Continuous milli-scale and micro-scale structures such as FlowPlate® microreactors have emerged as a promising element of process intensification due to their inherently effective rates of mass and heat transfer. These microfluidic devices have proven to be a preferred solution in place of energy-intensive batch processes for certain pathways of fine chemical and pharmaceutical synthesis, most notably fast reactions taking place on the scale of milliseconds to seconds. Computational fluid dynamics (CFD) has become an increasingly valuable tool in the field of microreactor design and optimization for its ability to locally map complex fluid flow patterns and resolve microscopic scales of reactive mixing that are challenging to characterize experimentally. The primary objective of this research was thus to develop and validate a mathematical model for the simulation of chaotic flow and homogeneous mixing in continuous microreactors. The model needed to be versatile enough to handle transition between flow regimes within a given reactor as well as the coexistence of both chaotic and laminar flow patterns in the micromixing elements that comprise said reactors. This was successfully achieved through the implementation of a k-ω SST (shear-stress transport) turbulence model that accounts for the impact of small-scale temporal and spatial fluctuations generated in the micromixer geometries studied herein; be it a liquid-liquid mixer (LLM), a serpentine (SZ) or a tangential (TG) mixer. In a first CFD study, the computational predictions were validated based on excellent agreement with experimental pressure loss (R^2 > 0.997) and residence time distribution (RTD) data (R^2 > 0.97) in several LL microreactors at Reynolds numbers ranging from 210 to 2140. Furthermore, the local velocity distribution and streamlines were mapped across the 3D domain of these reactors and it was discovered, based on the emergence of advective recirculation zones and turbulent dispersion, that a drastic change in flow behaviour occurred in these mixing elements at a Reynolds number of about 640. The interspacing of LLM elements with straight microchannels proved to be a suitable approach to modulating pressure loss while concurrently maintaining the chaotic secondary flow patterns generated from the mixers. In a second CFD study, the impact of micromixer geometry on the local velocity fields and advective transport performance was investigated both from a macromixing and micromixing perspective. Like the LLM, the SZ and TG mixers conferred chaotic secondary flow patterns at characteristic Reynolds numbers between 500 and 1000. As such, it was concluded that it would be ideal to operate these mixers at water flow rates of at least 30 ml/min. Contour plots of the velocity magnitude coupled with the computation of RTD showed that the SZ virtually mimics a plug-flow profile over a volume of 77 mm3 or greater at 50 g/min. The RTD of the LLM and TG resembles that of a mixed flow pattern given that approximately 65-80% of their fluid volume is occupied by recirculation zones. As such, it required 65 LLMs in series (3105 mm3) and 80 TGs (1142 mm3) to approach the same pattern as 10 SZs (77 mm3) from a macromixing perspective. Micromixing time distributions (MTD) were also characterized by locally computing the decay time of small-scale segregation (t_SSS) as a function of flow rate, wherein higher flow rates generated lower characteristic mixing times. The TG and LLM conferred the broadest range of mixing times, spanning nearly four orders of magnitude in the range of [0.02 ms, 10 ms], whereas the SZ generated a much narrower MTD ranging between [0.024 ms, 0.69 ms]. Finally, the impact of geometry and flow conditions on reaction yield was assessed by characterizing the extent of a finite-rate reaction relative to an infinitely fast reaction taking place in parallel. The calculated yield for the competitive-parallel reaction scheme showed that the second Damköhler number (Dall) computed based on the mean tSSS provides useful information about whether the process will be limited by the intrinsic rate of reaction or by the rate of mass transfer, even though the reaction process is controlled by a combination of the RTD as well as loss of LSS and SSS. It was concluded that the change in MTD as a function of power dissipation should coincide with the reaction yield response, and that any deviation in that relationship is because of macroscopic blending of reactants in the entrance region.

Hydrologic catchment response varies in time. The goal of this dissertation is to investigate how and why it varies and what controls these variations. In order to tackle these questions the first step is to develop a method that permits the capturing of the temporal variation of transit time distributions (TTDs). To this end, the established transfer function-convolution approach using time series of stable water isotopes was modified so that it is now able to determine variable mean transit times (mTTs). The type and the shape parameter of the transfer function also vary in time. We found that antecedent moisture content, saturated hydraulic conductivity, soil depth and subsequent precipitation intensity are all potential controls. We propose a dimensionless number that integrates these controls and relates available storage to incoming and outgoing water fluxes in combination with information on antecedent moisture conditions to predict TTD type and shape. The individual TTDs for every time step produced by this model can be superimposed, summed and normalized to create a classification tool for catchments that is based on its general response behavior to precipitation events: the master transit time distribution. With this model in hand the hydrologic response for three consecutive monsoon seasons in ten nested subcatchments was examined. It was found that the major response controls were changing between the years in accordance with three hydrologic response modes. The mTT correlated most strongly with soil depth in the first year, with hydraulic conductivity in the second year and with curvature in the third year. These variations were produced by differences in precipitation patterns that led to differences in soil saturation and consequently to different dominant flow processes: in the first year most of the water left the catchment via fast flow paths (macropore flow, overland flow), in the second year shallow subsurface flow in the soil matrix was more dominant and in the third year most outflowing water derived from slow base flow. To better predict hydrologic catchment response we propose to apply a dimensionless number to determine the catchment response mode for every time step before selecting the appropriate response control.

Modèle monodimensionnel de type Piston-Dispersion. Le terme de dispersion axiale englobe alors toutes les imperfections de l'écoulement : injection des fluides non homogène dans l’espace et étalée dans le temps, effet de parois, et enfin volumes morts derrière les obstacles noyés dans le tamis (poutres, conduites...) dans le cas des Lits Mobiles Simulés. Cette représentation, quoique très simpliste, s'avère généralement suffisante tant que l’étalement des fronts de concentration est d'abord induit par les limitations au transfert externe, interne (macro/microporeux) et par la thermodynamique du système. Par contre, lorsque l’adsorbant employé présente d’excellentes performances de transfert, une approche aussi simple s'avère extrêmement risquée. En effet, les phénomènes dispersifs associés à l’adsorbant (transfert et thermodynamique) et à l’hydrodynamique ont des contributions de même ordre de grandeur sur la dispersion des fronts de concentration. Dans ce cas, une description plus réaliste de l'écoulement est requise afin de mieux appréhender son effet sur les performances de séparation.Dans ce contexte, l’objectif de ce projet de thèse est de mettre en place une méthodologie pour prendre en compte ces phénomènes hydrodynamiques lors de l’extrapolation d’un procédé de séparation par adsorption. Pour cela, nous proposons une étude du couplage entre les phénomènes hydrodynamiques et le phénomène d’adsorption. / Hydrodynamics inside industrial Simulated Moving Bed (SMB) adsorption columns can be complex due to the presence of internal distribution devices, free flow chambers and heterogeneous injections. These have to be taken into account in SMB numerical models to scale-up purposes. In the present thesis, a CFD approach is adopted as an intermediate step to develop a 1D model simple enough to be used for cyclic SMB simulations while being able to represent realistic hydrodynamics. This model results from the interpretation of the moments of the fluid age distribution, transported by CFD according to the method developed by Liu and Tilton (2010) that allows to estimate the degree of mixing (Liu, 2011) of the adsorption columns. The resulting 1D model consists in the two examples provided by Zwietering (1959) of a completely segregated system and a maximum mixedness system. This model is able to reproduce the residence time distribution of the CFD model of an adsorption column, while being representative of the internal flow patterns. This results in a good representation of the coupling of adsorption and hydrodynamics by the 1D model. When integrated in a SMB simulator and compared to the traditionally used dispersed plug flow model, the new 1D model demonstrates that for most of the adsorption column geometries considered a detailed hydrodynamic description is mandatory. Such detailed hydrodynamic description is even more important when employing adsorbents with better mass transfer performances than those currently used for the p-xylene purification, which is expected in the upcoming years.

É apresentado um estudo de distribuição do tempo de residência nas etapas de um processo de pasteurização contínuo por trocador de calor a placas (aquecimento, resfriamento, regeneração e retenção). Para o estudo experimental, foi adotada a técnica condutimétrica usando cloreto de sódio em solução aquosa como traçador. Foram verificadas as influências da vazão, da configuração do trocador de calor a placas (número de passes para o arranjo em série) e do tipo de tubo de retenção (tubo em \"S\" e tubo helicoidal). Modelos de distribuição foram usados para representar o comportamento experimental (dispersão axial, tanques em série, laminar modificado, combinado PFR+CSTR). Este estudo foi aplicado para as condições de pasteurização HTST de leite, visando a futura implementação de uma modelagem matemática rigorosa do processo, para otimização do projeto e operação do processo. / It is presented a study of residence time distribution in the steps of a process of continuous pasteurization by plate heat exchanger (heating, cooling, regeneration and holding). For the experimental study, it was adopted a conductimetric technique using sodium chloride in aqueous solution as a tracer. It was also studied the influence of the flow rate, the configuration of the plate heat exchanger (number of passes in series arrangement) and the type of holding tube (\"S\"- shaped tube and helicoidal tube). Distribution models were used for representing the experimental behavior (axial dispersion, tank in series, modified laminar, combined PFR+CSTR). This study was applied for the conditions of HTST pasteurization of milk, targeting the future implementation of a rigorous mathematical modeling of the process, which can be applied for the process operation and optimization of the project design.

Os trocadores de calor tubulares são muito utilizados para o processamento térmico de alimentos líquidos viscosos por possuírem um maior diâmetro hidráulico em comparação aos trocadores de calor a placas. O cálculo da letalidade neste tipo de trocador está diretamente relacionado ao perfil de velocidade e à distribuição do tempo de residência (DTR). Para escoamento laminar de fluidos viscosos, Newtonianos e não-Newtonianos, geralmente adota-se um perfil de velocidade laminar e de lei de potência, respectivamente. No entanto, algumas características do equipamento como irregularidades na tubulação, a corrugação do tubo ou as curvas podem modificar o perfil de velocidade ideal. Esse desvio da idealidade pode ser caracterizado através da determinação experimental da distribuição do tempo de residência do processo. Este trabalho teve como objetivo a determinação experimental da DTR de fluidos viscosos em um equipamento bitubular de processamento térmico e o ajuste do perfil de velocidade associado. Modelos clássicos de DTR foram ajustados aos dados, assim como foram propostos e testados novos modelos generalizados de DTR, a fim de caracterizar o escoamento laminar não ideal em tubos. A determinação da DTR experimental foi realizada para vazões entre 10 e 50 L/h utilizando água, solução de carboximeticelulose 1,0% (pseudoplástico) e mistura glicerina/água 80%. Os dados de DTR foram obtidos através de duas técnicas: condutimétrica e colorimétrica. A primeira técnica baseia-se na injeção de solução saturada de cloreto de sódio e detecção online por um condutivímetro, porém, não apresentou resultados satisfatórios mostrando que o método não é adequado para fluidos viscosos. Já a segunda técnica utilizada se baseia na injeção de corante e posterior detecção em espectrofotômetro. Os modelos que melhor se ajustaram aos dados experimentais para os três fluidos estudados foram os modelos generalizados y-laminar e exponencial. A letalidade foi calculada a partir da distribuição de temperatura no trocador de calor em estado estacionário e do tempo médio de residência obtido experimentalmente e permitiu detectar o sobreprocessamento no processo estudado. / Tubular heat exchangers are widely used for thermal processing of viscous liquid foods because they have larger hydraulic diameters than the plate heat exchangers. The calculation of lethality in this type of exchanger is directly related to velocity profile and the residence time distribution (RTD). For the laminar flow of viscous fluids, Newtonian and non-Newtonian, generally laminar and power law velocity profiles are used, respectively. However, some features of the equipment as irregularities in the pipe, the corrugation of the pipe or the presence of curves can change the ideal velocity profile. This ideality deviation can be characterized through the experimental determination of the residence time distribution of the process. The aim of this work was the experimental determination of the RTD of a viscous fluid in a bitubular thermal processing equipment and the determination of the associated velocity profile. Classic models of RTD were fitted to the data, as well as were proposed and tested new generalized models of RTD, in order to characterize the non ideal laminar flow in tubes. The experimental determination of RTD was performed to volumetric flow rates between 10 and 50 L/h using water, carboximeticelulose solution 1,0% (pseudoplastic) and glycerin/water mixture 80%. The RTD data were obtained through two techniques: conductimetric and colorimetric. The first technique is based on injection of saturated solution of sodium chloride and online detection with a conductivimeter however, unsatisfactory results showed that the method was not suitable for viscous fluids. The second technique is based on the injection of dye and subsequent detection with a spectrophotometer. The best fitted models to the experimental data for the three studied fluids were: ylaminar and exponential generalized models. The lethality was calculated from the temperature distribution in the heat exchanger at steady state and average residence time obtained experimentally and allowed the evaluation of the overprocessing of this process.

O processo de pasteurização tem como objetivo garantir a segurança e qualidade nutricional do alimento e aumentar sua vida de prateleira. O conhecimento da distribuição do tempo de residência (DTR) do alimento em cada etapa do processo contínuo é importante para uma avaliação adequada do processo e das alterações que causa no alimento. Este trabalho tem como objetivo estudar a DTR em um processo de pasteurização contínuo assistido por micro-ondas aplicado a alimentos líquidos e propor modelos de escoamento para representá-la. Para isso, foram realizados experimentos de estímulo-resposta com alimentação tipo pulso por técnica condutimétrica utilizando uma solução saturada de NaCl como traçador. Com isso, foram obtidas as curvas de DTR do sistema completo, dos trocadores de calor das seções de pré-aquecimento e resfriamento, de seis tubos de retenção com diferentes diâmetros e comprimentos (volumes entre 40 e 125 mL) e do sistema de aquisição de dados de condutividade elétrica. Os experimentos foram realizados em quatro vazões volumétricas (0,5, 0,7, 0,9 e 1,1 L/min), a temperatura ambiente (19 a 26 °C) e como fluido de trabalho foi utilizada uma corrente de alimentação de água com concentração 0,5 g/L de NaCl para estabilizar a leitura de condutividade elétrica. Foram realizadas três repetições por vazão para o processo completo, trocadores de calor e tubos de retenção, e cinco repetições por vazão para o sistema de aquisição de dados, dada a maior sensibilidade. Observou-se a necessidade de realizar o procedimento de convolução numérica para avaliar a distorção na curva de DTR do processo causada pelo escoamento na célula do sistema de aquisição de dados. Foram testados cinco modelos de escoamento: dispersão axial, compartimentado PFR+CSTR, tanques em série, convecção generalizada e y-laminar. O critério de ajuste dos modelos foi a minimização do erro quadrático entre valores experimentais e calculados da curva E(t). Os modelos de dispersão axial e y-laminar foram o que apresentaram melhor ajuste para os tubos de retenção e o modelo de convecção generalizada apresentou melhor ajuste para os trocadores de calor. O regime de escoamento durante os experimentos variou entre laminar e de transição (valores de Reynolds entre 1259 e 4238). Os resultados para o sistema completo e trocadores de calor foram satisfatórios, para os tubos de retenção foi observada uma grande incerteza nos valores dos parâmetros e foi observada a importância da convolução numérica em sistemas de pequeno volume. / Pasteurization process aims to ensure the safety and nutritional quality of the food and increase its shelf life. The knowledge of residence time distribution (RTD) of the food in each step of continuous processes is important to evaluate the process and changes that it causes in foods. This work aims to study the RTD in a continuous pasteurization process assisted by microwave applied to liquid foods and propose flow models to represent it. For this reason, stimulus-response experiments by pulse injection were conducted by conductimetric technique using a saturated solution of NaCl as a tracer. Thus, it was obtained the RTD of the complete process, heat exchangers of preheating section and cooling section, six retention tubes with different diameters and lengths (volumes between 40 and 125 mL) and of the electrical conductivity data acquisition system. The experiments were carried out at four volumetric flow rates (0.5, 0.7, 0.9 and 1.1 L/min), at room temperature (19 to 26 °C) and water with 0.5 g/L of NaCl was used as the work fluid to stabilize the electrical conductivity reading. Three repetitions per volumetric flow rate were performed for the complete process, heat exchangers and holding tubes, and five repetitions per volumetric flow rate were performed for the data acquisition system, given the higher sensibility. It was observed the need to apply the numerical convolution procedure to evaluate the distortion in the RTD curve of the process caused by the flow through the data acquisition system. Five flow models were tested: axial dispersion, PFR+CSTR association, tanks in series, generalized convection and y-laminar. The adjustment criterion of the parameters was the minimization of the quadratic error between experimental and calculated E(t) values. The axial dispersion and y-laminar models provided the best adjustments for the holding tubes and the generalized convection model provided the best adjustment for the heat exchangers. The flow regime during the experiments varied between laminar and transition (Reynolds values between 1259 and 4238). The results for the complete system and heat exchangers were satisfactory, for the holding tubes was observed a great uncertainty in the parameters values and was observed the importance of numerical convolution in small volume systems.

The current work has developed a CFD model to characterise a pseudo-annular photocatalytic bubble column reactor. The model development was divided into three stages. Firstly, hydrodynamic assessment of the multiphase fluid flow in the vessel, which incorporated residence time distribution analysis both numerically and experimentally for validation purposes. Secondly, the radiation distribution of the UV source was completed. The final stage incorporated the kinetics for the degradation the model pollutant, sodium oxalate. The hydrodynamics were modelled using an Eulerian-Eulerian approach to the multiphase system with the standard k- turbulence model. This research established that there was significant deviation in the fluid behaviour in the pseudo-annular reactor when compared with traditional cylindrical columns due to the nature of the internal structure. The residence time distribution study showed almost completely mixed flow in the liquid phase, whereas the gas phase more closely represented plug flow behaviour. Whilst there was significant dependence on the superficial gas flow rate the mixing behaviour demonstrated negligible dependence on the liquid superficial velocity or the liquid flow direction, either co- or counter- current with respect to the gas phase. The light distribution was modelled using a conservative variant of the Discrete Ordinate method. The model examined the contribution to the incident radiation within the reactor of both the gas bubbles and titanium dioxide particles. This work has established the importance of the gas phase in evaluating the light distribution and showed that it should be included when examining the light distribution in a gas-liquid-solid three-phase system. An optimal catalyst loading for the vessel was established to be 1g/L. Integration of the kinetics of sodium oxalate degradation was the final step is developing the complete CFD model. Species transport equations were employed to describe the distribution of pollutant concentration within the vessel. Using a response surface methodology it was shown that the reaction rate exhibited a greater dependency on the lamp power that the lamp length, however, the converse was true with the quantum efficiency. This work highlights the complexity of completely modelling a photocatalytic system and has demonstrated the applicability of CFD for this purpose.

<p>The international environment today has been undergoing unprecedented change and many companies are seeking new ways to stand out from the competition by sustaining their competitive advantage. Internationalization and firms’ consolidation increase competition in the dynamic marketplace .Companies are no longer staying competitive simply through focusing on product quality and pricing as customers are becoming more high-demanding related to customer service offer. This issue directs the companies’ main focus today to address the customer needs in the ever-changing environment.In order to be the winners in the marketplace, timing and superior customer service are becoming the keys to attain competitive advantage for a company. Time-based competition is an important issue that many companies are facing currently as customers are becoming more time-sensitive and time-oriented in terms of better services, reliability and delivery. To keep up with the changes in demand from customers, it is important to satisfy customers’ objectives and needs in order to provide superior customer service, thus, establish good relationship with them. In the ever-changing and dynamic business environment company needs to adapt and exploit the changes in order to meet the new challenges in the marketplace. It is crucial for the company to respond to changing needs of existing customers and seeking to serve new customers externally. The ways to renew the customers’ services and how they are delivered are critical capabilities for many companies to acquire nowadays. This leads to increasing interaction between marketing and logistics where logistics is considered a platform for supporting new strategic moves on the market.This master thesis originates from a need to research the links between customer service improvement and Just-in-time distribution in order to sustain competitive advantage. We propose to extend the Just-In-Time concept to incorporate a customer perspective, which results in changes the warehousing, ordering and delivering routines. Subsequently, this creates timing ability as well as coordination of information and material flows through timely decisions, which are difficult for competitors to emulate. Based on our analysis and conclusion, companies are recommended to shift from the traditional production-oriented to market-oriented focuses through incorporation of customers' perspective into the value chain. To deploy this, companies should start from the customer end and understand customers' needs and establish mutual beneficial relationships with customers. Long-lasting business relationships ultimately determine the success of the company. Furthermore, we conclude that successful learning to change the routines requires time for the transformation of traditional delivery practice to perform direct deliveries activities. They are based on the common understanding of the tasks and rules as well as common codes of internal coordination processes.</p>

The international environment today has been undergoing unprecedented change and many companies are seeking new ways to stand out from the competition by sustaining their competitive advantage. Internationalization and firms’ consolidation increase competition in the dynamic marketplace .Companies are no longer staying competitive simply through focusing on product quality and pricing as customers are becoming more high-demanding related to customer service offer. This issue directs the companies’ main focus today to address the customer needs in the ever-changing environment.In order to be the winners in the marketplace, timing and superior customer service are becoming the keys to attain competitive advantage for a company. Time-based competition is an important issue that many companies are facing currently as customers are becoming more time-sensitive and time-oriented in terms of better services, reliability and delivery. To keep up with the changes in demand from customers, it is important to satisfy customers’ objectives and needs in order to provide superior customer service, thus, establish good relationship with them. In the ever-changing and dynamic business environment company needs to adapt and exploit the changes in order to meet the new challenges in the marketplace. It is crucial for the company to respond to changing needs of existing customers and seeking to serve new customers externally. The ways to renew the customers’ services and how they are delivered are critical capabilities for many companies to acquire nowadays. This leads to increasing interaction between marketing and logistics where logistics is considered a platform for supporting new strategic moves on the market.This master thesis originates from a need to research the links between customer service improvement and Just-in-time distribution in order to sustain competitive advantage. We propose to extend the Just-In-Time concept to incorporate a customer perspective, which results in changes the warehousing, ordering and delivering routines. Subsequently, this creates timing ability as well as coordination of information and material flows through timely decisions, which are difficult for competitors to emulate. Based on our analysis and conclusion, companies are recommended to shift from the traditional production-oriented to market-oriented focuses through incorporation of customers' perspective into the value chain. To deploy this, companies should start from the customer end and understand customers' needs and establish mutual beneficial relationships with customers. Long-lasting business relationships ultimately determine the success of the company. Furthermore, we conclude that successful learning to change the routines requires time for the transformation of traditional delivery practice to perform direct deliveries activities. They are based on the common understanding of the tasks and rules as well as common codes of internal coordination processes.

This thesis compares actual and perceived travel times and presents a model for predicting traffic flows when there is a network disruption. The goal of this research is to demonstrate the necessity of accounting for possible differences in travel time perception and actual travel times, and also to show trends in how the route choices change based on the transformation of the perceived travel times. A pilot test was done to determine actual travel time perceptions, and the results provided the foundation for the tests presented in this thesis and the model framework. The model is separated into three phases: equilibrium assignment, link travel time transform, and logit assignment. The transform of the link travel times is best represented by an inverse cumulative Normal distribution, and the corresponding values provide quantifiable measure of the severity of a traffic network disruption. The methodology is presented and applied to two test networks to demonstrate the resulting route choice patterns. Both networks are tested for three severity levels and three levels of demand. / text