Flow phenomena, heat and mass transfer in microchannel reactors

The studies of flow phenomena, heat and mass transfer in microchannel reactors are beneficial to estimate and evaluate the ability of microchannel reactors to be operated for a given process reaction such as Fischer-Tropsch synthesis. The flow phenomena, for example, the flow regimes and flow patterns in microchannel reactors for both single phase and multiphase flow are affected by the configuration of the flow channel. The reviews of the previous works about the analysis of related parameters that affect the flow phenomena are shown in this report. In order to predict the phenomena of Fischer-Tropsch synthesis in microchannel reactors, the 3-dimensional computational fluid dynamic simulation with commercial software package FLUENT was done to study the flow phenomena and heat transfer for gas phase Fischer-Tropsch products flow in rectangular microchannel with hydraulic diameter 500 ¿m and length 15 cm. Numerical solution with slip boundary condition was used in the simulation and the flowphenomena and heat transfer were determined.

Modeling reaction kinetics and mass transfer in ozonation in water solutions

This dissertation is based on four articles dealing with modeling of ozonation. The literature part of this considers some models for hydrodynamics in bubble column simulation. A literature review of methods for obtaining mass transfer coefficients is presented. The methods presented to obtain mass transfer are general models and can be applied to any gas-liquid system. Ozonation reaction models and methods for obtaining stoichiometric coefficients and reaction rate coefficients for ozonation reactions are discussed in the final section of the literature part. In the first article, ozone gas-liquid mass transfer into water in a bubble column was investigated for different pH values. A more general method for estimation of mass transfer and Henry’s coefficient was developed from the Beltrán method. The ozone volumetric mass transfer coefficient and the Henry’s coefficient were determined simultaneously by parameter estimation using a nonlinear optimization method. A minor dependence of the Henry’s law constant on pH was detected at the pH range 4 - 9. In the second article, a new method using the axial dispersion model for estimation of ozone self-decomposition kinetics in a semi-batch bubble column reactor was developed. The reaction rate coefficients for literature equations of ozone decomposition and the gas phase dispersion coefficient were estimated and compared with the literature data. The reaction order in the pH range 7-10 with respect to ozone 1.12 and 0.51 the hydroxyl ion were obtained, which is in good agreement with literature. The model parameters were determined by parameter estimation using a nonlinear optimization method. Sensitivity analysis was conducted using object function method to obtain information about the reliability and identifiability of the estimated parameters. In the third article, the reaction rate coefficients and the stoichiometric coefficients in the reaction of ozone with the model component p-nitrophenol were estimated at low pH of water using nonlinear optimization. A novel method for estimation of multireaction model parameters in ozonation was developed. In this method the concentration of unknown intermediate compounds is presented as a residual COD (chemical oxygen demand) calculated from the measured COD and the theoretical COD for the known species. The decomposition rate of p-nitrophenol on the pathway producing hydroquinone was found to be about two times faster than the p-nitrophenol decomposition rate on the pathway producing 4- nitrocatechol. In the fourth article, the reaction kinetics of p-nitrophenol ozonation was studied in a bubble column at pH 2. Using the new reaction kinetic model presented in the previous article, the reaction kinetic parameters, rate coefficients, and stoichiometric coefficients as well as the mass transfer coefficient were estimated with nonlinear estimation. The decomposition rate of pnitrophenol was found to be equal both on the pathway producing hydroquinone and on the path way producing 4-nitrocathecol. Comparison of the rate coefficients with the case at initial pH 5 indicates that the p-nitrophenol degradation producing 4- nitrocathecol is more selective towards molecular ozone than the reaction producing hydroquinone. The identifiability and reliability of the estimated parameters were analyzed with the Marcov chain Monte Carlo (MCMC) method. @All rights reserved. No part of the publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without the prior permission of the author.

Fundamentals of heat transfer

Following over 170+ pages and additional appendixes are formed based on content of Course: Fundamentals of Heat Transfer. Mainly this summarizes relevant parts on Book of Fundamentals of Heat and Mass Transfer (Incropera), but also other references introducing the same concepts are included. Student’s point of view has been consideredwith following highlights: (1) Relevant topics are presented in a nutshell to provide fast digestion of principles of heat transfer. (2) Appendixes include terminology dictionary. (3) Totally 22 illustrating examples are connecting theory to practical applications and quantifying heat transfer to understandable forms as: temperatures, heat transfer rates, heat fluxes, resistances and etc. (4) Most important Learning outcomes are presented for each topic separately. The Book, Fundamentals of Heat and Mass Transfer (Incropera), is certainly recommended for those going beyond basic knowledge of heat transfer. Lecture Notes consists of four primary content-wise objectives: (1) Give understanding to physical mechanisms of heat transfer, (2)Present basic concepts and terminology relevant for conduction, convection and radiation (3) Introduce thermal performance analysis methods for steady state and transient conduction systems. (4) Provide fast-to-digest phenomenological understanding required for basic design of thermal models

Theoretical and numerical study of thermomagnetic convection in magnetic fluids

In this thesis, the magnetic field control of convection instabilities and heat and mass transfer processesin magnetic fluids have been investigated by numerical simulations and theoretical considerations. Simulation models based on finite element and finite volume methods have been developed. In addition to standard conservation equations, themagnetic field inside the simulation domain is calculated from Maxwell equations and the necessary terms to take into account for the magnetic body force and magnetic dissipation have been added to the equations governing the fluid motion.Numerical simulations of magnetic fluid convection near the threshold supportedexperimental observations qualitatively. Near the onset of convection the competitive action of thermal and concentration density gradients leads to mostly spatiotemporally chaotic convection with oscillatory and travelling wave regimes, previously observed in binary mixtures and nematic liquid crystals. In many applications of magnetic fluids, the heat and mass transfer processes including the effects of external magnetic fields are of great importance. In addition to magnetic fluids, the concepts and the simulation models used in this study may be applied also to the studies of convective instabilities in ordinary fluids as well as in other binary mixtures and complex fluids.

Particle transport method for convection-diffusion-reaction problems

Convective transport, both pure and combined with diffusion and reaction, can be observed in a wide range of physical and industrial applications, such as heat and mass transfer, crystal growth or biomechanics. The numerical approximation of this class of problemscan present substantial difficulties clue to regions of high gradients (steep fronts) of the solution, where generation of spurious oscillations or smearing should be precluded. This work is devoted to the development of an efficient numerical technique to deal with pure linear convection and convection-dominated problems in the frame-work of convection-diffusion-reaction systems. The particle transport method, developed in this study, is based on using rneshless numerical particles which carry out the solution along the characteristics defining the convective transport. The resolution of steep fronts of the solution is controlled by a special spacial adaptivity procedure. The serni-Lagrangian particle transport method uses an Eulerian fixed grid to represent the solution. In the case of convection-diffusion-reaction problems, the method is combined with diffusion and reaction solvers within an operator splitting approach. To transfer the solution from the particle set onto the grid, a fast monotone projection technique is designed. Our numerical results confirm that the method has a spacial accuracy of the second order and can be faster than typical grid-based methods of the same order; for pure linear convection problems the method demonstrates optimal linear complexity. The method works on structured and unstructured meshes, demonstrating a high-resolution property in the regions of steep fronts of the solution. Moreover, the particle transport method can be successfully used for the numerical simulation of the real-life problems in, for example, chemical engineering.

Development of a process for the direct synthesis of hydrogen peroxide in a novel microstructured reactor

Microreactors have proven to be versatile tools for process intensification. Over recent decades, they have increasingly been used for product and process development in chemical industries. Enhanced heat and mass transfer in the reactors due to the extremely high surfacearea- to-volume ratio and interfacial area allow chemical processes to be operated at extreme conditions. Safety is improved by the small holdup volume of the reactors and effective control of pressure and temperature. Hydrogen peroxide is a powerful green oxidant that is used in a wide range of industries. Reduction and auto-oxidation of anthraquinones is currently the main process for hydrogen peroxide production. Direct synthesis is a green alternative and has potential for on-site production. However, there are two limitations: safety concerns because of the explosive gas mixture produced and low selectivity of the process. The aim of this thesis was to develop a process for direct synthesis of hydrogen peroxide utilizing microreactor technology. Experimental and numerical approaches were applied for development of the microreactor. Development of a novel microreactor was commenced by studying the hydrodynamics and mass transfer in prototype microreactor plates. The prototypes were designed and fabricated with the assistance of CFD modeling to optimize the shape and size of the microstructure. Empirical correlations for the mass transfer coefficient were derived. The pressure drop in micro T-mixers was investigated experimentally and numerically. Correlations describing the friction factor for different flow regimes were developed and predicted values were in good agreement with experimental results. Experimental studies were conducted to develop a highly active and selective catalyst with a proper form for the microreactor. Pd catalysts supported on activated carbon cloths were prepared by different treatments during the catalyst preparation. A variety of characterization methods were used for catalyst investigation. The surface chemistry of the support and the oxidation state of the metallic phase in the catalyst play important roles in catalyst activity and selectivity for the direct synthesis. The direct synthesis of hydrogen peroxide was investigated in a bench-scale continuous process using the novel microreactor developed. The microreactor was fabricated based on the hydrodynamic and mass transfer studies and provided a high interfacial area and high mass transfer coefficient. The catalysts were prepared under optimum treatment conditions. The direct synthesis was conducted at various conditions. The thesis represents a step towards a commercially viable direct synthesis. The focus is on the two main challenges: mitigating the safety problem by utilization of microprocess technology and improving the selectivity by catalyst development.

Viilun kuivauksen energiatehokkuuden parantaminen

Tämän työn tavoitteena on parantaa viilun kuivauksen energiatehokkuutta. Työssä käsitellään puun rakennetta kuivauksen kannalta, kuivumiseen liittyviä lämmönja massansiirron ilmiöitä ja nykyisiä viilun kuivaus koneita. Viilun kuivaamisen energiansäästö mahdollisuuksissa keskitytään pääasiassa kuivaajan lämmön talteenottoon ja kiertopuhaltimien sähkötehon pienentämiseen. Työn tulosten perusteella viilun kuivauksen energiatehokkuutta voidaan parantaa huomattavasti.

Computational modelling of non-equilibrium condensing steam flows in low-pressure steam turbines

The steam turbines play a significant role in global power generation. Especially, research on low pressure (LP) steam turbine stages is of special importance for steam turbine man- ufactures, vendors, power plant owners and the scientific community due to their lower efficiency than the high pressure steam turbine stages. Because of condensation, the last stages of LP turbine experience irreversible thermodynamic losses, aerodynamic losses and erosion in turbine blades. Additionally, an LP steam turbine requires maintenance due to moisture generation, and therefore, it is also affecting on the turbine reliability. Therefore, the design of energy efficient LP steam turbines requires a comprehensive analysis of condensation phenomena and corresponding losses occurring in the steam tur- bine either by experiments or with numerical simulations. The aim of the present work is to apply computational fluid dynamics (CFD) to enhance the existing knowledge and understanding of condensing steam flows and loss mechanisms that occur due to the irre- versible heat and mass transfer during the condensation process in an LP steam turbine. Throughout this work, two commercial CFD codes were used to model non-equilibrium condensing steam flows. The Eulerian-Eulerian approach was utilised in which the mix- ture of vapour and liquid phases was solved by Reynolds-averaged Navier-Stokes equa- tions. The nucleation process was modelled with the classical nucleation theory, and two different droplet growth models were used to predict the droplet growth rate. The flow turbulence was solved by employing the standard k-ε and the shear stress transport k-ω turbulence models. Further, both models were modified and implemented in the CFD codes. The thermodynamic properties of vapour and liquid phases were evaluated with real gas models. In this thesis, various topics, namely the influence of real gas properties, turbulence mod- elling, unsteadiness and the blade trailing edge shape on wet-steam flows, are studied with different convergent-divergent nozzles, turbine stator cascade and 3D turbine stator-rotor stage. The simulated results of this study were evaluated and discussed together with the available experimental data in the literature. The grid independence study revealed that an adequate grid size is required to capture correct trends of condensation phenomena in LP turbine flows. The study shows that accurate real gas properties are important for the precise modelling of non-equilibrium condensing steam flows. The turbulence modelling revealed that the flow expansion and subsequently the rate of formation of liquid droplet nuclei and its growth process were affected by the turbulence modelling. The losses were rather sensitive to turbulence modelling as well. Based on the presented results, it could be observed that the correct computational prediction of wet-steam flows in the LP turbine requires the turbulence to be modelled accurately. The trailing edge shape of the LP turbine blades influenced the liquid droplet formulation, distribution and sizes, and loss generation. The study shows that the semicircular trailing edge shape predicted the smallest droplet sizes. The square trailing edge shape estimated greater losses. The analysis of steady and unsteady calculations of wet-steam flow exhibited that in unsteady simulations, the interaction of wakes in the rotor blade row affected the flow field. The flow unsteadiness influenced the nucleation and droplet growth processes due to the fluctuation in the Wilson point.

Gas-liquid mass transfer in bubbly flow: Estimation of mass transfer, bubble size and reactor performance in various applications

Gas-liquid mass transfer is an important issue in the design and operation of many chemical unit operations. Despite its importance, the evaluation of gas-liquid mass transfer is not straightforward due to the complex nature of the phenomena involved. In this thesis gas-liquid mass transfer was evaluated in three different gas-liquid reactors in a traditional way by measuring the volumetric mass transfer coefficient (kLa). The studied reactors were a bubble column with a T-junction two-phase nozzle for gas dispersion, an industrial scale bubble column reactor for the oxidation of tetrahydroanthrahydroquinone and a concurrent downflow structured bed.The main drawback of this approach is that the obtained correlations give only the average volumetric mass transfer coefficient, which is dependent on average conditions. Moreover, the obtained correlations are valid only for the studied geometry and for the chemical system used in the measurements. In principle, a more fundamental approach is to estimate the interfacial area available for mass transfer from bubble size distributions obtained by solution of population balance equations. This approach has been used in this thesis by developing a population balance model for a bubble column together with phenomenological models for bubble breakage and coalescence. The parameters of the bubble breakage rate and coalescence rate models were estimated by comparing the measured and calculated bubble sizes. The coalescence models always have at least one experimental parameter. This is because the bubble coalescence depends on liquid composition in a way which is difficult to evaluate using known physical properties. The coalescence properties of some model solutions were evaluated by measuring the time that a bubble rests at the free liquid-gas interface before coalescing (the so-calledpersistence time or rest time). The measured persistence times range from 10 msup to 15 s depending on the solution. The coalescence was never found to be instantaneous. The bubble oscillates up and down at the interface at least a coupleof times before coalescence takes place. The measured persistence times were compared to coalescence times obtained by parameter fitting using measured bubble size distributions in a bubble column and a bubble column population balance model. For short persistence times, the persistence and coalescence times are in good agreement. For longer persistence times, however, the persistence times are at least an order of magnitude longer than the corresponding coalescence times from parameter fitting. This discrepancy may be attributed to the uncertainties concerning the estimation of energy dissipation rates, collision rates and mechanisms and contact times of the bubbles.

Effect of antifoams on oxygen mass transfer in pulp and paper mill effluents

Vaahdonestoaineiden haitallinen vaikutus hapen liukenemisnopeuteen biologisen puhdistamon jätevesissä on yleisesti tunnettua. Aineiden eri vaikutusmekanismien takia on silti vaikea etukäteen arvioida, miten ja kuinka paljon aineensiirto muuttuu. Työn tavoitteena oli saada tietoa vaahdonestoaineiden ja muiden pinta-aktiivisten aineiden vaikutuksesta kuplakokoon, kaasun tilavuusosuuteen ja kaasu-neste aineensiirtoon. Työn teoriaosassa on kuvailtu vaahdon muodostumiseen vaikuttavia tekijöitä sekä eri vaahdonestoaineiden vaikutusmekanismeja sellu- ja paperitehtaan jätevedessä. Edelleen on esitetty useita hapen siirtoa estäviä ja parantavia aineita. Työn kokeellisessa osassa tutkittiin kahdenkymmenenviiden eri pinta-aktiivisen aineen vaikutusta hapen liukenemisnopeuteen yksivaiheisessa kuplakolonnissa. Kokeet tehtiin kahdella pitoisuudella, kahdella eri kaasunjakolaitteella ja kolmella eri kaasun tyhjäputkinopeudella. Aineensiirtokokeiden rinnalla tutkittiin jätevesien laatu- ja fysikaalisiaominaisuuksia, niiden vaikutusta hapen liukenemisnopeuteen sekä testattavien koeaineiden vaikutusta fysikaalisin ominaisuuksiin. Kokeet osoittavat että pinta-aktiivisten aineiden vaikutus hapen aineensiirtoon vaihtelee riippuen kaasunjakolaitteesta ja aineen pitoisuuksista. Testatuista vaahdonestonaineista pienin negatiivinen vaikutus oli aineella AT 35 ja positiivinen vaikutustodettiin olevan vaahdonestoaineiden komponenteilla: P2, S1, F4 ja T9.

Modeling of non-isothermalvapor membrane separation with thermodynamic models and generalized mass transfer equations

A rigorous unit operation model is developed for vapor membrane separation. The new model is able to describe temperature, pressure, and concentration dependent permeation as wellreal fluid effects in vapor and gas separation with hydrocarbon selective rubbery polymeric membranes. The permeation through the membrane is described by a separate treatment of sorption and diffusion within the membrane. The chemical engineering thermodynamics is used to describe the equilibrium sorption of vapors and gases in rubbery membranes with equation of state models for polymeric systems. Also a new modification of the UNIFAC model is proposed for this purpose. Various thermodynamic models are extensively compared in order to verify the models' ability to predict and correlate experimental vapor-liquid equilibrium data. The penetrant transport through the selective layer of the membrane is described with the generalized Maxwell-Stefan equations, which are able to account for thebulk flux contribution as well as the diffusive coupling effect. A method is described to compute and correlate binary penetrant¿membrane diffusion coefficients from the experimental permeability coefficients at different temperatures and pressures. A fluid flow model for spiral-wound modules is derived from the conservation equation of mass, momentum, and energy. The conservation equations are presented in a discretized form by using the control volume approach. A combination of the permeation model and the fluid flow model yields the desired rigorous model for vapor membrane separation. The model is implemented into an inhouse process simulator and so vapor membrane separation may be evaluated as an integralpart of a process flowsheet.

Selective catalytic reduction of nitrogen oxides with ammonia in forced unsteady state reactors - Case based reasoning and mathematical model simulation reasoning

The application of forced unsteady-state reactors in case of selective catalytic reduction of nitrogen oxides (NOx) with ammonia (NH3) is sustained by the fact that favorable temperature and composition distributions which cannot be achieved in any steady-state regime can be obtained by means of unsteady-state operations. In a normal way of operation the low exothermicity of the selective catalytic reduction (SCR) reaction (usually carried out in the range of 280-350°C) is not enough to maintain by itself the chemical reaction. A normal mode of operation usually requires supply of supplementary heat increasing in this way the overall process operation cost. Through forced unsteady-state operation, the main advantage that can be obtained when exothermic reactions take place is the possibility of trapping, beside the ammonia, the moving heat wave inside the catalytic bed. The unsteady state-operation enables the exploitation of the thermal storage capacity of the catalyticbed. The catalytic bed acts as a regenerative heat exchanger allowing auto-thermal behaviour when the adiabatic temperature rise is low. Finding the optimum reactor configuration, employing the most suitable operation model and identifying the reactor behavior are highly important steps in order to configure a proper device for industrial applications. The Reverse Flow Reactor (RFR) - a forced unsteady state reactor - corresponds to the above mentioned characteristics and may be employed as an efficient device for the treatment of dilute pollutant mixtures. As a main disadvantage, beside its advantages, the RFR presents the 'wash out' phenomena. This phenomenon represents emissions of unconverted reactants at every switch of the flow direction. As a consequence our attention was focused on finding an alternative reactor configuration for RFR which is not affected by the incontrollable emissions of unconverted reactants. In this respect the Reactor Network (RN) was investigated. Its configuration consists of several reactors connected in a closed sequence, simulating a moving bed by changing the reactants feeding position. In the RN the flow direction is maintained in the same way ensuring uniformcatalyst exploitation and in the same time the 'wash out' phenomena is annulated. The simulated moving bed (SMB) can operate in transient mode giving practically constant exit concentration and high conversion levels. The main advantage of the reactor network operation is emphasizedby the possibility to obtain auto-thermal behavior with nearly uniformcatalyst utilization. However, the reactor network presents only a small range of switching times which allow to reach and to maintain an ignited state. Even so a proper study of the complex behavior of the RN may give the necessary information to overcome all the difficulties that can appear in the RN operation. The unsteady-state reactors complexity arises from the fact that these reactor types are characterized by short contact times and complex interaction between heat and mass transportphenomena. Such complex interactions can give rise to a remarkable complex dynamic behavior characterized by a set of spatial-temporal patterns, chaotic changes in concentration and traveling waves of heat or chemical reactivity. The main efforts of the current research studies concern the improvement of contact modalities between reactants, the possibility of thermal wave storage inside the reactor and the improvement of the kinetic activity of the catalyst used. Paying attention to the above mentioned aspects is important when higher activity even at low feeding temperatures and low emissions of unconverted reactants are the main operation concerns. Also, the prediction of the reactor pseudo or steady-state performance (regarding the conversion, selectivity and thermal behavior) and the dynamicreactor response during exploitation are important aspects in finding the optimal control strategy for the forced unsteady state catalytic tubular reactors. The design of an adapted reactor requires knowledge about the influence of its operating conditions on the overall process performance and a precise evaluation of the operating parameters rage for which a sustained dynamic behavior is obtained. An apriori estimation of the system parameters result in diminution of the computational efforts. Usually the convergence of unsteady state reactor systems requires integration over hundreds of cycles depending on the initial guess of the parameter values. The investigation of various operation models and thermal transfer strategies give reliable means to obtain recuperative and regenerative devices which are capable to maintain an auto-thermal behavior in case of low exothermic reactions. In the present research work a gradual analysis of the SCR of NOx with ammonia process in forced unsteady-state reactors was realized. The investigation covers the presentationof the general problematic related to the effect of noxious emissions in the environment, the analysis of the suitable catalysts types for the process, the mathematical analysis approach for modeling and finding the system solutions and the experimental investigation of the device found to be more suitable for the present process. In order to gain information about the forced unsteady state reactor design, operation, important system parameters and their values, mathematical description, mathematicalmethod for solving systems of partial differential equations and other specific aspects, in a fast and easy way, and a case based reasoning (CBR) approach has been used. This approach, using the experience of past similarproblems and their adapted solutions, may provide a method for gaining informations and solutions for new problems related to the forced unsteady state reactors technology. As a consequence a CBR system was implemented and a corresponding tool was developed. Further on, grooving up the hypothesis of isothermal operation, the investigation by means of numerical simulation of the feasibility of the SCR of NOx with ammonia in the RFRand in the RN with variable feeding position was realized. The hypothesis of non-isothermal operation was taken into account because in our opinion ifa commercial catalyst is considered, is not possible to modify the chemical activity and its adsorptive capacity to improve the operation butis possible to change the operation regime. In order to identify the most suitable device for the unsteady state reduction of NOx with ammonia, considering the perspective of recuperative and regenerative devices, a comparative analysis of the above mentioned two devices performance was realized. The assumption of isothermal conditions in the beginningof the forced unsteadystate investigation allowed the simplification of the analysis enabling to focus on the impact of the conditions and mode of operation on the dynamic features caused by the trapping of one reactant in the reactor, without considering the impact of thermal effect on overall reactor performance. The non-isothermal system approach has been investigated in order to point out the important influence of the thermal effect on overall reactor performance, studying the possibility of RFR and RN utilization as recuperative and regenerative devices and the possibility of achieving a sustained auto-thermal behavior in case of lowexothermic reaction of SCR of NOx with ammonia and low temperature gasfeeding. Beside the influence of the thermal effect, the influence of the principal operating parameters, as switching time, inlet flow rate and initial catalyst temperature have been stressed. This analysis is important not only because it allows a comparison between the two devices and optimisation of the operation, but also the switching time is the main operating parameter. An appropriate choice of this parameter enables the fulfilment of the process constraints. The level of the conversions achieved, the more uniform temperature profiles, the uniformity ofcatalyst exploitation and the much simpler mode of operation imposed the RN as a much more suitable device for SCR of NOx with ammonia, in usual operation and also in the perspective of control strategy implementation. Theoretical simplified models have also been proposed in order to describe the forced unsteady state reactors performance and to estimate their internal temperature and concentration profiles. The general idea was to extend the study of catalytic reactor dynamics taking into account the perspectives that haven't been analyzed yet. The experimental investigation ofRN revealed a good agreement between the data obtained by model simulation and the ones obtained experimentally.

Mass transfer and particleinteractions in granular systems and suspension flows

The purpose of this study was to investigate some important features of granular flows and suspension flows by computational simulation methods. Granular materials have been considered as an independent state ofmatter because of their complex behaviors. They sometimes behave like a solid, sometimes like a fluid, and sometimes can contain both phases in equilibrium. The computer simulation of dense shear granular flows of monodisperse, spherical particles shows that the collisional model of contacts yields the coexistence of solid and fluid phases while the frictional model represents a uniform flow of fluid phase. However, a comparison between the stress signals from the simulations and experiments revealed that the collisional model would result a proper match with the experimental evidences. Although the effect of gravity is found to beimportant in sedimentation of solid part, the stick-slip behavior associated with the collisional model looks more similar to that of experiments. The mathematical formulations based on the kinetic theory have been derived for the moderatesolid volume fractions with the assumption of the homogeneity of flow. In orderto make some simulations which can provide such an ideal flow, the simulation of unbounded granular shear flows was performed. Therefore, the homogeneous flow properties could be achieved in the moderate solid volume fractions. A new algorithm, namely the nonequilibrium approach was introduced to show the features of self-diffusion in the granular flows. Using this algorithm a one way flow can beextracted from the entire flow, which not only provides a straightforward calculation of self-diffusion coefficient but also can qualitatively determine the deviation of self-diffusion from the linear law at some regions nearby the wall inbounded flows. Anyhow, the average lateral self-diffusion coefficient, which was calculated by the aforementioned method, showed a desirable agreement with thepredictions of kinetic theory formulation. In the continuation of computer simulation of shear granular flows, some numerical and theoretical investigations were carried out on mass transfer and particle interactions in particulate flows. In this context, the boundary element method and its combination with the spectral method using the special capabilities of wavelets have been introduced as theefficient numerical methods to solve the governing equations of mass transfer in particulate flows. A theoretical formulation of fluid dispersivity in suspension flows revealed that the fluid dispersivity depends upon the fluid properties and particle parameters as well as the fluid-particle and particle-particle interactions.

Mass transfer and reaction kinetics in single droplet systems

As reactive extraction grown more and more popular in a variety of technological applications, optimizing its performance becomes more and more important. The process of complex formation is affected by a great number of both physical and chemical properties of all the components involved, and sometimes their interference with one another makes improving the effectiveness of such processes very difficult. In this Master’s Theses, the processes of complex formation between the aqueous phase - represented by copper sulfate water solution, and organic phase – represented by Acorga M5640 solvent extractor, were studied in order to establish the effect these components have on reactive extraction performance and to determine which step is bottlenecking the process the most.

Heterogeneous mass transfer in fluidized beds by computational fluid dynamics

The main objective of this research is to estimate and characterize heterogeneous mass transfer coefficients in bench- and pilot-scale fluidized bed processes by the means of computational fluid dynamics (CFD). A further objective is to benchmark the heterogeneous mass transfer coefficients predicted by fine-grid Eulerian CFD simulations against empirical data presented in the scientific literature. First, a fine-grid two-dimensional Eulerian CFD model with a solid and gas phase has been designed. The model is applied for transient two-dimensional simulations of char combustion in small-scale bubbling and turbulent fluidized beds. The same approach is used to simulate a novel fluidized bed energy conversion process developed for the carbon capture, chemical looping combustion operated with a gaseous fuel. In order to analyze the results of the CFD simulations, two one-dimensional fluidized bed models have been formulated. The single-phase and bubble-emulsion models were applied to derive the average gas-bed and interphase mass transfer coefficients, respectively. In the analysis, the effects of various fluidized bed operation parameters, such as fluidization, velocity, particle and bubble diameter, reactor size, and chemical kinetics, on the heterogeneous mass transfer coefficients in the lower fluidized bed are evaluated extensively. The analysis shows that the fine-grid Eulerian CFD model can predict the heterogeneous mass transfer coefficients quantitatively with acceptable accuracy. Qualitatively, the CFD-based research of fluidized bed process revealed several new scientific results, such as parametrical relationships. The huge variance of seven orders of magnitude within the bed Sherwood numbers presented in the literature could be explained by the change of controlling mechanisms in the overall heterogeneous mass transfer process with the varied process conditions. The research opens new process-specific insights into the reactive fluidized bed processes, such as a strong mass transfer control over heterogeneous reaction rate, a dominance of interphase mass transfer in the fine-particle fluidized beds and a strong chemical kinetic dependence of the average gas-bed mass transfer. The obtained mass transfer coefficients can be applied in fluidized bed models used for various engineering design, reactor scale-up and process research tasks, and they consequently provide an enhanced prediction accuracy of the performance of fluidized bed processes.