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Orientador: Mario de Jesus Mendes / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-07T19:04:30Z (GMT). No. of bitstreams: 1 Schmitz_JonesErni_D.pdf: 1427141 bytes, checksum: 5c994ce371331fd4c3ac0f3e3861f49b (MD5) Previous issue date: 2006 / Resumo: A simulação de processos é um componente fundamental de uma grande variedade de atividades de Engenharia de Processos, tais como a Otimização Online, o controle em Tempo Real, a Identificação, etc. O cálculo de Equilíbrio de Fases é uma atividade fundamental em qualquer simulação de processos de separação. O elevado tempo computacional deste cálculo provocado pela sua natureza iterativa pode criar incompatibilidades entre a atividade de simulação e as aplicações em tempo real que ela integra. O objetivo deste trabalho foi desenvolver um método alternativo simples, mas suficientemente preciso, para realizar os cálculos de equilíbrio de fases na simulação de processos de separação de sistemas complexos. Entende-se por tal, sistemas que apresentam problemas de Equilíbrio Líquido-Líquido e de Equilíbrio Líquido-Líquido-Vapor, como é o caso dos que possuem um Azeótropo Heterogêneo. Pelas suas propriedades, as Redes Neurais Artificiais surgem naturalmente como candidatas alternativas para esta tarefa. Como objeto de aplicação foram escolhidos dois sistemas que apresentam um azeótropo heterogêneo, o sistema binário acetato de etila - água e o sistema ternário etanol - acetato de etila - água. Para gerar os dados usados no treinamento das redes foi implementado um método convencional de cálculo de equilíbrio de fases, adequado à complexidade dos sistemas escolhidos, o método de Pham & Doherty. Para a resolução do problema da estabilidade de fases, a primeira etapa do cálculo do equilíbrio de fases, foram testados dois tipos de redes neurais artificiais (RNAs), as Redes Neurais Artificiais Probabilísticas (RNAPs) e os Perceptrons. Com os perceptrons foram encontradas dificuldades para atingir a precisão desejada, sendo necessário recorrer a perceptrons com várias camadas escondidas. Já as RNAPs apresentaram uma excelente precisão, embora a sua simulação seja mais lenta. Perceptrons simples de uma só camada escondida foram usados com êxito na solução da segunda etapa do cálculo de equilíbrio de fases, o problema da divisão de fases. Combinando as redes desenvolvidas para cada uma das etapas foi criada uma ferramenta que permite resolver qualquer problema de equilíbrio de fases para os sistemas estudados. A precisão dos resultados fornecidos pelas redes neurais é comparável à dos apresentados pelos métodos tradicionais, mas os cálculos do equilíbrio de fases feitos usando redes neurais foram mais rápidos. Pode-se concluir que as redes neurais artificiais constituem uma alternativa válida aos métodos tradicionais do cálculo do equilíbrio de fases baseados em equações de estado para sistemas complexos como os avaliados / Abstract: Process simulation is a basic component of different Process Engineering activities such as On-line Optimization, Model Predictive Control, Identification, etc. The calculation of Phase Equilibrium appears as a fundamental task in any simulation of a separation process. However, the high computational time due to the iterative nature of this calculation makes it oft unsuitable for use with real time process analysis and synthesis strategies. The objective of this work is to develop a simple but accurate method to perform the phase equilibrium calculations required to the study of the behavior of complex systems. As such we mind those systems who present liquid-liquid and vapor-liquid-liquid phase equilibrium problems, such as systems with a heterogeneous azeotrope do. Given their inherent ability to learn and recognize non-linear and highly complex relationships, artificial neural networks (ANNs) appear to be well suited for such a task. Two chemical systems, the binary ethyl acetate ¿ water and the ternary ethanol ¿ ethyl acetate ¿ water were chosen; both systems present a miscibility gap and a heterogeneous azeotrope. The data sets used to train the ANNs were computed using the method of Pham & Doherty. Two kinds of neural networks were tried to solve the phase stability problem, namely the probabilistic neural networks (PNNs) and the perceptrons. In order to attain an acceptable precision perceptrons had to be trained with several hidden layers. Even though, PNNs got slightly better results than the perceptrons. Simple perceptrons were able to deliver the required precision when trained to predict the compositions of phases in equilibrium. Coupling the ANNs trained for phase stability with those trained for phase division a tool was obtained that can solve any phase equilibrium problem for the two chosen systems. Predictions made with the use of neural networks were faster than those made using the traditional methods, and delivered comparable precision / Doutorado / Sistemas de Processos Quimicos e Informatica / Doutor em Engenharia Química

Yes / Three equations of state with a group contribution model for binary interaction parameters were employed to calculate the vapor-liquid equilibria of synthetic and real natural gas mixtures with heavy fractions. In order to estimate the binary interaction parameters, critical temperatures, critical pressures and acentric factors of binary constituents of the mixture are required. The binary interaction parameter model also accounts for temperature. To perform phase equilibrium calculations, the heavy fractions were first discretized into 12 Single Carbon Numbers (SCN) using generalized molecular weights. Then, using the generalized molecular weights and specific gravities, the SCN were characterized. Afterwards, phase equilibrium calculations were performed employing a set of (nc + 1) equations where nc stands for the number of known components plus 12 SCN. The equations were solved iteratively using Newton's method. Predictions indicate that the use of binary interaction parameters for highly sour natural gas mixtures is quite important and must not be avoided. For sweet natural gas mixtures, the use of binary interaction parameters is less remarkable, however.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第23918号 / 工博第5005号 / 新制||工||1781(附属図書館) / 京都大学大学院工学研究科分子工学専攻 / (主査)教授 佐藤 啓文, 教授 作花 哲夫, 教授 佐藤 徹 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

Multilayers provide an ideal tool to study thermodynamics of heterogeneous systems far from equilibrium. In this study, synthesis, characterization, thermal stability and phase equilibrium of multilayers are investigated based on Au-Pt system. Au-50%Pt multilayers were first formed by repeated rolling and folding. The microstructure was investigated by x-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). These methods revealed that the process reduced layer thicknesses to below 30nm. However, delaminating and non-uniform spacings were also observed in some regions. To get well- welded and regular multilayers, the experiment was redesigned. The improved approach, involving repeated cutting, stacking, annealing and cold rolling, has yielded uniform multilayers with interlamellar spacings as low as 6nm. XRD demonstrated the formation of a homogeneous solid solution during cold rolling at room temperature. TEM suggested that the multilayers were discontinuously homogenized via steady state motion of boundaries. The reason for the solid solution formation is that the stored interface energy is higher than the energy barrier for solid solution formation. The solid solution is unstable. It decomposes into Au and Pt after heating to 500°C at 50°C/min by differential scanning calorimetry (DSC). The phase diagram is strongly modified in the nanometer range when we take into account of interface energy. The grain size dependent phase diagram model of Au-Pt system shows that the melting points of Au and Pt can be lowered more than 300K if the average grain size is reduced to 10nm. The melting temperature of Au/Pt multilayers has been studied with theoretical and experimental approaches. High speed laser heating was used to minimize any modification of the multilayer structure prior to melting. The qualitative experimental results are shown to be in agreement with expectations. / Thesis / Master of Applied Science (MASc)

Miscible gas flooding is a common method for enhanced oil recovery. Reliable design of miscible gas flooding requires compositional reservoir simulation that can accurately predict the fluid properties resulting from mass transfer between reservoir oil and injection gas. Drawbacks of compositional simulation are the efficiency and robustness of phase equilibrium calculations consisting of flash calculations and phase stability analysis. Simulation of multicontact miscible gas flooding involves a large number of phase equilibrium calculations in a near-critical region, where the calculations are time-consuming and difficult. Also, mixtures of reservoir oil and solvent such as CO₂ and rich gas can exhibit complex phase behavior at temperatures typically below 120°F, where three hydrocarbon-phases can coexist. However, most compositional simulators do not attempt to solve for three hydrocarbon-phases because three-phase equilibrium calculations are more complicated, difficult, and time-consuming than traditional two-phase equilibrium calculations. Due to the lack of robust algorithms for three-phase equilibrium calculations, the effect of a third hydrocarbon-phase on low-temperature oil displacement is little known. We develop robust and efficient algorithms for phase equilibrium calculations for two and three phases. The algorithms are implemented in a compositional reservoir simulator. Simulation case studies show that our algorithms can significantly decrease the computational time without loss of accuracy. Speed-up of 40% is achieved for a reservoir simulation using 20 components, compared to standard algorithms. Speed-up occurs not only because of improved computational efficiency but also because of increased robustness resulting in longer time-step sizes. We demonstrate the importance of three-phase equilibrium calculations, where simulations with two-phase equilibrium approximations proposed in the literature can result in complete failure or erroneous simulation results. Using the robust phase equilibrium algorithms developed, the mechanism is investigated for high efficiency of low-temperature oil displacements by CO₂ involving three hydrocarbon-phases. Results show that high displacement efficiency can be achieved when the composition path goes near the critical endpoint where the gaseous and CO₂-rich liquid phases merge in the presence of the oleic phase. Complete miscibility may not be developed for three-phase flow without considering the existence of a tricritical point. / text

Blendas poliméricas de biopolímeros, além de apresentarem uma melhora das propriedades do material, ainda possuem as vantagens de serem biocompatíveis, biodegradáveis e apresentar baixa toxicicidade, como no caso de blendas de alginato de sódio e fibroína de seda. Membranas confeccionadas a partir desta mistura apresentam grande potencial no desenvolvimento de curativos de alto desempenho, proporcionando condições ótimas de cicatrização. Entretanto, o processo de mistura destes biopolímeros é bastante complexo e resulta na separação de fases, processo que ainda não foi muito explorado. Este trabalho buscou explorar experimentalmente o comportamento do equilíbrio de fases dos sistemas aquosos contendo fibroína de seda e alginato de sódio em diversos valores de pH. Soluções aquosas de fibroína foram previamente preparadas por meio de processo de diálise, e soluções de alginato, por meio de dissolução direta em água. Ambas as soluções eram misturadas em concentrações em que se desejava avaliar o comportamento de fases. Após a separação de fases, a fase líquida sobrenadante era coletada, a fibroína quantificada via espectrofotometria e o alginato, via calcinação. Observou-se que a região monofásica do diagrama de fases é pequena, e a separação de uma segunda fase ocorre em concentrações baixas dos dois biopolímeros. A separação de fases pôde ser descrita como a precipitação da fibroína pela adição de alginato, e a solubilidade da fibroína pôde ser descrita por meio da equação de Cohn. As curvas de solubilidade obtidas não apresentaram diferenças significativas em função do pH. Medidas do potencial Zeta de soluções de alginato e fibroína em diversas faixas de pH não mostraram diferenças significativas quanto à carga superficial das moléculas, o que é compatível com a ausência de influência do pH no equilíbrio de fases. / Polymer blends formed by biopolymers may show an improvement of material properties (compared to the pure biopolymers), and present advantages such as biocompatibility, biodegradability and low toxicity. An interesting biopolymer blend is that formed by sodium alginate and silk fibroin. Membranes prepared with this mixture show great potential in the development of high-performance wound dressing, since it provides optimum healing conditions. However, the mixing process of these two biopolymers is complex and has not been extensively explored. In this work the phase equilibrium behavior of aqueous systems containing silk fibroin and sodium alginate was experimentally studied at different pH values. Fibroin aqueous solutions were previously prepared through dialysis, and alginate solutions were prepared by direct dissolution in water. Both solutions were mixed at the concentration range in which the phase behavior of the system was to be assessed. After phase separation, the supernatant liquid phase was separated, the fibroin was quantified through spectrophotometry. and the alginate was quantified through calcination. The single-phase region of the phase diagram is small, and the separation of a second phase occurs at low concentrations of both biopolymers. The phase separation could be described as the precipitation of fibroin due to the addition of alginate, and the solubility of fibroin was described by the Cohn equation. The solubility was not significantly affected by the pH. The Zeta potential of either alginate or fibroin, measured in solutions of different pH values, did not present any significant difference concerning the surface charges of these macromolecules. This finding agrees with the absence of pH influence upon the phase equilibrium.

Blendas poliméricas de biopolímeros, além de apresentarem uma melhora das propriedades do material, ainda possuem as vantagens de serem biocompatíveis, biodegradáveis e apresentar baixa toxicicidade, como no caso de blendas de alginato de sódio e fibroína de seda. Membranas confeccionadas a partir desta mistura apresentam grande potencial no desenvolvimento de curativos de alto desempenho, proporcionando condições ótimas de cicatrização. Entretanto, o processo de mistura destes biopolímeros é bastante complexo e resulta na separação de fases, processo que ainda não foi muito explorado. Este trabalho buscou explorar experimentalmente o comportamento do equilíbrio de fases dos sistemas aquosos contendo fibroína de seda e alginato de sódio em diversos valores de pH. Soluções aquosas de fibroína foram previamente preparadas por meio de processo de diálise, e soluções de alginato, por meio de dissolução direta em água. Ambas as soluções eram misturadas em concentrações em que se desejava avaliar o comportamento de fases. Após a separação de fases, a fase líquida sobrenadante era coletada, a fibroína quantificada via espectrofotometria e o alginato, via calcinação. Observou-se que a região monofásica do diagrama de fases é pequena, e a separação de uma segunda fase ocorre em concentrações baixas dos dois biopolímeros. A separação de fases pôde ser descrita como a precipitação da fibroína pela adição de alginato, e a solubilidade da fibroína pôde ser descrita por meio da equação de Cohn. As curvas de solubilidade obtidas não apresentaram diferenças significativas em função do pH. Medidas do potencial Zeta de soluções de alginato e fibroína em diversas faixas de pH não mostraram diferenças significativas quanto à carga superficial das moléculas, o que é compatível com a ausência de influência do pH no equilíbrio de fases. / Polymer blends formed by biopolymers may show an improvement of material properties (compared to the pure biopolymers), and present advantages such as biocompatibility, biodegradability and low toxicity. An interesting biopolymer blend is that formed by sodium alginate and silk fibroin. Membranes prepared with this mixture show great potential in the development of high-performance wound dressing, since it provides optimum healing conditions. However, the mixing process of these two biopolymers is complex and has not been extensively explored. In this work the phase equilibrium behavior of aqueous systems containing silk fibroin and sodium alginate was experimentally studied at different pH values. Fibroin aqueous solutions were previously prepared through dialysis, and alginate solutions were prepared by direct dissolution in water. Both solutions were mixed at the concentration range in which the phase behavior of the system was to be assessed. After phase separation, the supernatant liquid phase was separated, the fibroin was quantified through spectrophotometry. and the alginate was quantified through calcination. The single-phase region of the phase diagram is small, and the separation of a second phase occurs at low concentrations of both biopolymers. The phase separation could be described as the precipitation of fibroin due to the addition of alginate, and the solubility of fibroin was described by the Cohn equation. The solubility was not significantly affected by the pH. The Zeta potential of either alginate or fibroin, measured in solutions of different pH values, did not present any significant difference concerning the surface charges of these macromolecules. This finding agrees with the absence of pH influence upon the phase equilibrium.