the main portion of the failure surface of the specimen developed just after peak. During the whole test in both rocks, the lowest velocities (vp) of the specimen were recorded in the central core. Although microcracking was induced at the contact region, the highest velocities vp of the specimen were registered there, because of the confinement effect produced by the platens, which lead to a local increase in the stiffness of the specimen. The non-homogeneous distribution of vp in the specimen has revealed that the utilization of this parameter as a constant and equal to the value measured in the specimen before testing (as usually adopted in the literature), does not represent the real condition of the damaged specimen. In monzogranite, microcracks propagate mainly through quartz crystals, following a tortuous path subparallel to the loading direction, by releasing high-level of absolute energy, while in marble the propagation of microcracks follows the cleavage planes of calcite, by releasing low-level of absolute energy. The histograms of spatial strength distribution in both rocks have shown good adjustment to a Weibull distribution, but monzogranite exhibited a more accurate adjustment with lower variability than marble. The analysis of signals in the frequency domain showed that the microcracking is characterized by wide band emissions.

<p>The present work is focused on the synthesis of small-scale (modular processes) to produce olefins from light alkane resources in shale gas.</p> <p>Olefins, which are widely used to produce important chemicals and everyday consumer products, can be produced from light alkanes - ethane, propane, butanes etc. Shale gas is comprised of light alkanes in significant proportion; and is available in abundance. Meanwhile, shale gas wells are small sized in nature and are distributed over many different areas or regions. In this regard, using shale gas as raw material for olefin production would require expensive transportation infrastructure to move the gas from the wells or local gas gathering stations to large central processing facilities. This is because existing technologies for natural gas conversions are particularly suited for large-scale processing. One possible way to take advantage of the abundance of shale resource for olefins production is to place small-sized or modular processing plants at the well sites or local gas gathering stations.</p> <p>In this work, new process concepts are synthesized and studied towards developing simple technologies for on-site and modular processing of light alkane resources in shale gas for olefin production. Replacing steam with methane as diluent in conventional thermal cracking processes is proposed to eliminate front-end separation of methane from the shale gas processing scheme. Results from modeling studies showed that this is a promising approach. To eliminate the huge firebox volume associated with thermal cracking furnaces and allow for a compact cracking reactor system, the use of electricity to supply heat to the cracking reactor is considered. Synthesis efforts led to the development of two electrically powered reactor configurations that have improved energy efficiency and reduced carbon footprints over and compare to conventional thermal cracking furnace configurations.</p> <p>The ideas and results in the present work are radical in nature and could lead to a transformation in the utilization of light alkanes, natural gas and shale resources for the commercial production of fuels and chemicals.</p>