Tropfenbasierte Multiphasen – Mikroreaktionstechnologie in organisch-chemischer Synthese

In der vorliegenden Doktorarbeit werden neue, mikrofluidische Verfahren, zur Durchführung chemischer Reaktionen in mehrphasigen Systemen präsentiert. rnDas Einschließen von Reaktionspartnern in einzelne Segmente, deren Volumina im Bereich von Mikro- bis Femtoliter liegen und die dadurch erzeugten enormen, spezifischen Oberflächen, ermöglichen Massentransportprozesse über die Phasengrenzfläche zwischen einzelnen Segmenten, drastisch zu intensivieren. Aufgrund geringer räumlicher Ausdehnungen einzelner Kompartimente und durch vorherrschende, zirkulierende Strömungen in den einzelnen Abschnitten, sind Diffusions- und Konvektionsprozesse in diesen rasch, sodass an der Grenzfläche gebildete, reaktive Intermediate in sehr kurzen Zeitintervallen umgesetzt werden können. rnrn

Galactic fountain flows in high-resolution hydrodynamical simulations of galaxy disks

Feedback from the most massive components of a young stellar cluster deeply affects the surrounding ISM driving an expanding over-pressured hot gas cavity in it. In spiral galaxies these structures may have sufficient energy to break the disk and eject large amount of material into the halo. The cycling of this gas, which eventually will fall back onto the disk, is known as galactic fountains. We aim at better understanding the dynamics of such fountain flow in a Galactic context, frame the problem in a more dynamic environment possibly learning about its connection and regulation to the local driving mechanism and understand its role as a metal diffusion channel. The interaction of the fountain with a hot corona is hereby analyzed, trying to understand the properties and evolution of the extraplanar material. We perform high resolution hydrodynamical simulations with the moving-mesh code AREPO to model the multi-phase ISM of a Milky Way type galaxy. A non-equilibrium chemical network is included to self consistently follow the evolution of the main coolants of the ISM. Spiral arm perturbations in the potential are considered so that large molecular gas structures are able to dynamically form here, self shielded from the interstellar radiation field. We model the effect of SN feedback from a new-born stellar cluster inside such a giant molecular cloud, as the driving force of the fountain. Passive Lagrangian tracer particles are used in conjunction to the SN energy deposition to model and study diffusion of freshly synthesized metals. We find that both interactions with hot coronal gas and local ISM properties and motions are equally important in shaping the fountain. We notice a bimodal morphology where most of the ejected gas is in a cold $10^4$ K clumpy state while the majority of the affected volume is occupied by a hot diffuse medium. While only about 20\% of the produced metals stay local, most of them quickly diffuse through this hot regime to great scales.

Three dimensional finite element simulation of polymer melting and flow in a single-screw extruder : optimization of screw channel geometry

Single-screw extrusion is one of the widely used processing methods in plastics industry, which was the third largest manufacturing industry in the United States in 2007 [5]. In order to optimize the single-screw extrusion process, tremendous efforts have been devoted for development of accurate models in the last fifty years, especially for polymer melting in screw extruders. This has led to a good qualitative understanding of the melting process; however, quantitative predictions of melting from various models often have a large error in comparison to the experimental data. Thus, even nowadays, process parameters and the geometry of the extruder channel for the single-screw extrusion are determined by trial and error. Since new polymers are developed frequently, finding the optimum parameters to extrude these polymers by trial and error is costly and time consuming. In order to reduce the time and experimental work required for optimizing the process parameters and the geometry of the extruder channel for a given polymer, the main goal of this research was to perform a coordinated experimental and numerical investigation of melting in screw extrusion. In this work, a full three-dimensional finite element simulation of the two-phase flow in the melting and metering zones of a single-screw extruder was performed by solving the conservation equations for mass, momentum, and energy. The only attempt for such a three-dimensional simulation of melting in screw extruder was more than twenty years back. However, that work had only a limited success because of the capability of computers and mathematical algorithms available at that time. The dramatic improvement of computational power and mathematical knowledge now make it possible to run full 3-D simulations of two-phase flow in single-screw extruders on a desktop PC. In order to verify the numerical predictions from the full 3-D simulations of two-phase flow in single-screw extruders, a detailed experimental study was performed. This experimental study included Maddock screw-freezing experiments, Screw Simulator experiments and material characterization experiments. Maddock screw-freezing experiments were performed in order to visualize the melting profile along the single-screw extruder channel with different screw geometry configurations. These melting profiles were compared with the simulation results. Screw Simulator experiments were performed to collect the shear stress and melting flux data for various polymers. Cone and plate viscometer experiments were performed to obtain the shear viscosity data which is needed in the simulations. An optimization code was developed to optimize two screw geometry parameters, namely, screw lead (pitch) and depth in the metering section of a single-screw extruder, such that the output rate of the extruder was maximized without exceeding the maximum temperature value specified at the exit of the extruder. This optimization code used a mesh partitioning technique in order to obtain the flow domain. The simulations in this flow domain was performed using the code developed to simulate the two-phase flow in single-screw extruders.

Identification of platelet function defects by multi-parameter assessment of thrombus formation.

Assays measuring platelet aggregation (thrombus formation) at arterial shear rate mostly use collagen as only platelet-adhesive surface. Here we report a multi-surface and multi-parameter flow assay to characterize thrombus formation in whole blood from healthy subjects and patients with platelet function deficiencies. A systematic comparison is made of 52 adhesive surfaces with components activating the main platelet-adhesive receptors, and of eight output parameters reflecting distinct stages of thrombus formation. Three types of thrombus formation can be identified with a predicted hierarchy of the following receptors: glycoprotein (GP)VI, C-type lectin-like receptor-2 (CLEC-2)>GPIb>α6β1, αIIbβ3>α2β1>CD36, α5β1, αvβ3. Application with patient blood reveals distinct abnormalities in thrombus formation in patients with severe combined immune deficiency, Glanzmann's thrombasthenia, Hermansky-Pudlak syndrome, May-Hegglin anomaly or grey platelet syndrome. We suggest this test may be useful for the diagnosis of patients with suspected bleeding disorders or a pro-thrombotic tendency.

A review of flow modeling for dense medium cyclones

A critical assessment is presented for the existing fluid flow models used for dense medium cyclones (DMCs) and hydrocyclones. As the present discussion indicates, the understanding of dense medium cyclone flow is still far from the complete. However, its similarity to the hydrocyclone provides a basis for improved understanding of fluid flow in DMCs. The complexity of fluid flow in DMCs is basically due to the existence of medium as well as the dominance of turbulent particle size and density effects on separation. Both the theoretical and experimental analysis is done with respect to two-phase motions and solid phase flow in hydrocyclones or DMCs. A detailed discussion is presented on the empirical, semiempirical, and the numerical models based upon both the vorticity-stream function approach and Navier-Stokes equations in their primitive variables and in cylindrical coordinates available in literature. The existing equations describing turbulence and multiphase flows in cyclone are also critically reviewed.

Numerical simulation of magnetite segregation in a dense medium cyclone

Numerical simulations of turbulent driven flow in a dense medium cyclone with magnetite medium have been conducted using Fluent. The predicted air core shape and diameter were found to be close to the experimental results measured by gamma ray tomography. It is possible that the Large eddy simulation (LES) turbulence model with Mixture multi-phase model can be used to predict the air/slurry interface accurately although the LES may need a finer grid. Multi-phase simulations (air/water/medium) are showing appropriate medium segregation effects but are over-predicting the level of segregation compared to that measured by gamma-ray tomography in particular with over prediction of medium concentrations near the wall. Further, investigated the accurate prediction of axial segregation of magnetite using the LES turbulence model together with the multi-phase mixture model and viscosity corrections according to the feed particle loading factor. Addition of lift forces and viscosity correction improved the predictions especially near the wall. Predicted density profiles are very close to gamma ray tomography data showing a clear density drop near the wall. The effect of size distribution of the magnetite has been fully studied. It is interesting to note that the ultra-fine magnetite sizes (i.e. 2 and 7 mu m) are distributed uniformly throughout the cyclone. As the size of magnetite increases, more segregation of magnetite occurs close to the wall. The cut-density (d(50)) of the magnetite segregation is 32 gm, which is expected with superfine magnetite feed size distribution. At higher feed densities the agreement between the [Dungilson, 1999; Wood, J.C., 1990. A performance model for coal-washing dense medium cyclones, Ph.D. Thesis, JKMRC, University of Queensland] correlations and the CFD are reasonably good, but the overflow density is lower than the model predictions. It is believed that the excessive underflow volumetric flow rates are responsible for under prediction of the overflow density. (c) 2006 Elsevier Ltd. All rights reserved.

EM optimization of latent-variable density models

There is currently considerable interest in developing general non-linear density models based on latent, or hidden, variables. Such models have the ability to discover the presence of a relatively small number of underlying `causes' which, acting in combination, give rise to the apparent complexity of the observed data set. Unfortunately, to train such models generally requires large computational effort. In this paper we introduce a novel latent variable algorithm which retains the general non-linear capabilities of previous models but which uses a training procedure based on the EM algorithm. We demonstrate the performance of the model on a toy problem and on data from flow diagnostics for a multi-phase oil pipeline.

GTM: the generative topographic mapping

Latent variable models represent the probability density of data in a space of several dimensions in terms of a smaller number of latent, or hidden, variables. A familiar example is factor analysis which is based on a linear transformations between the latent space and the data space. In this paper we introduce a form of non-linear latent variable model called the Generative Topographic Mapping, for which the parameters of the model can be determined using the EM algorithm. GTM provides a principled alternative to the widely used Self-Organizing Map (SOM) of Kohonen (1982), and overcomes most of the significant limitations of the SOM. We demonstrate the performance of the GTM algorithm on a toy problem and on simulated data from flow diagnostics for a multi-phase oil pipeline.

GTM: A principled alternative to the self-organizing map

The Self-Organizing Map (SOM) algorithm has been extensively studied and has been applied with considerable success to a wide variety of problems. However, the algorithm is derived from heuristic ideas and this leads to a number of significant limitations. In this paper, we consider the problem of modelling the probability density of data in a space of several dimensions in terms of a smaller number of latent, or hidden, variables. We introduce a novel form of latent variable model, which we call the GTM algorithm (for Generative Topographic Mapping), which allows general non-linear transformations from latent space to data space, and which is trained using the EM (expectation-maximization) algorithm. Our approach overcomes the limitations of the SOM, while introducing no significant disadvantages. We demonstrate the performance of the GTM algorithm on simulated data from flow diagnostics for a multi-phase oil pipeline.

GTM: the generative topographic mapping

Latent variable models represent the probability density of data in a space of several dimensions in terms of a smaller number of latent, or hidden, variables. A familiar example is factor analysis which is based on a linear transformations between the latent space and the data space. In this paper we introduce a form of non-linear latent variable model called the Generative Topographic Mapping, for which the parameters of the model can be determined using the EM algorithm. GTM provides a principled alternative to the widely used Self-Organizing Map (SOM) of Kohonen (1982), and overcomes most of the significant limitations of the SOM. We demonstrate the performance of the GTM algorithm on a toy problem and on simulated data from flow diagnostics for a multi-phase oil pipeline.

Flow patterns on distillation trays

Studies into the two-phase flow patterns produced on a sieve tray were carried out using an air-water simulator of 2.44 m in diameter. The flow patterns were investigated by a number of methods, direct observation using directional flow pointers; by water-cooling to simulate mass transfer; and by measurement of the height of clear liquid across the tray with manometers. The flow rates used were designed to show how the flow pattern changed with the change in the gas and liquid rates. The results from water-only studies on an un-perforated tray were compared with those produced on a sieve tray with holes of 12.7 mm diameter. The presence of regions on the sides of the tray where the liquid was circulating was noted from the water-only experiments. The presence and magnitude of the circulations was reduced when the air was passed through the liquid. These were similar to the findings of Hine (1990) and Chambers (1993). When circulation occurred, the flow separated at the ends of the inlet downcomer and circulations of up to 30% of the tray area were observed. Water-cooling and the manometer measurements were used to show the effect of the flow pattern on the tray efficiency and the height of clear liquid respectively. The efficiency was severely reduced by the presence of circulations. The height of clear liquid tended to rise in these areas. A comparison of data collected on trays with different hole diameters showed that the larger hole diameter inhibited the on-set of separation to a greater extent than small hole diameters. The tray efficiency was affected by a combination of the better mixing on smaller hole trays and detrimental effect of greater circulation on these trays. Work on a rectangular tray geometry was carried out to assess the effect of hole size on the height of clear liquid. It was found that the gradient on the outlet half of the tray was very small and that the highest clear liquid height was given by the highest hole size. Overall, the experiments helped to clarify the effect that the flow pattern had on the operation of the tray. It is hoped that the work can be of use in the development of models to predict the flow pattern and hence the tray efficiency.

Use of computational fluid dynamics in the design of bubble column reactors

Investigations into the modelling techniques that depict the transport of discrete phases (gas bubbles or solid particles) and model biochemical reactions in a bubble column reactor are discussed here. The mixture model was used to calculate gas-liquid, solid-liquid and gasliquid-solid interactions. Multiphase flow is a difficult phenomenon to capture, particularly in bubble columns where the major driving force is caused by the injection of gas bubbles. The gas bubbles cause a large density difference to occur that results in transient multi-dimensional fluid motion. Standard design procedures do not account for the transient motion, due to the simplifying assumptions of steady plug flow. Computational fluid dynamics (CFD) can assist in expanding the understanding of complex flows in bubble columns by characterising the flow phenomena for many geometrical configurations. Therefore, CFD has a role in the education of chemical and biochemical engineers, providing the examples of flow phenomena that many engineers may not experience, even through experimentation. The performance of the mixture model was investigated for three domains (plane, rectangular and cylindrical) and three flow models (laminar, k-e turbulence and the Reynolds stresses). mThis investigation raised many questions about how gas-liquid interactions are captured numerically. To answer some of these questions the analogy between thermal convection in a cavity and gas-liquid flow in bubble columns was invoked. This involved modelling the buoyant motion of air in a narrow cavity for a number of turbulence schemes. The difference in density was caused by a temperature gradient that acted across the width of the cavity. Multiple vortices were obtained when the Reynolds stresses were utilised with the addition of a basic flow profile after each time step. To implement the three-phase models an alternative mixture model was developed and compared against a commercially available mixture model for three turbulence schemes. The scheme where just the Reynolds stresses model was employed, predicted the transient motion of the fluids quite well for both mixture models. Solid-liquid and then alternative formulations of gas-liquid-solid model were compared against one another. The alternative form of the mixture model was found to perform particularly well for both gas and solid phase transport when calculating two and three-phase flow. The improvement in the solutions obtained was a result of the inclusion of the Reynolds stresses model and differences in the mixture models employed. The differences between the alternative mixture models were found in the volume fraction equation (flux and deviatoric stress tensor terms) and the viscosity formulation for the mixture phase.

Further studies on flow distribution on distillation sieve trays

The thesis describes experimental work on the possibility of using deflection baffles in conventional distillation trays as flow straightening devices, with the view of enhancing tray efficiency. The mode of operation is based on deflecting part of the liquid momentum from the centre of the tray to the segment regions in order to drive stagnating liquid at the edges forward. The first part of the work was a detailed investigation into the two-phase flow patterns produced on a conventional sieve tray having 1 mm hole size perforations. The data provide a check on some earlier work and extend the range of the existing databank, particularly to conditions more typical of industrial operation. A critical survey of data collected on trays with different hole sizes (Hine, 1990; Chambers, 1993; Fenwick, 1996; this work) showed that the hole diameter has a significant influence on the flow regime, the size of the stagnant regions and the hydraulic and mass transfer performance. Five modified tray topologies were created with different configurations of baffles and tested extensively in the 2.44 m diameter air-water pilot distillation simulator for their efficacy in achieving uniform flow across the tray and for their impact on tray loading capacity and mass transfer efficiency. Special attention was given to the calibration of the over 100 temperature probes used in measuring the water temperature across the tray on which the heat and mass transfer analogy is based. In addition to normal tray capacity experiments, higher weir load experiments were conducted using a 'half-tray' mode in order to extend the range of data to conditions more typical of industrial operation. The modified trays show superior flow characteristics compared to the conventional tray in terms of the ability to replenish the zones of exceptionally low temperatures and high residence times at the edges of the tray, to lower the bulk liquid gradient and to achieve a more uniform flow across the tray. These superior flow abilities, however, tend to diminish with increasing weir load because of the increasing tendency for the liquid to jump over the barriers instead of flowing over them. The modified tray topologies showed no tendency to cause undue limitation to tray loading capacity. Although the improvement in the efficiency of a single tray over that of the conventional tray was moderate and in some cases marginal, the multiplier effect in a multiple tray column situation would be significant (Porter et al., 1972). These results are in good agreement with an associated CFD studies (Fischer, 1999) carried out by partners in the Advanced Studies in Distillation consortium. It is concluded that deflection baffles can be used in a conventional distillation sieve tray to achieve better liquid flow distribution and obtain enhanced mass transfer efficiency, without undermining the tray loading capacity. Unlike any other controlled-flow tray whose mechanical complexity impose stringent manufacturing and installation tolerances, the baffled-tray models are simple to design, manufacture and install and thus provide an economic method of retrofitting badly performing sieve trays both in terms of downtime and fabrication. NOTE APPENDICES 2-5 ARE ON A SEPARATE FLOPPY DISK ONLY AVAILABLE FOR CONSULTATION AT ASTON UNIVERSITY LIBRARY WITH PRIOR ARRANGEMENT

Studies in three phase gas-liquid-solid fluidised systems

The work is a logical continuation of research started at Aston some years ago when studies were conducted on fermentations in bubble columns. The present work highlights typical design and operating problems that could arise in such systems as waste water, chemical, biochemical and petroleum operations involving three-phase, gas-liquid-solid fluidisation; such systems are in increasing use. It is believed that this is one of few studies concerned with `true' three-phase, gas-liquid-solid fluidised systems, and that this work will contribute significantly to closing some of the gaps in knowledge in this area. The research work was mainly experimentally based and involved studies of the hydrodynamic parameters, phase holdups (gas and solid), particle mixing and segregation, and phase flow dynamics (flow regime and circulation patterns). The studies have focused particularly on the solid behaviour and the influence of properties of solids present on the above parameters in three-phase, gas-liquid-solid fluidised systems containing single particle components and those containing binary and ternary mixtures of particles. All particles were near spherical in shape and two particle sizes and total concentration levels were used. Experiments were carried out in two- and three-dimensional bubble columns. Quantitative results are presented in graphical form and are supported by qualitative results from visual studies which are also shown as schematic diagrams and in photographic form. Gas and solid holdup results are compared for air-water containing single, binary and ternary component particle mixtures. It should be noted that the criteria for selection of the materials used are very important if true three-phase fluidisation is to be achieved: this is very evident when comparing the results with those in the literature. The fluid flow and circulation patterns observed were assessed for validation of the generally accepted patterns, and the author believes that the present work provides more accurate insight into the modelling of liquid circulation in bubble columns. The characteristic bubbly flow at low gas velocity in a two-phase system is suppressed in the three-phase system. The degree of mixing within the system is found to be dependent on flow regime, liquid circulation and the ratio of solid phase physical properties. Evidence of strong `trade-off' of properties is shown; the overall solid holdup is believed to be a major parameter influencing the gas holdup structure.

Thin film bearings with phase change of lubricant

The possible evaporation of lubricant in fluid film bearings has been investigated theoretically and by experiment using a radial flow hydrostatic bearing supplied with liquid refrigerant R114. Good correlation between measured and theoretical values was obtained using a bespoke computational fluid dynamic model in which the flow was assumed to be laminar and adiabatic. The effects of viscous dissipation and vapour generation within the fluid film are fully accounted for by applying a fourth order Runge-Kutta routine to satisfy the radial and filmwise transverse constraints of momentum, energy and mass conservation. The results indicate that the radial velocity profile remains parabolic while the flow remains in the liquid phase and that the radial rate of enthalpy generation is then constant across the film at a given radius. The results also show that evaporation will commence at a radial location determined by geometry and flow conditions and in fluid layers adjacent to the solid boundaries. Evaporation is shown to progress in the radial direction and the load carrying capacity of such a bearing is reduced significantly. Expressions for the viscosity of the liquid/vapour mixture found in the literature survey have not been tested against experimental data. A new formulation is proposed in which the suitable choice of a characteristic constant yields close representation to any of these expressions. Operating constraints imposed by the design of the experimental apparatus limited the extent of the surface over which evaporation could be obtained, and prevented clear identification of the most suitable relationship for the viscosity of the liquid/vapour mixture. The theoretical model was extended to examine the development of two phase flow in a rotating shaft face seal of uniform thickness. Previous theoretical analyses have been based on the assumption that the radial velocity profile of the flow is always parabolic, and that the tangential component of velocity varies linearly from the value at the rotating surface, to zero at the stationary surface. The computational fluid dynamic analysis shows that viscous shear and dissipation in the fluid adjacent to the rotating surface leads to developing evaporation with a consequent reduction in tangential shear forces. The tangential velocity profile is predicted to decay rapidly through the film, exhibiting a profile entirely different to that assumed by previous investigators. Progressive evaporation takes place close to the moving wall and does not occur completely at a single radial location, as has been claimed in earlier work.