L'absorption du CO2 à l'ammoniaque au sein d'une colonne garnie est une technologie prometteuse pour capter le CO2 en postcombustion. La fuite d'NH3 engendrée par la volatilité de ce solvant gêne néanmoins le déploiement de ce procédé. Dans cette étude, la faculté des contacteurs membranaires à permettre des performances d'absorption du CO2 intensifiées et des pertes en NH3 réduites par rapport au procédé conventionnel est évaluée. Pour cela, l'emploi de fibres composites innovantes constituées d'une peau dense assurant un transport sélectif du CO2 vis-à-vis de NH3 a été proposé. Compte tenu des propriétés de ces molécules, aucun matériau ne présentait jusqu'alors de sélectivité de séparation favorable au CO2. Des essais de temps-retards ont permis de révéler 6 matériaux fluorés présentant les propriétés de sélectivités inverses recherchées. Le Teflon AF2400, polymère hautement perméable au CO2, a été choisi pour constituer les fibres creuses composites employées lors d'expériences d'absorption. Leurs performances ont été comparées à celles de contacteurs commerciaux microporeux (Oxyphan) et composites (Oxyplus) pour différentes conditions opératoires. Alors qu'aucune expérience stable n'a pu être achevée avec les contacteurs microporeux du fait de la précipitation de sels d'ammonium, les contacteurs composites ont permis des performances de capture supérieures aux objectifs fixés. La modélisation 2D du transfert de matière a permis de révéler le rôle prépondérant du support microporeux dans les performances d'absorption observées. Enfin, une intensification élevée des performances d'absorption du CO2 et des pertes en NH3 fortement réduites par rapport au procédé conventionnel ont pu être démontrées / Aqueous ammonia as a solvent for post-combustion CO2 capture in a packed column is seen as a promising technology. Nevertheless, ammonia volatility is a considerable drawback for its large scale deployment. In this study, the ability of hollow fiber membrane contactors to significantly improve CO2 mass transfer performances while mitigating ammonia losses when compared to packed column is evaluated. In that purpose, the use of innovating composite fibers made of a thin dense layer selective for CO2 over NH3 is proposed. Up to now, a faster permeation of CO2 compared to NH3 in dense polymers was totally unexpected and to our knowledge unexplored. Time-lag experiments have revealed a series of 6 fluorinated structures showing the desired reverse selectivity properties. Teflon AF2400 has been selected as the dense skin of composite fibers used during absorption experiments. Their performances have been compared, for different operating conditions, to those given by commercial microporous (Oxyphan) and composite (Oxyplus) membrane contactors. Due to ammonium salt precipitation issues, no stable experiment has been achieved using microporous membrane contactors. At the opposite, absorption efficiencies higher than post-combustion capture standards have been reached using composite membrane contactors. 2D mass transfer modeling has revealed the controlling role of the microporous support in the observed absorption performances. Finally, high CO2 mass transfer intensification factor and drastically reduced ammonia losses have been shown

Les colonnes à bulles sont utilisées en minéralurgie et en traitement des eaux pour capturer différents types de particules. Leur capacité d’échange bénéficie aujourd’hui d’un regain d’intérêt pour assurer la production de micro-algues destinées à un usage médicinal, alimentaire, ou énergétique : les concentrations d’oxygène et de dioxyde de carbone peuvent être contrôlées grâce à la considérable aire interfaciale gaz-liquide dans la colonne à bulles. Une étude expérimentale en boucle fermée a été menée pour simuler le passage du gaz dans une succession de colonnes en série. Le modèle théorique associé confirme le rôle critique du diamètre des bulles lors du transfert de masse. Un générateur de micro-bulles (MBG) innovant a été conçu et testé. Le prototype est capable de produire des micro-bulles d’un diamètre moyen Dbubble = 0.252 mm. L’invention a été officiellement déclarée. Le dernier chapitre a pour objet l’amélioration des méthodes de traitement de Fluorescence Induite par Plan Laser (PLIF), qui permettent d’obtenir les coefficients de transfert de masse kl. La première correction présentée prend en compte les variations de l’extinction de la fluorescence due au pH pendant la calibration et a été évaluée sur une mesure de concentration de CO2 dans le sillage d’une bulle en ascension libre dans une colonne d’eau. La seconde correction proposée doit être appliquée quand la distance de la région de mesure où les variations de pH sont observées augmente. La nécessité de cette correction a été illustrée par un cas test dans le sillage d’un nuage de bulles en ascension libre dans une colonne d’eau / Bubble column are involved in many industrial fields ranging from chemical industry to mineral processing. It recently became an industrial stake for the production of micro-algae intended for medicinal use, food or energy: the oxygen and carbon dioxide concentrations can be controlled via the efficient mass transfer induced by the significant gas-liquid interfaciale area into the bubble column. Firstly, experimental closed-loop study has been carried out to simulate the passage of gas in a succession of columns in series. The associated theoretical model confirms the critical importance of the bubble diameter for mass transfer.Therefore, an innovative Micro-Bubble Generator (MBG) has been designed and tested. The prototype is able to produce micro-bubbles of average diameter Dbubble = 0.252 mm. The invention has been officially declared. The last chapter aims at improving data treatment methods for Planar Laser-Induced Fluorescence (PLIF), which enables to obtain experimentally mass transfer coefficient kl through concentration measurements. The first presented correction takes into account variations of the fluorescence extinction due to pH during the calibration step, and has been evaluated on CO2 concentration measurement in the wake of a free rising bubble. The second proposed correction should be applied when the length in the measurement region over which pH variations are observed increases: variations of the extinction coefficient will affect the local incident light intensity and therefore the measurements. The need for this correction has been illustrated on a test case in the wake of a cloud of free rising bubbles

L’étude du transfert de masse turbulent aux interfaces gaz-liquide est d’un grand intérêt dans de nombreuses applications environnementales et industrielles. Bien que ce problème soit étudié depuis de nombreuses années, sa compréhension n’est pas encore suffisante pour la création de modèles de transfert de masse réalistes (de type RANS ou LES sous maille), en particulier en présence d’une phase liquide à rhéologie complexe. Ce travail expérimental a pour but l’étude des aspects fondamentaux du transfert de masse turbulent à une interface plane horizontale entre du dioxyde de carbone gazeux et une phase liquide newtonienne ou non, agitée par une turbulence homogène quasi isotrope. Les milieux liquides non newtoniens étudiés sont des solutions aqueuses d’un polymère dilué à des concentrations variables et aux propriétés viscoélastiques et rhéofluidifiantes. Deux méthodes de mesure optiques permettant l’obtention du champ de vitesse de la phase liquide (SPIV) et de concentration du gaz dissout (I-PLIF) sont couplées tout en maintenant une haute résolution spatiale, afin de déduire les statistiques de vitesse et de concentration couplées dans les premiers millimètres sous la surface. Une nouvelle version de I-PLIF est développée pour les mesures en proche surface. Elle peut également s’appliquer dans différentes études de transfert de masse. La turbulence de fond est générée par un dispositif de grille oscillante. Les mécanismes de production et les caractéristiques de la turbulence sont étudiés. L’importance de la composante oscillante de la turbulence est discutée, et un phénomène d’amplification de l’écoulement moyen est mis en évidence. Les mécanismes du transfert de masse turbulent à l’interface sont finalement observés pour l’eau et une solution de polymère dilué à faible concentration. L’analyse conditionnelle des flux de masse turbulent permet de mettre en évidence les évènements contribuant au transfert de masse et de discuter de leur impact relatif sur le transfert total. / The study of turbulence induced mass transfer at the interface between a gas and a liquid is of great interest in many environmental phenomena and industrial processes. Even though this issue has already been studied for several decades, its understanding is still not good enough to create realistic models (RANS or sub-grid LES), especially when considering a liquid phase with a complex rheology. This experimental work aims at studying fundamental aspects of turbulent mass transfer at a flat interface between carbon dioxide and a Newtonian or non-Newtonian liquid, stirred by homogeneous and quasi isotropic turbulence. Non-Newtonian fluids studied are aqueous solutions of a model polymer, Xanthan gum (XG), at various concentrations, showing viscoelastic and shear-thinning properties. Optical techniques for the acquisition of the liquid phase velocity field (Stereoscopic Particle Image Velocimetry, SPIV) and dissolved gas concentration field (Inhibited Planar Laser Induced Fluorescence, I-PLIF) are for the first time coupled, keeping a high spatial resolution, to access velocity and concentration statistics in the first few millimetres under the interface. A new version of I-PLIF is developed. It is designed to be more efficient for near surface measurements, but its use can be generalized to other single or multiphase mass transfer situations. Bottom shear turbulence in the liquid phase is generated by an oscillating grid apparatus. The mechanisms of turbulence production and the characteristics of oscillating grid turbulence (OGT) are studied. The importance of the oscillatory component of turbulence is discussed. A mean flow enhancement effect upon polymer addition is evidenced. The mechanisms of turbulent mass transfer at a flat interface are finally observed in water and low concentration polymer solutions. A conditional analysis of turbulent mass fluxes allows to distinguish the type of events contributing to mass transfer and discuss their respective impact in water and polymer solutions.

La diminution de la qualité des collectes des papiers récupérés ainsi que l’accumulation de substances dissoutes dans les eaux de procédés affecte l’efficacité des lignes de désencrage industrielles et contamine davantage les effluents liquides. Dans ce contexte, le LGP2 a développé depuis quelques années un procédé innovant de désencrage, la flottation réactive à l’ozone, afin de dégrader chimiquement les polluants dissouts en parallèle de l’élimination de l’encre. Afin de mieux comprendre les mécanismes mis en jeu, des essais de flottation à l’air et à un mélange ozone/oxygène, sur trois contaminants modèles, sélectionnés après une étude bibliographique préalable, ont été réalisés dans un milieu diphasique gaz/liquide, en l’absence de fibres cellulosiques. Les expérimentations ont été conduites sur deux pilotes de laboratoire instrumentés : une colonne à bulles fonctionnant avec de l’air uniquement, pour l’étude du comportement hydrodynamique (taille et distribution de bulles, rétention gazeuse) en présence des contaminants dissouts, et une deuxième colonne à bulles, similaire mais conçue avec des matériaux résistants aux gaz corrosifs, dédiée à l’étude des réactions d’oxydation en présence d’ozone. L’examen du comportement hydrodynamique montre que les conditions de débit de gaz et d’injection retenues conduisent à des tailles de bulles optimales pour une flottation efficace, que ce soit en présence ou absence de contaminants. Ces conditions obtenues avec de l’air ont été transposées en première approximation au système ozone/oxygène. L’étude du transfert de l’ozone et de sa réactivité avec les trois contaminants modèles, à différentes températures et concentrations en ozone, a conduit à la détermination des constantes cinétiques de réaction et a montré que les contaminants étaient, selon leur nature, oxydés ou dépolymérisés. Bien que la DCO des solutions traitées diminue très peu après la flottation réactive à l’ozone, la qualité des effluents est améliorée sur le plan de leur biodégradabilité. / The decrease of the recovered paper collection quality and the accumulation of dissolved substances in process water affect the deinking line efficiency and contaminate more and more the liquid effluents. In this context the LGP2 has developed an innovative deinking process, the ozone reactive flotation, to chemically degrade dissolved pollutants in parallel with ink removal. To better understand the mechanisms involved, air and ozone/oxygen flotation trials have been conducted on three model contaminants selected in a preliminary bibliographic review, in a two-phase gas/liquid system, in the absence of fibers. Experiments have been carried out on two instrumented laboratory pilots: a bubble column operating only with air for the study of the hydrodynamics of the reactor (bubbles size and distribution, gas hold-up) in the presence of dissolved contaminants, and a second one, similar in its conception but built using materials resistant to corrosive gas, dedicated to the study of the oxidation reactions with ozone. The evaluation of the hydrodynamics related to gas flow and injection system selected, studied with air but supposed to be the same with ozone/oxygen gas mixture, shows that the bubble size, with or without contaminants, is optimal for an efficient flotation process. The study of ozone mass transfer and reactivity with the three model contaminants, for several temperatures and ozone concentrations, leads to the calculation of kinetic constants and shows that the contaminants, depending on their nature, have been oxidized or depolymerized. Although the COD of the treated solutions does not decrease a lot after the ozone reactive flotation, the effluent quality has been improved in terms of biodegradability since contaminants are partially degraded.

Operações de produção de petróleo, que utilizam sistemas de bombeamento centrífugo submerso, constantemente encontram a presença de gás livre nos poços, o que pode gerar ou agravar problemas como cavitação e falhas dinâmicas, quando o gás é succionado pela bomba. O separador gravitacional do tipo shroud invertido é uma solução possível para este problema nos casos de operação em poços direcionais de petróleo. O trabalho tem como objetivo apresentar um estudo do diâmetro das bolhas que ocorrem no interior de um separador gravitacional gás-líquido do tipo shroud invertido. A finalidade é o aprimoramento de um modelo fenomenológico do funcionamento deste tipo de separador, aplicado à indústria petrolífera, sendo que o modelo fenomenológico garante total separação de gás, fornecidas determinadas condições. O modelo prevê, através do cálculo da energia cinética turbulenta, o tamanho médio das bolhas carregadas para o seio do líquido por aeração no duto anular. Partindo de estudos anteriores, uma verificação do modelo fenomenológico foi feita utilizando um aparato experimental com misturas bifásicas ar-água e ar-óleo em três diferentes inclinações. O aparato possui dimensões radiais reais de um poço de petróleo offshore. Foi utilizado um sensor 3D ORM para a medição do tamanho médio (sauter) das bolhas arrastadas pelo líquido até a entrada do tubo de produção, em diversas combinações de vazões da mistura água-ar. Esta medição permite o ajuste das correlações que regem o modelo fenomenológico, no que diz respeito às equações dependentes do diâmetro teórico de bolhas arrastadas pela fase líquida. As descobertas provenientes deste estudo foram implementadas em um código computacional que será utilizado pela PETROBRAS, financiadora do projeto, para suas operações de bombeamento. / Oil mining operations powered by centrifugal submersible pumping systems suffer constant setbacks due to the presence of free gas in wells. Decompression in the reservoir liberates this gas in the form of bubbles that, upon reaching the suction end of the pump, cause cavitation and dynamic failures resulting in production and equipment losses. The Inverted-shroud gravitational separator is a possible solution to this problem. This work presents a study on diameters of bubbles that occur inside this separator. The goal is the improvement of the understanding of this kind of separator as well as the enhancement of a previously reported phenomenological model, which ensures total gas separation when the separator is installed in directional wells and under specific operational conditions. Empirically adjusted correlations are used to ensure that all entrained bubbles do not reach the pump. The model was tested for two-phase flows of water-air and oil-air mixtures using three different inclinations. Tests were performed with an experimental apparatus that simulates a pilot-scale well casing with an inverted-shroud separator installed. A 3D ORM particle-size sensor was employed in order to measure the average (sauter) diameter of entrained bubbles that are dragged by the liquid flow towards the end of the production tube. This investigation will be used to improve the reliability of the phenomenological model and reduce its dependency on a theoretical prediction of the bubble size. The findings were incorporated to the final version of an in-house gas separator design software developed at the request of PETROBRAS, the project funder and Inverted-shroud patent holder, for usage on its oil mining operations.

O presente trabalho apresenta um estudo associado à separação de gás para escoamento gás-líquido em um duto anular inclinado. Esse tipo de escoamento e geometria são encontrados em separadores de gás do tipo shroud invertido na indústria de petróleo quando utilizadas técnicas de bombeamento para a exploração de poços. A presença de gás livre a montante da bomba é uma das maiores limitações dos sistemas de bombeamento, por acarretar cavitação e falhas dinâmicas nos equipamentos. O presente estudo tem por objetivo garantir a separação total de gás livre a montante da bomba através da proposição de um separador do tipo shroud invertido em tubulação inclinada para aplicação na exploração de petróleo em poços direcionais. Um estudo experimental com ar e água como fluidos de trabalho a pressão quase atmosférica foi desenvolvido visando a compreensão da fenomenologia do separador shroud invertido. Foram observados escoamentos em duto anular do tipo: bifásico gás-líquido ascendente, monofásico em canal livre e bifásico gás-líquido descendente devido ao fenômeno de aeração; foram coletados também dados de eficiência de separação em função do ângulo de inclinação, vazão do líquido e queda de pressão entre o shroud e a saída do tubo de produção. Encontrou-se uma variável de extrema importância no fenômeno de separação até agora não reportada na literatura: o nível do anular interno do shroud (NAI). Um modelo fenomenológico que prevê a separação total do gás foi desenvolvido a partir da interpretação dos fenômenos físicos observados experimentalmente. Uma correlação inédita para a modelagem do fenômeno de dissipação de energia cinética turbulenta vinculado à separação do gás é proposta. O modelo foi validado qualitativamente com dados da literatura e ajustado com os dados coletados neste trabalho, mostrando boa concordância. / This paper presents a study associated with gas separation in an inclined gas-liquid annular-duct flow. This type of flow and geometry are found in shroud-inverted gas separators applied to petroleum industries when using pumping technique for oil production. High void fraction at the pump suction of is one of the most important limitations of the SCP technique, causing cavitation and dynamics failures in the equipment. The present study aims to provide a solution for the total gas separation through the use of an innovative inclined inverted-shroud separator for directional wells. An experimental study, where air and water at near atmospheric pressure constituted the working fluids, was carried out to understand the phenomenology of the inclined inverted-shroud separator. Different annular-duct flows were observed: upward gas-liquid flow, single-phase open channel flow, downward gas-liquid flow due to the phenomenon of aeration; also new data of separation efficiency were collected as a function of inclination angle, liquid flow rate and pressure drop between the shroud and production pipe outlet. One of the most significant findings is that the liquid level of the inner annular channel (NAI) of the shroud is a very important variable in the phenomenon of separation; so far this was not reported in the literature. Based on the observations, a phenomenological model that predicts total gas separation is proposed. A new correlation for the modeling of the dissipation of turbulent kinetic energy associated with the gas separation is presented. The model was qualitatively compared with available data from the literature and quantitatively adjusted against the new experimental data obtained in this work, and the agreement was quite good.

"The next generation of aluminum alloys will have to operate at temperatures approaching 300°C. Traditional aluminum alloys cannot perform at these temperatures, but aluminum alloys reinforced with fine ceramic particles can. The objective of this research is to develop a process to synthesize Al-TiC composites by the Rotating Impeller Gas-Liquid In-situ method. This method relies on injecting methane into molten aluminum that has been pre-alloyed with titanium. The gas is introduced by means of a rotating impeller into the molten alloy, and under the correct conditions of temperature, gas flow, and rotation speed, it reacts preferentially with titanium to form titanium carbide particles. The design of the apparatus, the multi-physics phenomena underlying the mechanism responsible for particle formation and size control, and the operation window for the process are first elucidated. Then a parametric study that leads to the synthesis of aluminum reinforced with TiC microparticles and nanoparticles is described. Finally, potential technical obstacles that may stand in the way of commercializing the process are discussed and ways to overcome them are proposed. "

A vibração induzida por escoamento é parte intrínseca do transporte de fluidos. Por exemplo, na indústria de petróleo e gás esse fenômeno pode ser encontrado em tubulações, tanto no setor upstream, quando downstream. Essas vibrações são produto das forças geradas pelo escoamento e, portanto, carregam informações sobre sua fenomenologia. No caso de escoamento bifásico em tubo, resultados experimentais indicam forte influência da velocidade da mistura, fração de vazio e padrão de escoamento no comportamento dinâmico da estrutura. Contudo, pouco foi feito na tentativa de obter informações do escoamento a partir da reposta estrutural. Assim, o objetivo do presente estudo é desenvolver métodos para a previsão dos parâmetros do escoamento baseados na resposta de um tubo submetido a escoamento bifásico. Foi conduzido um trabalho experimental da vibração induzida por diversos padrões gás-líquido numa tubulação horizontal (PVC Ø3/4\'\') duplamente engastada, com água e ar como fluidos de trabalho. A partir de uma abordagem analítica, corroborada com resultados experimentais para escoamento monofásico e bifásico, estabelece-se a existência de uma relação, de natureza quadrática, entre a velocidade de atrito e o desvio padrão da aceleração. Dado que a velocidade de atrito é função do fator de atrito bifásico, um método para a sua previsão é desenvolvido. Ele prevê de maneira precisa os dados coletados; todos eles com erro percentual menor do que 30%. O método foi comparado também com dados experimentais e modelos da literatura, mostrando boa concordância. Além disso, apresenta-se uma relação entre a frequência pico da resposta e a fração de vazio homogênea. No fim, são apresentados: (i) um método de identificação de escoamento pistonado, baseado na superposição dos mecanismos de vibração por turbulência e intermitente, com desempenho mínimo de 81.8%; (ii) um método experimental para determinação da velocidade da mistura (J) e fração de vazio homogênea (β). Os melhores resultados são obtidos para os padrões disperso e pistonado, prevendo adequadamente os parâmetros J e β com erro percentual absoluto médio de 24.1% e 20.65%, respectivamente. / Flow-induced vibration is intrinsic to piping problems. For example, in the oil and gas industry the FIV phenomenon can be found in pipe flow both in upstream and downstream applications. The structural vibration response contains information about the flow phenomenology. In the case of two-phase pipe flow, experimental results show a strong influence of mixture velocity, void fraction and flow pattern on pipe structural dynamics. However, efforts to obtain information of the flow from pipe response have been scanty. The goal of this study is to develop two-phase flow parameters predictive methods based on the structural pipe response. An experimental study of flow-induced vibration was carried out for several flow patterns in a clamp-clamp straight pipe (PVC Ø3/4\'\'), with air and water as working fluids. From an analytical approach, a quadratic relationship between shear velocity and standard deviation of acceleration is proposed and validated against the experimental data of single and two-phase flow. Since the shear velocity depends on the friction factor, a method to predict two-phase friction factor is presented. The method predicts accurately our experimental data with a mean absolute error up to 30%. Good agreement was also found when it was compared with some models and experimental data from the literature. Furthermore, an expression to correlate peak frequency and homogeneous void fraction as a function of added mass is offered. Finally, we present: (i) a slug flow identification technique based on the superposition of the turbulence and intermittent flow-induced vibration mechanisms, with performance of 81.8% and (ii) an experimental methodology to estimate mixture velocity (J) and homogeneous void fraction (β). The latter method shows better agreement for dispersed and slug flow-patterns, predicting J and β with a mean absolute error of 24.1% e 20.65%, respectively.

Les réacteurs-échangeurs à plaques (HEX) sont une technologie clé en intensification des procédés. Cependant, la plupart des recherches existantes portant sur ce type d'équipement ont été réalisées dans le cas d’écoulements monophasiques. Pour les réactions gaz-liquide, peu d'études ont été conduites. Cette thèse a pour objectif d’étudier localement le transfert de matière gaz-liquide autour de bulles de Taylor en écoulement dans des canaux millimétriques droits et ondulés par une méthode dite colorimétrique. Ceci constitue une étape préliminaire indispensable avant la mise en œuvre de systèmes réactifs diphasiques. Il a d’abord déterminé si une possible accélération du transfert de matière gaz-liquide pouvait avoir lieu en présence de la réaction chimique utilisée. La deuxième phase de ce travail s’est focalisée sur l'étape de formation des bulles de Taylor dans un microréacteur. Ensuite, l'hydrodynamique gaz-liquide a été caractérisée et les effets des coudes sur le mécanisme de transfert de masse ont été étudiés localement dans un canal carré millimétrique ondulé. Enfin, une comparaison rigoureuse a pu être effectuée entre les différentes géométries de canaux (ondulé et droit). Elle a permis de montrer comment et pourquoi une géométrie ondulé permet d’intensifier le transfert de masse gaz-liquide (notamment en terme d’efficacité de transfert). L’ensemble de ces résultats ont conduit à la formulation une loi d'échelle, exprimée en termes de nombres de Sherwood, de Graetz et de Péclet, capable de décrire l'évolution du transfert de matière gaz-liquide en fonction de la position axiale dans le canal et des conditions opératoires mises en œuvre. / Compact Heat-EXchanger reactors (HEX) are an important part of process intensification technology. However, most of the existed research dealing with such type of equipment has been focused on the application of one-phase reactive flows. For gas-liquid reactions, few investigations have been out carried. This thesis aims at locally studying gas-liquid mass transfer around Taylor bubbles flowing in straight and meandering millimetric channels using a colorimetric method; this is a preliminary step essential before implementing two-phase reactive systems. Firstly, the occurrence of a possible enhancement of the gas-liquid mass transfer by the chemical reaction involved was investigated. Secondly, the gas-liquid mass transfer occurring in Taylor flows right after the bubble formation stage in a microreactor was studied. Thirdly, the gas-liquid hydrodynamics were characterized and the effects of bends on the mass transfer mechanism were locally investigated in a millimetric meandering channel. At last, a rigorous comparison could be made between the meandering and straight channels. It showed how and why the meandering geometry leads to intensify gas-liquid mass transfer. All these findings enabled to formulate a scaling law, expressed in terms of Sherwood, Graetz and Péclet numbers, able to describe the evolution of gas-liquid mass transfer as a function of axial position and operating conditions.

A eletroforese capilar (CE) é uma técnica de separação eficiente, que tem merecido grande atenção nas últimas duas décadas, e que oferece soluções analíticas alternativas ou complementares à cromatografia líquida num número crescente campos de aplicação, incluindo análises de fármacos, compostos biológicos e biogênicos, dentre outros. Entre as vantagens comparativas da técnica figuram separações mais rápidas com pequeno dispêndio de amostras, solução tampão (e solvente orgânico, se usado), baixo custo de operação e manutenção. Todavia, a exigüidade de amostra no capilar tem como reflexo, via de regra, limites de detecção menos favoráveis que os da HPLC, uma limitação significativa na análise de traços, suplantável por técnicas e procedimentos de extração/acumulação prévia dos analitos. Nesta tese concebeu-se e implementou-se a combinação inédita entre a CE e a préconcentração eletroquímica de metais. Novos dispositivos para extração líquido/gás/líquido mediada por membranas microporosas também foram propostos e aplicados à analise de aminas voláteis, sempre utilizando detector de condutância medida sem contato direto com a solução (C4D, contactless capacitively coupled conductivity detection). Primeiramente, sem recorrer à preconcentração, definiu-se condições de análise para 16 aminas (metilamina, dimetilamina, trimetilamina, propilamina, n-butilamina, s-butilamina, t-butilamina, hexilamina, DMAE, etanolamina, dietanolamina, trietanolamina, 1,3-diaminopropano, 1,4-diaminobutano, 1,5-diaminopentano e 1,6-diaminohexano) juntamente com íon amônio, e, para análise de 9 metais (TI++, Cd2+, Pb2+,Cr3+, Zn2+, Ag+, Cu2+, Co2+ e Ni2+). Um método completo para análise de dimetilaminoetanol em formulações cosméticas por CE-C4D foi desenvolvido e validado. Os estudos de extração e pré-concentração líquido/gás/líquido foram realizados utilizando filamento oco de Oxyphan preenchido com solução coletora. Foi construída cela para extração gasosa constituída de recipiente fechado no qual se introduz amostra com analitos voláteis, ou volatilizáveis pela adição de reagente e/ou aquecimento (pervaporação). A bobina coletora de filamento oco preenchido com solução coletora foi montada na parte interna da tampa da cela. Testes realizados com amostras de tecidos de peixe demonstraram o funcionamento do sistema, que poderá ser aperfeiçoado e aplicado, por exemplo, à análise de aminas biogênicas primárias de baixo peso molecular, indicadoras de decomposição de certos alimentos. Criou-se também extrator microvolumétrico em que o filamento de Oxyphan é montado concentricamente no interior de um capilar de sílica fundida, para realização de estudos de extração líquido/gás/líquido em fluxo. Um sistema em fluxo compreendendo válvulas e microbombas foi montado e colocado sob controle de um programa de computador (Labview), que, entre outras funções, controla o deslocamento da solução coletora exposta no filamento oco (13 µL) até o ponto exato da interface em que se dá a injeção no capilar da CE. Pela primeira vez recorreu-se à acumulação eletroquímica (ECPC) de analitos num sistema FIA-CE-C4D - uma configuração baseada inteiramente na eletroquímica -, visando expandir os limites de detecção das determinações e eliminar interferência de matriz por troca de meio. Implementou-se a pré-concentração catódica seguida de redissolução anódica com uma célula eletroquímica especial, em que o capilar da eletroforese é posicionado junto ao eletrodo de trabalho, feito de ouro obtido a partir de CD\'s graváveis. Uma célula microfluídica ECPC-FIA-CE-C4D também foi construída. Tomando íons Cu2+ como sistema modelo, demonstrou-se o aumento do sinal referente aos íons cobre(lI) no eletroferograma para tempos crescentes de acumulação eletroquímica. Para a solução de alto teor salino contendo mistura dos íons Cd(II), Pb(II), Zn(lI) e Cu(II), comprovou-se a eliminação da interferência da matriz por troca de meio antes da redissolução anódica. Os testes iniciais indicam que os novos dispositivos e sistemas propostos nesta tese para uso em conjunto com a CE têm potencialidade para desencadear novas pesquisas, desenvolvimento de métodos e aplicações, sendo passíveis também de miniaturização e automação. / Capillary electrophoresis (CE) is an efficient separation technique that evolved rapidly in the last couple of decades, now offering complementary or alternative analytical solutions to liquid chromatography for an expanding number of application fields including drugs, biological and biogenic compounds. Some comparative advantages of CE are faster separation, very low consumption of buffer solutions and samples (and organic solvents, if any), lower maintenance and operational costs. However, the quantification of a few nanoliters of analyte in a capillary, as a rule, compromises the detection limits attainable by HPLC, a shortcomming in trace analysis, suplantable by extraction/preconcentration of the analytes from the sample. The combination of electrochemical preconcentration (ECPC) with CE is first proposed in this thesis and tested with metal ions. New devices for liquid/gas/liquid extraction based on microporous filaments filled with a collector solution were proposed and applied to the analysis of volatile amines, The detector of choice was the C4D (capacitively coupled contactless conductivity detection) and CE-C4D working conditions were defined for the separation and determination of: i) 16 amines (methylamine, dimethylamine, trimethylamine, propylamine, n-butylamine, s-butylamine, t-butylamine, hexilamine, ethanolamine, diethanolamine, triethanolamine, DMAE, 1,3-diaminopropane, 1,4- diaminobutane, 1,5-diaminopentane and 1,6-diaminohexane) plus ammonium, ii) nine metallic ions (Tl+, Cd2+, Pb2+, Cr3+ Zn2+, Ag+, Cu2+, Co2+ e Ni2+). A complete method of analysis for Dimethyl-amino-ethanol (DMAE) in cosmetic formulations was established and validated. Liquid/gas/liquid extraction studies were based on the use of a polypropylene microporous filment (Oxyphan® ) filled with the collection solution. A closed cell was devised in which an Oxyphan® coil is installed beneath the cap and volatilization of sample components can be promoted by heating (pervaporation) or addition of a reactant. The device was successfully tested with fish samples by the detection of primary low molecular weight biogenic amines, a procedure of special interest in fast checking of fish or other foods for decomposition. A microvolumetric version of the liquid/gas/liquid extractor was created with an Oxyphan® hollow fiber mounted concentrically inside a silica capillary. A flow system comprising the micropumps, solenoid valves and the microextrator was designed, automatically operated under software control (Labview). This FIA-CE system was tested by the extraction/enrichment of volatile amines in the collecting solution (13 µL) followed by accurate displacement to the interface with the CE capillary by the micropumps. Pioneering work with ECPC-FIA-CE-C4D an all-electrochemical system was conducted in this thesis aiming expanded detection limits and matrix effect reduction. An electrochemical cell for the interface with FIA-CE system was built in acrylic using gold electrodes made from gold-sputtered CD-Rs. A microfluidic version of the cell interfaced with the CE capillary was also conceived. The full system was evaluated by using Cu2+ as a model specie; an increase in analytical signal was observed as a function of the cathodic deposition time before stripping. For a mixture of Cd2+, Cu2+, Zn2+ and Pb2+ in a high saline media, elimination of the matrix interference by medium exchange before stripping was demonstrated. Initial favorable evaluations show that the devices and systems proposed in 12 the thesis have the potential to engender further research of methods and applications as well as miniaturization and automation of procedures.