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Thesis (MScEng (Process Engineering))--University of Stellenbosch, 2010. / ENGLISH ABSTRACT: Distillation continues to be the most widely used method of separation in the processing industry, in spite of its inherently low thermodynamic efficiency. Two of the critical distillation research needs that arose from the US-Initiative Vision 2020 were to develop a better understanding of the physical phenomena as well as developing better predictive models. Also, characterisation of modern packing materials is required to assist in the CO2 capture optimisation. This thesis deals with both these aspects by establishing a facility that can accurately measure the hydraulic capacity of packed columns. This setup eliminates mass transfer and specific attention can be given to the hydrodynamic behaviour of packed columns. Two phenomena that have a large impact on the mass transfer efficiency of packing materials are the loading and flooding point. The loading point is signified by the following: a.) where the packed column hold-up increases, b.) higher increase in pressure drop, and c.) a decrease in Height Equivalent to a Theoretical Plate (HETP). The onset of flooding is where the shear forces between the gas and liquid become so large (relative to the gravitational forces) that a net upwards movement of liquid occurs, resulting in liquid droplets being heavily entrained. This is normally accompanied by a sharp increase in HETP, pressure drop and liquid hold-up. The prediction of these operating limits is of great value but, despite the many contributions that were made from 1960 to 2010, there is still room for improvement. The operating region of particular interest is between the loading and flooding point, especially for fluids with physical properties significantly different from that of water. In the past, this operating region was not of great importance, but industries are constantly striving to increase their production with minimal capital expenditure. Thus, packed columns are being pushed to their limits and a good understanding of the phenomena occurring near these operational limits is now required. A 400 mm diameter glass packed bed setup (with a bed height of 3000 mm) was designed and constructed to test the effect of the following parameters on packed bed pressure drop and liquid hold-up: · Gas and liquid physical properties · Gas and liquid rates · Type of packing (either random or structured) The experimental setup has been designed so that in the future the influences of the above mentioned parameters on entrainment can also be measured. Initially, hydrodynamic tests on random packing materials (1.5” Pall® Rings, 1.5” IMTP®, 1.5” Intalox® Ultra™) were conducted over a liquid range of 6 - 122 m3/(m2·h). Through a thorough literature study it was found that the most likely semi-theoretical model, that would be able to predict the pressure drop and the liquid hold-up over most of the random packing test range, was the model developed by Billet [1991; 1993; 1995; 1999]. The other models found throughout the literature had at least one of the following deficiencies: · Limited to only the pre-loading region. · Tested (and thus applicable) only over a very select group of packing materials with no attempt to generalise. · Lacked the proper validation of significantly variable fluid properties over multitudes of liquid and gas rates especially, at higher gas and liquid rates. The experimental setup was successfully commissioned, noting the following maximum experimental errors: Vapour flow factor - 2.6 %; liquid rate - 0.75 %; packed bed pressure drop - 0.75 %; liquid hold-up - 1.25 % and entrainment - 1.05 %. Significant deviations were observed between the experimental hold-up and the hold-up from the predictive model of Billet (using Pall® Rings). Careful inspection revealed that this predictive model potentially uses two definitions for hold-up at flooding, one which has a theoretical basis and the other purely empirical. Upon substituting the theoretical value with the empirical value, a significant improvement was observed between the measured and predicted results. Deviations were still observed near the flooding point and were attributed to the difficulty of obtaining reliable flooding data. The range of liquid hold-up prediction by Billet was only verified up to a liquid rate of 82 m3/(m2·h) and the pressure drop prediction only verified up to a liquid rate of 60 m3/(m2·h). This reinforces the need for high liquid, high gas rate data. Due to the empirical nature of the liquid hold-up at flooding prediction, and since pressure drop prediction is directly linked to liquid hold-up, another model was used to compare the experimental pressure drop data. The KG-TOWER® simulator was used to predict IMTP® data and compare it to the experimentally measured values. It was found that the experimental IMTP® data followed the same trends as those from KG-TOWER® within the operating limits of the program. Thus, since the experimental data follows similar trends as models found in the literature, as well as falling within their reliable limits, the experimental setup can correctly measure the parameters in question. The experimental data from the different random packings were compared to one another by using a statistical method to determine the loading point and onset of flooding. This method uses prediction confidence intervals by fitting empirical curves to each operating region and was found to be useful in determining these critical points from experimental hydraulic data (in the absence of HETP data).The only useful comparison was between IMTP® and Intalox® Ultra™ as they both have roughly the same density, size and void fraction. It was found that, on average, the pressure drop of Intalox® Ultra™ is 20 % lower than that of IMTP® over the entire operating range. The hydraulic operating range of Intalox® Ultra™ was found to be on average 16 % larger than that of IMTP®. It is recommended that further testing should be done to investigate the influence of fluid properties (specifically liquid viscosity and to a lesser extent surface tension) on the hydraulic capacity of packed columns. Also, high gas and high liquid rate data should be generated to assist current modelling techniques. Lastly, a comparative characterisation between Intalox® Ultra™ and Raschig Super-Rings would serve as a benchmark for fourth generation random packings. / AFRIKAANSE OPSOMMING: Distillasie is vandag nog die skeidingsproses wat die meeste gebruik word in the prosesnywerhede ten spyte van ‘n lae termodinamiese effektiwiteit. Twee van die kritieke distillasie navorsing behoeftes wat vanuit die US-Initiative Vision 2020 ontstaan het, was om die fisiese verskynsels beter te verstaan, asook om beter voorspellende modelle te ontwikkel. Die karakterisering van moderne pakking materiale is ook nodig vir die optimering van die verwydering van CO2 uit uitlaatstrome. Hierdie tesis spreek beide van hierdie faktore aan deur ‘n fasiliteit op te rig wat die hidrouliese kapasiteit van gepakte kolomme akkuraat kan meet. Hierdie opstelling elimineer massa-oordrag en dus kan spesifieke aandag gegee word aan die hidrodinamiese gedrag van gepakte kolomme. Twee verskynsels wat ‘n groot impak het op die massaoordrag effektiwiteit van pakkingsmateriale is die ladingspunt en die vloedpunt. Die ladingspunt word deur die volgende gekenmerk: a.) waar die vloeistof inhoud in die gepakte bed toeneem, b.) ‘n toename in drukval en c.) ‘n afname in die hoogte ekwivalent aan ‘n teoretiese plaat (HETP). Die vloed gebied word gekenmerk waar die skuifkragte tussen die vloeistof en gas so groot raak (relatief tot die gravitasionele kragte), dat daar ‘n netto opwaartse beweging van vloeistof druppels in die kolom is. Hierdie gaan normaalweg gepaard met ‘n skerp toename in HETP, drukval en vloeistof inhoud. Die voorspelling van hierdie bedryfslimiete is baie waardevol, maar ten spyte van die bydrae wat tussen 1960 en 2010 gemaak was, is daar nog steeds ruimte vir verbetering. Die spesifieke bedryfsgebied van belang is die gebied tussen die ladingspunt en die vloedpunt en spesifiek vir sisteme waar die fisiese eienskappe van die vloeistowwe drasties verskil van die van water. In die verlede was hierdie gebied van minder belang gewees, maar maatskappye probeer deesdae hul produksie opstoot met minimale kapitale uitleg. Dus is ‘n goeie kennis van massa-oordrag verskynsels naby aan die bedryfslimiete van kardinale belang. ‘n 400 mm Diameter gepakte kolom (met ‘n bed hoogte van 3000 mm en bestaande uit glas) opstelling is ontwerp en gebou om die effek van die volgende parameters te toets op gepakte bed drukval en vloeistof inhoud: · Gas en vloeistof fisiese eienskappe · Gas vloeistof vloeitempos · Tipe pakking (beide ongeordend en gestruktureerd) Die eksperimentele opstelling is ontwerp om die bogenoemde eienskappe op vloeistofmeesleuring te meet vir toekomstige navorsing. Hidrodinamiese toetse op ongeordende pakkingsmateriale (1.5” Pall® Ringe, 1.5” IMTP®, 1.5” Intalox® Ultra™) is uitgevoer vir vloeistof vloeitempos tussen 6 en 122 m3/(m2·h). Vanuit ‘n deeglike literatuurstudie is daar gevind dat die mees toepaslike semi-teoretiese model, wat die drukval sowel as die vloeistof inhoud kan voorspel oor al die bedryfsgebiede, is die model wat deur Billet [1991; 1993; 1995; 1999] ontwikkel is. Die ander modelle in die literatuur het ten minste een van die volgende tekortkominge gehad: · Is slegs van toepassing in die voor-ladings gebied. · Is slegs van toepassing vir ‘n paar pakkingsmateriale en geen poging is aangewend om dit te veralgemeen nie. · Is nie geldig waar die vloeistof eienskappe drasties verskil van ‘n lug/water sisteem nie, sowel as by hoë gas en vloeistof vloeitempos. Die eksperimentele opstelling is suksesvol in werking gestel met die volgende waargenome eksperimentele foute: Gas vloei faktor – 2.6 %; vloeistof vloeitempo – 0.75 %; gepakte bed drukval – 0.75 %; vloeistof inhoud – 1.25 %; vloeistof-meesleuring tempo – 1.05 %. Noemenswaardige verskille is waargeneem tussen die eksperimentele en teoretiese vloeistof inhoud (deur Pall® Ringe te gebruik). Na gelang van noukeurige inspeksie, is daar gevind dat die Billet-model twee moontlike definisies voorstel vir die voorspelling van vloeistofinhoud by die vloedpunt. Een van hierdie is teoreties van aard en die ander een suiwer empiries. ‘n Vervanging van die teoretiese waardes met die empiriese waardes het gelei tot ‘n merkwaardige verbetering tussen die eksperimentele en teoretiese voorspellings. Daar was nog steeds verskille naby aan die vloedpunt, maar dit kon toegeskryf word aan die feit dat min betroubare data naby aan die vloedpunt beskikbaar is. Die voorspelling van vloeistof inhoud deur Billet is slegs gekontroleer tot ‘n vloeistof vloeitempo van 82 m3/(m2·h) en die drukval slegs tot ‘n vloeistof vloeitempo van 60 m3/(m2·h). Die bogenoemde bewys dus die tekort aan hoë gas- en hoë vloeistofvloeitempo data. Die voorspellende model se drukval is gekoppel aan die vloeistof inhoud, en dus is ‘n ander model gebruik om die eksperimentele drukval data teen te vergelyk. Die KG-TOWER® simulasie program is gebruik om die IMTP® drukval te voorspel en dit het goed vergelyk met die eksperimentele data. Dus, aangesien die eksperimentele data dieselfde tendens toon as dié van die modelle in die literatuur en aangesien dit binne die modelle se foutbande val, kan die eksperimentele opstelling die verlangde parameters akkuraat meet. Die eksperimentele data van al drie pakkingsmateriale is teenoor mekaar vergelyk deur gebruik te maak van ‘n statistiese metode wat die ladings- en vloedpunt bepaal. Hierdie metode maak gebruik van voorspellings vertroue intervalle deur empiriese kurwes op die eksperimentele data in elke bedryfsgebied te pas. Hierdie metode is ontwikkel om toepaslike te wees in die afwesigheid van HETP data. Die enigste nuttige vergelyking is tussen IMTP® en Intalox® Ultra™ omdat albei dieselfde pakkingsdigtheid, grootte en pakkings oop ruimte het. Daar is gevind dat die drukval van Intalox® Ultra™ ‘n gemiddeld van 20 % laer is as dié van IMTP® oor die hele bedryfsgebied. Die hidrouliese bedryfsgebied van Intalox® Ultra™ is 16 % groter as dié van IMTP®. Daar word voorgestel dat bykomende toetswerk gedoen moet word om die invloed van vloeistof eienskappe (spesifiek vloeistof viskositeit en vloeistof oppervlak spanning) op die hidrouliese kapasiteit van gepakte kolomme te ondersoek. Bykomende toestwerk by hoë gas- en hoë vloeistofvloeitempo word benodig om die bestaande modelle aan te vul. Laastens, sal ‘n vergelykende studie tussen Intalox® Ultra™ en Raschig Super-Rings die grondslag lewer vir die karakterisering van vierde generasie ongeordende pakkingsmateriale.

Ce travail s’inscrit dans la convention CIFRE n°2012/0379 avec la startup Adionics pour le développement d’un procédé de dessalement par extraction liquide-liquide. La régénération de la phase organique est réalisée par désextraction du sel à chaud. Les isothermes de partage du NaCl, Na2SO4 et MgCl2 à 20 40 60 et 80°C ont été obtenues. Une stœchiométrie expliquant leur forme a été proposée et les constantes d’équilibre associées ont été déterminées. Les enthalpies d’extraction ont été déduites des variations des constantes d’équilibre avec la température.La prise en compte de l’effet de milieu en phase aqueuse a été réalisée à l’aide du modèle de Pitzer avec l’hypothèse des interactions spécifiques. Une correction pour les effets de milieu en phase organique a également été ajustée sur NaCl -Na2SO4 à 20 40 et 60°C.Les propriétés physico-chimiques du solvant (viscosité, masse volumique, chaleur spécifique, conductivité thermique, ...) ont été déterminées sur une plage de 20°C à 80°C. La tension interfaciale du solvant a également été obtenue à 20°C, avec de l'eau eau pure et salée. Une étude approchée de la solubilité du diluant en phase aqueuse a également été entreprise.Un prototype avec deux colonnes à garnissage de 4 mètres de haut a été élaboré pour tester la faisabilité du procédé en continu. L’extracteur a été modélisé par une cascade d’étages parfaitement agités avec prise en compte du mélange en retour. Les HUT (Hauteur d'une Unité de Transfert) expérimentales ont été comparées à celles calculées à l'aide de différentes corrélations des coefficients de transfert disponibles dans la littérature. Une adéquation satisfaisante a été obtenue entre modèle et expérience. Une réflexion sur le type d'extracteur doit être entreprise pour une amélioration de la performance de dessalement. / This work is a contribution to the development of an innovative desalination process by solvent extraction. The regeneration of the organic phase is achieved by desextraction of the salt at high temperature. Isotherms of distribution of NaCl, Na2SO4 and MgCl2 at 20 40 60 and 80°C were obtained. A stoichiometry able to account for their shapes was suggested and the associated equilibrium constants were determined. The extraction enthalpies were deduced from the variation of the constants with temperature.Non ideality in the aqueous phase was modeled with the Pitzer equations, simplified with the specific interaction principle. A thermodynamic correction to account for mixed salts effect in the organic phase was adjusted on binary data (NaCl, Na2SO4) at 20 40 and 60°C.Mechanical (viscosity, density) and thermal (specific heat, thermal conductivity) properties of the organic phase were characterised from 20 to 80°C. The interfacial tension was obtained at 20°C with pure water and filtrated natural seawater. The overall solubility of the solvant in water was measured. A prototype of the process with two extraction columns with a packed bed of 4 meters was tested. The HTU obtained were compared with a numerical model based on the classical stagewise backflow model expanded by a thermal balance.

During the last decades, batch distillation is preferably used with an increasing demand over continuous one, to separate fine chemicals in chemical and petroleum industries, due to its advantages like, flexibility and high product purity. Consequently, packed distillation columns, with newly generated packing materials, are advantageous compared to plate columns because of their smaller holdups, resistivity to corrosive materials and their higher separation efficiencies. Also, in many industrial applications, mathematical models of distillation systems are frequently used in order to design effective control systems, to train operating personnel and to handle fault diagnostics. Thus, the main objective of this study is to develop a mathematical model for a multicomponent batch distillation column, which is used to separate mixtures at low operating pressures, packed with random packing materials. In multicomponent batch packed distillation, operation with optimum reflux ratio profile is important for efficiency to maximize the amount of the distillate with a specified concentration, for a given time. Therefore, it is also aimed to find the optimum reflux ratio profile for the multicomponent batch packed distillation column. A simulation algorithm is written with the aid of MATLAB and FORTRAN programming languages by taking into account pressure drop and variation of physical properties. The selected incremental bed height, &amp / #916 / z, to be used in the simulation program has an effect on the accuracy of the results. This is analyzed and the optimal incremental height is found to be 3.5 cm for a 1.5m bed height. The change in distillate compositions with a given constant reflux ratio is found to be similar with those of previous studies. The simulation code is also used to obtain responses in distillate compositions for different reflux ratios, condenser holdups and reboiler duties and compared with similar studies found from literature and found to be adequate. Finally, experiments are conducted to verify simulation algorithm by using a lab-scale packed distillation column for the separation of a polar mixture of ethanol and water. It is observed that, there is a good agreement between the experimental and simulation results. After the verification of dynamic model, optimum operation policy to maximize product amount is investigated numerically by using capacity factor approach. The column is operated with and without recycling of the holdups of the slop cut tanks, in order to examine the effect of recycling on capacity factor, CAP. It is observed that, recycling of the molar holdups of the slop cut tanks is resulted in a 28% increase in the separation efficiency.

Thesis submitted in fulfilment of the requirements for the degree of Masters of Technology: Chemical Engineering in the Faculty of Engineering Cape Peninsula University of Technology, South Africa Supervisor: Prof TV Ojumu Cape Town Campus September 2013 / Jarosite formation is regarded as undesirable in the bioleaching processes as it depletes ferric reagent; a critical reagent for the oxidation of most sulphide minerals, from bioleach solution. It creates kinetic barriers and clogs on mineral surfaces, thereby retarding leach rates of most minerals. However, jarosite has also been shown to serve as support for the attachment of bioleaching microbes, facilitating a high ferric-iron generation rate. In this study, a series of experiments on microbial ferrous-iron oxidation by a mesophilic microbe were carried out in a novel packed-column bioreactor with a view to investigating the potential use of solution pH to manage jarosite accumulation in the bioreactor. The kinetics of the oxidation was also investigated to establish base case data for the novel bioreactor. The bioreactor was packed with glass balls 15 mm in diameter. The experiments were conducted at a constant temperature of 38.6 °C, residence time of 18 hrs, airflow rate of 20 mL.s-1 and at desired solution pHs (1.3, 1.5 and 1.7). The results showed that the amount of jarosite accumulation is proportional to the operating solution pH and also to the duration of operation of the bioreactor. Jarosite precipitate of 4.95, 5.89 and 7.08 g.L-1 were obtained after 10 days of continuous operation at solution pH of 1.3, 1.5 and 1.7 respectively, while after 15 days the precipitate concentration increased to 5.50, 7.90 and 9.98 g.L-1respectively. The results also showed that a 33% and 52% reduction in jarosite accumulation could be achieved by a gradual decrease of the bioreactor solution pH after being continuously operated for 10 days from pH 1.7 to 1.5 and pH 1.7 to 1.3, respectively, for an additional five days of continuous operation. The results of the ferrous-iron biooxidation kinetics investigated at pH 1.3 show a maximum ferrous oxidation rate ( max 2 Fe r ) of 6.85 mmol.L-1.h-1 and apparent affinity kinetics constants (   2 Fe K , 2 Fe K ) of 0.001 mmol Fe2+.L-1 and 0.006 (dimensionless) using Hansford and Monod equations, respectively. Although a direct relationship exists between jarosite formation and solution pH, the results of this study may be relevant in bioleach heaps, or at least in column bioreactors, to manage and control jarosite accumulation, thereby improving leach kinetics of sulphide minerals.

Thesis submitted in fulfilment of the requirements for the degree of Masters of Technology: Chemical Engineering in the Faculty of Engineering Cape Peninsula University of Technology, South Africa, 2013 / Jarosite formation is regarded as undesirable in the bioleaching processes as it depletes ferric reagent; a critical reagent for the oxidation of most sulphide minerals, from bioleach solution. It creates kinetic barriers and clogs on mineral surfaces, thereby retarding leach rates of most minerals. However, jarosite has also been shown to serve as support for the attachment of bioleaching microbes, facilitating a high ferric-iron generation rate. In this study, a series of experiments on microbial ferrous-iron oxidation by a mesophilic microbe were carried out in a novel packed-column bioreactor with a view to investigating the potential use of solution pH to manage jarosite accumulation in the bioreactor. The kinetics of the oxidation was also investigated to establish base case data for the novel bioreactor. The bioreactor was packed with glass balls 15 mm in diameter. The experiments were conducted at a constant temperature of 38.6 °C, residence time of 18 hrs, airflow rate of 20 mL.s-1 and at desired solution pHs (1.3, 1.5 and 1.7). The results showed that the amount of jarosite accumulation is proportional to the operating solution pH and also to the duration of operation of the bioreactor. Jarosite precipitate of 4.95, 5.89 and 7.08 g.L-1 were obtained after 10 days of continuous operation at solution pH of 1.3, 1.5 and 1.7 respectively, while after 15 days the precipitate concentration increased to 5.50, 7.90 and 9.98 g.L-1respectively. The results also showed that a 33% and 52% reduction in jarosite accumulation could be achieved by a gradual decrease of the bioreactor solution pH after being continuously operated for 10 days from pH 1.7 to 1.5 and pH 1.7 to 1.3, respectively, for an additional five days of continuous operation. The results of the ferrous-iron biooxidation kinetics investigated at pH 1.3 show a maximum ferrous oxidation rate ( max 2 Fe r ) of 6.85 mmol.L-1.h-1 and apparent affinity kinetics constants (   2 Fe K , 2 Fe K ) of 0.001 mmol Fe2+.L-1 and 0.006 (dimensionless) using Hansford and Monod equations, respectively. Although a direct relationship exists between jarosite formation and solution pH, the results of this study may be relevant in bioleach heaps, or at least in column bioreactors, to manage and control jarosite accumulation, thereby improving leach kinetics of sulphide minerals.

Essa dissertação de mestrado descreve o desenvolvimento de hardwares de colunas para cromatografia líquida capilar. O processo de desenvolvimentos desses dispositivos é descrito gradativamente e os pontos fortes e as limitações de cada modelo de hardware são discutidos. O melhor modelo de hardware desenvolvido apresentou produção simples, fácil conexão ao sistema cromatográfico e resistência a pressões superiores a 900 bar. Sucessivamente ao estabelecimento de um modelo de hardware apropriado, os efeitos dos materiais do hardware na eficiência das colunas foram avaliados. Poucos estudos relatam a influência do hardware nas separações em escala capilar, de forma que essa dissertação contribui para o preenchimento dessa lacuna. Capilares de aço inoxidável e sílica fundida e frits de aço inoxidável e fibra de vidro foram avaliados. Colunas com eficiências superiores a 100.000 pratos por metro foram produzidas. / This master\'s dissertation describes the development of hardware for capillary liquid chromatography columns. The development process of the devices is described gradually and the strengths and limitations of each model of hardware are discussed. The best-developed hardware model presented easy production, practice connection to the chromatographic system and resistance to pressures greater than 900 bar. After the establishment of an appropriate hardware model, the effects of hardware materials on the efficiency of the columns were evaluated. Few studies report the influence of the hardware on capillary scale separations; therefore, this dissertation contributes to fill this gap. Capillaries of stainless steel and fused silica and frits of stainless steel and glass fiber were evaluated. Columns with efficiencies greater than 100,000 plates per meter were produced.

Essa dissertação de mestrado descreve o desenvolvimento de hardwares de colunas para cromatografia líquida capilar. O processo de desenvolvimentos desses dispositivos é descrito gradativamente e os pontos fortes e as limitações de cada modelo de hardware são discutidos. O melhor modelo de hardware desenvolvido apresentou produção simples, fácil conexão ao sistema cromatográfico e resistência a pressões superiores a 900 bar. Sucessivamente ao estabelecimento de um modelo de hardware apropriado, os efeitos dos materiais do hardware na eficiência das colunas foram avaliados. Poucos estudos relatam a influência do hardware nas separações em escala capilar, de forma que essa dissertação contribui para o preenchimento dessa lacuna. Capilares de aço inoxidável e sílica fundida e frits de aço inoxidável e fibra de vidro foram avaliados. Colunas com eficiências superiores a 100.000 pratos por metro foram produzidas. / This master\'s dissertation describes the development of hardware for capillary liquid chromatography columns. The development process of the devices is described gradually and the strengths and limitations of each model of hardware are discussed. The best-developed hardware model presented easy production, practice connection to the chromatographic system and resistance to pressures greater than 900 bar. After the establishment of an appropriate hardware model, the effects of hardware materials on the efficiency of the columns were evaluated. Few studies report the influence of the hardware on capillary scale separations; therefore, this dissertation contributes to fill this gap. Capillaries of stainless steel and fused silica and frits of stainless steel and glass fiber were evaluated. Columns with efficiencies greater than 100,000 plates per meter were produced.