The heat transfer phenomena in the near-wall region of a randomly packed pebble bed are important in the design of a Pebble Bed Reactor (PBR), especially when considering the safety case during accident conditions. At higher temperatures the contribution of the radiation heat transfer component to the overall heat transfer in a PBR increases significantly. The wall effect present in the near-wall region of a packed pebble bed affects the heat transfer in this region. Various correlations exist to predict the effective thermal conductivity through a packed pebble bed, but not all of the correlations consider the contribution of radiation and some are only applicable to the bulk region. Experimental research has been done on the heat transfer through a packed pebble bed. However, most of the results are case specific and cannot necessarily be used to validate models or simulations to predict the effective thermal conductivity of a pebble bed. The objective of this study is to develop a methodology that uses experimental work together with Computational Fluid Dynamics (CFD) simulations to predict the effective thermal conductivity in the near-wall region of a randomly packed pebble bed, and to separate the conduction and radiation components of the effective thermal conductivity. The proposed methodology inter alia includes experimental tests and the calibration of a CFD model to obtain numerical results that correlate well with the experimental results. To illustrate the proposed methodology the newly constructed Near-wall Effect Thermal Conductivity Test Facility (NWETCTF) was used to gather experimental results for the temperature and heat transfer distribution through a randomly packed pebble bed. Two identical but separate experimental tests were performed and the results of the two tests were in good agreement. From the experimental results the effective thermal conductivity was derived. The effect of the near-wall region on the heat transfer and the significance of radiation at higher temperatures are evident from the results. Recommendations were made for future experimental work with the NWETCTF from the findings of the investigation. A numerically packed pebble bed that is representative of the experimental pebble bed was generated using the Discrete Element Method (DEM) and a CFD model was set up for the heat transfer through the pebble bed using STAR-CCM+.. The CFD results showed trends similar to that of the experimental results. However, some discrepancies were identified that must be addressed in future studies by calibrating the CFD model. The effective thermal conductivity for the numerical simulation was determined using the CFD results and the conduction and radiation components were separated. / MSc (Mechanical Engineering), North-West University, Potchefstroom Campus, 2015

The heat transfer phenomena in the near-wall region of a randomly packed pebble bed are important in the design of a Pebble Bed Reactor (PBR), especially when considering the safety case during accident conditions. At higher temperatures the contribution of the radiation heat transfer component to the overall heat transfer in a PBR increases significantly. The wall effect present in the near-wall region of a packed pebble bed affects the heat transfer in this region. Various correlations exist to predict the effective thermal conductivity through a packed pebble bed, but not all of the correlations consider the contribution of radiation and some are only applicable to the bulk region. Experimental research has been done on the heat transfer through a packed pebble bed. However, most of the results are case specific and cannot necessarily be used to validate models or simulations to predict the effective thermal conductivity of a pebble bed. The objective of this study is to develop a methodology that uses experimental work together with Computational Fluid Dynamics (CFD) simulations to predict the effective thermal conductivity in the near-wall region of a randomly packed pebble bed, and to separate the conduction and radiation components of the effective thermal conductivity. The proposed methodology inter alia includes experimental tests and the calibration of a CFD model to obtain numerical results that correlate well with the experimental results. To illustrate the proposed methodology the newly constructed Near-wall Effect Thermal Conductivity Test Facility (NWETCTF) was used to gather experimental results for the temperature and heat transfer distribution through a randomly packed pebble bed. Two identical but separate experimental tests were performed and the results of the two tests were in good agreement. From the experimental results the effective thermal conductivity was derived. The effect of the near-wall region on the heat transfer and the significance of radiation at higher temperatures are evident from the results. Recommendations were made for future experimental work with the NWETCTF from the findings of the investigation. A numerically packed pebble bed that is representative of the experimental pebble bed was generated using the Discrete Element Method (DEM) and a CFD model was set up for the heat transfer through the pebble bed using STAR-CCM+.. The CFD results showed trends similar to that of the experimental results. However, some discrepancies were identified that must be addressed in future studies by calibrating the CFD model. The effective thermal conductivity for the numerical simulation was determined using the CFD results and the conduction and radiation components were separated. / MSc (Mechanical Engineering), North-West University, Potchefstroom Campus, 2015

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.

Phosphorylcholine (PC) based phospholipid bilayers have been explored as coating materials for various substrates due to their inherent resistance to non-specific protein adsorption. Phospholipids have been used for coatings in capillary electrophoresis (CE) to suppress electroosmotic flow (EOF) and to obtain better separation of proteins. Here, a series of investigations geared towards developing highly stable phospholipid based biomimetic stationary phases for chromatographic separations was performed.Fluid phospholipid bilayers lack the desired chemical and physical stability to serve as long-term coatings. In this work, highly stable phospholipid coatings generated via crosslinking polymerization of bis-SorbPC monomers were investigated. Reproducible EOF and migration times for model proteins were obtained for coated capillaries that were kept at room temperature for up to two months. Furthermore, the effects of surfactants, pH and capillary inner diameter (i.d.) on the stability of the lipid coating were investigated.In an alternate approach, stabilized phospholipid coatings for capillary electrophoresis were investigated via formation of hybrid monolayers. The capillary surface was chemically modified with a cyano group followed by deposition of phospholipid monomers. In this approach, marked enhancements in coating stability were attained with commercially available reagents. The hybrid coating was utilized for protein separations and gave efficiencies comparable to non-stabilized lipid coated capillaries.Fused silica capillaries were modified with phospholipid bilayers that were chemically tuned to introduce specific affinity binding agents, while minimizing nonspecific protein adsorption to the capillary wall. The wall of fused silica was functionalized with DOGS-NTA-Ni2+ lipid to present binding sites inside the capillary for 6xHis-tagged proteins. Fluorescence microscopy and changes in electrophoretic mobility were used to follow the interaction of the model proteins with the functionalized silica surface.The structural similarity of lipid vesicles to cell membranes made them attractive in developing stationary phases for both liquid chromatography and capillary electrophoresis to study interactions between analytes and phospholipid membranes. Stabilized PLB coated silica microspheres were prepared via polymerization of lipid monomers and displayed enhanced stability to extended storage and organic solvent. These highly stable microspheres, while minimizing nonspecific protein adsorption, were also functionalized with DOGS-NTA-Ni2+ and effectively bind 6xHis-EGFP proteins.

In this diploma thesis, capillary columns with an inner diameter of 530 microns filled with gel particles were prepared. These columns are intended for gel chromatography. Three various methods of filling were used for their preparation. The first method was based on filling of wet particles in suspension with the organic solvent, followed by drying and swelling of particles with water into the form of gel. The second method used filling of wet particles in the suspension form with the aqueous phase. The last method started with suction of dry gel particles by air and continued with their subsequent swelling with water into the form of the gel. The prepared columns have been compared analysing hyaluronic acid and thiourea. The basic parameters specified for the gel column chromatography were determined by using phenylalanine. The pressure characteristics depending on the flow rate of mobile phase were used to compare the quality of packing of the columns prepared by various methods.

O objetivo desse trabalho foi o estudo da utilização do carbonato de potássio para a absorção de CO2, tendo como principal foco o uso dessa tecnologia para o beneficiamento de biogás em instalações de pequeno e médio porte. O estudo foi dividido em três partes. Na primeira, realizou-se um projeto fatorial, baseado em resultados obtidos por meio de simulação via ASPEN Plus, com o intuito de quantificar a influência da vazão de líquido, da vazão de gás, da concentração da solução e da temperatura do líquido na quantidade de gás carbônico absorvida. Na segunda, foram realizados ensaios de absorção de CO2 em coluna recheada com anéis de Raschig de vidro, utilizando soluções de carbonato de potássio, com objetivo de comparar os resultados obtidos pelo projeto fatorial e estudar o seu potencial para o processo de beneficiamento de biogás. Na terceira, quatro substâncias foram separadamente utilizadas em mistura com solução de carbonato de potássio, de maneira a verificar seu poder como promotores da reação de gás carbônico com carbonato de potássio. Os resultados do projeto fatorial apresentaram a temperatura, vazão e concentração de líquido como as variáveis independentes de maior influência positiva na absorção de CO2, enquanto que a vazão de gás teve influência negativa de baixa intensidade. A quantidade de gás carbônico absorvida em solução sem promotores e em pressão ambiente foi baixa, como relata a literatura. A utilização de promotores possibilitou um aumento substancial da absorção, principalmente com o uso da piperazina. / The objective of this work is to study the use of potassium carbonate for CO2 absorption, aiming to use this technology for biogas upgrade for small and medium scale plants. The study was divided in three parts. In the first one, a factorial design was done, based in results obtained by simulation via ASPEN Plus, to verify the influence of four process variables, namely: liquid volumetric flow rate, gas volumetric flow rate, solution concentration and liquid temperature. Secondly, CO2 absorption experiments were run in columns packed with glass Raschig rings, using potassium carbonate, in order to compare the results obtained by the factorial design and to study the solution\'s potential for biogas upgrade. Lastly, four substances were separately mixed into potassium carbonate solutions, aiming to verify their potential as CO2 absorption promoters. The results of the factorial design presented the liquid temperature, the liquid volumetric flow rate and the solution concentration as the most positively influential independent variables in carbon dioxide absorption, while the gas volumetric flow rate had a negative influence with low intensity. The amount of CO2 absorbed in solution without promoters and in ambient pressure was low, fact that is mentioned by other researchers. The use of promoters allowed a substantial increase in efficiency of CO2 absorption, mainly with the use of piperazine.

O presente trabalho teve como objetivo aprimorar a síntese de biodiesel por via enzimática empregando óleo de babaçu pela rota etílica. A motivação do uso do óleo de babaçu é referente ao seu forte potencial para a produção de combustível, tendo em vista que é de baixo custo e abundante em localidades carentes de fontes de energia, o que estimula a realização de pesquisas nesta área, procurando benefícios ambientais, energéticos e econômicos. Para atingir o objetivo proposto, teve-se como proposta a transesterificação do óleo de babaçu com etanol mediada pela enzima lipase em fluxo contínuo empregando reator de leito fixo. A enzima selecionada para condução dos experimentos foi a lipase microbiana de Burkholderia cepacia (lipase PS) imobilizada covalentemente em matriz híbrida sílica-PVA com comprovada eficiência na síntese de biodiesel a partir de diferentes matérias-primas lipídicas. Todos os experimentos foram efetuados na ausência de solventes a 50?C. A parte experimental foi iniciada pelos testes comparativos de desempenho da montagem experimental proposta utilizando a preparação de lipase previamente selecionada e a lipase Novozym® 435 disponível comercialmente na forma imobilizada, de comprovada eficiência para utilização em reatores de leito fixo. Os resultados indicaram que ambas as preparações de lipase são adequadas para catalisar a síntese de biodiesel em regime contínuo, entretanto a grande limitação de operação do reator está relacionada com a elevada composição em ácidos graxos saturados (? 83%) na matéria-prima lipídica, que acarreta entupimentos nas conexões e obstrução do leito. Para contornar as limitações identificadas foi proposto um sistema de aquecimento para manter constante a temperatura na faixa requerida (45-50?C) em todo o aparato experimental. O desempenho do reator (diâmetro interno X altura: 15 mm X 210 mm) foi avaliado para substratos constituídos de óleo de babaçu e etanol em duas razões molares (1:7 e 1:12), definindo os limites de operação em termos de vazão do substrato. Foi quantificado o desempenho do sistema para 4 diferentes vazões volumétricas correspondendo a tempos espaciais entre 7 a 13h e determinadas para cada condição a influência do tempo espacial na concentração de ésteres de etila formados, rendimentos de transesterificação e produtividade. A razão molar entre os materiais de partida interferiu de maneira marcante no alcance de elevadas conversões dos ácidos graxos presentes no óleo de babaçu em seus ésteres de etila correspondentes, sendo o sistema maximizado para substratos contendo maior excesso de etanol (razão molar óleo: etanol de 1:12). Nessas condições, o funcionamento do sistema foi comprovado quantitativamente para tempos espaciais no reator iguais ou superiores a 11h, fornecendo rendimentos de transesterificação médios de 95,00 ? 4,68 % e produtividade de 54,80 ? 2,70 mgéster.gmeio-1.h-1. A lipase PS imobilizada em SiO2-PVA foi estável quanto a suas características morfológicas e catalíticas revelando tempo médio de meia-vida (t1/2) de 40 dias, sendo ainda possível sua reutilização em um novo ensaio. As características globais do desempenho do sistema contínuo proposto tornam atrativo a continuidade dos estudos em escala ampliada de processo, entretanto recomenda-se a utilização de óleos vegetais com menor teor de ácidos graxos saturados. / The purpose of this work was to enhance the enzymatic synthesis of biodiesel from babassu oil by ethanolic route. Babassu oil was chosen as a feedstock due to its potential for fuel production, including low cost and availability in regions where energy sources are needed; stimulating the developing of research projects looking for environmental, energetic and economical benefits. To attain this purpose, the transesterification reaction of babassu oil with ethanol was mediated by the enzyme lipase on packed bed reactor running on continuous mode. The selected enzyme was the microbial lipase from Burkholderia cepacia (lipase PS) covalent immobilized on hybrid matrix silica-PVA (SiO2-PVA) which showed already satisfactory performance in the biodiesel synthesis from different lipidic feedstocks. The experiments were carried out in solvent free system at 50°C. The experimental work was started by performing comparative tests of the proposed experimental assembly, using the previously selected lipase preparation and a commercial available immobilized lipase Novozym® 435, which has consistent high performance to be used on fixed packed reactors. The results indicated that both lipase preparations are able to catalyze the biodiesel synthesis under continuous operation; however limitations were found to maintain stable operation. This was related to the high concentration of saturated fatty acids (83%) present in the feedstock, which blocked the tube connections and led to bed obstruction. To overcome these limitations, a warming system was proposed to ensure constant the temperature at the required range (45-50°C) in the entirely experimental apparatus. The performance of the reactor (inner diameter X height: 15 mm X 210 mm) was evaluated for substrates composed by babassu oil and ethanol in two molar ratios (1:7 e 1:12), determining its operation limits in terms of substrate flow rate. The system performance was quantified for four different flow rates corresponded to spatial times between 7 and 13 h. For each condition, the influence of spatial times in the ethyl esters formation, transesterification yields and productivities were determined. The raw materials molar ratio interfered, in a remarkable way, the conversion of babassu oil into the correspondent ethyl esters and the system was optimized for the substrates containing high excess of ethanol (oil-to-ethanol molar ratio of 1:12). In these conditions, the reactor operation was demonstrated for spatial times higher than 11h, attaining transesterification yields of 95,00 ? 4,60% and productivities of 54,80 ? 2,70 mgesters.gmedium-1.h-1The lipase PS immobilized on SiO2-PVA was found to be stable regarding its morphological and catalytic characteristics, showing half-life time (t1/2) of 40 days. The immobilized enzyme can be also reused in a new run and the presence of substrate containing high ethanol levels did not affected the lipase stability. The performance characteristics of the proposed continuous system made attractive to develop further studies aiming at scaling up the process, however it is recommended to use vegetable oils having lower saturated fatty acids levels.

The objective for this master thesis project was to perform simulations for high and low Reynolds number for a porousmedia modelled as quadratic packed cylinders. The simulations were to be performed by using the open source codeOpenFOAM and the turbulence should be modelled by the LES turbulence model in order to resolve details about theturbulence. In Hellström et al. (2009) simulations were performed for a similar setup but for the k-Omega SST turbulencemodel. In this project simulations were performed not only for LES but also with the k-Omega SST model and for the laminar description in order to validate the LES problem setup. For the simulations Reynolds number was calculatedbased on the porosity and the cylinder diameter and was denoted Re’. The simulations were performed for a set of Re’and for each Re’ the permeability was calculated based on Darcy’s law. The calculations of the permeability showed,in line with the results from Hellström, that at Re’ around 20 there is a drop in the permeability both for the LESand SST simulations. From the permeability simulations it was also seen that for low Re’ flows the LES and laminardescriptions agreed with each other, but that the SST simulations yielded lower values of the permeability. Accordingto Hellström the permeability drop was due to onset of inertia effects. When looking at the resulting flow field plots itgave the idea that the amount of turbulence could also have influence on the resulting permeability.

Hydrogen isotope separation systems using palladium (Pd) are currently being designed for both reactor designs with the aim of separating and purifying the reactor exhaust products which contain valuable unspent hydrogen isotopes. Hydrogen isotope exchange in Pd offers an efficient, ambient condition process that can produce pure isotopic species in a process far simpler and less costly than the current state of the art cryogenic distillation processes. The method is applicable whether separating hydrogen (protium), deuterium or tritium and any combination of these. If practical fusion devices are ever to be realised it is essential to produce an economical and efficient fuel cycle capable of separating and purifying hydrogen isotopes. Hydrogen isotope exchange in Pd is also of interest to the waste separation and purification industries, in particular those using hydrogen separation membranes which used Pd and Pd-alloy membranes. Understanding hydrogen isotope exchange, with particular regard to the formation of the intermediate (and often unwanted) hydrogen deuteride (HD), will aid significantly in future designs of hydrogen isotope separation systems. Novel hydrogen isotope exchange experiments involving hydrogen and deuterium at a number of temperatures (208 K, 293 K and 373 K) and pressures (1.3 bar – 8 bar) not yet explored are presented in this thesis. The experiments were carried out on a unique piece of laboratory apparatus provided to and further developed at the University of Bath. Alongside experimentation, a novel comprehensive multidimensional multi-physics model has been created to analyse the experimental data obtained using the new apparatus and elucidate the kinetics and mechanisms of the reactions occurring between hydrogen isotopic species and Pd during hydrogen isotope exchange based on Langmuir-Hinshelwood surface reaction mechanism. The surface reaction rates, kinetic rate constants and heat effects have been examined in detail, and in tandem, for the first time.

Computational Fluid Dynamics (CFD) is one of the fields that has strongly developed since the recent development of faster computers and numerical modeling. CFD is also finding its way into chemical engineering on several levels. We have used CFD for detailed modeling of heat and mass transfer in a packed bed. One of the major questions in CFD modeling is whether the computer model describes reality well enough to consider it a reasonable alternative to data collection. For this assumption a validation of CFD data against experimental data is desired. We have developed a low tube to particle, structured model for this purpose. Data was gathered both with an experimental setup and with an identical CFD model. These data sets were then compared to validate the CFD results. Several aspects in creating the model and acquiring the data were emphasized. The final result in the simulation is dependent on mesh density (model detail) and iteration parameters. The iteration parameters were kept constant so they would not influence the method of solution. The model detail was investigated and optimized, too much detail delays the simulation unnecessarily and too little detail will distort the solution. The amount of data produced by the CFD simulations is enormous and needs to be reduced for interpretation. The method of data reduction was largely influenced by the experimental method. Data from the CFD simulations was compared to experimental data through radial temperature profiles in the gas phase collected directly above the packed bed. It was found that the CFD data and the experimental data show quantitatively as well as qualitatively comparable temperature profiles, with the used model detail. With several systematic variances explained CFD has shown to be an ample modeling tool for heat and mass transfer in low tube to particle (N) packed beds.