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Thesis (MScEng (Process Engineering))--Stellenbosch University, 2008. / A full scale, three dimensional, transient, mathematical model was developed to simulate fluid flow and mixing in gas stirred ladles. The volume of fluid (VOF) and discrete phase (DPM) models were used in combination to account for multiphase aspects, and a slightly modified version of the standard - model was employed for turbulence modelling. The model was validated to compare well against published physical modelling results. Model results were interpreted from the fundamental grounds of kinetic energy transport within the ladle. This approach led to the specification of three key measures of mixing efficiency: The rate and efficiency of kinetic energy transfer from the buoyant gas to the bulk steel as well as the total kinetic energy holding capacity of the ladle. These measures describe the quantity of mixing in any specific ladle setup, whereas the traditional measure of mixing time reflects mixing quality, i.e. the degree of kinetic energy distribution through the entire ladle. The model was implemented in designed experiments to assess various operating and design variables pertaining to mixing quantity and quality. Considerable time was invested in finding the correct balance between numerical accuracy and computational time so that the model could be used to generate the required data within the given time frame. Experiments on the operating variables drew an important distinction between factors influencing the shape and the strength of gas induced flow patterns. Flow pattern strengthening variables, such as gas purge rate, significantly affected the quantity of mixing, but had a limited effect on mixing quality. Variables such as mass loading that influence the shape of the flow patterns had much larger potential to influence both the quantity and quality of mixing. Minimization of turbulence losses in the region of the plume eye was identified as the primary outcome of ladle design. It was shown that a taller vessel allowed more distance over which the plume could disperse, thereby reducing velocity gradients and subsequent turbulence generation at the free surface. Multiple tuyere systems yielded similar improvements by dividing the gas flow into several weakened plumes. Surface wave formation was investigated as an added mixing mechanism and demonstrated to be impractical for application in full scale gas stirred ladles. The conditions for resonance between the surface wave and the bubble plume were met only in vessels with a very low aspect ratio. Performance improvements offered by swirl in these ladles could easily be replicated in more practical ways. This study demonstrated the potential of mathematical modelling as a tool for in-depth investigation into fluid flow and mixing in the hostile environment of a full scale gas stirred ladle. Scaled-down cold models are the only alternative and can offer no more than a reasonably reliable predictive framework. The ease of flow data extraction from the numerical model also proved invaluable in facilitating a fundamental understanding of the effects of various important independent variables on ladle hydrodynamics. At this stage of development, however, the model is recommended for use on a comparative basis only. Two important developments are required for complete quantitative agreement: The inclusion of turbulence modulation by the bubbles and the increased turbulence kinetic energy dissipation rate in the vicinity of the free surface. A general strategy was developed to account for these effects and it compared favourably with published cold model results. Further research is required to generalize this approach for application in full scale gas stirred ladles.

The focus of this thesis is the study of turbulent solid-liquid stirred suspensions, which are involved in many common unit operations in the chemical, pharmaceutical and food industries. The studies of two-phase flows present a big challenge to researchers due to the complexity of experiments; hence there is a lack of quantitative solid and liquid hydrodynamic measurements. Therefore, an investigation of turbulence modulation by dispersed particles on the surrounding fluid in stirred vessels has been carried out, via two-phase fluorescent Particle Image Velocimetry (FPIV) and micromixing experiments. The main property of interest has been the local dissipation rate, as well as root-mean-square (rms) velocities and turbulent kinetic energy (TKE) of the fluid. Initially a single-phase PIV study was conducted to investigate the flow field generated by a sawtooth (EkatoMizer) impeller. The purpose of this study was to gain insight into various PIV techniques before moving on to more complex two-phase flows. Subsequently stereo-, highspeed and angle-resolved measurements were obtained. The EkatoMizer formed a good case study as information regarding its hydrodynamics is not readily available in literature, hence knowledge has been extended in this area. An analysis of the mean flow field elucidated the general structure of fluid drawn into the impeller region axially and discharged radially; the latter characterised the impeller stream. The radial rms velocity was considered to represent best the system turbulence, even though the tangential rms velocity was greater close to the blade; however the radial component was more prevalent in the discharge stream. Due to differences in rms velocities, TKE estimates obtained from two and three velocity components deviated, being greater in the latter case. Integral (1-D and 2-D) length scales were overestimated by the quantity W / 2 in the impeller region. Ratios of longitudinal-to-lateral length scales also indicated flow anisotropy (as they deviated from 2:1). The anisotropy tensor showed that the flow was anisotropic close to the blade, and returned to isotropy further away from the impeller. Instantaneous vector plots revealed vortices in the discharge stream, but these were not associated with flow periodicity. Alternatively, the vortex structures were interpreted as low frequency phenomena between 0-200 Hz; macro-instabilities were found to have a high probability of occurrence in the discharge stream. Dissipation is the turbulent property of most interest as it directly influences micromixing processes, and its calculation is also the most difficult to achieve. Its direct determination from definition requires highly resolved data. Alternative methods have been proposed in the literature, namely dimensional analysis, large eddy simulation (LES) analogy and deduction from the TKE balance. All methods were employed using 2-D and 3-D approximations from stereo-PIV data. The LES analogy was deemed to provide the best estimate, since it accounts for three-dimensionality of the flow and models turbulence at the smallest scales using a subgrid scale model. (Continues...).

Le chauffage par micro-ondes (MO) est employé depuis plus de 20 ans dans nombreux laboratoires pour l’activation de réactions en synthèse chimique. Il existe un débat sur l’existence d’effets MO sur la vitesse des réactions puisque des augmentations des vitesses des réactions ont été parfois observées. Des caractéristiques du chauffage MO peuvent être intéressantes pour l’intensification des procédés mais cette technique a rarement fait l’objet de productions à grande échelle. Peu de méthodes d’extrapolation de ces applications ont été proposées et celles qui existent sont purement empiriques. Nous avons voulu établir une méthodologie d’extrapolation de réacteurs MO en nous servant d’observations expérimentales fiables. La méthodologie des travaux a d’abord consisté au choix d’une réaction cible pour nos études : l’estérification de l’acide acétique avec le pentanol catalysée par une résine acide d’échange ionique. Nous avons conçu et construit un réacteur agité avec application monomode des MO. Des études dans le pilote ont montré le comportement hydrodynamique parfaitement agité du réacteur, la reproductibilité et la haute efficacité du chauffage. De plus, aucun gradient de température dans le réacteur n’a été mis en évidence. Des tests chimiques sous MO en réacteur fermé et en continu, ainsi qu’en milieu peu polaire ont montré que l’application des MO n’a pas eu d’influence sur la cinétique de la réaction cible. Finalement, nous avons développé une procédure d’extrapolation de réacteurs micro-ondes de type cuve agitée, qui est basée sur l’absence d’effet MO sur la chimie et sur le contrôle des zones chaudes dans le réacteur / Microwave (MW) assisted organic synthesis has been employed in many laboratories since more than 20 years. There is a controversy concerning the effects of MW on the kinetics of reactions since some enhancement of reaction rates have been observed. While MW heating advantages could be of interest for processes intensification, this technique has rarely been employed for large-scale productions. Scaling-up methods are rare and the existed techniques are generally empirical. The aim of our project is to propose a methodology for the extrapolation of MW reactors, using experimental reliable observations. Our research strategy has enabled us the choice of the target reaction to be carried out under MW irradiation: the esterification of acetic acid with pentanol over an acidic cation-exchange resin. A stirred reactor with MW single mode application was designed and constructed. Studies on the pilot have showed the perfectly stirred hydrodynamic behaviour of the reactor, the stability and the high heating efficiency. Moreover, no thermal gradients in the reactor have been observed. Tests in the reactor operated in batch and continuous mode, as well as in weak polar media, showed that there is no influence of MW heating on the kinetics of the target reaction. Finally, a guideline for the scaling-up of MW reactors was developed, based on the absence of MW effects on the reaction kinetics and on the control of hot zones in the reactor

An extensive study has been made of the factors affecting sample dispersion in flow injection analysis. This has included the effect of different manifold parameters on peak height and shape, and the use of various flow models to describe the physical processes involved. The factors investigated included sample flow-rate, tube length and diameter, sample volume, and the diffusion coefficient of the solute. The role of the detector has also been investigated, and was found to exert a strong influence on the observed dispersion behaviour of a flow injection manifold. In the light of this, a low volume flow cell was constructed which minimised the contribution of the detector to dispersion. Different modes of sample injection ("time" and "slug" injection) have been studied, and an automatic valve constructed in connection with the work. Both new and existing flow models have been evaluated in terms of their ease-of-use and ability to predict peak shape. Conditions for which the different models were valid were derived both experimentally and from consideration of the assumptions of the models. The applications of such models to the characterisation and design of flow manifolds has also been considered, and this approach compared to the purely theoretical and empirical approaches that have been described in the literature. The models examined in this thesis are the convection, diffusion, tanks-in-series, well-stirred tank, two-tanks in- parallel and two-tanks-in-series models. Finally, the practical implications of this work for the design of flow injection manifolds and the derivation of so-called "rules for dispersion" have been discussed, and suggestions made for further areas of research.

Este trabalho estudou a aplicação de oito métodos clássicos de escalonamento de tanques condicionadores, testando sua validade para dois tanques de geometria semelhante, mas com diferentes volumes (V1=10 e V2=49 decímetros cúbicos). No interior dos tanques, operavam impulsores (diâmetro D1=0,078m x D2=0,132m) que exibiam três distintos desenhos (2 pás versus 4 pás inclinadas em 45 graus versus turbina de Rushton). Sua rotação (N1 no tanque menor x N2 no tanque maior) visava à suspensão de partículas grossas de apatita (diâmetro médio = 254 micrometros) em polpas com 40% de sólidos em massa. Para balizar o escalonamento, adotou-se como variável de controle a mínima rotação do impulsor (Njs) que é capaz de fazer com que nenhuma partícula repouse no fundo do tanque por mais do que 1 ou 2 segundos (Critério 1-s), além de perfis axiais de distribuição de sólidos e a extensão da Zona Turbulenta versus Zona Quiescente no interior dos tanques. A diferença entre o valor previsto de Njs para o tanque de 49 decímetros cúbicos (N2) pelos métodos de escalonamento versus o valor de Njs (N2) determinado experimentalmente foi expressa como erro percentual (E). Consideraram-se como adequados para a aplicação que constitui o objetivo desta dissertação todos os métodos que exibiram E menor que 10%. Para o impelidor de 2 pás inclinadas, a adequação do método baseado na constância da razão potência/volume (E=2%) e também do método empírico de Rautzen (E=6%), indica a expressão N2=N1.(D1/D2) com seu expoente da relação entre os diâmetros variando entre 0,67 e 0,75 para a aplicação desejada. Considerando o impulsor de 4 pás inclinadas, a adequação do método da constância da razão potência/volume (E=4%); assim como dos métodos empíricos de Rautzen (E=0%) e Zwietering (5%), sugere o uso da expressão N2=N1.(D1/D2) com seu expoente da relação entre os diâmetros variando entre 0,67 e 0,85. Para a turbina de Rushton, o único método que exibiu E menor que 10% foi o da constância da relação potência/volume (E=8%), cuja expressão é N2=N1.(D1/D2) com seu expoente da relação entre os diâmetros igual a 0,67. Uma vez que a determinação do valor real de N2 foi baseada numa técnica experimental influenciada pelas limitações do observador, pode-se inferir que uma expressão geral de escalonamento do tipo N2=N1.(D1/D2) com seu expoente da relação entre os diâmetros igual a 0,75 atende aos propósitos desta aplicação. Por outro lado, o uso da relação P/V provê um critério mais objetivo para se balizar o escalonamento, haja vista que ele se adequou a todos os três tipos de impelidores contemplados por este estudo. / This work has studied the application of eight classical methods appointed by literature to accomplish the scale-up of stirred tanks which aimed to suspend slurries of 40% of solids, containing coarse (mean diameter=254 micrometers) apatite particles. The validity of the methods was accomplished by using two tanks of similar geometry but different capacity (V1=10 e V2=49 cubic decimeter), together with impellers of different diameter (D1=0,078m versus D2=0,132m) and design (turbine of 2 or 4 blades inclined at 45 degrees and Rushton turbine). To assist the process of validation, the impeller speed (Njs) under which no particle rests on the bottom of the tank for more than 1-2 seconds (1-s Criterium) was used together with the axial profile of solids percent distribution plus the extension of the turbulent versus quiescent zones within the two tanks. For any of the eight scale-up methods, the difference between the predicted value of Njs (N2) for the 49 cubic decimeter tank and the actual value (experimental) of the same variable was determined and its magnitude was expressed in terms of the percent error (E). The methods that yielded E less than 10% were considered as suitable for the aimed application. Considering the 2-inclined blade impeller, low value of E yielded by the method based on the constancy of the ratio power/volume (E=2%) and also by the empiric method of Rautzen (E=6%) indicate that the expression N2=N1.(D1/D2) with its exponent of the relation between diameters ranging between 0,67 and 0,75 is suitable for the desired application. Regarding the 4-inclined blade impeller, because the method based on the constancy of the ratio power/volume (E=4%) and also the empiric methods of Rautzen (E=0%) and Zwietering (E=5%) yielded the lowest values of E, the expression N2=N1.(D1/D2) with its exponent of the relation between diameters ranging between 0,67 and 0,85 is suitable for the aimed application. Moreover, for the Rusthon turbine, only the method based on the constancy of the ratio power/volume (E=8%) was adequate for the aimed application and, thus, the expression N2=N1.(D1/D2) with its exponent of the relation between the diameters equal to 0,67 is suitable for the purpose of this dissertation. Once the actual value of N2 is determined by visual observation, it is not possible to get very accurate results. This way, a generic scale-up expression is proposed: N2=N1.(D1/D2) with its exponent of the relation between the diameters equal to 0,75. On the other hand, the ratio P/V may provide a more objective criterium for scale-up, because the three sort of impellers used in this study yielded E less than 10% when the power/volume method was applied for the purpose of scale-up.

Many daily life products consist of mixtures of oil and water. When an immiscible material is dispersed an interface in-between the two phases is created which gives rise to rheological phenomena which can be exploited for product formulation; this is the case in products such as hand-creams and food products. Furthermore emulsions are used to transport hydrophobic materials, for example, many pharmaceuticals are injected as emulsions into the bloodstream. The performance of such products depends on their microstructure, which is determined by its formulation and how its constituents are mixed together; therefore the microstructure depends on the properties of the dispersed phases, the emulsifier used, the equipment used and its processing conditions. Emulsified products are seldom mono-dispersed due to the complex drop breakup mechanism in the turbulent fields inside the equipment in which the phases are forced together. The chaotic breakup mechanism of highly viscous dispersed phases yield complex and broad drop size distributions (DSD) as a result of the dominating viscous cohesive stresses inside the parent drop. Former studies have used the Sauter mean diameter and/or the size of the largest drop as the characteristic measure of central tendency of the DSD to correlate their results and to prove mechanistic or phenomenological models; however these parameters in isolation are insufficient to characterise the whole DSD of highly polydisperse emulsions. In this dissertation a vast amount of silicon oils of different viscosity were used as dispersed phase to study the effect of various processing conditions and formulations on the resulting DSD. The effect of several formulation and processing parameters were studied for two different mixing devices: stirred vessels and in-line high-shear mixers. (1) For stirred vessels, the effect of stirring speed, continuous phase viscosity and dispersed phase volume fraction were studied in combination with the viscosity of the dispersed phase for steady-state systems. (2) For in-line high-shear mixers a model that links batch and multi-pass continuous emulsification for multimodal DSD was derived from a transient mass balance. Processing parameters such as time and volume, flow rate and number of passes through the mixer, and stirring speed were studied for a wide dispersed phase viscosity range. The analytical methodology implemented included the use of one or more probability density functions to describe the shape of the DSD. The models proposed gave reasonable approximations of the Sauter mean diameter and allowed to study the drop size changes and the relative amount of different types of drops resulting from different breakup mechanisms.

This thesis examines the bioleaching of six different Canadian nickel sulphide ores at pH levels above what is generally considered optimum (~ 2). The majority of work discussed in this thesis was conducted with a low-grade metamorphosed ultramafic nickel sulphide ore from Manitoba, Canada (Ore 3), which is not currently exploitable with conventional technologies. The ore contains 21% magnesium and 0.3% nickel. Nickel is the only significant metal value, and is present primarily as pentlandite. A substantial fraction of the magnesium is present as the serpentine mineral lizardite, making processing difficult with conventional pyro- and biohydrometallurgical techniques. The work with this ore has two equally important objectives: to minimize magnesium mobilization and to obtain an acceptable level of nickel extraction. Batch stirred-tank bioleaching experiments were conducted with finely ground ore ( 147 µm) with temperature and pH control. The first phase of experimentation examined the effect of pH (2 to 6) at 30 °C, and the second phase examined all combinations of three pH levels (3, 4 and 5) and five temperatures (5, 15, 22.5, 30, and 45 °C).

This thesis examines the bioleaching of six different Canadian nickel sulphide ores at pH levels above what is generally considered optimum (~ 2). The majority of work discussed in this thesis was conducted with a low-grade metamorphosed ultramafic nickel sulphide ore from Manitoba, Canada (Ore 3), which is not currently exploitable with conventional technologies. The ore contains 21% magnesium and 0.3% nickel. Nickel is the only significant metal value, and is present primarily as pentlandite. A substantial fraction of the magnesium is present as the serpentine mineral lizardite, making processing difficult with conventional pyro- and biohydrometallurgical techniques. The work with this ore has two equally important objectives: to minimize magnesium mobilization and to obtain an acceptable level of nickel extraction. Batch stirred-tank bioleaching experiments were conducted with finely ground ore ( 147 µm) with temperature and pH control. The first phase of experimentation examined the effect of pH (2 to 6) at 30 °C, and the second phase examined all combinations of three pH levels (3, 4 and 5) and five temperatures (5, 15, 22.5, 30, and 45 °C).