This thesis presents a multiscale model of an industrial nylon-6 leacher. We develop several models at various spatial scales and implement them together in a simplistic, efficient way to develop an overall leacher model. We solve dynamic transport differential equations using the finite-volume method and method of lines in an in-house-developed FORTRAN program. We use the ODEPACK package of ordinary differential equation (ODE) solvers to solve our system of coupled ODEs. Our multiscale model performs transport, thermodynamic, physical property, and mass-transfer calculations at a finite-volume scale. We introduce two additional scales: a mesoscale, in which we perform computational fluid dynamic (CFD) simulations, and a molecular scale. Our CFD simulations solve for turbulent properties of fluid flowing over a packed bed. We incorporate the turbulent diffusivity of the fluid into our finite-volume leacher model. We perform molecular simulations and use the conductor-like screening model-segment activity coefficient (COSMO-SAC) model to generate solubility predictions of small, cyclic oligomers in water and ε-caprolactam. Additionally, we develop an extension of COSMO-SAC to model polymer species, which we refer to as Polymer-COSMO-SAC, and apply it to solve liquid-liquid equilibrium equations. We present a unique methodology to apply COSMO-based models to polymer species, which shows reasonable results for nylon-6. Because of the computational intensity of our Polymer-COSMO-SAC liquid-liquid equilibrium algorithm, we generate pre-computed tables of equilibrium predictions that we may import into our leacher model. Our integration of multiscale models maximizes efficiency and feasibility with accuracy. We are able to use our multiscale models to estimate necessary parameters, but we need to fit two mass-transfer related parameters to industrial data. We validate our model against the plant data and find average-absolute errors in the final mass percent of ε-caprolactam and cyclic dimer in polymer chips of 25.0% and 54.7%, respectively. Several plant data sets are suspected outliers and we believe an unforeseen equilibrium limitation may cause this discrepancy. If we remove these outlying data sets, we then find average-absolute errors of 7.5% and 19.3% for ε-caprolactam and cyclic dimer, respectively. We then use our validated model to perform application and sensitivity studies to gain critical insight into the leacher's operating conditions. / Master of Science

Made available in DSpace on 2014-12-17T15:01:30Z (GMT). No. of bitstreams: 1 JessicaCSLM_DISSERT.pdf: 2011571 bytes, checksum: 8e087d35d6e4c83d4f7eda24cd8d3e57 (MD5) Previous issue date: 2012-09-21 / Anhydrous ethanol is used in chemical, pharmaceutical and fuel industries. However, current processes for obtaining it involve high cost, high energy demand and use of toxic and pollutant solvents. This problem occurs due to the formation of an azeotropic mixture of ethanol + water, which does not allow the complete separation by conventional methods such as simple distillation. As an alternative to currently used processes, this study proposes the use of ionic liquids as solvents in extractive distillation. These are organic salts which are liquids at low temperatures (under 373,15 K). They exhibit characteristics such as low volatility (almost zero/ low vapor ), thermal stability and low corrosiveness, which make them interesting for applications such as catalysts and as entrainers. In this work, experimental data for the vapor pressure of pure ethanol and water in the pressure range of 20 to 101 kPa were obtained as well as for vapor-liquid equilibrium (VLE) of the system ethanol + water at atmospheric pressure; and equilibrium data of ethanol + water + 2-HDEAA (2- hydroxydiethanolamine acetate) at strategic points in the diagram. The device used for these experiments was the Fischer ebulliometer, together with density measurements to determine phase compositions. The experimental data were consistent with literature data and presented thermodynamic consistency, thus the methodology was properly validated. The results were favorable, with the increase of ethanol concentration in the vapor phase, but the increase was not shown to be pronounced. The predictive model COSMO-SAC (COnductor-like Screening MOdels Segment Activity Coefficient) proposed by Lin & Sandler (2002) was studied for calculations to predict vapor-liquid equilibrium of systems ethanol + water + ionic liquids at atmospheric pressure. This is an alternative for predicting phase equilibrium, especially for substances of recent interest, such as ionic liquids. This is so because no experimental data nor any parameters of functional groups (as in the UNIFAC method) are needed / O etanol anidro tem ampla aplica??o em ind?strias qu?mica, farmac?utica e de combust?veis. No entanto, os processos atuais para a sua obten??o envolvem custo elevado, alta demanda de energia e a utiliza??o de solventes t?xicos e poluentes. Esse problema ocorre devido ? forma??o de aze?tropo na mistura etanol + ?gua, n?o permitindo a separa??o completa por m?todos convencionais tais como destila??o simples. Como uma alternativa aos processos atualmente utilizados, este estudo prop?e a utiliza??o de l?quidos i?nicos como agentes na destila??o extrativa. Trata-se de sais org?nicos l?quidos a baixas temperaturas (abaixo de 373,15 K). Suas caracter?sticas, tais como baixa volatilidade (press?o de vapor muito baixa), estabilidade t?rmica e baixa corrosividade os tornam interessantes para aplica??es como catalisadores e solventes. Neste trabalho, dados experimentais de press?o de vapor de etanol e ?gua puros na faixa de press?o de 20 a 101 kPa, assim como dados de equil?brio l?quido-vapor(ELV) do sistema etanol + ?gua a press?o atmosf?rica, e dados de equil?brio do sistema etanol + ?gua + 2-HDEAA (acetato de 2-hidrodietanolamina) foram obtidos em pontos estrat?gicos do diagrama. O dispositivo usado para esses experimentos foi o ebuliometro de Fischer, juntamente com medidas de densidade para determinar a composi??o das fases. Os dados obtidos apresentaram coer?ncia com dados da literatura e consist?ncia termodin?mica, desta forma, a metodologia foi devidamente validada. Os resultados foram favor?veis, com o aumento da concentra??o de etanol na fase vapor, por?m o aumento n?o demonstrou ser elevado. O modelo preditivo COSMO-SAC (COnductor-like Screening MOdels Segment Activity Coefficient), desenvolvido por Lin e Sandler (2002), foi aplicado para os c?lculos de predi??o de Equil?brio L?quido-Vapor do sistema etanol + ?gua com l?quido i?nico a press?o atmosf?rica. Essa ? uma alternativa para a previs?o do equil?brio de fases, especialmente para subst?ncias de interesse recente, tais como l?quidos i?nicos, uma vez que nem dados experimentais, nem par?metros de grupos funcionais (como no m?todo UNIFAC) s?o necess?rios

[ES] El presente estudio pretende establecer la importancia de la colaboración como un elemento integral para el desarrollo de la Red Chilena de Fab Labs y su vinculación con el ecosistema de innovación local. Esta noción se apoya en un marco teórico que valida la colaboración como un elemento clave al interior de la innovación abierta y su implementación en los espacios de innovación, en este caso específico, los Fab Labs. Junto con ello, surge el concepto de Cosmo-localismo, como un modelo integrador de la colaboración y la innovación, que busca el bienestar de los territorios y sus comunidades. Este se fundamenta en la cultura maker, la cual vincula el diseño abierto con las tecnologías de fabricación digital, para la generación de un nuevo conocimiento, siendo estos distribuidos globalmente. Es aquí donde los Fab Labs juegan un rol fundamental como espacios de articulación, buscando empoderar a sus comunidades mediante el acceso a herramientas, para generar un impacto positivo en lo social, económico y medioambiental. A partir de la importancia de vincular el entorno dentro de la innovación, surge la Quíntuple hélice como un elemento integrador en el proceso de innovación actual, reforzando la importancia del concepto de desarrollo sostenible. Bajo una investigación de enfoque mixto, se analizan los Fab Labs en Chile, caracterizándolos según su ubicación, modelo de trabajo, temáticas y disciplinas. A modo de identificar la vinculación de estos laboratorios con el ecosistema de innovación, se analiza el contexto chileno según el Modelo TE-SER, el cual establece sus características basadas en los roles de cada actor. De la misma forma, se establece para la Red Chilena de Fab Labs y los laboratorios que la componen. Como resultado de esta investigación se propone el diseño de un modelo de colaboración para el desarrollo de la Red Chilena de Fab Labs que promueva su vinculación con el ecosistema de innovación local para alcanzar el desarrollo sostenible de sus territorios, apoyándose en los principios del diseño abierto y la cultura maker. Los hallazgos identificados se basan en la importancia del ODS 17, "Alianza para cumplir todos los objetivos", al interior de la comunidad Fab Lab. Y también en el perfilamiento de los Fab Labs chilenos, el cual puede delinear los roles y actividades de los laboratorios al interior de la red y del ecosistema de innovación local. Además, a partir del modelo propuesto, se identifican actores claves para articular instancias de colaboración de forma eficiente, lo que desarrolla una estrategia de implementación basada en el Cosmo-localismo, promoviendo la Quíntuple hélice. / [CA] Aquest estudi pretén establir la importància de la col·laboració com un element integral per al desenvolupament de la Xarxa Xilena de Fab Labs i la vinculació amb l'ecosistema d'innovació local. Aquesta noció es recolza en un marc teòric que valida la col·laboració com un element clau a l'interior de la innovació oberta i la seva implementació als espais d'innovació, en aquest cas específic, els Fab Labs. Juntament amb això, sorgeix el concepte de Cosmo- localisme, com un model integrador de la col·laboració i la innovació, que cerca el benestar dels territoris i les seves comunitats. Aquest es fonamenta en la cultura maker, la qual vincula el disseny obert amb les tecnologies de fabricació digital, per a la generació d'un nou coneixement, i aquests es distribueixen globalment. És aquí on els Fab Labs juguen un rol fonamental com a espais d'articulació, buscant empoderar les seves comunitats mitjançant l'accés a eines, per generar un impacte positiu en allò social, econòmic i mediambiental. A partir de la importància de vincular l'entorn dins de la innovació, la Quíntuple hèlix sorgeix com un element integrador en el procés d'innovació actual, reforçant la importància del concepte de desenvolupament sostenible. Sota una investigació d'enfocament mixt, s'analitzen els Fab Labs a Xile, caracteritzant-los segons la ubicació, el model de treball, les temàtiques i les disciplines. Per identificar la vinculació d'aquests laboratoris amb l'ecosistema d'innovació, s'analitza el context xilè segons el Model TE-SER, el qual estableix les seves característiques basades en els rols de cada actor. De la mateixa manera, s'estableix per a la Xarxa Xilena de Fab Labs i els laboratoris que la componen. Com a resultat d'aquesta investigació es proposa el disseny d'un model de col·laboració per al desenvolupament de la Xarxa Xilena de Fab Labs que promogui la seva vinculació amb l'ecosistema d'innovació local per assolir el desenvolupament sostenible dels territoris, recolzant-se en els principis del disseny obert i la cultura maker. Les troballes identificades es basen en la importància de l'ODS 17, "Aliança per complir tots els objectius", a l'interior de la comunitat Fab Lab. I també en el perfilament dels Fab Labs xilens, el qual pot delinear els rols i activitats dels laboratoris dins de la xarxa i de l'ecosistema d'innovació local. A més, a partir del model proposat, s'identifiquen actors claus per articular instàncies de col·laboració de forma eficient, cosa que desenvolupa una estratègia d'implementació basada en el Cosmo-localisme, promovent la Quíntuple hèlix. / [EN] This study aims to establish the importance of collaboration as an integral element for the development of the Chilean Network of Fab Labs and its link with the local innovation ecosystem. This notion is supported by a theoretical framework that validates collaboration as a key element within open innovation and its implementation in innovation spaces, in this specific case, the Fab Labs. Along with this, the concept of Cosmo- localism, as an integrating model of collaboration and innovation, which seeks the well-being of the territories and their communities. This is based on the maker culture, which links open design with digital manufacturing technologies, for the generation of new knowledge, which is distributed globally. This is where the Fab Labs play a fundamental role as spaces for articulation, seeking to empower their communities through access to tools, to generate a positive social, economic and environmental impact. Based on the importance of linking the environment within innovation, the Quintuple Helix emerges as an integrating element in the current innovation process, reinforcing the importance of the concept of sustainable development. Under a mixed approach research, the Fab Labs in Chile are analyzed, characterizing them according to their location, work model, themes and disciplines. In order to identify the link between these laboratories and the innovation ecosystem, the Chilean context is analyzed according to the TE-SER Model, which establishes its characteristics based on the roles of each actor. In the same way, it is established for the Chilean Network of Fab Labs and the laboratories that comprise it. As a result of this research, the design of a collaborative model is proposed for the development of the Chilean Network of Fab Labs that promotes its link with the local innovation ecosystem to achieve the sustainable development of its territories, based on the principles of open design. and the maker culture. The identified findings are based on the importance of SDG 17, "Alliance to meet all objectives", within the Fab Lab community. And also, on the profiling of Chilean Fab Labs, which can outline the roles and activities of the Fab Labs. laboratories within the network and the local innovation ecosystem. In addition, based on the proposed model, key actors are identified to efficiently articulate instances of collaboration, which develops an implementation strategy based on Cosmo-localism, promoting the Fivefold Helix. / Valenzuela Zubiaur, MDP. (2022). Contribución de la Red Chilena de Fab Labs al ecosistema de innovación local para alcanzar el desarrollo sostenible [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/183278 / TESIS

Relatively little is known of European artists who worked for short periods of time in the American Colonies during the eighteenth century. Perhaps Cosmo Alexander was typical of other artists who came to America seeking greater opportunity than in their homeland, only to leave several years later, perhaps disillusioned and no wealthier. Artists who are better known stayed in America long enough to build up clientele in a broad area and produced enough works to have many survive long enough to be documented by later sources. As the subjects in many of Alexander's portraits show, there was a large prosperous middle-class patronage of the art of portraiture. Considering the social conventions of the time, personal references and letters of recommendation would have facilitated travel and introduction to prospective clients. The emphasis of this research is the patronage which Cosmo Alexander found in the American Colonies as evidenced by portraits executed between 1765 and 1771. Family connections, Scottish ancestry and communities having large Scottish populations have played a part in determining probable routes. In 1961 Gavin L. M. Goodfellow submitted a thesis to Oberlin College on Cosmo Alexander. This was the first and (to date) the only extensive monograph on the artist. The thesis was general in nature, covering Alexander's life and listing all paintings known at that time, only sixteen of which were believed to have been painted in America. Because he dealt in detail with Alexander's total biography and stylistic characteristics, only one chapter was devoted to American works. Since Goodfellow's research the number of American paintings signed by or attributed to Alexander has increased from sixteen to twenty-six. With greater documentary evidence available, patterns can be established and generalizations made which possibly are typical of other artists in similar circumstances.

A grande dificuldade na simulação de processos envolvendo substâncias naturais é o reduzido número de propriedades termo físicas e dados experimentais disponível na literatura. Devido à diversidade e complexidade das moléculas presentes, o estudo do processamento de compostos naturais ainda é pequeno. Neste trabalho, são investigados modelos para predição de tais propriedades termodinâmicas, fundamentais à modelagem e simulação do processo de destilação em batelada de óleos essenciais. Um método de contribuição de grupos é utilizado para predição da pressão de vapor de substâncias puras (CSGC-PVR), quando dados experimentais não são disponíveis. Em relação ao cálculo do coeficiente de atividade, um modelo totalmente preditivo baseado em química quântica computacional é utilizado (COSMO-SAC). De modo geral, este trabalho tem como objetivo a aplicação de propriedades termodinâmicas preditas em um modelo dinâmico, capaz de descrever o processo de retificação através da destilação em batelada. As simulações foram realizadas no simulador orientado a equações EMSO, a fim de demonstrar a viabilidade do método. Os óleos essenciais de Eucalyptus globulus Labill, Eucalyptus citriodora Hook e Cymbopogon winterianus Jowitt foram selecionados devido ao potencial econômico de suas frações. Inicialmente, um conjunto de dados experimentais é comparado às simulações para validação do método. Em um segundo momento, as simulações são realizadas para correlacionar as condições operacionais e cortes de destilado para as misturas dadas. Os perfis de composição e a determinação dos cortes majoritários são apresentados. Duas alternativas são avaliadas para obtenção de maior pureza nos cortes; o uso de bateladas de reciclo e o controle da razão de refluxo através de uma ação proporcional. A influência de diferentes configurações de coluna também é avaliada, variando o número de estágios teóricos, regime de refluxo e acúmulo de coluna. Os métodos utilizados se mostram capazes de predizer o comportamento do processo de fracionamento e podem ser aplicados a um grande número de óleos essenciais. / The great obstacle in simulating processes involving natural products is the small number of thermo-physical properties and experimental data available in the literature. Due to the diversity and complexity of these molecules, studies concerning essential oils processing is still limited. In this work, thermodynamic models are investigated in order to predict such properties, which are requisites to the modelling and simulation of the essential oil batch distillation process. In this work a group contribution method is used to predict the vapor pressure (CSGC-PVR) when experimental data was unavailable. Regarding the activity coefficients, a fully predictive model based on quantum calculations (COSMO-SAC) is used. Moreover, this work also aims the use of those predicted properties in a dynamic model, capable of describing the fractionation process by batch distillation. The simulations were performed in the equation-oriented simulator EMSO, in order to demonstrate the feasibility of the method. Oils of Eucalyptus globulus Labill, Eucalyptus citriodora Hook and Cymbopogon winterianus Jowitt were selected due to their high production and economic potential of its fractions. Initially, a set of experimental data is compared to the simulations in order to validate the method. Then, simulations are performed to relate operational conditions and distillate cuts for the given mixtures. The distillate composition profiles and the determination of the major cuts are presented. Two alternatives are evaluated in order to obtain cuts of higher purity; the use of a recycle batch and a reflux ratio proportional control based on the distillate composition. The influence of different column configurations is also evaluated, varying its number of theoretical stages, reflux ratio regime and column holdup. The methods used are shown able to predict a reasonable behavior for the fractionation process of the essential oils tested and the method can be extended to most of the essential oils.

Because of the growth in income per capita as a consequent to the growth of global economy, skin care and cosmetic products have changed from luxury items to daily essentials. Together with the human nature of pursuing attractive appearance, factors such as decrease in the level of average age of cosmetic consumers, the increase of frequency of using cosmetic products, strong demand for high end skin care products with medical effects, and government support in developing cosmetic manufacturing as a key industry, suggest that the cosmetic market still has a significant growth potential. In addition, the recent popularity of ¡§cosmo-ceutical products¡¨ is pushing a number of major local corporations to enter the cosmetic market with biotech innovations. Because of the ease of transforming from chemical-related product manufacturing to cosmetic manufacturing, the local cosmetic industry is now saturated by small to medium-sized manufacturers. However, the local manufacturers are faced with the challenges of lack of GMP related legislation system for the cosmetics industry, shortage of financial resources, insignificant company size, and local R&D still awaits effective improvement. Therefore, it impossible for local companies to compete with the international cosmetics corporate giants. This paper will discuss the example of Taiwan Salt¡¦s successful transformation to a cosmetics manufacturer with collagen products. The example will be followed by analysis on the cosmetics industry in Taiwan and the competitiveness of global cosmetics companies such as P&G, L¡¦Oreal, Estee Lauder, and Shiseido. Selected companies will be analyzed for comparing their operational strategies. The findings will be further elaborated into the discussion of the current condition and demands in the local market of skin care product with whitening effect. The research suggested that the companies under study attempt to increase their competitiveness through product diversification and a focused operational strategy. Taiwan Salt for example started with specialized salt-related skin care products, and later on diversified the product lines to include collagen-related products. On the other hand, S-company capitalized on the unique demand for whitening products in the Asian market by orienting the product innovations with whitening and freckle-control effects. The company is faced with major threats of potential leak of production knowledge and counterfeit products. Due to the significant reduction of tariff, imported cosmetics from Europe and North America are increasing popular in the local market. Under the joint impact of decreased effectiveness of the traditional distribution channels, and change in consumer preference, brand diversification and distribution through multiple channels will be the future trends for survival. To succeed in the cosmetics industry, local companies must be dedicated to establishing new brands and promoting the brand recognition, and innovating new formula (i.e. skin care products with Chinese herbal medicine and natural herbal essences). In turn, to constitute a constructive persuasion for profitability in this industry, government would have to establish a GMP legislation system specialized for cosmetics manufacturing to improve the competitiveness of the local companies.

A grande dificuldade na simulação de processos envolvendo substâncias naturais é o reduzido número de propriedades termo físicas e dados experimentais disponível na literatura. Devido à diversidade e complexidade das moléculas presentes, o estudo do processamento de compostos naturais ainda é pequeno. Neste trabalho, são investigados modelos para predição de tais propriedades termodinâmicas, fundamentais à modelagem e simulação do processo de destilação em batelada de óleos essenciais. Um método de contribuição de grupos é utilizado para predição da pressão de vapor de substâncias puras (CSGC-PVR), quando dados experimentais não são disponíveis. Em relação ao cálculo do coeficiente de atividade, um modelo totalmente preditivo baseado em química quântica computacional é utilizado (COSMO-SAC). De modo geral, este trabalho tem como objetivo a aplicação de propriedades termodinâmicas preditas em um modelo dinâmico, capaz de descrever o processo de retificação através da destilação em batelada. As simulações foram realizadas no simulador orientado a equações EMSO, a fim de demonstrar a viabilidade do método. Os óleos essenciais de Eucalyptus globulus Labill, Eucalyptus citriodora Hook e Cymbopogon winterianus Jowitt foram selecionados devido ao potencial econômico de suas frações. Inicialmente, um conjunto de dados experimentais é comparado às simulações para validação do método. Em um segundo momento, as simulações são realizadas para correlacionar as condições operacionais e cortes de destilado para as misturas dadas. Os perfis de composição e a determinação dos cortes majoritários são apresentados. Duas alternativas são avaliadas para obtenção de maior pureza nos cortes; o uso de bateladas de reciclo e o controle da razão de refluxo através de uma ação proporcional. A influência de diferentes configurações de coluna também é avaliada, variando o número de estágios teóricos, regime de refluxo e acúmulo de coluna. Os métodos utilizados se mostram capazes de predizer o comportamento do processo de fracionamento e podem ser aplicados a um grande número de óleos essenciais. / The great obstacle in simulating processes involving natural products is the small number of thermo-physical properties and experimental data available in the literature. Due to the diversity and complexity of these molecules, studies concerning essential oils processing is still limited. In this work, thermodynamic models are investigated in order to predict such properties, which are requisites to the modelling and simulation of the essential oil batch distillation process. In this work a group contribution method is used to predict the vapor pressure (CSGC-PVR) when experimental data was unavailable. Regarding the activity coefficients, a fully predictive model based on quantum calculations (COSMO-SAC) is used. Moreover, this work also aims the use of those predicted properties in a dynamic model, capable of describing the fractionation process by batch distillation. The simulations were performed in the equation-oriented simulator EMSO, in order to demonstrate the feasibility of the method. Oils of Eucalyptus globulus Labill, Eucalyptus citriodora Hook and Cymbopogon winterianus Jowitt were selected due to their high production and economic potential of its fractions. Initially, a set of experimental data is compared to the simulations in order to validate the method. Then, simulations are performed to relate operational conditions and distillate cuts for the given mixtures. The distillate composition profiles and the determination of the major cuts are presented. Two alternatives are evaluated in order to obtain cuts of higher purity; the use of a recycle batch and a reflux ratio proportional control based on the distillate composition. The influence of different column configurations is also evaluated, varying its number of theoretical stages, reflux ratio regime and column holdup. The methods used are shown able to predict a reasonable behavior for the fractionation process of the essential oils tested and the method can be extended to most of the essential oils.

A grande dificuldade na simulação de processos envolvendo substâncias naturais é o reduzido número de propriedades termo físicas e dados experimentais disponível na literatura. Devido à diversidade e complexidade das moléculas presentes, o estudo do processamento de compostos naturais ainda é pequeno. Neste trabalho, são investigados modelos para predição de tais propriedades termodinâmicas, fundamentais à modelagem e simulação do processo de destilação em batelada de óleos essenciais. Um método de contribuição de grupos é utilizado para predição da pressão de vapor de substâncias puras (CSGC-PVR), quando dados experimentais não são disponíveis. Em relação ao cálculo do coeficiente de atividade, um modelo totalmente preditivo baseado em química quântica computacional é utilizado (COSMO-SAC). De modo geral, este trabalho tem como objetivo a aplicação de propriedades termodinâmicas preditas em um modelo dinâmico, capaz de descrever o processo de retificação através da destilação em batelada. As simulações foram realizadas no simulador orientado a equações EMSO, a fim de demonstrar a viabilidade do método. Os óleos essenciais de Eucalyptus globulus Labill, Eucalyptus citriodora Hook e Cymbopogon winterianus Jowitt foram selecionados devido ao potencial econômico de suas frações. Inicialmente, um conjunto de dados experimentais é comparado às simulações para validação do método. Em um segundo momento, as simulações são realizadas para correlacionar as condições operacionais e cortes de destilado para as misturas dadas. Os perfis de composição e a determinação dos cortes majoritários são apresentados. Duas alternativas são avaliadas para obtenção de maior pureza nos cortes; o uso de bateladas de reciclo e o controle da razão de refluxo através de uma ação proporcional. A influência de diferentes configurações de coluna também é avaliada, variando o número de estágios teóricos, regime de refluxo e acúmulo de coluna. Os métodos utilizados se mostram capazes de predizer o comportamento do processo de fracionamento e podem ser aplicados a um grande número de óleos essenciais. / The great obstacle in simulating processes involving natural products is the small number of thermo-physical properties and experimental data available in the literature. Due to the diversity and complexity of these molecules, studies concerning essential oils processing is still limited. In this work, thermodynamic models are investigated in order to predict such properties, which are requisites to the modelling and simulation of the essential oil batch distillation process. In this work a group contribution method is used to predict the vapor pressure (CSGC-PVR) when experimental data was unavailable. Regarding the activity coefficients, a fully predictive model based on quantum calculations (COSMO-SAC) is used. Moreover, this work also aims the use of those predicted properties in a dynamic model, capable of describing the fractionation process by batch distillation. The simulations were performed in the equation-oriented simulator EMSO, in order to demonstrate the feasibility of the method. Oils of Eucalyptus globulus Labill, Eucalyptus citriodora Hook and Cymbopogon winterianus Jowitt were selected due to their high production and economic potential of its fractions. Initially, a set of experimental data is compared to the simulations in order to validate the method. Then, simulations are performed to relate operational conditions and distillate cuts for the given mixtures. The distillate composition profiles and the determination of the major cuts are presented. Two alternatives are evaluated in order to obtain cuts of higher purity; the use of a recycle batch and a reflux ratio proportional control based on the distillate composition. The influence of different column configurations is also evaluated, varying its number of theoretical stages, reflux ratio regime and column holdup. The methods used are shown able to predict a reasonable behavior for the fractionation process of the essential oils tested and the method can be extended to most of the essential oils.

The purpose of this research is to understand the senses of the sound practice called “música propia” (own music) in the ontology of Misak amerindian collective, that inhabits the southwest of Colombia, through an ethnography. The central concerns were triggered during a dialogic relationship in a participant observation that was modulated by the visual and auditory perceptions. These are the main two points: what do the Misaks call “música propia”, and what do they mean with the frequent claim that “música propia” differs from the "chirimía". The latter consists of a type of musical ensemble that has been associated with festive and catholic practices which manifests itself in different variations, common near the Misak territory and in other regions of the country. The sonority of the “música propia” comes from the mixing of two flutes timbres and two or more drums, whose sounds refer to the presence of non-human alterities performed in public and ritualized events within what Misaks call the “Ciclo de Vida” (Life Cycle). Drawing from performance studies, and on the discussion of epistemologies of sound in ethnomusicology and anthropology of music (Seeger, Feld, Bastos), I propose that the idea of cosmo-sonic (Stein) is a possibility to understand the música propia. Sonoro-performatic categories, socio-cosmological conceptions and the ideal principles of being Misak are all articulated within the Misak’s cosmo-sonic. In this sense, the Misak cosmo-sonic is a sonic ontology that enters cosmopolitical scene when disputing with other worlds its existence. One of these worlds is in the process of patrimonialization of the type of ensemble of “chirimía caucana” that is underway and intendes to include in it the música propia. Here I interpret this attempt of patrimonialization as a state’s mechanism of simplification supported by global policies that tries to incorporate the música propia within a standardized logics. It is a hegemonic form of the ontology of modernity that is not detached from the coloniality of power, and which is revealed in the effects of the interactions of subjects. Faced with this process, some Misak musicians have reacted and, based on the field of cosmopolitics, these reactions are taken in here as an indicator of an ontological conflict. / El objetivo de esta investigación es, mediante una etnografía, comprender los sentidos de la práctica sonora de la “música propia” en la ontología del colectivo amerindio misak, que habita en el sudoeste de Colombia. Las inquietudes centrales fueron provocadas durante la relación dialógica en la observación participante, modulada por lo visual y lo auditivo, concretándose en las dos siguientes: qué es lo que los misak llaman música propia y a qué se refiere el frecuente esclarecimiento de que la música propia se diferencia de la “chirimía”. Esta última consiste en un tipo de conjunto musical que ha estado relacionado con prácticas festivas y católicas, y que se manifiesta en diferentes variaciones, comunes en las proximidades del territorio misak y en otras regiones del país. La sonoridad de la música propia surge del trenzado tímbrico de dos flautas y dos o más tambores, cuyos sonidos remiten a la presencia de alteridades no humanas performadas en eventos públicos y ritualizados dentro de lo que los misak llaman el Ciclo de Vida. Basado en los estudios de performance, y en la discusión sobre epistemologías sonoras en la etnomusicología y en la antropología de la música (Seeger, Feld, Bastos) planteo que la idea de cosmosónica (Stein) es una posibilidad de entender la música propia. En la cosmosónica misak se articulan categorías sonoro-performáticas, las concepciones sociocosmológicas y los principios ideales del ser misak. En este sentido, la cosmosónica misak es una ontología sonora que entra en escena cosmopolítica (De la Cadena, Blaser) al disputar con otros mundos su existencia. Uno de estos mundos es el proceso de patrimonialización del conjunto de chirimía caucana que está en curso y pretende incluir en él a la música propia. Aquí interpreto esta tentativa de patrimonialización como un mecanismo de simplificación del estado apoyado en políticas globales, que intenta incorporar a la música propia dentro de unas lógicas estandarizadas. Se trata de una forma hegemónica de la ontología de la modernidad que no se desliga de la colonialidad del poder, y que se revela en los efectos de las interacciones de los sujetos. Frente a este proceso, las reacciones por parte de algunos músicos misak se revelan en el campo de la cosmopolítica como un conflicto ontológico.

Os Mbyá-Guarani são um subgrupo indígena de fala Guarani, pertencente à família lingüística Tupi-Guarani. Estima-se que cerca de 5.000 pessoas da etnia Mbyá vivam entre o Sul e o Sudeste brasileiro. As crianças indígenas Mbyá-Guarani e as performances musicais e lúdicas que as envolvem cotidianamente são o tema central desta tese desenvolvida a partir de uma etnografia norteada pela Etnomusicologia, em uma aldeia Mbyá-Guarani, no estado do Rio Grande do Sul, Brasil. Neste estudo reflito sobre o protagonismo das crianças Mbyá como agentes sociais co-responsáveis pela construção do modo de ser Mbyá-Guarani e problematizo o estudo da música nos moldes ocidentais, no sentido de descrever etnograficamente categorias êmicas Mbyá relacionadas ao âmbito sonoro, cuja centralidade na sociocosmologia Mbyá indico pelo termo "cosmo-sônico". A partir da análise músico-performática, textual e músicoestrutural de três âmbitos de performance musical de que as crianças participam - as apresentações dos mboraí (cantos sagrados) pelos grupos de cantos e danças tradicionais Guarani, as gravações dos mboraí em diversos CDs e as performances cotidianas dos kyringüé mboraí (cantos das crianças) -, apresento os significados que os Mbyá compartilham e negociam sobre estas performances, sobre ser criança e sobre sua musicalidade. A análise destes cenários indica seu vínculo a uma outra esfera performático-musical, às rezas xamânicas, assim como aos processos de construção da pessoa, da etnia e do território. Interpretei que a agentividade (agency) entre as kyringüé se expressa, por um lado, no âmbito ontológico. A concepção de uma criança é vista como um sinal de satisfação das divindades na relação com os humanos e ao mesmo tempo propulsora desta relação; os adultos, ao se tornarem mais alegres e sábios no convívio com as crianças, ganham força para criar cantos e cantar, no caminho de se tornarem mais próximos às divindades. Por outro, no âmbito da cosmo-sônica Mbyá, a performance cantada das crianças, variavelmente conforme o âmbito de performance musical em que se realiza, desencadeia emoções nos humanos, colaborando na constituição de caminhos de comunicação destes com as divindades e na perpetuação da vida na Terra; media a relação dos Mbyá com os não-indígenas; faz circular capacidades e notícias entre os Mbyá de diferentes aldeias; ou ainda media as relações afetivas, de cuidado e de diálogo das kyringüé entre si e com seus afins adultos. / The Mbyá-Guarani are an indigenous subgroup of Guarani speech that belongs to the Tupi-Guarani linguistic family. It is estimated that nearly 5.000 people of the Mbyá ethnical group live between the South and South-east Brazil. The Mbyá-Guarani indigenous children and the music and play performances that involve them in their daily life are the central theme of this work, developed from one oriented by a ethnomusicological ethnography, in a Mbyá-Guarani village, in the state of Rio Grande do Sul, Brazil. In this study I reflect about the role of Mbyá children as social agents, co-responsible for the construction of the way of being Mbyá-Guarani, and I consider the problem of the study of the music in the western ways, in the sense of to describe ethnographically emics Mbyá categories related to the sound ambit, which centrality in the Mbyá socio-cosmology I refer by the term "cosmo-sonic". Beginning from performing-musical, textual and structural-musical analysis of three ambits of music performance in which participate the children - presentations of the mboraí (sacred songs) by the Guarani groups of traditional songs and dances, the records in CD of mboraí, and the daily performances of kyringüé mboraí (children's songs), I present the meaning that the Mbyá share and negotiate about these performances, about being a child and about their musicality. The analysis of these settings points to their vinculum to another performing-musical context, of the shamanic prayers, so as to the construction of the person, the ethnical group and the territory. I interpreted that the agency between the kyringüé expresses itself, by one side, in the ontological domain. The conception of a child is seen as a sign of satisfaction of the divinities in face of the human beings and, at the same time, as stimulating to this relationship; so that the adults, becoming more happy and wise in the life sharing with the children, gain force to create songs and to sing, in the way to become more close to the divinities. On the other side, in the ambit of Mbyá cosmo-sonic, the singing performance of children, variously, in accord of the domain of musical performance in which it happens, it provokes emotions in the humans, collaborating to the constitution of ways of communication between humans and divinities and to the perpetuation of life on Earth; makes the mediation between the Mbyá with the not-indigenous people; makes circulate capacities and news between the Mbyá of different villages; or still mediates de affective relations, the care, and the dialog of the children to each other and to the related adults.