At Anglo American Platinum's Precious Metal Refinery, rhodium separates from a base metal-rich solution by precipitation. Hexachlororhodate (III) ions and cationic protonated diethylenetriamine ions exchange to form diethylenetriammonium hexachlororhodate (III) crystals, a rhodium metal precursor. The objective of this work is to determine nucleation and growth kinetics of diethylenetriammonium hexachlororhodate (III) salt. Two reactor configurations, namely a transient continuous stirred tank reactor (CSTR) and a t-mixer plug flow reactor (PFR), were used to determine nucleation and growth rates. The objective of the configurations was to eliminate kinetic biases that may be caused by mixing at the mesoscale. Transient saturation in the CSTR ranged up to 43, and in the PFR saturation was varied between 2 and 64. Precipitation kinetic parameters were estimated through data fitting concentration and volume average crystal size profiles to a mass and population balance model. Temperature dependence of kinetic parameters was found to be universal between reactor configurations. Both growth through interfacial attachment and agglomeration, as defined in this work, were exothermic processes with activation energies of -192.9kJ/mol and -656.1kJ/mol respectively. Nucleation was found to be an endothermic process with an activation energy of 50.9kJ/mol in accord with the observed heat of crystallisation. No evidence of heterogeneous primary nucleation in the form of crystals adhering to the side walls of the reactor or the agitator blades was observed. The experiments were not explicitly designed to distinguish between primary and secondary nucleation mechanisms, therefore excluding one over the other is not justified. However, considering the presence of nucleated crystals in each system combined with the good model fit using a nucleation rate expression typically associated with secondary nucleation, it is likely that the dominating nucleation mechanism is secondary in nature. In the PFR configuration, nucleation and growth occur at a faster rate compared to the CSTR under the experimental conditions in this work. This observation is inferred from the fitted temperature independent kinetic parameters and is linked to a much higher mixing intensity achieved in the PFR relative to the CSTR. Flow conditions, described by the Reynolds number, can limit conversion in the PFR configuration by a mixing limitation at the micro- or mesoscale. Micro- and mesoscale mixing were represented by a characteristic length scale that was empirically related to temperature for the microscale and fluid velocity for the mesoscale. Under conditions where the Reynolds number is below the point where conversion is independent of the Reynolds number, either micromixing or mesomixing can become a rate limitation. At a sufficiently high Reynolds number neither micromixing nor mesomixing limits conversion and the system equilibrium becomes the limitation. In the CSTR, the system equilibrium limited reaction conversion as the micro- and mesoscale mixing zones were sufficiently small relative to the reactor volume. Parameters related to mixing were found to differ between the configurations, which was caused by different flow patterns within each configuration. Scanning electron microscopy (SEM) photographs suggest that crystals in the PFR configuration collide both in the radial and axial direction, giving rise to a feathery flat and elongated agglomerated crystal cluster. In contrast, the crystals in the CSTR configuration collide in a chaotic but consistent pattern, giving rise to a desert rose-like agglomerated crystal cluster. The derived model used to describe agglomeration is based on the agglomeration principles proposed by Von Smoluchowski coupled with Fick's law of diffusion and gives a good representation of crystal size. The PFR growth rate supersaturation exponent was 1.13, suggesting a Burton-Cabrera-Frank type growth model, and is indicative of crystal growth from screw dislocations that is limited either through mass transfer to the crystal surface, or surface integration. Thus, in this instance, the rate of aqueous hexachlororhodate (III) conversion to crystal would be responsive to mixing conditions on the micro- or mesoscale, as was experimentally found in the PFR configuration. In comparison, the CSTR growth rate supersaturation exponent was 2.31 and is more in line with polynuclear growth that appears to be limited by interfacial attachment kinetics, as the system equilibrates in the bulk. Lastly, a key finding of this work is the ability to manipulate the crystal morphology by changing reactor configuration. By creating elongated flat crystal structures in the PFR configuration as opposed to a desert rose crystal structure in the CSTR, it may be possible to reduce impurities within the crystal by entraining less mother liquor.

Bioreactors are used to carry out bioprocesses and are commonly used in e.g. biogas production and wastewater treatment. Two common hydraulic models of bioreactors are the continuous stirred tank reactor (CSTR) and the plug-flow reactor (PFR). In this paper, a differential equation system that describes the substrate, biomass and inert biomass in the bioreactors is presented. It is used in a steady-state analysis and design of CSTRs in series. Monod kinetics were used to describe the specific growth rate and the decay of biomass was included. Using the derived systems of differential equations, two optimization problems were formulated and solved for both CSTRs in series and for a CSTR+PFR. The first optimization problem was to minimize the effluent substrate level given a total volume, and the second was to minimize the total volume needed to obtain a certain substrate conversion. Results show that the system of differential equations presented can be used to find optimal volume distributions that solves the optimization problems. The optimal volume for N CSTRs in series decreases as N increases, converging towards a configuration of a CSTR followed by a PFR. Analyzing how the decay rate affects the results showed that when the total volume was kept constant, increasing the decay rate caused less difference between the configurations. When the total volume was minimized, increasing the decay rate caused the configurations to diverge from each other. The presented model can be used to optimally divide reactors into smaller zones and thereby increasing the substrate conversion, something that could be of interest in e.g. existing wastewater treatment plants with restricted space. A fairly accurate approximation to the optimal design of N CSTRs in series is to use the optimal volume for the CSTR in the configuration with a CSTR+PFR and equally distribute the remaining volumes. / Bioreaktorer används för att utföra olika biologiska processer och används vanligen inom biogasproduktion eller för rening av avloppsvatten. Två vanliga hydrauliska modeller som används vid modellering av bioreaktorer är helomblandad bioreaktor (på engelska continuous stirred tank reactor, CSTR) eller pluggflödesreaktor (på engelska plug-flow reactor, PFR). I den här rapporten presenteras ett system av differentialekvationer som används för att beskriva koncentrationerna av substrat, biomassa och inert biomassa i både CSTR och PFR. Ekvationssystemet används för analys och design av en serie CSTRs vid steady-state. Tillväxten av biomassa beskrivs av Monod-kinetik. Avdödning av biomassa är inkluderat i studien. Från ekvationssystemet formulerades två optimeringsproblem som löstes för N CSTRs i serie och för CSTR+PFR. Det första optimerinsproblemet var att minimera substrathalten i utflödet givet en total volym. I det andra minimerades den totala volymen som krävs för att nå en viss substrathalt i utflödet. Resultaten visade att ekvationssystemet kan användas för att hitta den optimala volymsfördelningen som löser optimeringsproblemen. Den optimala volymen för N CSTRs i serie minskade när antalet CSTRs ökade. När N ökade konvergerade resultaten mot de för en CSTR sammankopplad med en PFR. En analys av hur avdödningshastigheten påverkade resultaten visade att en ökad avdödningshastighet gav mindre skillnad mellan de två olika konfigurationerna när den totala volymen hölls konstant. När den totala volymen istället minimerades ledde en ökad avdödningshastighet till att de två konfigurationerna divergerade från varandra. Modellen som presenteras i studien kan användas för att fördela en total reaktorvolym i mindre zoner på ett optimalt sätt och på så vis öka substratomvandlingen, något som kan vara av intresse i exempelvis befintliga avloppsreningsverk där utrymmet är begränsat. En relativt bra approximation till den optimala designen av N CSTRs i serie är att optimera volymerna för en CSTR+PFR, använda volymen för CSTR som första volym i konfigurationen med N CSTR i serie, och sedan fördela den kvarvarande volymen lika mellan de övriga zonerna.

Το Πι-κριτήριο των Bittanti et al. (1973) έχει χρησιμοποιηθεί εκτενώς σε εφαρμογές με στόχο την πρόβλεψη ενδεχόμενης βελτίωσης της απόδοσης ενός μη γραμμικού συστήματος υπό περιοδική είσοδο. Το κριτήριο όμως έχει τοπική ισχύ και περιορίζεται σε περιοδικές διαταραχές μικρού πλάτους. Η παρούσα εργασία αναπτύσσει μια μέθοδο προσδιορισμού διορθώσεων υψηλότερης τάξης στο πι-κριτήριο, προερχόμενη από βασικά αποτελέσματα της θεωρίας κεντρικής πολλαπλότητας (Center Manifold theory). Η προτεινόμενη μέθοδος βασίζεται στην επίλυση της μερικής διαφορικής εξίσωσης της κεντρικής πολλαπλότητας με χρήση δυναμοσειρών. Το τελικό αποτέλεσμα της προτεινόμενης προσέγγισης είναι ο κατά προσέγγιση υπολογισμός του δείκτη απόδοσης υπό μορφή σειράς, η οποία παρέχει ακριβή αποτελέσματα σε μεγαλύτερα εύρη. Η προτεινόμενη μέθοδος εφαρμόζεται σε έναν συνεχή αντιδραστήρα πλήρους ανάδευσης (CSTR), όπου στόχος είναι η μεγιστοποίηση της παραγωγής του επιθυμητού προϊόντος. Κατασκευάστηκε αλγόριθμος που προβλέπει την μόνιμη κατάσταση στην οποία καταλήγει ένα σύστημα απομάκρυνσης αζώτου που αποτελείται από αντιδραστήρα εμβολικής ροής και δεξαμενή δευτεροβάθμιας καθίζησης με ανακύκλωση. Με χρήση υπολογιστικού μοντέλου βασιζόμενο στο ASM3 υπολογίστηκαν οι μόνιμες καταστάσεις αυτού του συστήματος για ένα εύρος καταστάσεων λειτουργίας. Βρέθηκαν οι βέλτιστες τιμές των βαθμών ελευθερίας για την ελαχιστοποίηση του συνολικού αερισμού και για την ελαχιστοποίηση του συνολικού αζώτου στην απορροή. Και στις δύο περιπτώσεις στις βέλτιστες μόνιμες καταστάσεις παρατηρήθηκε έκπλυση των Nitrobacter δηλαδή παράκαμψη της παραγωγής των νιτρικών. / The frequency-dependent Pi criterion of Bittanti et al. (1973) has been used extensively in applications to predict potential performance improvement under periodic forcing in a nonlinear system. The criterion, however, is local in nature and is limited to periodic forcing functions of small magnitude. The present work develops a method to determine higher-order corrections to the pi criterion, derived from basic results of Center Manifold theory. The proposed method is based on solving the Center Manifold partial differential equation via power series. The end result of the proposed approach is the approximate calculation of the performance index in the form of a series expansion, which provides accurate results under larger amplitudes. The proposed method is applied to a continuous stirred tank reactor, where the yield of the desired product must be maximized. An algorithm was constructed, that predicts the steady state of a nitrogen removal system consisting of a plug flow reactor and a secondary clarifier with recycle. Using a numerical model based on ASM3 and a grid of degrees of freedom, the steady states of this system were calculated. The optimal values for minimizing the total aeration were found, as well as those for minimizing the total nitrogen exit flow. In both cases the Nitrobacter bacteria were washed out thus indicating the bypassing of nitrate production.

Novel integrated ozone contactor design and optimization tools which consist of an instrument that measures ozone decay kinetics, a program that performs predictive simulation, and an experimental method to examine mixing characteristics within the ozone contactor, were developed in this study. A multi-channel stopped-flow reactor (MC-SFR) is an instrument that performs automatic, real-time, and continuous analysis of ozone decay kinetics in natural waters. Ozone Contactor Model (OCM) is the software to simulate the performance of full-scale ozone bubble-diffuser contactors in support of current and future regulations regarding pathogen and bromate control in drinking water. The MC-SFR and OCM developed in this study were further applied to simulate Cryptosporidium parvum oocyst log inactivation and bromate formation in Linnwood Water Plant Ozone Facility (LWPOF) at Milwaukee Water Works, Milwaukee, WI and model predictions were verified with experimental results. Three dimensional laser induced fluorescence(3DLIF) allowed real time characterization of mixing conditions in a physical model ozone contactors by capturing fluorescence image emitted from a laser dye (i.e. Rhodamine 6G) using a high speed CCD camera. 3DLIF system was applied to analyze the hydrodynamics of two representative types of ozone contactor: direct discharge side-stream venturi injector (SVI) and multi-chambered fine bubble diffuser (FBD). Experimental results verified the presence of circulative swirling related for low dispersion for SVI reactor and the existence of non-ideal flow including short circuiting and internal recirculation in FBD reactor. Finally, integrated tools were applied to the design of a new ozone contactor under planning stage to assess current design and to recommend the improvement.

La réalisation par des procédés robotisés de pièces composites à destination, notamment, de l’aéronautique vise à en augmenter la productivité. Cependant le Placement de Fibres Robotisé (PFR) est encore en phase de maturation et requiert de nombreux développements, en particulier dans le cas des composites à matrice thermoplastique ou à fibre sèche. Dans cette thèse, nous proposons différents outils qui permettent in fine de déterminer à l’avance la meilleure puissance de chauffe pour la mise en œuvre de ces composites. La difficulté réside dans le fait que cette puissance dépend de nombreux paramètres, non seulement au niveau de la matière utilisée (densité, chaleur spécifique. . .), mais encore au niveau du procédé lui-même (vitesse de déplacement, nombre et orientation des plis. . .). Nous avons construit un modèle réduit multi-paramétrique en utilisant la technique appelée Proper Generalised Decomposition (PGD). Les résultats ont été confrontés à ceux obtenus par des méthodes plus conventionnelles et aussi à des données expérimentales. / Realising composite parts mainly dedicated to aeronautics sector by robotised processes tends to increase productivity. However, Automated Tape Placement (ATP) is still in ripening stage and requires various developments, particularly in case of thermoplastic composites or dry fibres. In this manuscript, we propose different tools allowing to determine in advance the best heating power to drape composite fibres. Difficulty arises from dependence on many parameters, from material (density, specific heat) or from process itself (velocity, number and orientation of plies). Therefore we construct a multi-parametric reduced order model using the so called Proper Generalised Decomposition (PGD). Results have been faced to those obtained from more conventional methods but also to experimental data.

Eleven years ago Cisco introduced three types of applications on the same converged network and named it AVVID (Architecture for Voice, Video and Integrated Data). In spite of the initial interest and hype surrounding AVVID, the feature was and still is unable to confront problems such as: data priority, load balancing and network congestion. The work in this report addressed these issues within the network. Different Cisco Internetwork Operating System (IOS) methods: routing protocols, Cisco IOS QoS (including LLQ, LFI and Header Compression), Path Control and Cisco Performance Routing (PfR) were all tested to see which feature would work best at enhancing network performance. A practical network was created in which these features were carefully implemented one after another. In every step, the results were observed and recorded and if necessary repeated in order to check their validity. The results for RTT (Round Trip Time) and MOS (Mean Opinion Score) showed that in comparison to Path Control and Cisco IOS QoS (Quality of Service) mechanisms, Cisco PfR was able to generate routes on the fly during times of network congestion. This cannot be achieved with the use of Cisco QoS and Path Control which makes Cisco Performance Routing a far more superior feature. Although the focus of the work was VoIP (Voice over Internet Protocol) data, it is possible to construct a network with any application as Cisco PfR is able to reroute data. Cisco PfR is an easily accessible IOS feature which, once implemented, requires very little updating and maintenance.