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Continuous counter current extraction (CCCE) or dual flow counter current chromatography (DFCCC) is a promising technique where components can be separated continuously by two liquid phases that flow in opposite directions through a continuous length of coiled tubing. Specially designed end connectors and a coil planet centrifuge allow each respective phase to be pumped into each end of the tubing and the other phase to elute at each opposite end. In this thesis the feasibility and the mechanics of CCCE are investigated using stroboscopic photography on an experimental rig and a specially built pilot-scale CCCE centrifuge. The mechanics of the hydrodynamics in the coil was investigated systematically by comparing the measured volumes with photographic images of the process. This investigation revealed that the phases are not distributed evenly throughout the coil, which was previously assumed, but that there is a transition area where the phases switch from mainly upper phase at the head end of the tubing to mainly lower phase at the tail end. This means that the sample encounter three different phase distribution zones in the coil. At the head the upper phase is the dominant phase with a small volume of lower phase running through. At the tail the reverse situation is found and lower phase is dominant. The third zone is a short segment of the coil where there is a transition between the dominant phase conditions that exist at each end. The position of the transition zone and the volume of the other two zones are profoundly affected by the relative flow rates of the two phases. This work indicates that the volume distribution in the coil is affected most by the upper phase flow rate. The pilot-scale CCCE centrifuge was used to successfully separate industrially supplied samples. Crude reaction liquor was processed in both batch and continuous modes achieving the separation of the multi-component mixture into two groups. Changing the flow rate combinations changed the location of elution of some of the components in the mixture. Separation efficiency was maintained even when sample loading was increased. The separations were shown to be predictable with the dual flow theoretical model.

Concentrated animal feeding operations such as cattle feedlots and dairies produce a large amount of manure, cattle biomass (CB), which may lead to land, water, and air pollution if waste handling systems and storage and treatment structures are not properly managed. However, the concentrated production of low quality CB at these feeding operations serves as a good feedstock for in situ gasification for syngas (CO and H2) production and subsequent use in power generation. A small scale (10 kW) countercurrent fixed bed gasifier was rebuilt to perform gasification studies under quasisteady state conditions using dairy biomass (DB) as feedstock and various air-steam mixtures as oxidizing sources. A DB-ash (from DB) blend and a DB-Wyoming coal blend were also studied for comparison purposes. In addition, chlorinated char was also produced via pure pyrolysis of DB using N2 and N2-steam gas mixtures. The chlorinated char is useful for enhanced capture of Hg in ESP of coal fired boilers. Two main parameters were investigated in the gasification studies with air-steam mixtures. One was the equivalence ratio ER (the ratio of stochiometric air to actual air) and the second was the steam to fuel ratio (S:F). Prior to the experimental studies, atom conservation with i) limited product species and ii) equilibrium modeling studies with a large number of product species were performed on the gasification of DB to determine suitable range of operating conditions (ER and S:F ratio). Results on bed temperature profile, gas composition (CO, CO2, H2, CH4, C2H6, and N2), gross heating value (HHV), and energy conversion efficiency (ECE) are presented. Both modeling and experimental results show that gasification under increased ER and S:F ratios tend to produce rich mixtures in H2 and CO2 but poor in CO. Increased ER produces gases with higher HHV but decreases the ECE due to higher tar and char production. Gasification of DB under the operating conditions 1.59<ER less than6.36 and 0.35<s:f>less than0.8 yielded gas mixtures with compositions as given below: CO (4.77 - 11.73 %), H2 (13.48 - 25.45%), CO2 (11-25.2%), CH4 (0.43-1.73 %), and C2H6 (0.2- 0.69%). In general, the bed temperature profiles had peaks that ranged between 519 and 1032 degrees C for DB gasification.

In a counter-current two-phase flow system, flooding can be defined as the onset of flow reversal of the liquid component which results in an upward co-current flow. Flooding in the surge line of pressurized water reactors poses a significant technical challenge in the analysis of several postulated nuclear reactor accident scenarios. Despite the importance of flooding in these analyses, previous work does not identify a universally accepted rigorous physics-based model of flooding, even for the simple case of flooding in adiabatic, vertical tubes. This can be attributed to a lack of conclusive understanding of the physics of two-phase counter-current flow, specifically the mechanism of flooding, and the large amount of uncertainty among data from various flooding experiments. This deficiency in phenomenological and experimental knowledge has led to the use of many empirical and semi-empirical correlations for specific system conditions and geometries. The goal of this work is the development of a model for flooding in vertical, adiabatic tubes from first principles. To address a source of uncertainty in the analysis of flooding, a model for the prediction of average film thickness in annular co- and counter-current flows has been developed by considering the conservation of momentum of the liquid and gas flows. This model is shown to be a quantitative improvement over the most commonly used models, those of Nusselt and Belkin, Macleod, Monrad, and Rothfus. The new model better considers the effects of interfacial shear and tube curvature by using closure relations known to represent forces appropriately in co- and counter-current flow. Previous work based on semi-empirical flooding models has been analyzed to develop a new theory on the hydrodynamic mechanism which causes flooding. It is postulated that the growth of an interfacial wave due to interfacial instability results in a flow reversal to ensure that momentum is conserved in the counter-current flow system by causing a partial or complete co-current flow. A model for the stability of interfacial waves in a counter-current flow system is proposed and has been developed herein. This model accurately represents the geometric and flow conditions in vertical adiabatic tubes and has been shown to have limits that are consistent with the physical basis of the system. The theory of waves of finite amplitude was employed to provide closure to an unknown parameter in the new model, the wave number of the wave that generates the interfacial instabil- ity. While this model underpredicts the flooding superficial gas velocity, the result is a conservative estimate of what conditions will generate flooding for a system. In the context of the analysis of a nuclear reactor, specifically a pressurized water reactor, conservatism means that the gas flow rate predicted to cause flooding for a fixed liquid flow rate will be less than the flow rate found experimentally, mean- ing that liquid delivery to the core would be safely underestimated. Future work includes the improvement of the closure relation for the limiting wave number that will cause unstable interfacial waves, as well as an assessment of the applicability of the stability-based model to flooding in the presence of phase change and flooding in complex geometries.

The potential of countercurrent chromatography (CCC) as a small footprint bioreactor/separator for manufacture of enantiopure chiral molecules was explored, using as a model reaction the isolation of L-amino butyric acid (L-ABA) from a DL-ABA racemate and the enantioselectivity of D-amino acid oxidase (DAAO). Bioconversion of D-ABA to ketobutyric acid (KBA) by DAAO, immobilised by selective partitioning in the stationary phase of the CCC centrifuge, was accompanied by separation of unreacted L-ABA from KBA by the countercurrent action of the centrifuge. For effective bioreactor/separator action, a high partition of the biocatalyst to the stationary phase was required in order to retain the biocatalyst in the coil, with differing partitions of substrates and products between the stationary phase (SP) and mobile phase (MP) so that these could be separated. Aqueous two-phase systems (ATPS) were the major two-phase systems used to provide SP and MP, as these are well reported to be effective in preserving enzyme activity. The distribution ratios of DL-ABA, KBA and DAAO were measured in a range of phases with polyethylene glycols (PEGs) of different molecular weights, different salts, and different compositions of PEG and salt, using an automated robotic method, developed for the purpose. A system of 14% w/w PEG 1000/ 14% w/w potassium phosphate, pH 7.6, gave the best combination of distributions ratios (CPEG phase/Csalt phase = CSP/CMP) for ABA, KBA and biocatalyst (DAAO) of 0.6, 2.4 and 19.6 respectively. A limited number of aqueous-organic and ionic liquid two-phase systems were also reviewed, but found unsatisfactory. CCC operating conditions such as substrate concentration, biocatalyst concentration, the mobile phase flow rate (residence time in the CCC coil), temperature, rotational speed and operational modes (single flow and multiple-dual flow) and types of mixing (cascade and wave-like) were optimised to produce total conversion of D-ABA to KBA, which was then completely separated from unreacted, enantiomerically pure (>99% ee), LABA. Advantages of the CCC bioreactor over conventional technology include reduced equipment footprint, cheaper running costs, and faster purifications. However, in its current format the drawbacks, such as enzyme instability and excessive optimisation time, reduce its commercial appeal. Additional investigations into the use of whole cell preparations of biocatalyst in the CCC bioreactor showed potential to overcome the problem of enzyme instability and this may in the future give the CCC bioreactor a place in the enantioseparation field.

This work analyzes the solid flow dynamics of gas-solid downer fluidized bed reactor in co-current and, particularly, in counter-current mode. This reactor is potentially interesting for catalytic applications where very short (sub second) and precise contact times are required between the solid catalyst and the gaseous reactants-products. To this aim, a 1.5 m and 36 mm ID downer reactor setup was built to replicate the conditions in a real unit in cold flow and using materials that enable the observation of the solid particle dynamics. Specifically, two state-of-the-art techniques have been used: Particle Image Velocimetry (PIV) and Digital Image Analysis (DIA). Three types of particles have been used: two commercial fluidized catalytic cracking (FCC) particles (ρp = 1300 kg/m3, dp = 75 and 56 μm) and sand (ρp=2600 kg/m3, dp= 370 μm). High-speed cameras were positioned in two axial positions: 70 and 140 cm from the top, to reveal the flow behavior across the reactor. It was found that the solid flow initially was segregated because of the solid feeding design. Thus, 3D printed re-distributer was used to even the solid flow. The solid particles in the counter-current downer was approaching the plug-flow behavior with 23% variation in the velocity gradient across the radial direction, compared with 40% for the co-current counterpart. A method to estimate solid hold-up based on images was developed, yielding values in a good agreement with literature. Keywords: Hydrodynamics, counter-current, downer, PIV, DIA, Solid hold-up

No / In this paper, a model for urea prilling tower with co-current flow of cooling air and urea prills (particles) is presented. The process is modelled by simultaneous solution of the differential equations for hydrodynamics, heat and mass transfer between the air and prills. The process variables such as temperature, absolute and relative humidity of air along the height of the tower were obtained from this model. Temperature and moisture distribution of urea prills and their radial and vertical velocities were also calculated. The results of the present model were compared with the counter-current operation model available in the literature. The simulation results show that heat transfer performance for co-current operation is significantly less than that of the counter-current scenario. This is more pronounced for small prills, i.e. 1.0 mm than that of the large prills. The advantage of the model is that it can be used to investigate influence of operating parameters on efficiency of the co-current process. This also helps us to set the process control strategies for design and quality control purposes of the process.

In order to investigate the two-phase flow behaviour in a complex reactor-typical geometry and to supply suitable data for CFD code validation, a model of the hot leg of a pressurised water reactor was built at FZD. The hot leg model is operated in the pressure chamber of the TOPFLOW test facility, which is used to perform high-pressure experiments under pressure equilibrium with the inside atmosphere of the chamber. This technique makes it possible to visualise the two-phase flow through large windows, also at reactor-typical pressure levels. In order to optimise the optical observation possibilities, the test section was designed with a rectangular cross-section. Experiments were performed with air and water at 1.5 and 3.0 bar at room temperature as well as with steam and water at 15, 30 and 50 bar and the corresponding saturation temperature (i.e. up to 264°C). The total of 194 runs are divided into 4 types of experiments covering stationary co-current flow, counter-current flow, flow without water circulation and transient counter-current flow limitation (CCFL) experiments. This report provides a detailed documentation of the experiments including information on the experimental setup, experimental procedure, test matrix and on the calibration of the measuring devices. The available data is described and data sheets were arranged for each experiment in order to give an overview of the most important parameters. For the cocurrent flow experiments, water level histograms were arranged and used to characterise the flow in the hot leg. In fact, the form of the probability distribution was found to be sensitive to the boundary conditions and, therefore, is useful for the CFD comparison. Furthermore, the flooding characteristics of the hot leg model plotted in terms of the classical Wallis parameter or Kutateladze number were found to fail to properly correlate the data of the air/water and steam/water series. Therefore, a modified Wallis parameter is proposed, which takes the effect of viscosity into account.

Field flow fractionation of particles in rotating coiled column has been investigated in recent year. In contrast to the classical mode of field flow fractionation in narrow channels, the use of rotating coiled columns offers the possibility of large sample loading. In this thesis, the potential for new cell separation methods based on the use of flow fractionation in fluctuating g-fields generated in rotating coil columns is examined. The effects of operational conditions (flow rate and rotational speed – Chapter 3 and Chapter 5); cell properties (cell flexibility – Chapter 4); and column shapes (different inner diameters and coil geometries – Chapter 6) on the flow behaviour of a model system of red blood cells (RBCs) from different species, which differ markedly in size, shape & density, flowing in a single phase of buffered saline have been characterised. Operational Conditions: For a particular rotational speed, there was a minimum flow rate which caused all the cells to be retained in the column and a maximum flow rate at which all cells were eluted. Both the minimum and maximum flow rate were increased when a higher rotational speed was applied. Differences in the behaviour of sheep & hen RBCs have been used to develop a separation method using a continuously increasing flow gradient. This separation could be speeded up by using a step flow gradient. The effects of cell load and rotational direction on the behaviour of RBCs in the column was also studied in this thesis. Cell Properties: The minimum flow rate was found to correlate with cell diameter/cell volume of the RBCs as expected for a sedimentation related process and was partially described by a theoretic equation developed for particles by Fedotov and colleagues (Fedotov et al. 2005). However cell dependent departures from this equation were found which appear to indicate that cell specific surface properties may also be involved for cells (Chapter 3). By contrast the maximum flow rate showed no correlation with cell diameter/cell volume. An effect of cell deformability on the flow separation behaviour of the cells has been demonstrated. Chemical fixation of sheep RBCs with glutaraldehyde rendered the normally deformable RBCs rigid and non-deformable and resulted in the fixed sheep RBCs eluting significantly earlier than unfixed sheep RBCs. This difference was great enough that a mixture of deformable (unfixed) and non-deformable (fixed) sheep RBCs could be separated. Fixed cells tended to show cell aggregation, which could be reduced by the addition of surfactant. Column Geometry: An effect of column shapes on the flow separation behaviour of cells has been demonstrated showing that the optimisation of column design is an important feature of this mode of cell separation. For columns with the same cross sectional area, a “horizontal” rectangular column provided better separation than a circular column and a “vertical” rectangular column gave the least efficient separation. A possible explanation for this behaviour is suggested the thinner sedimentation layer and less secondary flow. Differences in the behaviour of various species of RBCs in the “horizontal” rectangular column have been used to study the efficiency of separation of a mixture of sheep and hen RBCs, and a mixture of rabbit and hen RBCs. This work shows similarities and differences with other reports on cell/particle separations in rotating coiled columns in single phases and also in aqueous two phases systems (ATPS) and these are discussed. Fedotov P.S., Kronrod V.A. & Kasatonova O.N. (2005). Simulation of the motion of solid particles in the carries liquid flow in a rotating coiled column. J. Anal. Chem., 60, 4, 310-316.