The present work had as objective to study the hydration process of grains and its possible enhancement using the ultrasound technology. For that, it was studied the hydration kinetics of different grains (Andean lupin, Adzuki beans, sorghum grains and corn kernels) correlating the morphology with mathematical models and the mass transfer mechanisms. Moreover, the effect of the soaking water temperature and the grain initial moisture content were studied to complement the description of this process. The ultrasound application was studied for improving the hydration process, describing the possible mechanisms (direct and indirect effects) that improve the mass transfer process. Therefore, it was established the way by how water enters in the studied grains, demonstrating that the water transfer into the grains is a complex phenomenon and takes place not only due to diffusional mechanisms, but also by capillarity. In addition, suitable mathematical models were proposed and used to explain the processes, describing their parameters according to the grains morphology and the mass transfer mechanisms. Further, it was determined how ultrasound enhances the mass transfer and in which conditions the direct (inertial flow and sponge effect) and the indirect effects (micro channels formation by acoustic cavitation) take place in the process, maximizing the effect of this technology. Finally, it was demonstrated that the ultrasound technology enhanced the hydration process for corn kernels, reducing significantly the process time in approximately 35 %, without modifying the thermal, structural and rheological properties of their starch. In conclusion, the present work improved the description of the grain hydration phenomenon and proved that the ultrasound technology can be used to enhance this process without changing its main industrial component. It is highlighted that the obtained results are thus high desirable for both the industrial and academic point of view. / O presente trabalho teve como objetivo estudar o processo de hidratação de grãos e sua possível melhora usando a tecnologia do ultrassom. Estudou-se a cinética de hidratação de diferentes grãos (tremoço andino, feijão Adzuki, grãos de sorgo e grãos de milho) correlacionando a morfologia com modelos matemáticos e os mecanismos de transferência de massa. Também foi estudado o efeito da temperatura e o conteúdo de umidade inicial do grão para complementar a descrição deste processo. Estudou-se a aplicação do ultrassom no processo de hidratação descrevendo-se os possíveis mecanismos (efeito diretos e indiretos) que melhoram a transferência de massa. Como resultado, foi estabelecida a forma como a água entra nos grãos estudados, demostrando que a transferência de água dentro dos grãos é um fenômeno complexo e que acontece por difusão e capilaridade. Foram propostos e utilizados modelos matemáticos apropriados para explicar os processos, descrevendo os parâmetros de acordo com a morfologia dos grãos e os mecanismos de transferência de massa. Ainda, determinou-se como o ultrassom melhora a transferência de massa e em que condições do processo acontecem os efeitos diretos (fluxo inercial e efeito esponja) e efeitos indiretos (formação de micro canais pela cavitação acústica), maximizando o efeito dessa tecnologia. Finalmente, demonstrou-se que a tecnologia do ultrassom melhora o processo de hidratação de grãos de milho, diminuindo significativamente o tempo do processo em cerca de 35 % sem alterar as propriedades térmicas, reológicas e estruturais do seu amido. Como conclusão, o presente trabalho melhorou a descrição de como os grãos são hidratados, demonstrando que o ultrassom pode ser usado para melhorar o processo de hidratação de grãos sem alterar os seus principais produtos industriais. Ressalta-se que os resultados obtidos são desejáveis tanto do ponto de vista acadêmico quanto industrial.

La lyophilisation est le procédé de choix dans l'industrie pharmaceutique pour la stabilisation de produits thermosensibles tels que les vaccins. Cependant, en raison du pré-conditionnement du produit dans des flacons individuels, ce processus est difficile à concevoir et aboutit souvent à des lots présentant une hétérogénéité significative dans la qualité du produit final. L'objectif principal de ce doctorat a été le développement d'un modèle mathématique pour la conception du processus de lyophilisation à un niveau de risque donné, c'est à dire un pourcentage de flacons potentiellement non conformes. Le travail a porté sur la compréhension et la quantification des sources possibles responsables de la variabilité des transferts de chaleur et de matière lors du processus. Dans un premier temps, la variabilité du transfert de chaleur entre les flacons a été étudiée en considérant les dimensions du flacon et sa position sur l'étagère de l'équipement. La variabilité des dimensions géométriques observées dans un lot de flacons (i.e., l'aire de contact entre l'étagère et le flacon et la profondeur de concavité du fond) a influencé la distribution du coefficient de transfert de chaleur entre les flacons. De plus, un modèle mathématique original en 3D a été développé dans COMSOL Multiphysics pour expliquer et prédire les transferts de chaleur atypiques observés dans les flacons situés sur les bords de l'étagère lors du processus de lyophilisation. Les phénomènes conductifs à basse pression au sein de la vapeur d'eau ont été reportés comme un mécanisme dominant expliquant ces transferts de chaleur atypiques alors que les phénomènes radiatifs liés à la présence des parois de l'équipement ont toujours été cités dans la littérature. Par ailleurs, ce modèle mathématique en 3D a été utilisé pour étudier l'effet de la configuration de chargement du lyophilisateur et des caractéristiques de l'équipement sur la variabilité du transfert de chaleur. Dans un deuxième temps, la variabilité des transferts de matière a été évaluée sur une solution de saccharose à 5 % en considérant deux paramètres, la résistance de la couche sèche au transfert de matière pendant la sublimation et le temps caractéristique de désorption. La résistance à la couche sèche a été évaluée en combinant deux approches complémentaires, les tests de remontée de pression et la méthode gravimétrique. La variabilité estimée de la résistance à la couche séchée a eu un impact plus important sur la distribution de la température du produit que la variabilité du coefficient de transfert de chaleur. La valeur et la variabilité du temps caractéristique de désorption ont été évaluées pour différentes températures et ont permis de simuler l'hétérogénéité de la teneur en eau finale entre les flacons. Dans la dernière partie du travail, les principales sources quantifiées de variabilité des transferts de chaleur et de matière ont été intégrées dans un modèle mathématique de lyophilisation. Ce modèle dynamique multi-flacons a été utilisé non seulement pour prédire l'évolution de la température et de la teneur en eau du produit pendant la lyophilisation pour un lot de 100 flacons, mais aussi pour estimer le pourcentage de flacons potentiellement non conformes. L'approche de modélisation proposée, étendue à un plus grand nombre de flacons simulés, pourrait être utilisée pour calculer les "design spaces" (espaces de travail) des étapes de dessiccation primaire et secondaire du processus de lyophilisation à un risque connu de pourcentage de flacons non conformes. / Freeze-drying is the process of choice in pharmaceutical industry for the stabilization of heat sensitive products such as vaccines. However, due the product pre-conditioning in individual vials, this process is difficult to design and often results in batches presenting a significant heterogeneity in the quality of the final product. The main goal of this Ph.D. project was the development of a mathematical model making it possible to predict the risk of failure when designing the freeze-drying process, i.e., the percentage of "rejected vials". To this end, the work focused on the understanding and quantification of the sources responsible for heat and mass transfer variability during the process. Firstly, the vial-to-vial heat transfer variability was investigated by taking the vial bottom dimensions and the vial position on the shelf of equipment into account. The variability of geometrical dimensions observed within a batch of vials (i.e., contact area between the shelf and the vial and the mean bottom curvature depth) moderately influenced the heat transfer coefficient distribution among vials (by less than 10 %). Secondly, a original 3D mathematical model was developed in COMSOL Multiphysics to explain and predict atypical heat transfer observed in vials located at the border of the shelf during the freeze-drying process. Conduction through low-pressure water vapour appeared as the dominant mechanism explaining the additional heat transfer to border vials rather than as reported in literature radiation from the walls of the drying chamber. Furthermore, this 3D mathematical model was used to investigate the effect of the vial loading configuration and of the equipment characteristics on heat transfer variability. In a second part, mass transfer variability was quantified on a 5% sucrose solution and by focusing on two parameters, the resistance of the dried layer to mass transfer during sublimation and the characteristic desorption time. The dried layer resistance was assessed by combining complementary approaches, the pressure rise test and gravimetric methods. The estimated variability of the dried layer resistance was found to have a higher impact on the product temperature distribution than the heat transfer coefficient variability. The value and variability of characteristic desorption time was evaluated for different temperatures and made it possible to simulate moisture content heterogeneity between vials in the batch. In the last part of the work, the main quantified sources of heat and mass transfer variability were integrated in a mathematical model of freeze-drying process. This multi-vial, dynamic model was used not only to predict the evolution of product temperature and moisture content during freeze-drying for a batch of 100 vials, but also to estimate the percentage of vials that could potentially be rejected. The proposed approach, extended to a greater number of simulated vials, could be applied to calculate design spaces of the primary and secondary drying steps of freezedrying process at a known risk of failure.

L'objectif de cette thèse fut de développer un process pour la production d'acide peroxycarbolique à partir du peroxyde d'hydrogène et d'un acide carboxylique dans un réacteur continu. Dans un premier temps, la stabilité des espèces peroxydées fut étudiée en utilisant une méthode d'analyse en direct (spectromètre de masse). Un effort particulier a été apporté pour trouver un catalyseur hétérogène ne provoquant pas la décomposition des espèces peroxydées et ayant une activité catalytique similaire à l'acide sulfurique. Un réacteur en continu en lit fixe a été construit en utilisant des résines échangeuses de cation. / The purpose of this thesis was to find a way to produce peroxycarboxylic acid from hydrogen peroxide and carboylic acid in a continuous reactor by using heterogeneous catalysts. In the first step the stability of peroxyde species xas studied by using an online analytic method (Mass spectrometer). One of the main challenge was to find a suitable solid acid catalyst, wich does no decompose the peroxyde species and can catalyze the reaction as sulfuric acid. A continuous fixed bed reactor was built by using caion exchange resins as a catalyst.

Ce travail se situe dans le cadre des recherches du laboratoire sur un procédé d’extraction et desextraction, qui implique trois phases liquides, deux phases aqueuses et une phase organique. La faisabilité d’un tel procédé passe par le choix de la phase organique et par l’étude des équilibres mis en jeu lors du processus d’extraction.Le principal objectif concerne : la récupération et la concentration de phénol contenu dans une solution aqueuse, en utilisant un pertracteur à disques tournants alternatifs en régime batch, semi-batch et continu. Par un mécanisme du transfert de matière entre les phases, le phénol passe de la phase aqueuse d’alimentation vers la phase organique puis de la phase organique vers la phase aqueuse réceptrice.La faisabilité de la méthode est testée en mode fermé. Nous étudions l’influence de certains paramètres : tels que la concentration du phénol, la variation de pH de la phase d’alimentation, la vitesse de rotation des disques et le volume de la phase organique, sur l’évolution du transfert du phénol entre les phases. Une solution aqueuse à pH 2, ayant une concentration en phénol égale à 50, 100 ou 300 mg.L-1, est mise en contact avec de l’huile de colza, qui est elle-même en contact avec une solution aqueuse à pH 13. Les résultats montrent qu’au bout de six heures de fonctionnement, 70% à 99% du phénol contenu initialement dans la solution aqueuse à pH 2, se trouve dans la phase aqueuse à pH 13.Afin de récupérer et de concentrer le phénol dans la phase réceptrice, nous avons réalisé des expériences dans le pertracteur fonctionnant en mode semi-ouvert et en mode ouvert.En système semi-ouvert, l’influence de trois paramètres est étudiée : la concentration initiale de phénol, la vitesse de rotation des disques et le débit de la phase d’alimentation. En système ouvert, seul l’influence du débit à la phase aqueuse est analysée. Enfin, grâce à la modélisation basée sur la théorie du double film, nous avons estimé l’ordre de grandeur des coefficients de transferts de matière partiels pour différentes vitesses de rotation en système fermé. / This work is focused on a pertraction process, coupling extraction and stripping steps in the same apparatus and involving three liquid phases, two aqueous phases and one organic phase. The process feasibility requires the choice of a appropriate organic phase (membrane) and a phase equilibria studies.The main objective was recovery and concentration of phenol contained in dilute aqueous solutions using a rotating discs pertractor in batch, semi-batch and continuous mode. The phenol is transferred from the feed phase (aqueous phase) through the membrane (organic phase) in the receiving phase (aqueous phase).The feasibility of the method is tested in a batch system. We studied the influence of some parameters such as the phenol concentration, the feed pH, the discs rotational speed and the volume of the organic phase. An aqueous solution at pH 2 (feed) with a phenol concentration equal to 50, 100 and 300 mg.L-1, is placed in contact with rapeseed oil (liquid membrane), that is itself in contact with an aqueous solution at pH 13 (receiving phase). The obtained results show that after 6 hours, 70% to 99% of phenol initially contained in the aqueous solution at pH 2, is transferred in the aqueous phase at pH 13.To concentrate phenol in the receiving phase, we performed experiments in semi-batch and continuous mode.In semi-batch system, the influence of three parameters is studied: the feed concentration, the discs rotation speed and the feed flowrate. In open system, (continuous mode), only the influence of the aqueous phases flowrates is analyzed.Finally, using mass transfer model based on a double film theory, we estimate the partial mass transfer coefficients for three phases at different rotation speeds in batch system.

L'utilisation du CO2 comme matière première pour la synthèse de produits à haute valeur ajoutée, comme les carbonates cycliques, est aujourd'hui l'une des alternatives proposées dans la réduction des émissions gazeuses à effet de serre. Ce travail de thèse vise à comprendre et concevoir un procédé de valorisation de CO2 à partir de la modélisation de la thermodynamique et des cinétiques de transfert de matière et de réactions, qui sont engendrées dans la synthèse de carbonates cycliques à partir des époxydes et un composé hétérocyclique comme catalyseur. Grâce à ce nouveau système, les carbonates cycliques très utilisés dans l'industrie de polymères, cosmétique ou pharmaceutique, sont obtenus avec de bons rendements, dans des conditions opératoires douces et en absence de solvants. Des propriétés thermodynamiques telles que la solubilité et la constante de Henry ont été estimées pour les systèmes binaires CO2/époxyde. L'étude du transfert de matière sans ou avec réactions a permis de déterminer respectivement le coefficient de transfert de matière en phase liquide et le régime de la réaction. Des suivis cinétiques ont été réalisés afin de proposer un modèle cinétique capable de représenter la réaction et d'estimer les paramètres cinétiques. Ces derniers ont été utilisés pour la conception préliminaire et la simulation du procédé de production du carbonate d' épichlorohydrine sur Aspen Hysys. / Today, the utilisation of CO2 as raw material for the synthesis of high-value added products like cyclic carbonates, is one of the alternatives used for reducing greenhouse gases. This thesis aims to understand and design a CO2 valorisation process by modelling the thermodynamic and the mass transfer/reaction kinetics generated during the cyclic carbonates synthesis from CO2, epoxides and a heterocyclic compound as catalyst. By using this new catalytic system, cyclic carbonates, which are used in the polymeric, pharmaceutic or cosmetic industry, can be produced with good yields at low temperatures and pressures and without any solvent. Thermodynamic properties as solubility and Henry's law constant have been estimated for CO2/epoxide binary systems. Mass transfer occurring without and with reaction has been studied in order to determine respectively the liquid volumetric mass transfer coefficient and the reaction regime. A kinetic study has been performed to propose a model able to represent the reaction and to estimate the kinetic parameters. This information has been used in the design and the simulation of the production process of epichlorohydrin carbonate on Aspen Hysys.

Depuis 2006, l’arrêt des pompages d’exhaure dans le Bassin Houiller Lorrain (France) a conduit à l’ennoyage des travaux miniers abandonnés, avec pour conséquence la mise en place d’un nouvel équilibre hydrodynamique régional. De récentes recherches portant sur l’exploitation de la chaleur des réservoirs ennoyés ont suscité de nouvelles interrogations, auxquelles nous nous sommes proposé de répondre. Notre travail avait pour objectif de chercher à comprendre le comportement thermo-hydrodynamique de l’eau de mine au sein d’un système en cours d’ennoyage ou récemment ennoyé. Dans un premier temps, les contextes géographique, géologique et hydrogéologique du Bassin Houiller Lorrain ont fait l’objet d’une synthèse, et une zone d’étude a été choisie. Dans un second temps, des profils de température et de conductivité électrique, complétés par des jaugeages, ont été mesurés dans d’anciens puits de mine du Bassin Houiller Lorrain, offrant une meilleure compréhension du comportement de l’eau à l’échelle d’un ouvrage profond. À partir de l’analyse de ces données, un modèle thermo-hydrodynamique et des simulations numériques ont pu être réalisés à cette échelle. Les résultats permettent d’expliquer les phénomènes observés. Leur stabilité est également étudiée. Dans un troisième temps, un modèle spatialisé maillé a été construit pour aborder la problématique du comportement hydrodynamique d’un réservoir minier entier. La montée de l’eau observée a été correctement reproduite ; le modèle peut par ailleurs être utilisé de façon prédictive pour la période suivant l’ennoyage. Plusieurs outils ont été testés, améliorés ou développés afin de faciliter l’étude des réservoirs ennoyés, notamment concernant l’homogénéisation tridimensionnelle des conductivités hydrauliques et le couplage d’un modèle spatialisé maillé avec un réseau de drains-conduits / Since 2006, cessation of dewatering in Lorraine Coal Basin (France) led to the flooding of abandoned mines, resulting in a new hydrodynamical balance in the area. Recent researches concerning geothermal exploitation of flooded reservoirs raised new questions, which we propose to answer. Our work aimed to understand the thermo-hydrodynamical behaviour of mine water in a flooding or flooded system. Firstly, we synthetized the geographical, geological and hydrogeological contexts of the Lorraine Coal Basin, and we chose a specific area for our studies. Secondly, temperature and electric conductivity log profiles were measured in old pits of the Lorraine Coal Basin, giving a better understanding of the water behaviour at a deep mineshaft scale. We were able to build a thermo-hydrodynamical model and simulate water behaviour at this scale. Flow regime stability is also studied. Thirdly, a hydrodynamical spatialized meshed model was realized to study the hydrodynamical behaviour of a mine reservoir as a whole. Observed water-table rise was correctly reproduced : moreover, the model can be used in a predictive way after the flooding. Several tools were tested, improved or developed to ease the study of flooded reservoirs, as three-dimensional upscaling of hydraulic conductivities and a coupled spatialized meshed model with a pipe network

Thesis (PhD (Chemical Engineering))--Cape Peninsula University of Technology, 2019 / The South African wine industry is constantly facing several challenges which affect the quality of wine, the local/global demand and consequently the revenue generated. These challenges include the ongoing drought, bush fires, climate change and several liquor amendment bills aimed at reducing alcohol consumption and alcohol outlets in South Africa. It is therefore critical for the wine industry to expand and find alternative ways in which sub-standard or surplus wine grapes can be used to prevent income losses and increase employment opportunities. Traditional Balsamic Vinegar (TBV) is a geographically and legislative protected product produced only in a small region in Italy. However, the methodology can be used to produce similar vinegars in other regions. Balsamic-styled vinegar (BSV), as defined in this thesis, is a vinegar produced by partially following the methods of TBV while applying process augmentation techniques. Balsamic-styled vinegar is proposed to be a suitable product of sub-standard quality or surplus wine grapes in South Africa. However, the production of BSV necessitates the use of cooked (high sugar) grape must which is a less favourable environment to the microorganisms used during fermentation. Factors that negatively affect the survival of the microorganisms include low water activity due to the cooking, high osmotic pressure and high acidity. To counteract these effects, methods to improve the survival of the non-Saccharomyces yeasts and acetic acid bacteria used are essential. The primary aim of this study was to investigate several BSV process augmentation techniques such as, aeration, agitation, cell immobilization, immobilized cell reusability and oxygen mass transfer kinetics in order to improve the performance of the microbial consortium used during BSV production. The work for this study was divided into four (4) phases. For all the phases a microbial consortium consisting of non-Saccharomyces yeasts (n=5) and acetic acid bacteria (n=5) was used. Inoculation of the yeast and bacteria occurred simultaneously. The 1st phase of the study entailed evaluating the effect of cells immobilized by gel entrapment in Ca-alginate beads alongside with free-floating cells (FFC) during the production of BSV. Two Ca-alginate bead sizes were tested i.e. small (4.5 mm) and large (8.5 mm) beads to evaluate the effects of surface area or bead size on the overall acetification rates. Ca-alginate beads and FFC fermentations were also evaluated under static and agitated (135 rpm) conditions. The 2nd phase of the study involved studying the cell adsorption technique for cell immobilization which was carried-out using corncobs (CC) and oak wood chips (OWC), while comparing to FFC fermentations. At this phase of the study, other vinegar bioreactor parameters such as agitation and aeration were studied in contrast to static fermentations. One agitation setting (135 rpm) and two aeration settings were tested i.e. high (0.3 vvm min−1) and low (0.15 vvm min−1) aeration conditions. Furthermore, to assess the variations in cell adsorption capabilities among individual yeast and AAB cells, the quantification of cells adsorbed on CC and OWC prior- and post-fermentation was conducted using the dry cell weight method. The 3rd phase of the study entailed evaluating the reusability abilities of all the matrices (small Ca-alginate beads, CC and OWC) for successive fermentations. The immobilized cells were evaluated for reusability on two cycles of fermentation under static conditions. Furthermore, the matrices used for cell immobilization were further analysed for structure integrity by scanning electron microscopy (SEM) before and after the 1st cycle of fermentations. The 3rd phase of the study also involved the sensorial (aroma and taste) evaluations of the BSV’s obtained from the 1st cycle of fermentation in order to understand the sensorial effects of the Ca-alginate beads, CC and OWC on the final BSV. The 4th phase of the study investigated oxygen mass transfer kinetics during non-aerated and aerated BSV fermentation. The dynamic method was used to generate several dissolved oxygen profiles at different stages of the fermentation. Consequently, the data obtained from the dynamic method was used to compute several oxygen mass transfer parameters, these include oxygen uptake rate ( 𝑟𝑟𝑂𝑂2 ), the stoichiometric coefficient of oxygen consumption vs acid yield (𝑌𝑌𝑂𝑂/𝐴𝐴), the oxygen transfer rate (𝑁𝑁𝑂𝑂2 ), and the volumetric mass transfer coefficients (𝐾𝐾𝐿𝐿𝑎𝑎). During all the phases of the study samples were extracted on weekly intervals to evaluate pH, sugar, salinity, alcohol and total acidity using several analytical instruments. The 4th phase of the study involved additional analytical tools, i.e. an oxygen µsensor to evaluate dissolved oxygen and the ‘Speedy breedy’ to measure the respiratory activity of the microbial consortium used during fermentation. The data obtained from the 1st phase of the study demonstrated that smaller Ca-alginate beads resulted in higher (4.0 g L-1 day−1) acetification rates compared to larger (3.0 g L-1 day−1) beads, while freely suspended cells resulted in the lowest (0.6 g L-1 day−1) acetification rates. The results showed that the surface area of the beads had a substantial impact on the acetification rates when gel entrapped cells were used for BSV fermentation. The 2nd phase results showed high acetification rates (2.7 g L-1 day−1) for cells immobilized on CC in contrast to cells immobilized on OWC and FFC, which resulted in similar and lower acetification rates. Agitated fermentations were unsuccessful for all the treatments (CC, OWC and FFC) studied. Agitation was therefore assumed to have promoted cell shear stress causing insufficient acetification during fermentations. Low aerated fermentations resulted in better acetification rates between 1.45–1.56 g L-1 day−1 for CC, OWC and FFC. At a higher aeration setting, only free-floating cells were able to complete fermentations with an acetification rate of 1.2 g L-1 day−1. Furthermore, the adsorption competence data showed successful adsorption on CC and OWC for both yeasts and AAB with variations in adsorption efficiencies, whereby OWC displayed a lower cell adsorption capability compared to CC. On the other hand, OWC were less efficient adsorbents due to their smooth surface, while the rough surface and porosity of CC led to improved adsorption and, therefore, enhanced acetification rates. The 3rd phase results showed a substantial decline in acetification rates on the 2nd cycle of fermentations when cells immobilized on CC and OWC were reused. While cells entrapped in Ca-alginate beads were able to complete the 2nd cycle of fermentations at reduced acetification rates compared to the 1st cycle of fermentations. The sensory results showed positive ratings for BSV’s produced using cells immobilized in Ca-alginate beads and CC. However, BSV’s produced using OWC treatments were neither ‘liked nor disliked’ by the judges. The SEM imaging results further showed a substantial loss of structural integrity for Ca-alginate beads after the 1st cycle fermentations, with minor changes in structural integrity of CC being observed after the 1st cycle fermentations. OWC displayed the same morphological structure before and after the 1st cycle fermentations which was attributed to their robustness. Although Ca-alginate beads showed a loss in structural integrity, it was still assumed that Ca-alginate beads provided better protection against the harsh environmental conditions in contrast to CC and OWC adsorbents due to the acetification rates obtained on both cycles. The 4th phase data obtained from the computations showed that non-aerated fermentations had a higher 𝑌𝑌𝑂𝑂/𝐴𝐴, 𝑟𝑟𝑂𝑂2 , 𝑁𝑁𝑂𝑂2 and a higher 𝐾𝐾𝐿𝐿𝑎𝑎 . It was clear that aerated fermentations had a lower aeration capacity due to an inappropriate aeration system design and an inappropriate fermentor. Consequently, aeration led to several detrimental biochemical changes in the fermentation medium thus affecting 𝐾𝐾𝐿𝐿𝑎𝑎 and several oxygen mass transfer parameters which serve as a driving force. Overall, it was concluded that the best method for BSV production is the use of cells entrapped in small alginate beads or cells adsorbed on CC under static and non-aerated fermentations. This conclusion was based on several factors such as cell affinity/cell protection, acetification rates, fermentation period and sensorial contributions. However, cells entrapped in Ca-alginate beads had the highest acetification rates. The oxygen mass transfer computations demonstrated a high 𝐾𝐾𝐿𝐿𝑎𝑎 when Ca-alginate beads were used under static-non-aerated conditions compared to fermentations treated with CC. Therefore, a fermentor with a high aeration capacity needs to be designed to best suit the two BSV production systems (Ca-alginate beads and CC). It is also crucial to develop methods which can increase the robustness of Ca-alginate beads in order to improve cell retention and reduce the loss of structural integrity for subsequent cycles of fermentation. Studies to define parameters used for upscaling the BSV production process for large scale productions are also crucial.

La présence de fines particules de matières oxydables est rencontrée dans de nombreuses situations industrielles. Le risque d'explosion de poussières présente une menace constante pour les industries de transformation qui fabriquent, utilisent ou manipulent des poudres ou despoussières de matières combustibles. Dans le secteur nucléaire, les scénarios envisagés traitent,en particulier, le risque d'explosion de poussières de graphite liées aux opérations dedémantèlement des réacteurs Uranium Naturel Graphite Gaz. La problématique considérée, dans le cadre de ce travail de thèse, est celle de la combustion d'un mélange dilué gaz-particules.L'objectif de cette thèse est de développer un modèle Euler-Lagrange macroscopique permettantde prédire la vitesse laminaire de flamme qui est une des données essentielles pour les modèlesde vitesse de flamme turbulente utilisés dans l'évaluation des risques d'explosion de poussières.Dans un premier temps, les équations macroscopiques de transferts massique et thermique sont dérivées à partir de la méthode de prise de moyenne volumique. L'intérêt de l'approche utilisée ici est de proposer des problèmes de fermeture permettant d'estimer les coefficients de transfertseffectifs, tels que les coefficients d'échanges thermiques et le coefficient effectif de la réactionhétérogène. Dans un deuxième temps, des simulations Euler-Lagrange sont utilisées pourdéterminer la vitesse de flamme laminaire diphasique plane en fonction des caractéristiques du mélange gazeux et des poussières de graphite. Le modèle proposé dans ce travail est comparé au modèle Euler-Lagrange classique basé sur la résolution du problème de couche limite pourune particule isolée en milieu infini. Cette étude montre que les effets du taux de dilution et deséchanges indirects entre les particules ne sont pas systématiquement négligeables dans leséchanges macroscopiques entre les deux phases. D'autre part, la présente étude laisse entrevoir la potentialité de l'approche proposée pour les simulations détaillées de l'écoulement diphasique / The presence of fine particles of oxidizable materials is encountered in many industrial situations.The risk of dust explosion presents a constant threat in transformation industries that manufacture,use or manipulate powders or combustible materials dusts. In nuclear safety analysis, one of themain scenarios is the risk of graphite dust explosion that may occur during decommissioningoperations of Uranium Natural Graphite Gas reactors. The issue considered in this thesis isrelated to combustion of a dilute gas-particle mixture. This work aims at developing a macroscopicEuler-Lagrange model for predicting laminar flame velocity, which is one of the essential data forturbulent flame velocity models used to evaluate the risk of dust explosion. First, the macroscopicheat and mass transfer equations are derived using the volume averaging method. The majorinterest of the proposed approach is to provide closure problems that allow to estimate theeffective transport coefficients, such as heat exchange coefficients and the effective coefficient ofthe heterogeneous reaction. Second, Euler-Lagrange simulations are used to determine the planetwo-phase laminar flame velocity as a function of gas mixture and graphite dust characteristics.The proposed model is compared to the classical Euler-Lagrange model based on the resolutionof the boundary layer problem in the vicinity of an isolated particle in infinite medium. Results showthat the dilution rate and the indirect particle-particle exchanges are not systematically negligible inthe macroscopic exchanges between the two-phases. On the other hand, this study suggests thepotentiality of the proposed approach for detailed simulations of two-phase flow

Dropwise condensation, which collects the condensate liquid in the form of droplets, has attracted a growing interest due to much higher heat transfer coefficient. One important and challenging issue in dropwise condensation is the presence of non-condensable gas (NCG) which drastically reduces its heat transfer performance. Concerning the mechanism understanding, this thesis is aiming to investigate dropwise condensation in case of NCG by combing different methods. Firstly, convective dropwise condensation out of moist air is experimentally investigated under controllable conditions. In modeling, some crucial aspects are reasonably captured: the coupled heat and mass transfer during droplet growth by a multi-scale droplet growth model; the inter-droplet interaction defined by a distributed point sink method; the enhancement of the convective mass transfer using the droplet Sherwood number. Furthermore, a multi-component multi-phase thermal pseudopotential-based LB model is developed to advance the directly numerical simulation of dropwise condensation.

Zur Kühlung von Prozessströmen kommen aufgrund hoher Leistungsdichten häufig Verdunstungskühltürme zum Einsatz. Um die Übertragungsfläche für Wärme und Stoff zu vergrößern, werden in diesen Kühltürmen Struktureinbauten integriert. Die Weiterentwicklung von Kühlturmeinbauten und die Untersuchung der den Kühlprozess beeinflussenden Faktoren erfolgt empirisch, was eine Vielzahl von Versuchen notwendig macht. Eine numerische Simulation des Kühlprozesses kann diese Messungen unterstützen und so helfen eine Vielzahl an Versuchen einzusparen. Des Weiteren können bei versuchsbegleitender Simulation mit einem geeigneten Modell weitere Untersuchungen durchgeführt und Erkenntnisse gewonnen werden, die bei Messungen am Versuchskühlturm verborgen bleiben. In dieser Arbeit werden zwei Ansätze der numerischen Simulation eines Verdunstungskühlturms betrachtet. Es werden eine CFD-Simulation und ein vereinfachtes Modellkonzept hinsichtlich der Anwendbarkeit auf diese Problemstellung untersucht. Schwerpunkt der vorliegenden Arbeit ist die methodische Entwicklung eines solchen vereinfachten mathematischen Modells. Dieses beruht auf der physikalisch deterministischen Beschreibung der im Kühlturm ablaufenden Prozesse der Wärme- und Stoffübertragung unter Berücksichtigung des Stoffverhaltens. Aufgrund der Nichtlinearität des Stoffverhaltens und der erforderlichen Inkrementierung des Berechnungsgebiets ist ein methodisches Vorgehen erforderlich, um die Erstellung der Modellgleichungen und deren Lösung überhaupt realisieren zu können. Hierfür wird auf allgemeine Methoden der gleichungsorientierten Simulation technischer Systeme zurückgegriffen. Das entwickelte Modellkonzept wird für die Modellierung und Simulation eines Versuchskühlturms angewandt. Mit den so ermittelten Messdaten wird das Modell kalibriert und validiert. Es zeigt sich, dass mit dem erstellten Modell quantitativ und qualitativ valide Ergebnisse erzielt werden können. / Due to the high power density, the cooling of process streams is often done bei evaporative cooling towers. To enlarge the exchange area for the heat and mass transfer, these cooling towers contain integrated structural fills. The future development of cooling tower fills and the research regarding the cooling process and its influencing parameters will be carried out empirically, resulting in a large number of required experiments. A numeric simulation of the cooling process can support theses measurements and reduce the vast number of needed experiments. Furthermore, with the use of test-related simulations and adapted models, it will be possible to gain knowledge and do research in areas which are omitted during regular measurements on cooling towers. In this study it is looked to two different approaches of numeric simulation of a evaporative cooling tower. There will be an examination of a CFD-Simulation and a simplified model concept regarding their respective applicability for this problem. This work is focussed on the systematic developement of such simplified mathematical models, based on the physical deterministic description of the occurring processes of heat and mass transfer in cooling towers considering the stock behaviour. Due to the non-linearity of the stock behaviour and the required incrementation of the calculation area, a systematic approach is needed to model equations and their respective solutions. For this purpose it is necessary to access general techniques of equation-based simulations of technological systems. The developed model concept will be applied for the modelation and simulation of an experimental cooling tower. The model will be calibrated and validated with data from this experimental tower. It shows, that the results from this model are qualitatively and quantitatevily valid.