Yes / This work presents a steady-state one-dimensional model of the FCC riser considering the vaporisation of the gas oil feed and subsequent cracking reactions. The evaporation of droplets is studied using three models: the classical homogeneous model and the heterogeneous vaporisation models from the literature. Droplets are modelled using the Lagrangian framework model for particles moving through a fluid. This was coupled with the gas–solid flow field describing the catalyst particulate transport in the riser. Cracking reaction kinetics are modelled using a four-lumped model. The model was then validated against published plant data. The model performed well in terms of gas oil conversion, gasoline yield, pressure drop, and phase temperature profiles. Therefore, it is suitable for use in the design and optimisation of new and existing FCC unit risers, particularly in cost–benefit analysis considering the current push away from petroleum energy sources. It was found that vaporisation models are largely insignificant in terms of gas oil conversion profiles and gasoline yield for usual operation conditions of FCC risers, which is a finding that had yet to be proven in the literature. Vaporisation models are shown to only affect conversion and yield when the initial droplet exceeds 2000 μm.

This dissertation includes two accounts of rigorous modeling of petroleum refinery modeling using rigorous reaction and fractionation units. The models consider various process phenomena and have been extensively used during a course of a six-month study to understand and predict behavior. This work also includes extensive guides to allow users to develop similar models using commercial software tools. (1) Predictive Modeling of Large-Scale Integrated Refinery Reaction and Fractionation Systems from Plant Data: Fluid Catalytic Cracking (FCC) Process with Planning Applications: This work presents the methodology to develop, validate and apply a predictive model for an integrated fluid catalytic cracking (FCC) process. We demonstrate the methodology by using data from a commercial FCC plant in the Asia Pacific with a feed capacity of 800,000 tons per year. Our model accounts for the complex cracking kinetics in the riser-regenerator and associated gas plant phenomena. We implement the methodology with Microsoft Excel spreadsheets and a commercial software tool, Aspen HYSYS/Petroleum Refining from Aspen Technology, Inc. The methodology is equally applicable to other commercial software tools. This model gives accurate predictions of key product yields and properties given feed qualities and operating conditions. This work differentiates itself from previous work in this area through the following contributions: (1) detailed models of the entire FCC plant, including the overhead gas compressor, main fractionator, primary and sponge oil absorber, primary stripper and debutanizer columns; (2) process to infer molecular composition required for the kinetic model using routinely collected bulk properties of feedstock; (3) predictions of key liquid product properties not published alongside previous related work (density, D-86 distillation curve and flash point); (4) case studies showing industrially useful applications of the model; and (5) application of the model with an existing LP-based planning tool. (2) Predictive Modeling of Large-Scale Integrated Refinery Reaction and Fractionation Systems from Plant Data: Continuous Catalyst Regeneration (CCR) Reforming Process: This work presents a model for the rating and optimization of an integrated catalytic reforming process with UOP-style continuous catalyst regeneration (CCR). We validate this model using plant data from a commercial CCR reforming process handling a feed capacity of 1.4 million tons per year in the Asia Pacific. The model relies on routinely monitored data such ASTM distillation curves, paraffin-napthene- aromatic (PNA) analysis and operating conditions. We account for dehydrogenation, dehydrocyclization, isomerization and hydrocracking reactions that typically occur with petroleum feedstock. In addition, this work accounts for the coke deposited on the catalyst and product recontacting sections. This work differentiates itself from the reported studies in the literature through the following contributions: (1) detailed kinetic model that accounts for coke generation and catalyst deactivation; (2) complete implementation of a recontactor and primary product fractionation; (3) feed lumping from limited feed information; (4) detailed procedure for kinetic model calibration; (5) industrially relevant case studies that highlight the effects of changes in key process variables; and (6) application of the model to refinery-wide production planning. / Ph. D.

Naftos krekinge naudotas katalizatorius yra ceolitinė medžiaga, kurios unikalios savybės mažai išnaudojamos cementinių medžiagų gamybos technologijoje. Ugniai atspariuose betonuose naudojami įvairūs priedai-modifikatoriai yra labai brangūs, todėl naudoto katalizatoriaus panaudojimas, kaip modifikuojančio betono savybes priedo, turi ne tik ekologinį (atliekų utilizavimas) bet ir ekonominį pagrindą. Vykdant šį darbą sukurti vidutinio cemento kiekio ugniai atsparūs šamotbetoniai su 70 % ir 40 % aliuminio oksido turinčiais aliuminatiniais cementais ir naudoto katalizatoriaus priedu atitinkamai 2,5 % ir 5,0 %. Darbe taip pat atskleistas efektyvus katalizatoriaus poveikis aliuminatinio cemento hidratacijai, cemento akmens struktūros susidarymui kietėjimo metu ir jos pokyčiams veikiant aukštoms temperatūroms. / Fluidized bed catalytic cracking catalyst waste is a zeolite material. Its unique properties are underused in cementitious materials production technology. Various additives, modifiers used in refractory castables are very expensive, so the use of catalyst waste as a modifying additive of castable properties has not only an ecological (waste recycling) but also an economical basis. Medium cement refractory castable was developed using 70 % and 40 % of aluminium oxide containing aluminate cement and catalyst waste additive, respectively 2,5 % and 5,0 %. The work also reveals an efficient effect of catalyst waste on alumina cement hydration, structure formation during cement solidification and after treatment at high temperature.

Le craquage catalytique à lit fluidisé (FCC) est l'un des procédés les plus importants au sein d'une raffinerie moderne et joue un rôle économique primordial. Le fonctionnement du FCC pose des problèmes d'opération liés à sa complexité. L'étude a porté sur la simulation du FCC, sa commande prédictive multivariable et l'estimation de paramètres-clés. Après une revue de la littérature sur les FCC et les différentes approches de modélisation ainsi que des cinétiques de craquage, un modèle du FCC qui intègre les dynamiques importantes a été choisi pour les besoins de la commande prédictive. La simulation du riser a été effectuée pour différents modèles de craquage et a montré de grandes disparités entre modèles, créant une difficulté à définir un modèle général de riser pour les FCC. Outre le nombre de groupes considérés, les différences concernent la chaleur de réaction globale, les lois de formation de coke sur le catalyseur et la désactivation de ce dernier. Des algorithmes de commande prédictive linéaire et non linéaire basée sur le modèle ont été utilisés pour commander le FCC en tenant compte de sa nature multivariable et des contraintes imposées aux variables manipulées. Les sorties commandées, température en haut du riser et température du régénérateur ont été maintenues proches des consignes, tant en régulation qu'en poursuite, tout en respectant les contraintes portant sur les deux variables manipulées, le débit de catalyseur régénéré et le débit d'air entrant dans le régénérateur. Une commande à trois entrées manipulées, incluant le débit d'alimentation, a également été testée avec succès. La commande prédictive linéaire avec observateur a fourni des résultats encore meilleurs que la commande linéaire quadratique. La commande prédictive non linéaire a été testée mais présente des problèmes pour une implantation en temps réel. L'estimation du coke sur le catalyseur a été réalisée par le filtre de Kalman étendu, mais les erreurs d'estimation sont importantes, probablement à cause du choix insuffisant des mesures effectuées. L'ensemble de l'étude a montré que la commande avancée prédictive du FCC est performante et doit être recommandée, mais peut encore être améliorée en particulier par son réglage et l'estimation des états / Fluid catalytic cracking (FCC) is one of the most important processes in a modern refinery and is of essential economic importance. The FCC operation presents difficulties related to its complexity. The study was related to its simulation, multivariable control and estimation of key parameters. After a litterature review of the FCC, the different approaches of modelling and cracking kinetics, a FCC model that takes into account the important dynamics was chosen for model predictive control purposes. The riser simulation was carried out for different cracking models and shows great differences between these models, which makes it difficult to define a general riser model for the FCC. Besides the number of lumps, differences deal with the global heat of reaction, the coke formation laws and its deactivation functions. Linear and nonlinear model predictive algorithms were used for FCC control taking into account its multivariable nature and the constraints imposed on the manipulated variables. The controlled outputs, temperature at the riser top and temperature in the regenerator were maintained close to their respective set points in regulation and tracking modes while respecting the constraints on the two manipulated variable, the flow rate of regenerated catalyst and the flow rate of air entering the regenerator. A control with three manipulated variables including the feed flow rate was also successfully tested. Linear predictive control with an observer gave better results than linear quadratic control. Nonlinear predictive control was tested but presents problems for real time implementation. The estimation of coke on the catalyst was carried out using extended Kalman filter, but the estimation errors are important, probably due to an insufficient choice of measurements. The overall study showed that advanced predictive control of the FCC is efficient and must be recommended, but it can still be improved upon particularly by its tuning and state estimation

As zeólitas sintéticas contendo terras raras (TR) são os componentes principais de catalisadores FCC (Fluid Catalytic Cracking) empregados no craqueamento do petróleo e a porcentagem de TR nestes catalisadores pode chegar a 5%. As TR são adicionadas às zeólitas tipo Y para melhorar sua estabilidade térmica e hidrotérmica durante o processo de refino do petróleo. A produção brasileira destes catalisadores está em torno de 25 mil toneladas por ano, necessitando, para tanto, de 900 toneladas de óxido de lantânio no mesmo período. Atualmente, a China é responsável por 90% da produção e comercialização mundial das TR. Desde 2010, a China controla os preços das mesmas (ao final de 2011 chegou a elevar o preço do lantânio em mais de 20 vezes), bem como reduziu substancialmente sua cota de exportação. É nesse contexto que surge a necessidade da reciclagem de materiais que possuem TR em sua constituição, como é o caso dos catalisadores FCC provenientes do craqueamento do petróleo. Outra fonte que merece destaque, tendo sido igualmente explorada neste trabalho, é os pós-fosfóricos responsáveis por gerar a luz branca em lâmpadas fluorescentes. Atualmente a Rhodia, do grupo Solvay, já iniciou a recuperação das TR em pós-fosfóricos. As principais TR utilizadas em lâmpadas fluorescentes são La, Ce, Eu, Tb e Y, encontrados nos compostos Y2O3:Eu3+, BaMgAl10O17:Eu2+ e LaPO4:Ce3+,Tb3+. Os elementos Eu, Tb e Y têm alto valor agregado, representando de 5 a 20% em massa dos pós-fosfóricos. Sendo assim, o objetivo deste trabalho foi desenvolver uma metodologia economicamente viável e, sobretudo, com baixa utilização e produção de substâncias perigosas para a separação e recuperação de íons de TR contidos na zeólita tipo Y, componente dos catalisadores FCC desativados, previamente empregados no craqueamento de petróleo, bem como em lâmpadas fluorescentes. Inicialmente, realizou-se a caracterização preliminar dos componentes dos catalisadores FCC desativados. Posteriormente, buscou-se o desenvolvimento de metodologias de separação química para obtenção dos elementos de TR e caracterização dos mesmos por diversas técnicas, tais como espectroscopia de fotoluminescência, fluorescência de Raios-X, titulometria de complexação, microscopia eletrônica de varredura e espectroscopia de infravermelho / Synthetic zeolites containing rare earths (RE) are the major components of FCC (Fluid Catalytic Cracking) catalysts used in petroleum cracking, where the percentage of such elements is about 5%. RE ions improve the thermal and hydrothermal stability of zeolites-Y during the petroleum refining process. The Brazilian production of these catalysts is around 25 thousand tons per year, requiring 900 tons of lanthanum oxide in the same period. Currently, China is responsible for 90% of the world production and market of RE. Since 2010, China controls the prices of RE elements and substantially reduced the exportation quota. For instance, by the end of 2011 the price of lanthanum was risen by more than 20 times. In this context, the search for recycling materials that have rare earths in their constitution becomes crucial, as is the case of the FCC catalysts from the cracking of petroleum. Another source that deserves significant attention is the phosphoric powders that generate white light in fluorescent lamps, which were also investigated in this work. Rhodia from the Solvay group has already begun the recovery of rare earths in phosphoric powders. The main RE used in fluorescent lamps are La, Ce, Eu, Tb and Y, which occur as Y2O3: Eu3+, BaMgAl10O17:Eu2+ and LaPO4:Ce3+, Tb3+. Eu, Tb and Y are high-value elements, representing by 5 20% of the total mass of phosphoric powders. Therefore, the aim of this work was to develop economically feasible and environmental friendly methodologies for the separation and recovery of RE ions from zeolite-Yin deactivated FCC catalysts and from fluorescent lamp phosphors. To this end, we firstly performed a preliminary characterization of the components of deactivated FCC catalysts. The following steps comprised the development of chemical separation methodologies to obtain rare earth elements and their characterization by several techniques such as photoluminescence spectroscopy, X-ray fluorescence, complexation titration, scanning electron microscopy and infrared spectroscopy

Fluidized bed catalytic cracking catalyst waste is a zeolite material. Its unique properties are underused in cementitious materials production technology. Various additives, modifiers used in refractory castables are very expensive, so the use of catalyst waste as a modifying additive of castable properties has not only an ecological (waste recycling) but also an economical basis. Medium cement refractory castable was developed using 70 % and 40 % of aluminium oxide containing aluminate cement and catalyst waste additive, respectively 2,5 % and 5,0 %. The work also reveals an efficient effect of catalyst waste on alumina cement hydration, structure formation during cement solidification and after treatment at high temperature. / Naftos krekinge naudotas katalizatorius yra ceolitinė medžiaga, kurios unikalios savybės mažai išnaudojamos cementinių medžiagų gamybos technologijoje. Ugniai atspariuose betonuose naudojami įvairūs priedai-modifikatoriai yra labai brangūs, todėl naudoto katalizatoriaus panaudojimas, kaip modifikuojančio betono savybes priedo, turi ne tik ekologinį (atliekų utilizavimas) bet ir ekonominį pagrindą. Vykdant šį darbą sukurti vidutinio cemento kiekio ugniai atsparūs šamotbetoniai su 70 % ir 40 % aliuminio oksido turinčiais aliuminatiniais cementais ir naudoto katalizatoriaus priedu atitinkamai 2,5 % ir 5,0 %. Darbe taip pat atskleistas efektyvus katalizatoriaus poveikis aliuminatinio cemento hidratacijai, cemento akmens struktūros susidarymui kietėjimo metu ir jos pokyčiams veikiant aukštoms temperatūroms.

As zeólitas sintéticas contendo terras raras (TR) são os componentes principais de catalisadores FCC (Fluid Catalytic Cracking) empregados no craqueamento do petróleo e a porcentagem de TR nestes catalisadores pode chegar a 5%. As TR são adicionadas às zeólitas tipo Y para melhorar sua estabilidade térmica e hidrotérmica durante o processo de refino do petróleo. A produção brasileira destes catalisadores está em torno de 25 mil toneladas por ano, necessitando, para tanto, de 900 toneladas de óxido de lantânio no mesmo período. Atualmente, a China é responsável por 90% da produção e comercialização mundial das TR. Desde 2010, a China controla os preços das mesmas (ao final de 2011 chegou a elevar o preço do lantânio em mais de 20 vezes), bem como reduziu substancialmente sua cota de exportação. É nesse contexto que surge a necessidade da reciclagem de materiais que possuem TR em sua constituição, como é o caso dos catalisadores FCC provenientes do craqueamento do petróleo. Outra fonte que merece destaque, tendo sido igualmente explorada neste trabalho, é os pós-fosfóricos responsáveis por gerar a luz branca em lâmpadas fluorescentes. Atualmente a Rhodia, do grupo Solvay, já iniciou a recuperação das TR em pós-fosfóricos. As principais TR utilizadas em lâmpadas fluorescentes são La, Ce, Eu, Tb e Y, encontrados nos compostos Y2O3:Eu3+, BaMgAl10O17:Eu2+ e LaPO4:Ce3+,Tb3+. Os elementos Eu, Tb e Y têm alto valor agregado, representando de 5 a 20% em massa dos pós-fosfóricos. Sendo assim, o objetivo deste trabalho foi desenvolver uma metodologia economicamente viável e, sobretudo, com baixa utilização e produção de substâncias perigosas para a separação e recuperação de íons de TR contidos na zeólita tipo Y, componente dos catalisadores FCC desativados, previamente empregados no craqueamento de petróleo, bem como em lâmpadas fluorescentes. Inicialmente, realizou-se a caracterização preliminar dos componentes dos catalisadores FCC desativados. Posteriormente, buscou-se o desenvolvimento de metodologias de separação química para obtenção dos elementos de TR e caracterização dos mesmos por diversas técnicas, tais como espectroscopia de fotoluminescência, fluorescência de Raios-X, titulometria de complexação, microscopia eletrônica de varredura e espectroscopia de infravermelho / Synthetic zeolites containing rare earths (RE) are the major components of FCC (Fluid Catalytic Cracking) catalysts used in petroleum cracking, where the percentage of such elements is about 5%. RE ions improve the thermal and hydrothermal stability of zeolites-Y during the petroleum refining process. The Brazilian production of these catalysts is around 25 thousand tons per year, requiring 900 tons of lanthanum oxide in the same period. Currently, China is responsible for 90% of the world production and market of RE. Since 2010, China controls the prices of RE elements and substantially reduced the exportation quota. For instance, by the end of 2011 the price of lanthanum was risen by more than 20 times. In this context, the search for recycling materials that have rare earths in their constitution becomes crucial, as is the case of the FCC catalysts from the cracking of petroleum. Another source that deserves significant attention is the phosphoric powders that generate white light in fluorescent lamps, which were also investigated in this work. Rhodia from the Solvay group has already begun the recovery of rare earths in phosphoric powders. The main RE used in fluorescent lamps are La, Ce, Eu, Tb and Y, which occur as Y2O3: Eu3+, BaMgAl10O17:Eu2+ and LaPO4:Ce3+, Tb3+. Eu, Tb and Y are high-value elements, representing by 5 20% of the total mass of phosphoric powders. Therefore, the aim of this work was to develop economically feasible and environmental friendly methodologies for the separation and recovery of RE ions from zeolite-Yin deactivated FCC catalysts and from fluorescent lamp phosphors. To this end, we firstly performed a preliminary characterization of the components of deactivated FCC catalysts. The following steps comprised the development of chemical separation methodologies to obtain rare earth elements and their characterization by several techniques such as photoluminescence spectroscopy, X-ray fluorescence, complexation titration, scanning electron microscopy and infrared spectroscopy

Many metals used in modern engineering exhibit anisotropy. A common assumption when modelling anisotropic metals is that the level of anisotropy is fixed throughout the calculation. As it is well understood that processes such as cold rolling, forging or shock loading change the level of anisotropy, it is clear that this assumption is not accurate when dealing with large deformations. The aim of this project was to develop a tool capable to predict large deformations of a single crystal or crystalline aggregate of a metal of interest and able to trace an evolution of anisotropy within the material. The outcome of this project is a verified computational tool capable of predicting large deformations in metals. This computational tool is built on the Crystal Plasticity Finite Element Method (CPFEM). The CPFEM in this project is an implementation of an existing constitutive model, based on the crystal plasticity theory (the single crystal strength model), into the framework of the FEA software DYNA3D® . Accuracy of the new tool was validated for a large deformation of a single crystal of an annealed OFHC copper at room temperature. The implementation was also tested for a large deformation of a polycrystalline aggregate comprised of 512 crystals of an annealed anisotropic OFHC copper in a uniaxial compression and tension test. Here sufficient agreement with the experimental data was not achieved and further investigation was proposed in order to find out the cause of the discrepancy. Moreover, the behaviour of anisotropic metals during a large deformation was modelled and it was demonstrated that this tool is able to trace the evolution of anisotropy. The main benefit of having this computational tool lies in virtual material testing. This testing has the advantage over experiments in time and cost expenses. This tool and its future improvements, which were proposed, will allow studying evolution of anisotropy in FCC and BCC materials during dynamic finite deformations, which can lead to current material models improvement.

While localism is a particularly important aspect of Congress' mandate that broadcasters serve "the public interest, convenience or necessity," the history of US radio broadcasting exhibits persistent tensions between nationalism and localism, which have intensified in recent decades. Current concerns about the loss of localism in US radio broadcasting invite us to reinterpret US radio history from a local perspective. This dissertation traces the tensions between localism and nationalism in US radio broadcasting through four forms of radio broadcasting constructed specifically to serve localism and the public interest: the 10-watt Class D license, full power public radio as typified by National Public Radio, the Low Power FM (LPFM) license established in 2000, and the controversial use of low power radio by religious broadcasters. The Class D license, US public radio, and LPFM all originated with the stated objective of serving the public in meaningful ways which commercial broadcasting cannot. Yet to date, each of these has failed to meet this goal, whether due to legislative action, organizational failure or conflict amongst broadcast entities. Further, each of these case studies illustrates the conflict between nationalism and localism ever-present in efforts to establish radio broadcasting services that adequately and meaningfully serve local publics. Through a critical-historical analysis of the tensions between nationalism and localism in US radio broadcasting, this dissertation offers an understanding for the reasons and implications of the continued failure of radio's ability to serve local communities in the United States. In doing so, I look to the failures of the past to suggest how we may revise the current LPFM license to effectively serve local publics.

The purpose of this study was to identify Canadian critical care nurses’ attitudes about the importance of families in nursing care in adult intensive care units (ICUs), explore their perceptions of family-centered care (FCC), and examine policies and practices in place that promote FCC in adult ICUs. A web-based survey was used with a sample of members (N = 207) of the Canadian Association of Critical Care Nurses. Using the Families Importance in Nursing Care: Nurses’ Attitudes (FINC-NA) instrument, it was found that age and years of ICU experience were positively related to more positive attitudes (n = 193), while direct care providers had lower scores than nurses in other roles. Nurses identified benefits for patients, families, and staff associated with FCC, but also outlined challenges in implementing FCC, including comfort of nurses and a lack of support from team members. Nurses’ responses to questions about FCC policies and practices illustrated concerns with the implementation of FCC in the units the nurses worked in. The results of this study have implications for practice, education, and research.