Cette thèse porte sur le développement d’un capteur plasmonique intégrant une fonction d’actuation des objets visés. L’objectif est de passer outre la limite de diffusion rencontrée à basse concentration en piégeant les particules sur la surface de détection. La stratégie adoptée est de structurer le film d’or servant à la détection de manière à pouvoir l’utiliser pour mettre en mouvement le fluide et les molécules par le biais de champs électriques. Le transfert de masse est réalisé par diélectrophorèse et électroosmose, deux effets électrocinétiques mis en oeuvre par des électrodes servant à la fois d’actuateur et de capteur plasmonique. Un état de l’art exhaustif et des simulations multiphysiques ont permis de concevoir un prototype de capteur intégré constitué d’électrodes interdigitées en or permettant la détection plasmonique. Le dispositif proposé a été obtenu par microfabrication en salle blanche puis caractérisé avant l’étude de ses performances. Une première phase de tests sur un système modèle, des billes de polystyrène dans de l’eau, a permis d’apporter la preuve de concept du fonctionnement du capteur, qui est effectivement capable de piéger rapidement les objets visés à sa surface afin de les détecter. Les mécanismes de transfert de masse ont été expliqués et la preuve de l’amélioration de la limite de détection par un facteur supérieur à 100 a été apportée. Dans un second temps, les performances du capteur appliqué à des objets biologiques ont été évaluées. Celui-ci piège efficacement des levures et des protéines, mais aucune amélioration n’a été observée dans le cas de la détection spécifique de l’hybridation entre deux brins d’acide désoxyribonucléique (ADN). Les causes de ce résultat ont été discutées et comprises et deux solutions différentes ont été explorées : l’adaptation de la fréquence d’opération et l’optimisation de la géométrie des électrodes. Ainsi, cette étude a permis de souligner la problématique de la mise en oeuvre d’effets électrocinétiques dans des milieux biologiques et de réfléchir aux pistes pertinentes pour sa résolution. / This thesis focuses on the development of an integrated plasmonic sensor capable to perform mass transport on targeted objects. The goal is to overcome the diffusion limit by trapping particules directly on the sensing surface. The adopted strategy was to structure the gold layer used for plasmonic detection in order to use the sofabricated structures to set the fluid and the molecules in motion by applying electric fields in the fluid. The mass transfer is realized through dielectrophoresis and electroosmosis, those two electrokinetic effects being operated by electrodes acting as sensor and actuator at the same time. An exhaustive state of the art as well as multiphysical simulations allowed us for designing a prototype for an integrated sensor consisting in gold interdigitated electrodes enabling plasmoninc sensing. The proposed device was obtained through microfabrication in clean room facilities and was characterized before the study of its performances. A first sequence of tests on a model system – polystyrene microbeads in water – brought the proof of concept we needed to validate the correct operation of the sensor, which is indeed capable of quickly trapping targeted objects on its surface and detecting them. The mass transfer mechanisms were explained and we showed the enhancement of the limit of detection by a factor greater than 100. In a second phase, performances of the sensor applied to biological objects were evaluated. It can effectively trap yeasts and proteins but no enhancement has been observed while detecting DNA hybridization events. Causes for this result were discussed and understood and two different solutions were explored: the adaptation of the operating frequency and the optimization of the electrodes geometry. Thus, this study highlighted the problematic of operating electrokinetic effects in biological media and suggested relevant leads towards its resolution.

The performance of solid oxide fuel cells (SOFCs) at the cell and system levels is studied using computer simulation. At the cell level, a new model combining the cell micro and macro models is developed. Using this model, the microstructural variables of porous composite electrodes can be linked to the cell performance. In this approach, the electrochemical performance of porous composite electrodes is predicted using a micro-model. In the micro-model, the random-packing sphere method is used to estimate the microstructural properties of porous composite electrodes from the independent microstructural variables. These variables are the electrode porosity, thickness, particle size ratio, and size and volume fraction of electron-conducting particles. Then, the complex interdependency among the multi-component mass transport, electron and ion transports, and the electrochemical and chemical reactions in the microstructure of electrodes is taken into account to predict the electrochemical performance of electrodes. The temperature distribution in the solid structure of the cell and the temperature and species partial pressure distributions in the bulk fuel and air streams are predicted using the cell macro-model. In the macro-model, the energy transport is considered for the cell solid structure and the mass and energy transports are considered for the fuel and air streams. To demonstrate the application of the cell level model developed, entitled the combined micro- and micro-model, several anode-supported co-flow planar cells with a range of microstructures of porous composite electrodes are simulated. The mean total polarization resistance, the mean total power density, and the temperature distribution in the cells are predicted. The results of this study reveal that there is an optimum value for most of the microstructural variables of the electrodes at which the mean total polarization resistance of the cell is minimized. There is also an optimum value for most of the microstructural variables of the electrodes at which the mean total power density of the cell is maximized. The microstructure of porous composite electrodes also plays a significant role in the mean temperature, the temperature difference between the hottest and coldest spots, and the maximum temperature gradient in the solid structure of the cell. Overall, using the combined micro- and micro-model, an appropriate microstructure for porous composite electrodes to enhance the cell performance can be designed. At the system level, the full load operation of two SOFC systems is studied. To model these systems, the basic cell model is used for SOFCs at the cell level, the repeated-cell stack model is used for SOFCs at the stack level, and the thermodynamic model is used for the balance of plant components of the system. In addition to these models, a carbon deposition model based on the thermodynamic equilibrium assumption is employed. For the system level model, the first SOFC system considered is a combined heat and power (CHP) system that operates with biogas fuel. The performance of this system at three different configurations is evaluated. These configurations are different in the fuel processing method to prevent carbon deposition on the anode catalyst. The fuel processing methods considered in these configurations are the anode gas recirculation (AGR), steam reforming (SR), and partial oxidation reformer (POX) methods. The application of this system is studied for operation in a wastewater treatment plant (WWTP) and in single-family detached dwellings. The evaluation of this system for operation in a WWTP indicates that if the entire biogas produced in the WWTP is used in the system with AGR or SR fuel processors, the electric power and heat required to operate the plant can be completely supplied and the extra electric power generated can be sold to the electrical grid. The evaluation of this system for operation in single-family detached dwellings indicates that, depending on the size, location, and building type and design, this system with all configurations studied is suitable to provide the domestic hot water and electric power demands. The second SOFC system is a novel portable electric power generation system that operates with liquid ammonia fuel. Size, simplicity, and high electrical efficiency are the main advantages of this environmentally friendly system. Using a sensitivity analysis, the effects of the cell voltage at several fuel utilization ratios on the number of cells required for the SOFC stack, system efficiency and voltage, and excess air required for thermal management of the SOFC stack are studied.

La intensificación de procesos consiste en el desarrollo de equipos y técnicas innovadoras que ofrecen mejoras sustanciales en el proceso, principalmente mediante la disminución del volumen del equipo, consumo de energía o generación de residuos, dando lugar a tecnologías más baratas, seguras y sostenibles. Esta tesis enfatiza la intensificación de procesos como estrategia en la recuperación de dióxido de azufre mediante el empleo de la tecnología de membranas y de líquidos iónicos como absorbente con objeto de eliminar las pérdidas de disolvente.La intensificación del proceso se lleva a cabo en dos etapas:i) Sustitución del equipo convencional (e.g. scrubbers) por un sistema de membranas para eliminar el arrastre de gotas y,ii) Sustitución del disolvente de absorción (N,N-dimetilanilina) por líquidos iónicos para eliminar pérdidas de disolvente por su volatilización en la corriente de gas debido a su presión de vapor despreciable. La selección de un líquido iónico adecuado se basa en su afinidad hacia dióxido de azufre, baja viscosidad, bajo coste y baja ecotoxicidad.En resumen, esta tesis es el primer trabajo que combina el empleo de un contactor de membranas de fibra hueca con líquidos iónicos, contribuyendo al desarrollo de procedimientos innovadores para intensificar el proceso de absorción de dióxido de azufre. / Process intensification consists of the development of innovative devices and techniques that offer significant improvements in chemical manufacturing and processing, decreasing substantially equipment volume, energy consumption, or wastes, and ultimately leading to cheaper, safer and sustainable technologies. This thesis emphasizes the process intensification as the strategy to the recovery of sulfur dioxide, according to the material efficiency and environmental protection, by means of technology based on membranes and ionic liquids as absorption solvents in order to avoid solvent losses.Process intensification is performed in two steps:i) Substitution of conventional equipment (e.g. scrubbers) for a membrane device to avoid drops dragging and,ii) Substitution of the absorption solvent (N,N-dimethylaniline) for ionic liquids to avoid solvent losses due to volatilization of solvent into the gas stream because of their negligible vapor pressure. Selection of a suitable ionic liquid is based on its affinity towards sulfur dioxide, low viscosity, low cost and low ecotoxicity.Thus, this thesis is the first work that combines a hollow fibre membrane contactor and ionic liquids, contributing to the development of innovative procedures to intensify the sulfur dioxide absorption process.

Two and three-phase flow processes involving gas, liquid and solid, are common in nature and industry, and include some of the most complex and poorly-understood transport problems. In this research hydrodynamics, heat and mass transfer processes in complex two and three-phase flows were investigated. The interfacial surface area concentration in a short vertical column subject to the through flow of fiber-liquid-gas slurry was experimentally measured using the gas absorption technique. The experimental data were statistically analyzed for parametric effects, and were empirically correlated. The absorption of a gaseous species by a slurry droplet with internal circulation and containing reactive micro-particles was simulated, and parametrically studied. The micro-particles were found to enhance the absorption rate. The absorption rate was sensitive to droplet recirculation, and shrinkage of particles with time resulted in declining absorption rates. The transport of soot particles, suspended in laminar hot gas flowing in a tube, was modeled and parametrically studied. Due to coupled thermal radiation and thermophoresis, a radially-nonuniform temperature profile develops, leading to sharp, non-uniform radial soot-concentration profiles. The assumption of monodisperse particles leads to over-prediction of thermophoresis. The transport and removal of particles suspended in bubbles rising in a stagnant liquid pool were modeled based on a Eulerian – Monte Carlo method. The bubble hydrodynamics were treated in Eulerian frame, using the Volume-of-Fluid (VOF) technique, while particle equations of motion were numerically solved in Lagrangian frame. The bubbles undergo shape change, and have complex internal circulation, all of which influence the particle removal. Model predictions were also compared with experimental data. Using a resemblance between two-phase flow in microchannels, and in large channels at microgravity, a simple Weber number-based two-phase flow regime map was developed for microchannels. Based on the available air-water experimental data, a criterion for the prediction of conditions that lead to flow regime transition out of the stratified-wavy flow pattern in horizontal annular channels was proposed. The thermocapillary effects on liquid-vapor interface shape during heterogeneous bubble ebullition in microchannels were analytically studied.

Bei der Rektifikation werden heute zunehmend Füllkörperkolonnen mit geordneten Packungen eingesetzt. Die Maldistribution, ein bislang ungelöstes Problem in Füllkörperkolonnen, wirkt sich negativ auf die Stoffaustauschleistung aus. Zur Verringerung der Maldistribution wird zwischen den Packungssektionen mehrfach die Rücklaufflüssigkeit gesammelt und erneut gleichmäßig über den Kolonnenquerschnitt verteilt. Diese Neuverteilung realisieren Zwischenverteiler, die somit einen Großteil der Kolonnenhöhe beanspruchen und damit die Investitions- und Betriebskosten erheblich erhöhen. Hauptursache für die Bauhöhe der Zwischenverteiler ist der Wunsch nach einem vollständigen Konzentrationsausgleich vor der Neuverteilung. Um die Kolonnenhöhe zu verringern und dennoch die gleiche Trennleistung zu erreichen, mangelt es den Anlagenbauern bislang an einer praktikablen Lösung. Entgegen der bisherigen Lehrbuchmeinung wird in dieser Arbeit die Bedeutung des vollständigen Konzentrationsausgleich grundsätzlich in Frage gestellt. Es erfolgen deshalb theoretische und experimentelle Untersuchungen für ein besseres Verständnis der Neuverteilung der Rücklaufflüssigkeit und deren Auswirkung auf die Trennleistung. Durch Modifizierung des klassischen Zwei-Kolonnen-Modells gelingt es, den Einfluss der Maldistribution, der Dampfquervermischung und der hydraulisch gleichmäßigen Flüssigkeitsneuverteilung mit und ohne vollständigen Konzentrationsausgleich numerisch zu simulieren. Die Überprüfung der Simulationsmodelle erfolgt an einer Pilotkolonne mit einem inneren Durchmesser von 1 m. Die Kolonne ist mit Sulzer MellapakPlus 752.Y ausgerüstet und als Testgemisch dient trans-/cis-Dekalin. Im Ergebnis zeigt sich, dass vor allem der hydraulische Ausgleich erforderlich ist und es praktisch keinen Unterschied zwischen vollständigen und unvollständigen Konzentrationsausgleich bei sonst gleichen Betriebsbedingungen gibt. Überlegungen für deutlich flachere Verteilerkonstruktionen werden vorgestellt.

Αντικείμενο της διατριβής είναι η υπολογιστική και πειραματική διερεύνηση των φαι-νομένων μεταφοράς θερμότητας και μάζας σε πρότυπη εργαστηριακή μονάδα μηχανικής ξήρανσης δια συναγωγής, η οποία σχεδιάσθηκε, κατασκευάσθηκε και εξοπλίσθηκε με μετρητικό εξοπλισμό και ολοκληρωμένο σύστημα ελέγχου, συλλογής και επεξεργασίας των πειραματικών μετρήσεων. Στην εργαστηριακή μονάδα ξήρανσης παρέχεται η δυνατότητα μεταβολής και ελέγχου των βασικών παραμέτρων από τις οποίες επηρεάζεται η θερμική διεργασία της ξήρανσης, όπως η ταχύτητα, η θερμοκρασία και η υγρασία του αέρα ξήρανσης. Η μέτρηση της αποβολής της περιεχομένης υγρασίας στο υπό ξήρανση προϊόν πραγματοποιείται μέσω δυναμοκυψελών υψηλής ακρίβειας, ενώ η χωρική κατανομή της ταχύτητας ροής στην είσοδο του θαλάμου ξήρανσης κατά τη διεξαγωγή κάθε κύκλου πειραμάτων συνεχώς μετρείται με συστοιχία σωλήνων pitot και ενός συστήματος συγκροτούμενου από ηλεκτροβαλβίδες και μορφομετατροπέα πίεσης. Η χωρική κατανομή της θερμοκρασίας και της ταχύτητας στον θάλαμο ξήρανσης είναι δυνατή μέσω αισθητηρίων που προσαρμόζονται σε καρτεσιανό σύστημα μετακίνησης ελεγχόμενου από υπολογιστή το οποίο σχεδιάσθηκε, κατασκευάσθηκε και τοποθετήθηκε στην έξοδο του κατακόρυφου θαλάμου ξήρανσης αποτελώντας πλέον αναπόσπαστο τμήμα της εργαστηριακής μονάδας. Όλες οι μετρήσεις πραγματοποιήθηκαν στον κατακόρυφο θάλαμο ξήρανσης, ενώ παρέχεται η δυνατότητα διεξαγωγής μετρήσεων και στο θάλαμο ξήρανσης οριζόντιας διάταξης. Στα πλαίσια της διατριβής, έγινε συστηματική πειραματική διερεύνηση της ξήρανσης δια συναγωγής σε φέτες κυδωνιών και μελετήθηκε η επίδραση διαφόρων παραμέτρων που επηρεάζουν τη θερμική διεργασία της ξήρανσης σε αυτό το αγροτικό προϊόν, για θερμοκρασίες αέρα 40, 50 και 60οC και ταχύτητες αέρα 1, 2 και 3 m/s. Σκοπός των με-τρήσεων ήταν ο προσδιορισμός: (i) της επίδρασης της θερμοκρασίας και της ταχύτητας του αέρα στις καμπύλες ξήρανσης κυλινδρικών φετών κυδωνιού, (ii) της επίδρασης του πάχους των κυλινδρικών φετών του κυδωνιού στις καμπύλες ξήρανσης, (iii) της επίδρασης του προσανατολισμού των κυλινδρικών φετών κυδωνιού, ως προς τη διεύθυνση της προσπίπτουσας ροής, στις καμπύλες ξήρανσης, (iv) της προσαρμογής των καμπύλων ξήρανσης σε διάφορα απλά μοντέλα ξήρανσης λεπτού στρώματος, v) των ενεργών συντελεστών διάχυσης υγρασίας για την κάθε περίπτωση με την μέθοδο της κλίσης (slope method) και οι οποίοι συσχετίστηκαν με τη θερμοκρασία του αέρα ξήρανσης έτσι ώστε ο συντελεστής διάχυσης της υγρασίας να εκφρασθεί με την εξίσωση μορφής τύπου Arrhenius και vi) των διεπιφανειακών συντελεστών μεταφοράς θερμότητας και μάζας οι οποίοι στη εκφράζονται ως συνάρτηση των αδιάστατων αριθμών Nu, Re και Pr με τη μορφή Nu=aRebPr1/3. Η προσομοίωση του ρευστοθερμικού πεδίου στο θάλαμο ξήρανσης και ο υπολογισμός των διεπιφανειακών συντελεστών μεταφοράς θερμότητας και μάζας γύρω από την επι-φάνειας του προϊόντος πραγματοποιήθηκε με χρήση της εργαλείων της υπολογιστικής ρευστοδυναμικής (CFD). Έγιναν προσομοιώσεις CFD μόνιμης κατάστασης (steady-state), θεωρώντας τυρβώδη ροή ενώ ο θάλαμος ξήρανσης και η κυλινδρική φέτα του κυδωνιού εξιδανικεύθηκε ως μια δισδιάστατη αξονοσυμμετρική διαμόρφωση. Ως μοντέλο τύρβης χρησιμοποιήθηκε το μοντέλο SST (Shear Stress Transport) k-ω, ενώ για την προσέγγιση του οριακού στρώματος στα τοιχώματα του προϊόντος επιλέχθηκε το μοντέλο LRNM (Low Reynolds Number Model). Από την επίλυση των πεδίων ροής και θερμοκρασίας προσδιορίσθηκαν οι κατανομές των διεπιφανειακών συντελεστών στην προσήνεμη και στην υπήνεμη πλευρά της κυλινδρικής φέτας του κυδωνιού για όλες τις πειραματικές συνθήκες. Από τον υπολογισμό του μέσων σταθμισμένων τιμών του διεπιφανειακού συντελεστή μεταφοράς θερμότητας συνάγεται μια συσχέτιση των αδιάστατων αριθμών Nu, Re και Pr, στη μορφή Nu=aRebPr1/3, που ως εύρημα εμπλουτίζει την υφιστάμενη βιβλιογραφία. Στο τελικό στάδιο της διατριβής, αναπτύχθηκε και αποτιμήθηκε σε σύγκριση με τις πειραματικές μετρήσεις ένα μονοδιάστατο αριθμητικό μοντέλο μη-μόνιμης μεταφοράς θερμότητας και μάζας για την προσομοίωση των καμπυλών ξήρανσης σε κυλινδρικές φέτες κυδωνιών. Στο μοντέλο, η μεταφορά θερμότητας εντός του προϊόντος γίνεται με αγωγή ενώ η μεταφορά μάζας γίνεται με υγρή διάχυση, με την εξάτμιση του περιεχόμενου νερού στις φέτες του κυδωνιών να λαμβάνει χώρα από την προσήνεμη και την υπήνεμη επιφάνεια. Στο αριθμητικό μοντέλο, λαμβάνεται υπόψη η συρρίκνωση της κυλινδρικής φέτας του κυδωνιού, θεωρώντας ότι ο όγκος της προϊόντος μειώνεται κάθε φορά κατά τον όγκο του νερού που εξατμίζεται τις δύο επιφάνειες της φέτας. Στον αριθμητικό κώδικα, οι θερμοφυσικές ιδιότητες του κυδωνιού και του αέρα προσδιορίζονται από σχέσεις που συναντώνται στη βιβλιογραφία, ο ενεργός συντελεστής διάχυσης της υγρασίας εισάγεται ως αποτέλεσμα της επεξεργασίας των πειραματικών μετρήσεων, ενώ για τους συντελεστές μεταφοράς χρησιμοποιήθηκαν οι μέσες σταθμισμένες τιμές των διεπιφανειακών συντελεστών μεταφοράς θερμότητας και μάζας, ως αποτέλεσμα των CFD προσομοιώσεων και για περίπτωση μη-συζυγούς προσέγγισης (non-conjugated approach). Στοχεύοντας στην καλύτερη προσαρμογή των πειραματικών μετρήσεων και των υπολογιστικών αποτελεσμάτων, χρησιμοποιήθηκε η ανάλυση μη-γραμμικής παλινδρόμησης, με τους αλγόριθμους SQP (Sequential Quadratic Programming) και εσωτερικού σημείου (internal point), για τον προσδιορισμό των συντελεστών της εξίσωσης διάχυσης της υγρασίας, με μικρή όμως βελτίωση των υπολογιστικών αποτελεσμάτων, σε συνδυασμό με τη σημαντική αύξηση του χρόνου υπολογισμού. Συμπερασματικά, από τη συνολική αξιολόγηση των αποτελεσμάτων του αριθμητικού κώδικα αποδείχθηκε ότι το προτεινόμενο αριθμητικό μοντέλο που βασίζεται στη διάχυση είναι ικανό να περιγράψει αποτελεσματικά τη σύζευξη της μεταφοράς της θερμότητας και της μάζας όπως και να αποτυπώσει ικανοποιητικά τη χρονική εξέλιξη της περιεχόμενης υγρασίας και θερμοκρασίας εντός του προϊόντος, με την ελάχιστη χρήση πειραματικών μεταβλητών εισόδου ενώ έχει ελάχιστες υπολογιστικές απαιτήσεις. Για αυτούς τους λόγους μπορεί να θεωρηθεί κατάλληλο για την ανάλυση της διαδικασίας της ξήρανσης δια συναγωγής σε οποιοδήποτε οργανικό ή μη-οργανικό προϊόν. / The objective subject of this thesis is the computational and experimental investigation of heat and mass transfer phenomena in a new laboratory mechanical convection drying unit, which was designed, constructed and equipped with measuring equipment and an integrated control system of collection and processing of experimental measurements. In laboratory drying unit there is an option to change and control the main parameters of which affected the thermal drying process, such as speed, temperature and humidity of the drying air. Measurement of the removal of moisture content in the dried product is carried out through high-precision load cells, and the spatial distribution of the flow velocity at the entrance of the drying chamber during of each experiment, is continuously measured by pitot tube array and a system composed of solenoids and a pressure transducer. The spatial distribution of temperature and velocity in the drying chamber is possible by means of sensors fitted to a computer controlled cartesian motion system which is designed, constructed and placed at the outlet of the vertical drying chamber, constituting an integral part of the facility. All measurements were performed on the vertical drying chamber while it is possible to conduct measurements in a horizontal layout of the drying chamber. In this thesis became systematic experimental investigation of convective drying sliced quince and studied the effect of various parameters affecting the thermal drying process in this agricultural product, for air temperatures of 40, 50 and 60°C and air velocities 1, 2 and 3 m/s. The purpose of the measurements was to determine: (i) the effect of temperature and air velocity in drying curves of cylindrical quince slice, (ii) the effect of the thickness of the cylindrical slice of quince in drying curves, (iii) the effect of the orientation of the cylindrical quince slice, in the direction of incident flow, in the drying curves (iv) the adjusting of the drying curves in several simple thin layer drying models v) the effective moisture diffusivity coefficients for each case with the slope method which correlated with the temperature of the drying air so that the diffusion coefficient of moisture be expressed by Arrhenius type equation form and vi ) the interfacial heat and mass transfer coefficients which expressed as a function of dimensionless numbers Nu, Re and Pr in the form Nu = aRebPr1/3. The simulation of the flow and temperature fields in the drying chamber and the calcu-lation of the interfacial heat and mass transfer coefficients around the surface of the product were performed using the tools of Computational Fluid Dynamics (CFD). CFD simulations were steady state, considering turbulent flow while drying chamber and cy-lindrical slice of quince specialized as an axisymmetric two-dimensional configuration. As turbulence model was used the SST k-ω model while on the approximation of the boundary layer near the walls of the product the LRNM was chosen. By solving the flow and temperature fields determined distributions of interfacial heat and mass transfer coefficients in front and rear of the cylindrical slice of quince for all experimental conditions. The calculation of the weighted average prices of the interfacial heat transfer coefficient indicates a correlation between dimensionless numbers Nu, Re and Pr, in the form Nu = aRebPr1/3, which as finding enriches the existing literature. In the final stage of the thesis, developed and evaluated in comparison with the experi-mental measurements, a one-dimensional transient numerical model of heat and mass transfer to simulate drying curves in cylindrical slices of quince. The heat transfer inside the quince is considered to be by conduction while the moisture transfer is considered to be governed solely by liquid diffusion. Evaporation is considered to take place only from the windward and leeward surface of the quince slice. The numerical model takes into account the shrinkage of the cylindrical slice of quince, assuming that the cylindrical volume decreases each time as much as the volume of water that evaporates on both surfaces of the slice. The numerical code used the thermophysical properties of quince and air from the literature, the effective diffusion coefficient of moisture experimentally determined by the method of the slopes, while the transfer coefficients used the weighted average prices of interfacial heat and mass transfer coefficients derived from the simulations with CFD (non-conjugated approach). In order to achieve higher accuracy between experimental data and predictions, a non-linear regression analysis, using an Arrhenius type effective diffusion equation, was also performed. However, preliminary result, obtained using the SQP (Sequential Quadratic Programming) and Interior Point algorithms for the minimization of the Chi-square function (χ2) showed only small improvement of the calculated results with a significant increase of the computational cost. In conclusion, the overall assessment of the results of the numeric code shown that the proposed numerical model based on diffusion is able to effectively describe the coupling of heat transfer and mass, as to capture the time evolution of moisture content and temperature within the product, with minimum use of experimental input variables and minimum computational requirements. For these reasons it may be considered appropriate to analyze the convective drying process in any organic or non-organic product.

A significant amount of Viscous Oil (e.g., heavy oil, extra heavy oil, and bitumen) is trapped in Naturally Fractured Carbonate Reservoirs also known as NFCRs. The word VO endowment in NFCRs is estimated at ~ 2 Trillion barrels mostly reported in Canada, the USA, Russia, and the Middle East. To date, contributions to the world daily oil production from this immense energy resource remains negligible mainly due to the lack of appropriate production technologies. Implementation of a VO production technology such as steam injection is expensive (high capital investment), time-consuming, and people-intensive. Hence, before selecting a production technology for detailed economic analysis, use of cursory or broad screening tools or guides is a convenient means of gaining a quick overview of the technical feasibility of the various possible production technologies applied to a particular reservoir. Technical screening tools are only available for the purpose of evaluation of the reservoir performance parameters in oil sands for various thermal VO exploitation technologies such as Steam Assisted Gravity Drainage (SAGD), Cyclic Steam Stimulation (CSS), Horizontal well Cyclic steam Stimulation (HCS), and so on. Nevertheless, such tools are not applicable for VO NFCRs assessment without considerable modifications due to the different nature of these two reservoir types (e.g., presence and effects of fracture network on reservoir behavior, wettability, lithology, fabric, pore structure, and so on) and also different mechanisms of energy and mass transport. Considering the lack of robust and rapid technical reservoir screening tools for the purpose of quick assessment and performance prediction for VO NFCRs under thermal stimulation (e.g., steamflooding), developing such fast and precise tools seems inevitable and desirable. In this dissertation, an attempt was made to develop new screening tools for the purpose of reservoir performance prediction in VO NFCRs using all the field and laboratory available data on a particular thermal technology (vertical well steamflooding). Considering the complex and heterogeneous nature of the NFCRs, there is great uncertainty associated with the geological nature of the NFCRs such as fracture and porosity distribution in the reservoir which will affect any modeling tasks aiming at modeling of processes involved in thermal VO production from these types of technically difficult and economically unattractive reservoirs. Therefore, several modeling and analyses technqiues were used in order to understand the main parameters controlling the steamflooding process in NFCRs and also cope with the uncertainties associated with the nature of geologic, reservoir and fluid properties data. Thermal geomechanics effects are well-known in VO production from oil sands using thermal technologies such as SAGD and cyclic steam processes. Hence, possible impacts of thermal processes on VO NFCRs performance was studied despite the lack of adequate field data. This dissertation makes the following contributions to the literature and the oil industry: Two new statistical correlations were developed, introduced, and examined which can be utilized for the purpose of estimation of Cumulative Steam to Oil Ratio (CSOR) and Recovery Factor (RF) as measures of process performance and technical viability during vertical well steamflooding in VO Naturally Fractured Carbonate Reservoirs (NFCRs). The proposed correlations include vital parameters such as in situ fluid and reservoir properties. The data used are taken from experimental studies and also field trials of vertical well steamflooding pilots in viscous oil NFCRs reported in the literature. The error percentage for the proposed correlations is < 10% for the worst case and contains fewer empirical constants compared with existing correlations for oil sands. The interactions between the parameters were also considered. The initial oil saturation and oil viscosity are the most important predictive factors. The proposed correlations successfully predicted steam/oil ratios and recovery factors in two heavy oil NFCRs. These correlations are reported for the first time in the literature for this type of VO reservoirs. A 3-D mathematical model was developed, presented, and examined in this research work, investigating various parameters and mechanisms affecting VO recovery from NFCRs using vertical well steamflooding. The governing equations are written for the matrix and fractured medium, separately. Uncertainties associated with the shape factor for the communication between the matrix and fracture is eliminated through setting a continuity boundary condition at the interface. Using this boundary condition, the solution method employed differs from the most of the modeling simulations reported in the literature. A Newton-Raphson approach was also used for solving mass and energy balance equations. RF and CSOR were obtained as a function of steam injection rate and temperature and characteristics of the fractured media such as matrix size and permeability. The numerical solution clearly shows that fractures play an important role in better conduction of heat into the matrix part. It was also concluded that the matrix block size and total permeability are the most important parameters affecting the dependent variables involved in steamflooding. A hybrid Artificial Neural Network model optimized by co-implementation of a Particle Swarm Optimization method (ANN-PSO) was developed, presented, and tested in this research work for the purpose of estimation of the CSOR and RF during vertical well steamflooding in VO NFCRs. The developed PSO-ANN model, conventional ANN models, and statistical correlations were examined using field data. Comparison of the predictions and field data implies superiority of the proposed PSO-ANN model with an absolute average error percentage < 6.5% , a determination coefficient (R2) > 0.98, and Mean Squared Error (MSE) < 0.06, a substantial improvement in comparison with conventional ANN model and empirical correlations for prediction of RF and CSOR. This indicates excellent potential for application of hybrid PSO-ANN models to screen VO NFCRs for steamflooding. This is the first time that the ANN technique has been applied for the purpose of performance prediction of steamflooding in VO NFCRs and also reported in the literature. The predictive PSO-ANN model and statistical correlations have strong potentials to be merged with heavy oil recovery modeling softwares available for thermal methods. This combination is expected to speed up their performance, reduce their uncertainty, and enhance their prediction and modeling capabilities. An integrated geological-geophysical-geomechanical approach was designed, presented, and applied in the case of a NFCR for the purpose of fracture and in situ stresses characterization in NFCRs. The proposed methodology can be applied for fracture and in situ stresses characterization which is beneficial to various aspects of asset development such as well placement, drilling, production, thermal reservoir modeling incorporating geomechanics effects, technology assessment and so on. A conceptual study was also conducted on geomechanics effects in VO NFCRs during steamflooding which is not yet well understood and still requires further field, laboratory, and theoretical studies. This can be considered as a small step forward in this area identifying positive potential of such knowledge to the design of large scale thermal operations in VO NFCRs.

A significant amount of Viscous Oil (e.g., heavy oil, extra heavy oil, and bitumen) is trapped in Naturally Fractured Carbonate Reservoirs also known as NFCRs. The word VO endowment in NFCRs is estimated at ~ 2 Trillion barrels mostly reported in Canada, the USA, Russia, and the Middle East. To date, contributions to the world daily oil production from this immense energy resource remains negligible mainly due to the lack of appropriate production technologies. Implementation of a VO production technology such as steam injection is expensive (high capital investment), time-consuming, and people-intensive. Hence, before selecting a production technology for detailed economic analysis, use of cursory or broad screening tools or guides is a convenient means of gaining a quick overview of the technical feasibility of the various possible production technologies applied to a particular reservoir. Technical screening tools are only available for the purpose of evaluation of the reservoir performance parameters in oil sands for various thermal VO exploitation technologies such as Steam Assisted Gravity Drainage (SAGD), Cyclic Steam Stimulation (CSS), Horizontal well Cyclic steam Stimulation (HCS), and so on. Nevertheless, such tools are not applicable for VO NFCRs assessment without considerable modifications due to the different nature of these two reservoir types (e.g., presence and effects of fracture network on reservoir behavior, wettability, lithology, fabric, pore structure, and so on) and also different mechanisms of energy and mass transport. Considering the lack of robust and rapid technical reservoir screening tools for the purpose of quick assessment and performance prediction for VO NFCRs under thermal stimulation (e.g., steamflooding), developing such fast and precise tools seems inevitable and desirable. In this dissertation, an attempt was made to develop new screening tools for the purpose of reservoir performance prediction in VO NFCRs using all the field and laboratory available data on a particular thermal technology (vertical well steamflooding). Considering the complex and heterogeneous nature of the NFCRs, there is great uncertainty associated with the geological nature of the NFCRs such as fracture and porosity distribution in the reservoir which will affect any modeling tasks aiming at modeling of processes involved in thermal VO production from these types of technically difficult and economically unattractive reservoirs. Therefore, several modeling and analyses technqiues were used in order to understand the main parameters controlling the steamflooding process in NFCRs and also cope with the uncertainties associated with the nature of geologic, reservoir and fluid properties data. Thermal geomechanics effects are well-known in VO production from oil sands using thermal technologies such as SAGD and cyclic steam processes. Hence, possible impacts of thermal processes on VO NFCRs performance was studied despite the lack of adequate field data. This dissertation makes the following contributions to the literature and the oil industry: Two new statistical correlations were developed, introduced, and examined which can be utilized for the purpose of estimation of Cumulative Steam to Oil Ratio (CSOR) and Recovery Factor (RF) as measures of process performance and technical viability during vertical well steamflooding in VO Naturally Fractured Carbonate Reservoirs (NFCRs). The proposed correlations include vital parameters such as in situ fluid and reservoir properties. The data used are taken from experimental studies and also field trials of vertical well steamflooding pilots in viscous oil NFCRs reported in the literature. The error percentage for the proposed correlations is < 10% for the worst case and contains fewer empirical constants compared with existing correlations for oil sands. The interactions between the parameters were also considered. The initial oil saturation and oil viscosity are the most important predictive factors. The proposed correlations successfully predicted steam/oil ratios and recovery factors in two heavy oil NFCRs. These correlations are reported for the first time in the literature for this type of VO reservoirs. A 3-D mathematical model was developed, presented, and examined in this research work, investigating various parameters and mechanisms affecting VO recovery from NFCRs using vertical well steamflooding. The governing equations are written for the matrix and fractured medium, separately. Uncertainties associated with the shape factor for the communication between the matrix and fracture is eliminated through setting a continuity boundary condition at the interface. Using this boundary condition, the solution method employed differs from the most of the modeling simulations reported in the literature. A Newton-Raphson approach was also used for solving mass and energy balance equations. RF and CSOR were obtained as a function of steam injection rate and temperature and characteristics of the fractured media such as matrix size and permeability. The numerical solution clearly shows that fractures play an important role in better conduction of heat into the matrix part. It was also concluded that the matrix block size and total permeability are the most important parameters affecting the dependent variables involved in steamflooding. A hybrid Artificial Neural Network model optimized by co-implementation of a Particle Swarm Optimization method (ANN-PSO) was developed, presented, and tested in this research work for the purpose of estimation of the CSOR and RF during vertical well steamflooding in VO NFCRs. The developed PSO-ANN model, conventional ANN models, and statistical correlations were examined using field data. Comparison of the predictions and field data implies superiority of the proposed PSO-ANN model with an absolute average error percentage < 6.5% , a determination coefficient (R2) > 0.98, and Mean Squared Error (MSE) < 0.06, a substantial improvement in comparison with conventional ANN model and empirical correlations for prediction of RF and CSOR. This indicates excellent potential for application of hybrid PSO-ANN models to screen VO NFCRs for steamflooding. This is the first time that the ANN technique has been applied for the purpose of performance prediction of steamflooding in VO NFCRs and also reported in the literature. The predictive PSO-ANN model and statistical correlations have strong potentials to be merged with heavy oil recovery modeling softwares available for thermal methods. This combination is expected to speed up their performance, reduce their uncertainty, and enhance their prediction and modeling capabilities. An integrated geological-geophysical-geomechanical approach was designed, presented, and applied in the case of a NFCR for the purpose of fracture and in situ stresses characterization in NFCRs. The proposed methodology can be applied for fracture and in situ stresses characterization which is beneficial to various aspects of asset development such as well placement, drilling, production, thermal reservoir modeling incorporating geomechanics effects, technology assessment and so on. A conceptual study was also conducted on geomechanics effects in VO NFCRs during steamflooding which is not yet well understood and still requires further field, laboratory, and theoretical studies. This can be considered as a small step forward in this area identifying positive potential of such knowledge to the design of large scale thermal operations in VO NFCRs.

The performance of solid oxide fuel cells (SOFCs) at the cell and system levels is studied using computer simulation. At the cell level, a new model combining the cell micro and macro models is developed. Using this model, the microstructural variables of porous composite electrodes can be linked to the cell performance. In this approach, the electrochemical performance of porous composite electrodes is predicted using a micro-model. In the micro-model, the random-packing sphere method is used to estimate the microstructural properties of porous composite electrodes from the independent microstructural variables. These variables are the electrode porosity, thickness, particle size ratio, and size and volume fraction of electron-conducting particles. Then, the complex interdependency among the multi-component mass transport, electron and ion transports, and the electrochemical and chemical reactions in the microstructure of electrodes is taken into account to predict the electrochemical performance of electrodes. The temperature distribution in the solid structure of the cell and the temperature and species partial pressure distributions in the bulk fuel and air streams are predicted using the cell macro-model. In the macro-model, the energy transport is considered for the cell solid structure and the mass and energy transports are considered for the fuel and air streams. To demonstrate the application of the cell level model developed, entitled the combined micro- and micro-model, several anode-supported co-flow planar cells with a range of microstructures of porous composite electrodes are simulated. The mean total polarization resistance, the mean total power density, and the temperature distribution in the cells are predicted. The results of this study reveal that there is an optimum value for most of the microstructural variables of the electrodes at which the mean total polarization resistance of the cell is minimized. There is also an optimum value for most of the microstructural variables of the electrodes at which the mean total power density of the cell is maximized. The microstructure of porous composite electrodes also plays a significant role in the mean temperature, the temperature difference between the hottest and coldest spots, and the maximum temperature gradient in the solid structure of the cell. Overall, using the combined micro- and micro-model, an appropriate microstructure for porous composite electrodes to enhance the cell performance can be designed. At the system level, the full load operation of two SOFC systems is studied. To model these systems, the basic cell model is used for SOFCs at the cell level, the repeated-cell stack model is used for SOFCs at the stack level, and the thermodynamic model is used for the balance of plant components of the system. In addition to these models, a carbon deposition model based on the thermodynamic equilibrium assumption is employed. For the system level model, the first SOFC system considered is a combined heat and power (CHP) system that operates with biogas fuel. The performance of this system at three different configurations is evaluated. These configurations are different in the fuel processing method to prevent carbon deposition on the anode catalyst. The fuel processing methods considered in these configurations are the anode gas recirculation (AGR), steam reforming (SR), and partial oxidation reformer (POX) methods. The application of this system is studied for operation in a wastewater treatment plant (WWTP) and in single-family detached dwellings. The evaluation of this system for operation in a WWTP indicates that if the entire biogas produced in the WWTP is used in the system with AGR or SR fuel processors, the electric power and heat required to operate the plant can be completely supplied and the extra electric power generated can be sold to the electrical grid. The evaluation of this system for operation in single-family detached dwellings indicates that, depending on the size, location, and building type and design, this system with all configurations studied is suitable to provide the domestic hot water and electric power demands. The second SOFC system is a novel portable electric power generation system that operates with liquid ammonia fuel. Size, simplicity, and high electrical efficiency are the main advantages of this environmentally friendly system. Using a sensitivity analysis, the effects of the cell voltage at several fuel utilization ratios on the number of cells required for the SOFC stack, system efficiency and voltage, and excess air required for thermal management of the SOFC stack are studied.

Le contexte industriel est favorable aux échangeurs-réacteurs catalytiques intensifiés puisqu’ils permettent une diminution des limitations aux transferts de matière et de chaleur comparé aux réacteurs conventionnels. Toutefois, l'industrialisation de ces unités est problématique à cause de l'absence de logiciel d’ingénierie de prédiction et d’optimisation de leurs performances. Afin de construire un tel outil, les écoulements, les transferts de matière interne et externe liés aux réactions catalytiques hétérogènes, les transferts de chaleur convectif, conductif, diffusif et par rayonnement sont d’abord analysés, permettant de formuler des hypothèses simplificatrices. Les phénomènes pertinents identifiés sont ensuite mis en équations pour créer la base physique de ProSec Réaction, le nouveau logiciel de simulation des échangeurs-réacteurs. Ce logiciel est validé par comparaison avec les résultats expérimentaux du pilote de vaporeformage du méthane d'Air Liquide et par confrontation avec des simulations tri-dimensionnelles de celui-ci (CFD). L'excellente adéquation entre les résultats expérimentaux et numériques démontre le potentiel de prédiction du modèle mono-dimensionnel développé. Dans le cas particulier des échangeurs-réacteurs à plaques et ailettes catalytiques (wash-coat), une représentation bi-dimensionnelle discrète est construite et permet de tenir compte des effets thermiques radiaux intrinsèques à ces échangeurs particuliers. Enfin, ProSec Réaction est exploité pour évaluer les perspectives d'optimisation géométrique des canaux de l'échangeur-réacteur du pilote d'Air Liquide. Celles-ci montrent la flexibilité et l'intérêt de ce nouvel outil de simulation / Intensified heat exchanger reactors are promising technologies in the current industrial context because of their high potential to significantly reduce heat and mass transfer limitations compared to conventional reactors. However, the absence of simulation software for predicting their performances and optimising their geometry inside a flowsheet is limiting the industrialisation of these units. Preliminary to the development of such a simulation tool, flow characteristics, internal and external mass transfers inherent to heterogeneous catalytic reactions, convective, conductive, diffusive and radiative heat transfers are analysed, allowing the definition of simplifying assumptions. The identified relevant phenomena are then modelled and constitute the physical base of ProSec Reaction, the new heat exchanger-reactor simulation software. This software is validated by comparing the predicted values to the Air Liquide steam reforming pilot plant results and to three-dimensional simulation results as well (CFD). The excellent consistency between numerical and experimental results demonstrates the accuracy and the predictive potential of the developed one-dimensional model. In the specific case of wall-coated plate-fin heat exchanger reactors, a discrete two-dimensional model is built and allows the representation of radial temperature gradients in the material, which are intrinsic to these specific heat exchangers. Finally, optimisation perspectives of the Air Liquide pilot plant heat exchanger reactor channel geometry are evaluated thanks to ProSec Reaction. They demonstrate the flexibility and the benefits of this new simulation tool