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D. Tech. Chemical, Metallurgical and Materials Engineering / This study provides experimental data and new perspectives on selective precipitation of platinum group metals (PGMs) in the presence of base metals while at the same time reviewing the mass transfer characteristics and models associated with metal sulphides precipitation in liquid-liquid and gas-liquid systems. In this study, the objective was to investigate and validate the concept of selective precipitation of platinum from chloride media using sulphur-bearing liquids or gases.

Packed bed reactors with counter-current, gas-liquid flows have been considered to be applicable in CO2 capture systems for post-combustion processing from fossil-fueled power production units. However, the hydrodynamics within the packing used in these reactors under counter-current flow has not been assessed to provide insight into design and operational parameters that may impact reactor and reaction efficiencies. Hence, experimental testing of a laboratory-scale spherical ball, packed bed with two-phase flow was accomplished and then a meso-scale 3D CFD model was developed to numerically simulate the conditions and outcomes of the experimental tests. Also, the hydrodynamics of two-phase flow in a packed bed with structured packing were simulated using a meso-scale, 3D CFD model and then validated using empirical models. The CFD model successfully characterized the hydrodynamics inside the packing, with a focus on parameters such as the wetted surface areas, gas-liquid interactions, liquid distributions, pressure drops, liquid holdups, film thicknesses and flow regimes. The simulation results clearly demonstrated the development of and changes in liquid distributions, wetted areas and film thicknesses under various gas and liquid flow rates. Gas and liquid interactions were observed to occur at the interface of the gas and liquid through liquid entrainment and droplet formation, and it became more dominant as the Reynolds numbers increased. Liquid film thicknesses in the structured packing were much thinner than in the spherical ball packing, and increased with increasing liquid flow rates. Gas flow rates had no significant effect on film thicknesses. Film flow and trickle flow regimes were found in both the spherical ball and structured packing. A macro-scale, porous model was also developed which was less computationally intensive than the meso-scale, 3D CFD model. The macro-scale model was used to study the spherical ball packing and to modify its closure equations. It was found that the Ergun equation, typically used in the porous model, was not suitable for multi-phase flow. Hence, it was modified by replacing porosity with the actual pore volume within the liquid phase; this modification successfully accounted for liquid holdup which was predicted via a proposed equation.

The Onsager heat of transport for p-tert-butyltoluene was measured, as part of a series of preliminary experiments towards the determination of the importance of temperature gradients on the air-sea flux of carbon dioxide. The results presented in this thesis imply that the temperature gradient is a major contributor to the magnitude of the air-sea flux. The heat of transport has been measured for the p-tert-butyltoluene system by measuring stationary-state pressure changes for known temperature differences on the vapour side of the interface. At the pressure ranges used the number of mean free paths was always outside the Knudsen zone, but the values of Q* were approximately 100 % of the latent heat of vaporisation. Departures from linearity of plots of P against ΔT are attributed to temperature jumps at the surface of the dry upper plate. Both the results taken for p-tert-butyltoluene and the earlier results for water from this laboratory fit to a Type III BET isotherm, where the c parameter is not constant. They also reveal the importance of the temperature gradient in determining the value of the thermal accommodation coefficient, and provide a new method of measuring thermal accommodation coefficients for a variety of surfaces and vapours

Cette thèse est dédiée à l’étude de l’effet de la configuration des agitateurs (pales planes) et la nature du tensioactif sur la dispersion de gaz dans un liquide en vue d’obtenir un produit foisonné. Cette étude est menée à deux échelles pilote et locale. Le premier chapitre est dédié à une étude à l’échelle pilote. Les résultats ont montré qu’à conditions opératoires fixées, lorsque les agitateurs sont collés et décalés, l’aspect distributif de la dispersion de gaz est amélioré. L’aspect dispersif (taille des bulles), en revanche, reste peu sensible à la configuration des agitateurs. Les protéines sériques« WPI » comme agent tensioactif améliore l’efficacité de la rétention de gaz alors que le Tween 20 la réduit et provoque l’augmentation de la taille des bulles. Le deuxième chapitre concerne une approche locale qualitative (observation optique) et quantitative (détermination de capillaire critique). L’étude qualitative a montré que l’ajout d’un angle de décalage modifie l’écoulement du liquide et les bulles suivent la trajectoire imposée par le liquide. Lorsque les protéines WPI est utilisé comme agent tensioactif, sous l’action de la contrainte de cisaillement, les bulles subissent une déformation qui se termine par une rupture par extrémité. Un système couette a permis de déterminer un nombre capillaire critique correspondant à cette rupture. Par contre, en présence du Tween 20, la déformation ne conduit jamais à une rupture par extrémité. Le troisième chapitre de ce travail est dédié à une étude numérique de l’hydrodynamique de l’écoulement. Cette étude a permis de confirmer les résultats obtenus par l’approche qualitative. A titre d’exemple, un décalage entre deux agitateurs collés conduit à la multiplication des zones de vortex, à l’apparition des élongations supplémentaires et d’effet venturi favorables à l’aspect distributif de la dispersion. L’étude numérique montre également que le gradient maximal et moyen de vitesse reste indépendant de la configuration, ce qui explique pourquoi la taille moyenne est indépendante de la configuration. / Flat-blad impellers configuration coupled with tensioactif agents have been used to study gas dispersion in foaming process. The work has been conducted at pilot and local scales. The first chapter is devoted to a study at the pilot scale. The results showed that under a given operating conditions, a shift between two glued successive impellers promotes distributive aspect of the gas dispersion. However the dispersive aspect (bubble size), remains independent of the impellers configuration. The pilot-scale experiments have also shown that the "WPI" enhance foaming efficiency, while, Tween 20 reduces it and increases the size of the bubbles. The second chapter links with a qualitative (optical observation) and quantitative (determination of critical capillary) at local scale. It has been observed that shifted-impellers modify the flow pattern and promotes the distributive aspect of the mixture. When the WPI is used as a surfactant, shear stress induces bubble deformation until a tip-breakup occurs. Using a Couette system, it has been shown that there exist a critical capillary number corresponding to this rupture. However, the deformation does never induced tip-breakup when using Tween 20. The third chapter of this work is devoted to a numerical study of liquid hydrodynamics under different configuration. It appears that the configuration where the impellers are glued and shifted induces the multiplication of the vortex, the appearance of additional elongations and venturi effect. These effects seem to improve the distributive aspect of mixing in agreement with the results obtained previously. The numerical study also shows that the maximum and average shear gradient is independent of the configuration. This result explains why the mean bubble size remains independent of the configuration.

O trabalho apresenta uma investigação sobre a influência da umidade atmosférica no processo de absorção de oxigênio atmosférico por corpo de água através de sua superfície líquida livre. Os experimentos realizados em laboratório consistem na reoxigenação de uma massa de água, contida em um tanque cilíndrico, submetida à agitação mecânica. A atmosfera que reabastece de oxigênio a massa líquida é controlada e os ensaios são conduzidos com vários níveis de umidade do ar, o que provoca diferentes taxas de evaporação. Simultaneamente, determinam-se os coeficientes de reoxigenação, K2 (h-1), em cada experimento. Investiga-se neste trabalho a correlação entre esses dois parâmetros. O processo de reoxigenação é analisado inicialmente com o uso de metodologia clássica baseada em modelos matemáticos tradicionais (possivelmente inadequados). Propõe-se neste trabalho, um modelo original para essa mesma análise. / The influence of the atmospheric humidity on the process of absorption of oxygen by a water body through its free surface is presented herein. Laboratory experiments were run for the reoxygenation of a water mass kept in a cylindrical vessel under mechanical agitation. The quality of the atmospheric air transferring oxygen to water is controlled and the tests are run with several levels of air humidity, what renders different rates of evaporation. The corresponding coefficients of reaeration K2 (h-1) are determined for each experiment. The correlation between these two latter parameters is investigated. The process of reoxygenation is analyzed initially using a classical methodology based on traditional mathematical models (possibly inadequate). An original model for the same analysis is proposed in this work.

[pt] Na indústria do petróleo, a passagem de pigs em dutos tem sido largamente aplicada com diferentes propósitos: limpeza do tubo, inspeção, remoção de líquido e separação de produtos, entre outros. A eficiência e segurança de uma operação com pig demandam que diversos parâmetros operacionais, tais como pressões máximas e mínimas no duto e velocidade de movimentação do pig, sejam bem avaliados durante a etapa de planejamento e mantidos dentro de determinados limites durante o acompanhamento da operação. Tendo como objetivo a obtenção de uma ferramenta eficiente para ajudar no controle e projeto das operações de passagem de pigs, desenvolveu-se um código numérico baseado no método de diferenças finitas para a simulação de escoamentos transientes de dois fluidos, podendo estes ser líquido-líquido, gás-gás ou líquido-gás. Módulos para controle automático das variáveis do processo foram incluídos, visando à previsão do escoamento mediante diferentes estratégias para alcançar uma operação eficiente. Problemas teste foram realizados, validando a metodologia. Por fim, os resultados obtidos com o simulador são comparados com um caso real de esvaziamento de um trecho do oleoduto OSPAR, pertencente à Petrobras, com 30`` de diâmetro e extensão de 60 km. / [en] In the oil industry, pigging operations in pipelines have been largely applied for different purposes: pipe cleaning, inspection, liquid removal and product separation, among others. Pigging operations to be efficient and safe require a number of operational parameters, such as maximum and minimum pressures in the pipeline and pig velocity, to be well evaluated during planning stage and maintained within stipulated limits while the operation accomplishment. With the objective of providing an efficient tool to assist in the controlling and designing of pig operations through pipelines, a numerical code based on a finite difference scheme for a two-fluid transient flow simulation was developed. The model accounts for liquid-liquid, gas-gas and liquid-gas products in the pipeline. Automatic control modules for some process variables were included to permit the flow prediction by means of different strategies to reach an efficient operation. Test problems were performed to validate the methodology. At last, simulation results were compared with an actual liquid displacement operation at a 60 km segment of the 30`` diameter OSPAR pipeline, owned by Petrobras.

Cette thèse porte sur le développement d’un procédé industriel propre constitué par un couplage absorption-distillation, destiné aux traitements d’effluents gazeux chargés par un Composé Organique Volatil (COV). L’absorption est effectuée dans un microabsorbeur à film tombant. La première étape de ce travail consiste à caractériser le transfert de matière dans cet appareil, lors de l’absorption gaz/liquide du Perchloroéthylène (PCE) par le Di(2-EthylHexyl)Adipate (DEHA). Les expériences ont montré la faisabilité et l’intérêt de cette opération dans un micro-contacteur. En effet, les efficacités d’épuration obtenues sont comparables à celles des procédés classiques (jusqu’à 97%) et les quantités de solvant d’absorption utilisées sont très faibles. Une étude paramétrique a révélé une intensification significative du transfert de matière, côté gaz, et un gain en compacité, à la suite de la minimisation de l’épaisseur de la veine de gaz (2mm) et du débit de la phase gazeuse. Cette étude a également montré la limite du microabsorbeur à traiter de grands débits de gaz avec de bonnes efficacités, causée par la faible influence qu’exerce la vitesse du gaz sur le coefficient de transfert de matière. Ce comportement a été expliqué, grâce à des simulations en 2D, par une dispersion importante des profils de concentration indiquant une limitation diffusionnelle. Cette dernière provient essentiellement du régime laminaire lisse et de la petite taille caractérisant ce type de micro-procédé. Pour s’affranchir de cette limitation, la turbulence doit être favorisée dans le gaz. La deuxième étape de ce travail concerne l’extrapolation du microabsorbeur de laboratoire à l’échelle industrielle des PME/PMI, basée sur le concept du numbering-up. A l’issu des calculs, un absorbeur microstructuré efficace (95%), et compact (surface occupée ˜ 0,5m2) a été développé. Pour rentabiliser son fonctionnement, un recyclage par distillation flash du solvant d’absorption a été étudié. Les résultats obtenus ouvrent la voie sur une technique d’épuration prometteuse, qui nécessite néanmoins une validation théorique et expérimentale du couplage absorbeur-distillateur / This project focuses on the development of an industrial process, in which a coupled absorption/distillation unit is developed to treat gaseous effluents contaminated by a Volatile Organic Compound (VOC). Absorption is performed in a falling film microabsorber. The first stage of this work consists in characterizing the mass transfer in this device. The gas/liquid absorption of Perchloroethylene (PCE) by Di (2-EthylHexyl) Adipate (DEHA) is used as test case. Experiments showed the feasibility and the benefit of this separation process operated in a micro-contactor. Indeed, the purification efficiencies obtained are comparable to those of conventional processes (97%). Moreover, the required absorption solvent quantities are very low. A parametric study revealed significant mass transfer intensification on gas side and a gain in compactness due to the minimization of gas cavity thickness (2mm) and gas flowrate. This study also showed the limits of microabsorbers to handle large gas flowrates with good efficiencies, due to a low influence of gas velocity on the mass transfer coefficient. This behaviour was explained, thanks to 2D simulations, by a significant dispersion of concentration profiles, which indicates a diffusion limitation. The latter comes mainly from smooth laminar flow and the small size, a typical characteristic of micro-processes. To overcome this limitation, turbulence should be promoted in the gas. The second stage of this work concerns the microabsorber extrapolation from laboratory scale to industrial SMEs, based on the numbering-up concept. Calculations predict high throughputs with a microstructured absorber of competitive efficiency (95%) and high compactness (area occupied ˜ 0.5 m2). For profitable operation, solvent absorption recycling by a flash distillation is studied. The results lead to a promising treatment technique, which still requires a theoretical and experimental validation of the coupled absorber-distiller unit

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