Emulsion explosives have become the preferred choice as blasting agents for numerous industries including mining, agriculture, and construction. One of the most important components in such an emulsion is an emulsifier, which controls the emulsification properties of the explosive. The present study involves the production of one such emulsifier, which is produced by reacting two immiscible liquids, PIBSA (polyisobutylene succinic anhydride) and MEA (monoethanolamine). The study examines the effect of design variable such as the impeller speed, impeller type and the dispersed phase volume fraction on interfacial area. Experiments were carried out in a 0.15 m diameter fully baffled stirred tank using a 6-bladed Rushton turbine impeller and a marine propeller. Drop size was determined using a microscope with a video camera and image processing system. The transient concentration of PIBSA was determined using FTIR analysis and used to estimate the volume fraction of the dispersed phase (ƒÖ). The effective interfacial area was calculated using the Sauter mean drop diameter, d32 and ƒÖ. Impeller speeds ranging from 150 to 600 rpm and dispersed phase volume fractions, ƒÖ ranging from 0.01 to 0.028 were examined in the experimental study. It was found that that the evolution of Sauter mean drop diameter, d32 has four different trends depending on ƒÖ and impeller speed. At high impeller speeds and high ƒÖ, d32 values decrease initially and reach constant values after a long period of time. This trend is consistent with the findings in previous investigations. Under certain operating conditions, d32 values increase initially with stirring time to reach a maximum value and then decrease to reach a steady state value. The presence of these trends has been attributed to the effect of changing physical properties of the system as a result of chemical reaction. Results indicate that, in general, Sauter mean drop diameter d32 decreases with an increase in agitation intensity. However a decrease in the dispersed phase volume fraction is found to increase d32. These trends are found to be the same for both impeller types studied. Comparing the drop size results produced by the two impellers, it appears that low-power number propeller produces s ignificantly smaller drops than the Rushton turbine. It was found that the concentrations of reactants decrease with time for all impeller speeds thereby leading to a decrease in interfacial area with the progress of the reaction. Interfacial area values obtained at higher impeller speeds are found to be lower in spite of lower d32 values at these speeds. Also, these values decrease with time and become zero in a shorter duration indicating the rapid depletion of MEA. The interfacial area values obtained with the propeller at a given impeller speed are lower as compared to those for Rushton turbine. They also decrease and become zero in a shorter duration as compared to those for Rushton turbine suggesting propeller¡¦s performance is better in enhancing the reaction rate.

Les procédés continus par rapport aux procédés batch sont réputés être plus surs, plus économiques et plus sélectifs. Au regard de ces avantages, de plus en plus d'industries opérant traditionnellement en batch s'orientent vers des procédés continus. Si beaucoup de recherches ont été menées dans ce domaine en chimie fine, il n'en est pas de même pour les procédés de polymérisation et plus particulièrement pour le procédé de polymérisation en suspension du chlorure de vinyle. Ce procédé est à l'heure actuelle un des procédés batch les plus aboutis tant il a subi d'améliorations au cours des dernières décennies sur les plan chimiques (recette) et technologiques. Cependant, l'exposition au chlorure de vinyle est extrêmement toxique et le procédé présente notamment toujours des limitations en transfert thermique inhérentes à la technologie batch. De plus, l'étape réactionnelle constitue la seule étape batch du procédé total de production. Eu égard a la formation des grains de PVC au cours de la réaction, le procédé peut-être divise en trois principales étapes : une étape de dispersion liquide-liquide dans laquelle les gouttelettes de monomères (diamètre moyen 30-50μm) sont formées et stabilisées, une étape de réaction qui s'accompagne d'un phénomène d'agglomération contrôlée des gouttelettes de monomères et au cours duquel les particules polymérisant s’avèrent collantes et une pure étape réactionnelle au cours de laquelle la polymérisation est menée jusqu'à la conversion désirée. La présente étude se propose d'identifier les technologies adaptées pour chacune des étapes identifiées. Compte tenu des connaissances actuelles sur le comportement et l'évolution des grains avec la conversion et après une étude bibliographique sur les procédés continus de polymérisation, les technologies choisies dans ce travail sont les mélangeurs statiques et différents design de colonnes pulsées utilisées à co-courant. L'étape de dispersion liquide-liquide a été étudiée a l’aide de trois technologies différentes pour des systèmes de phases modèles. Concernant les mélangeurs statiques, les études ont démontré leur capacité à obtenir des gouttelettes de taille contrôlée et de la taille désirée. Dans la gamme étudiée, aucun effet de la concentration en phase dispersée n'a été démontre sur la taille des gouttes. Le paramètre physico-chimique le plus influent est la tension interfaciale. Celle-ci a d'ailleurs été estimée aux temps courts, correspondant aux temps de séjour (40-100 ms) dans les mélangeurs statiques, en modifiant la technique de la goutte pendante. Les résultats en termes de diamètre de goutte ont été corrélés via les nombres adimensionnels caractéristiques du système et de l'écoulement, à savoir les nombres de Reynolds et de Weber. A la lueur de ces résultats, les mélangeurs statiques ont été installes au pilote industriel pour effectuer des chargements de réacteurs batch de polymérisation. En plus de réduire considérablement les temps de chargement, leur utilisation a montré une meilleure répartition des agents de suspension et de l'initiateur au sein du grain. Ensuite, deux design de colonnes pulsées ont été utilises : la colonne pulsée a disques et couronnes a co-courant ascendant vertical et le COBR (continuous oscillatory baffled reactor, Nitech). Pour le premier design, les influence du matériau de garnissage et de son agencement (type et hauteur), des paramètres physicochimiques (concentration en phase dispersée, tensioactifs) et des paramètres hydrodynamiques (débit total, amplitude et fréquence d'oscillation) sur la taille des gouttes obtenues ont été examinées. Avec le second design, seuls les paramètres hydrodynamiques ont été étudiés. Une corrélation sur la taille des gouttes est proposée en fonction de nombres adimensionnels caractéristiques de ces appareils. Les trois technologies génératrices de la dispersion sont alors comparées en termes d'énergie dissipée et de puissance dissipée. [...] / Continuous processes present the benefit to be safer and more cost saving than batch processes. Many researches have been carried out in fine chemistry but few contributions refer to polymerization. We focus on the vinyl chloride suspension polymerization. This process has been extensively studied in batch with lots of improvement regarding the formulation and the technologies. This polymerization process is highly complex due to the toxic nature of the monomer, the good manage of heat transfer and stirring. Moreover the reaction step remains the only batch step of the PVC production. According to the PVC grain formation, the process can be divided into three steps (i) a liquid-liquid dispersion step in which the monomer droplet (30-50 µm) are generated and stabilized, (ii) a controlled agglomeration step of the reacting droplets exhibiting a sticky behaviour, (iii) a reaction step until the conversion rate is around 80-90% and the particles size is stable. In this study, the different technologies suitable for the different steps are pointed out. Based on the state of the art of the grain behaviour depending on the reaction conversion and on the literature concerning polymerization continuous process, static mixers and different co-current pulsed columns are proposed. Three technologies with different model system were chosen to study the liquid-liquid dispersion step. Static mixers allow the control of the droplet size under turbulent flow. In the range of the operating conditions, the dispersed phase concentration does not have a significant effect on the droplet size. The interfacial tension appears to be the most significant physico-chemical parameters. Correlation to predict the mean droplet size is proposed depending on different dimensionless numbers based on the hydrodynamics and on the systems: the Reynolds and Weber numbers. Given the promising results, static mixers are implemented at pilot scale to load the batch prior to polymerization. Their use demonstrates a noticeable reduction of the loading time and a better homogenisation of the different suspending agents and initiator inside the PVC grain. The two co-current pulsed columns design studied are the discs and doughnuts pulsed column and the COBR (continuous oscillatory baffled reactor, Nitech). For the first one, the effect of the packing materials (type and height), of the physico-chemical parameters (dispersed phase concentration, surfactant) and of hydrodynamic parameters (flowrate and oscillation conditions) on the droplet size are investigated where as for the second one the study is limited to the hydrodynamic parameters. A mean droplet size correlation is proposed based on the characteristic dimensionless numbers. The three continuous contactors used for liquid-liquid dispersion are compared in term of energy dissipation rate. The reaction is carried out in a continuous tubular reactor (the pulsed column). The column is suitable to transport solid-liquid suspension. Vinyl acetate suspension polymerization is performed to demonstrate the feasibility and particularly to study the encrusting and fouling problem. The first results are very promising.

Cette thèse est dédiée à l’étude de l’effet de la configuration des agitateurs (pales planes) et la nature du tensioactif sur la dispersion de gaz dans un liquide en vue d’obtenir un produit foisonné. Cette étude est menée à deux échelles pilote et locale. Le premier chapitre est dédié à une étude à l’échelle pilote. Les résultats ont montré qu’à conditions opératoires fixées, lorsque les agitateurs sont collés et décalés, l’aspect distributif de la dispersion de gaz est amélioré. L’aspect dispersif (taille des bulles), en revanche, reste peu sensible à la configuration des agitateurs. Les protéines sériques« WPI » comme agent tensioactif améliore l’efficacité de la rétention de gaz alors que le Tween 20 la réduit et provoque l’augmentation de la taille des bulles. Le deuxième chapitre concerne une approche locale qualitative (observation optique) et quantitative (détermination de capillaire critique). L’étude qualitative a montré que l’ajout d’un angle de décalage modifie l’écoulement du liquide et les bulles suivent la trajectoire imposée par le liquide. Lorsque les protéines WPI est utilisé comme agent tensioactif, sous l’action de la contrainte de cisaillement, les bulles subissent une déformation qui se termine par une rupture par extrémité. Un système couette a permis de déterminer un nombre capillaire critique correspondant à cette rupture. Par contre, en présence du Tween 20, la déformation ne conduit jamais à une rupture par extrémité. Le troisième chapitre de ce travail est dédié à une étude numérique de l’hydrodynamique de l’écoulement. Cette étude a permis de confirmer les résultats obtenus par l’approche qualitative. A titre d’exemple, un décalage entre deux agitateurs collés conduit à la multiplication des zones de vortex, à l’apparition des élongations supplémentaires et d’effet venturi favorables à l’aspect distributif de la dispersion. L’étude numérique montre également que le gradient maximal et moyen de vitesse reste indépendant de la configuration, ce qui explique pourquoi la taille moyenne est indépendante de la configuration. / Flat-blad impellers configuration coupled with tensioactif agents have been used to study gas dispersion in foaming process. The work has been conducted at pilot and local scales. The first chapter is devoted to a study at the pilot scale. The results showed that under a given operating conditions, a shift between two glued successive impellers promotes distributive aspect of the gas dispersion. However the dispersive aspect (bubble size), remains independent of the impellers configuration. The pilot-scale experiments have also shown that the "WPI" enhance foaming efficiency, while, Tween 20 reduces it and increases the size of the bubbles. The second chapter links with a qualitative (optical observation) and quantitative (determination of critical capillary) at local scale. It has been observed that shifted-impellers modify the flow pattern and promotes the distributive aspect of the mixture. When the WPI is used as a surfactant, shear stress induces bubble deformation until a tip-breakup occurs. Using a Couette system, it has been shown that there exist a critical capillary number corresponding to this rupture. However, the deformation does never induced tip-breakup when using Tween 20. The third chapter of this work is devoted to a numerical study of liquid hydrodynamics under different configuration. It appears that the configuration where the impellers are glued and shifted induces the multiplication of the vortex, the appearance of additional elongations and venturi effect. These effects seem to improve the distributive aspect of mixing in agreement with the results obtained previously. The numerical study also shows that the maximum and average shear gradient is independent of the configuration. This result explains why the mean bubble size remains independent of the configuration.

<p>In this research, liquid-liquid dispersion of viscous fluids was studied in an SMX static mixer in the laminar regime. Backlighting technique was used for flow visualization, and the Hough transform for circle detection was used in OpenCV to automatically detect and measure drop diameters for obtaining the size distribution. Silicone oil and an aqueous solution of high fructose corn syrup were used for dispersed and continuous phases respectively, and sodium dodecyl sulfate was used as the surfactant to modify the interfacial tension. Experiments were conducted at varying viscosity ratios and flow rates-each at zero, low (~200 ppm) and high (~1000 ppm) surfactant concentrations. The effect of holdup was explored only for a few cases, but it was found to have a minimal effect on the weighted average diameter D₄₃.</p> <p>It was found that the superficial velocity and the continuous phase viscosity had a dominant effect on D₄₃. The tail at the higher end of the droplet size distribution decreased with increasing superficial velocity and continuous phase viscosities. It was also found that D₄₃ decreased with lowering of the interfacial tension. Furthermore, the effect of the dispersed phase viscosity was significant only at non zero surfactant concentrations.</p> <p>An approximate model has been proposed that relates D₄₃ to the capillary number. It is based on an energy analysis of the work done by the viscous and surface forces on a drop of an initial diameter that is largely determined by the gap distance between the cross bars in the element</p> / Master of Applied Science (MASc)

Agitated dispersions of one liquid in another immiscible liquid are widely used in chemical industry in operations such as liquid-liquid extraction, suspension polymerisation, and blending of polymers. When holdup of the dispersed phase is increased, in an effort to increase the productivity, at a critical holdup, the dispersed phase catastrophically becomes the continuous phase and vice versa. This phenomenon is known as phase inversion. Although the inversion phenomenon has been studied off and on over the past few decades, the mechanism of phase inversion (PI) has yet not become clear. These studies have however brought out many interesting aspects of PI, besides unravelling the effect of physical and operational variables on PL Experiments show that oil-in-water (o/w) and water-in-oil (w/o) dispersions behave very differently, e.g water drops in w/o dispersions contain oil droplets in them, but oil drops in o/w dispersions contain none, dispersed phase hold up at which inversion occurs increases with agitation speed for w/o dispersions but decreases for o/w dispersions. A common feature of both types of dispersions however is that as agitation speed is increased to high values, inversion holdups reach a constant value. A further increase in agitation speed does not change inversion hold up. Although this finding was first reported a long time ago, the implications it may have not received any attentions. In fact, the work reported in the literature since then does not even mention it. The present work shows that this finding has profound implications. Starting with the finding that at high agitation speed inversion hold up does not change with agitation speed, the present work shows that inversion hold up also does not change with agitator diameter, type of agitator and vessel diameter. In these experiments, carried out in agitated vessel, energy was introduced as a point source. The experiments carried out with turbulent flow in annular region of two coaxial cylinders, inner one rotating, in which energy is introduced nearly uniformly throughout the system, show that the inversion holdup remains unchanged. These results indicate that constant values of inversion holdups for a given liquid-liquid systems (o/w and w/o) are properties of the liquid-liquid systems alone, independent of geometrical and operational parameters. A new hypothesis is proposed to explain the new findings. Phase inversion is considered to occur as a result of imbalance between breakup and coalescence of drops. Electrolytes, which affect only coalescence of drops, were therefore added to the system to investigate the effect of altering coalescence of drops on phase inversion. The experiments performed in the presence of electrolyte KI at various concentrations indicate that addition of electrolyte increases the inversion holdup for both o/w and w/o dispersions for three types of systems: non polar-water, polar-water and immiscible organic-organic. Higher the concentration of electrolyte used, higher was the holdup required for phase inversion. These findings indicate that while the addition of electrolyte increases coalescence of drops in lean dispersions, it has exactly opposite effect on imbalance of breakage and coalescence of drops at high holdups near phase inversion point. The opposite effect of electrolytes in lean and concentrated dispersions could be explained qualitatively, but only in part in the light of a new theory, involving multi-particle interactions. The phase inversion phenomenon is quantified in a simple manner by testing the breakage and coalescence rate expressions available in literature. It has been found that, equilibrium drop size (where breakage and coalescence events are in dynamic equilibrium) approaches infinity near phase inversion holdup which is not an ex perimentally observed fact. To capture the catastrophic nature of phase inversion, two steady state approach is proposed. The two steady states namely the stable steady state and unstable steady state, are achieved by modifying the expression for coalescence frequency on the basis of (i) shear coalescence mechanism and, (ii) recognising the fact that at high dispersed phase holdup the droplets are already in contact with each other at all times and hence rendering the second order coales cence process to a first order one. Using two steady states approach, catastrophic phase inversion is shown to occur at finite drop size.