The world energy supply and demand, together with limited available resources have resulted in the need to develop alternative energy sources to ensure sustainable and expanding economies. Hydrogen is being considered a viable option with particular application to fuel cells. The Hybrid Sulphur cycle has been identified as a process to produce clean hydrogen (carbon free process) and can have economic benefits when coupled to nuclear reactors (High Temperature Gas Reactor) or solar heaters for the supply of the required process energy. The sulphur trioxide decomposition reactor producing sulphur dioxide for the electrolytic cells in a closed loop system has been examined, but it is clear that development with respect to a more durable active catalyst in a reactor operating under severe conditions needs to be investigated. A suitable sulphur trioxide reactor needs to operate at a high temperature with efficient heating in view of the endothermic reaction, and has to consist of special materials of construction to handle the very corrosive reactants and products. This investigation was undertaken to address (1) the synthesis, characterisation, reactivity and stability of a suitable catalyst (2), determination the reaction rate of the chosen catalyst with a suitable micro reactor (3) construction and evaluation of a packed bed reactor for the required reaction, and (4) the development and validation of a reactor model using computational fluid dynamics with associated chemical reactions. A supported catalyst consisting of 0.5 wt% platinum and 0.5 wt% palladium on rutile (TiO2, titania) was prepared by the sintering of an anatase/rutile supported catalyst with the same noble metal composition, synthesized according to an incipient impregnation procedure using cylindrical porous pellets (±1.7 mm diameter and ±5 mm long). Characterization involving: surface area, porosity, metal composition, - dispersion, - particle size, support phase and sulphur content was carried out and it was found from reactivity determinations that the sintered catalyst, which was very different from the synthesized catalyst, had an acceptable activity and stability which was suitable for further evaluation. A micro pellet reactor was constructed and operated and consisted of a small number of pellets (five) placed apart from each other in a two-stage quartz reactor with sulphur trioxide generated from sulphuric acid in the first stage and the conversion of sulphur trioxide in the second stage, respectively. Attention was only confined to the second stage involving the conversion of sulphur trioxide with the supported catalyst. The overall reaction kinetics of the pellets involving momentum, heat and mass transfer and chemical reaction was evaluated and validated with constants obtained from literature and with an unknown reaction rate equation for which constants were obtained by regression. As result of the complexity of the flow, mass and heat transfer fields in the micro pellet reactor it was necessary to use a CFD model with chemical reactions which was accomplished with a commercial code COMSOL MultiPhysics® 4.3b. A reversible reaction rate equation was used and a least squares regression procedure was used to evaluate the activation energy and pre-exponential factor. The activation energy obtained for the first order forward reaction was higher than values obtained from literature for a first order reaction rate (irreversible reaction) for the platinum group metals on titania catalysts. Detailed analyses of the velocity, temperature and concentration profile revealed the importance of using a complex model for determination of the reaction parameters. A fixed bed reactor system consisting of a sulphuric acid vaporizer, a single reactor tube (1 m length, 25 mm OD) heated with a surrounding electrical furnace followed, by a series of condensers for the analysis of the products was constructed and operated. Three process variables were investigated, which included the inlet temperature, the weight hourly velocity and the residence time in order to assess the performance of the reactor and generate results for developing a model. The results obtained included the wall and reactor centreline temperature profiles together with average conversion. As a result of the complexity of the chemistry and the phases present containing the products from the reactor a detailed calculation was done using vapour/liquid equilibrium with the accompanying mass balance (Aspen-Plus®) to determine the distribution of sulphur trioxide, sulphur dioxide, oxygen and steam. A mass balance was successfully completed with analyses including SO2 with a GC, O2 with a paramagnetic cell analyser, acid/base titrations with sodium hydroxide, SO2 titrations with iodine and measurement of condensables (mass and volume). The results obtained showed that a steady state (constant conversion) was obtained after approximately six hours and that it was possible to obtain sulphur trioxide conversion approaching equilibrium conditions for bed lengths of 100 mm with very low weight hourly space velocities. A heterogeneous 2D model consisting of the relevant continuity, momentum, heat transfer and mass transfer and the reaction rate equation determined in this investigation was developed and solved with the use of the commercial code COMSOL MultiPhysics® 4.3b with an appropriate mesh structure. The geometry of the packed bed (geometry) was accomplished by generating a randomly packed bed with a commercial package DigiPac™. The model predicted results that agreed with experimental results with conversions up to 56%, obtained over the following ranges: weight hourly space velocity equal to 15 h-1, temperatures between 903 K and 1053 K and residence times between 0.1 and 0.07 seconds. The post-processing results were most useful for assessing the effect of the controlling mechanisms and associated parameters. / PhD (Chemical Engineering), North-West University, Potchefstroom Campus, 2014

Thesis (MScEng)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: The increased necessity to obtain power from other sources than conventional fossil fuels has led to the growing interest in solar power. The problem with the proposed technology is that it can only provide power during the day and therefore requires some sort of storage system, if power is to be supplied throughout the day and night. A number of storage systems exist, but the one of particular interest for this research, is packed rock beds. Rock beds have the advantage that if designed right, they have the potential to be one of the most cost effective means of storing thermal energy for solar power plants. Discrete Element Models (DEM) of rock beds were therefore developed through both experimental and numerical procedures, by conducting a series of sensitivity, calibration and verification studies. The developed models were then used to study various aspects associated with rock beds, which were either too impractical, impossible or too expensive to conduct through actual experimental work. This research focused specifically on the potential of constructing self-supporting tunnels within the rock beds in order to improve the air flow uniformity through the bed, while minimizing the pressure drop. It was observed that if the appropriate steps were followed, stable self-supporting tunnels could be formed. Valuable information such as the rock orientations resulting from different packing directions could also be derived from the models and finally, a method to convert the DEM models into the appropriate format such that it could be imported into a CFD preprocessor for future CFD studies, was developed. / AFRIKAANSE OPSOMMING: Die verhoogde noodsaaklikheid om energie te verkry uit ander bronne as konvensionele fossielbrandstowwe, het gelei tot die groeiende belangstelling in sonkrag energie. Die probleem met die voorgestelde tegnologie is dat dit net energie gedurende die dag kan voorsien en dus word daar ’n stoorstelsel benodig indien energie deur beide die dag en nag voorsien moet word. Tans bestaan daar wel ’n aantal van hierdie stoorstelsels, maar die een wat van besondere belang is in hierdie navorsing, is verpakte klip beddens. Klip beddens het die voordeel dat, indien dit reg ontwerp is, dit oor die potensiaal beskik om een van die mees koste-doeltreffende middels te wees vir die stoor van termiese energie vir sonkragstasies. Diskreet Element Modelle (DEM) van die klip beddens is ontwikkel deur gebruik te maak van beide experimentele en numeriese metodes waartydens ’n reeks sensitiwiteits-, kalibrasie- en verifiëring studies uitgevoer is. Die ontwikkelde modelle is gebruik om verskeie aspekte van klip beddens te ondersoek, wat of te onprakties, onmoontlik of te duur is vanuit ’n eksperimentele oogpunt. Hierdie navorsing het spesifiek gefokus op die potensiaal om self-ondersteunende tonnels binne in die klip beddens te vorm, ten einde die egaligheid van die lugvloei deur die bed te verbeter, terwyl die drukval geminimeer word. Daar is waargeneem dat stabiele self-ondersteunende tonnels wel gevorm kon word indien die toepaslike stappe gevolg is. Waardevolle inligting soos die klip oriëntasies wat as gevolg van die verskillende verpakkings rigtings onstaan kon ook vanuit die model verkry word. Ten slotte is ’n metode ontwikkel om die DEM modelle na die toepaslike formaat te omskep sodat dit ten einde gebruik kan word in numeriese vloeidinamika studies.

This study addressed the numerical modelling of flow and diffusion in packed beds of mono-sized spheres. Comprehensive research was conducted in order to implement various numerical approaches in explicit1 and implicit2 simulations of flow through packed beds of uniform spheres. It was noted from literature that the characterization of a packed bed using porosity as the only geometrical parameter is inadequate (Van Antwerpen, 2009) and is still under much deliberation due to the lack of understanding of different flow phenomena through packed beds. Explicit simulations are not only able to give insight into this lack of understanding in fluid mechanics, but can also be used to develop different flow correlations that can be implemented in implicit type simulations. The investigation into the modelling approach using STAR-CCM+®, presented a sound modelling methodology, capable of producing accurate numerical results. A new contact treatment was developed in this study that is able to model all the aspects of the contact geometry without compromising the computational resources. This study also showed, for the first time, that the LES (large eddy simulation) turbulence model was the only model capable of accurately predicting the pressure drop for low Reynolds numbers in the transition regime. The adopted modelling approach was partly validated in an extensive mesh independency test that showed an excellent agreement between the simulation and the KTA (1981) and Eisfeld and Schnitzlein (2001) correlations' predicted pressure drop values, deviating by between 0.54% and 3.45% respectively. This study also showed that explicit simulations are able to accurately model enhanced diffusion due to turbulent mixing, through packed beds. In the tortuosity study it was found that the tortuosity calculations were independent of the Reynolds number, and that the newly developed tortuosity tests were in good agreement with techniques used by Kim en Chen (2006), deviating by between 2.65% and 0.64%. The results from the TMD (thermal mixing degree) tests showed that there appears to be no explicit link between the porosity and mixing abilities of the packed beds tested, but this could be attributed to relatively small bed sizes used and the positioning and size of the warm inlet. A multi-velocity test showed that the TMD criterion is also independent of the Reynolds number. It was concluded that the results from the TMD tests indicated that more elaborate packed beds were needed to derive applicable conclusions from these type of mixing tests. The explicit BETS (braiding effect test section) simulation results confirmed the seemingly irregular temperature trends that were observed in the experimental data, deviating by between 5.44% and 2.29%. From the detail computational fluid dynamics (CFD) results it was possible to attribute these irregularities to the positioning of the thermocouples in high temperature gradient areas. The validation results obtained in the effective thermal conductivity study were in good agreement with the results of Kgame (2011) when the same fitting techniques were used, deviating by 5.1%. The results also showed that this fitting technique is highly sensitive for values of the square of the Pearson product moment correlation coefficient (RSQ) parameter and that the exclusion of the symmetry planes improved the RSQ results. It was concluded that the introduction of the new combined coefficient (CC) parameter is more suited for this type of fitting technique than using only the RSQ parameter. / Thesis (M.Ing. (Mechanical Engineering))--North-West University, Potchefstroom Campus, 2012

L'objectif de cette étude est de comprendre et de modéliser la phénoménologie du transport vertical dense descendant de particules de la classe A de la classification de Geldart. Dans un premier temps, une étude expérimentale est réalisée sur une maquette en statique (absence de circulation de solide) dans le but de déterminer expérimentalement l'effet des paramètres opératoires sur les grandeurs caractéristiques de la défluidisation des particules de FCC : vitesses de sédimentation, porosité de la phase dense, temps caractéristiques…. Ces données sont nécessaires pour l'étude de l'écoulement gaz/solide dense vertical descendant. La simulation numérique en 2D de la défluidisation est effectuée et les prédictions sont comparées aux données expérimentales. Dans un deuxième temps, des essais sur une maquette permettant de reproduire les phénomènes observés industriellement dans les écoulements denses verticaux descendants de particules sont entrepris. Les observations visuelles complètent les mesures de pressions locales obtenues le long de l'écoulement à différentes conditions avec et sans injection de gaz d'aération. L'étude expérimentale consiste à : - déterminer les limites des différents régimes en termes de débit surfacique de solide et de débit d'aération ; - établir les propriétés de l'écoulement dans les différents régimes. Dans un troisième temps, les propriétés des écoulements de différents régimes sont étudiées et modélisées par une approche monodirectionnelle du type bulle-émulsion. / The objective of this study is to understand and model the phenomenology of the vertical downward dense transport of class A particles of the Geldart classification. Initially, an experimental study is conducted on a static fluidized bed (no flow of solid) in order to determine experimentally the effect of operating parameters on the defluidization properties of FCC particles, such as, sedimentation rates, dense phase porosity, characteristic times ... These data are needed to study gas/solid dense downward flow. 2D numerical simulations of defluidization are performed and the predictions are compared with experimental data. In a second step, experiments are undertaken in a pilot unit able to reproduce the gas/solid dense downward flow phenomena observed in industrial units. Visual observations complement the local pressure measurements profile obtained for the different flow conditions with and without external injection of gas. The experimental study is conducted to: - determine the boundaries of different flow patterns in terms of solid mass flux and gas flowrate; - establish flow properties in different flow patterns. Finally, flow properties of the different patterns are studied and modelled by a monodimensional bubble/emulsion approach.

Single crystal nickel-based superalloys are used in modern gas turbines because of their remarkable resistance to creep deformation at elevated temperatures, which is ensured by the addition of significant amounts of refractory elements. Too high concentrations of refractory elements can lead to the formation of topologically-close packed (TCP) phases during exposure to conditions of high temperature and stress which result in the degradation of the creep properties. The traditional methods for predicting the occurrence of TCP phases in Ni-based superalloys have been based on the PHACOMP and newPHACOMP methodologies which are well-known to fail with respect to new generations of alloys. In this work a novel two-dimensional structure map (Nbar, deltaV/V) for TCP phases where Nbar is the valence-electron count and deltaV/V is a compositional dependent size factor. This map is found to separate the experimental data on the TCP phases of binary, ternary and multi-component TCP phases into well-defined regions corresponding to different structure types such as A15, sigma, chi, delta, P, R, mu, and Laves. In particular, increasing size factor separates the A15, sigma and chi phases from the delta, P, R, mu phases. The structure map is then also used in conjunction with CALPHAD computations of sigma phase stability to show that the predictive power of newPHACOMP for the seven component Ni–Co–Cr–Ta–W–Re–Al system is indeed poor. In order to gain a microscopic understanding of the observed structural trends, namely the differences between the two groups of TCP structures with increasing deltaV/V and the trend from A15 to sigma to chi with increasing Nbar, the electronic structure is coarse-grained from density functional theory (DFT) to tight-binding to bond-order potentials (BOPs). First, DFT is used to calculate the structural energy differences across the elemental 4d and 5d transition metal series and the heats of formation of the binary alloys Mo-Re, Mo-Ru, Nb-Re, and Nb-Ru. These calculations show that the valence electron concentration stabilizes A15, sigma and chi but destablizes mu and Laves phases. The latter are shown to be stabilized instead by relative size difference. Second, a simple canonical TB model and in combination with the structural energy difference theorem is found to qualitatively reproduce the energy differences predicted by the elemental DFT calculations. The structural energy difference theorem rationalizes the importance of the size factor for the stability of the mu and Laves binary phases as observed in the structure map and DFT heats of formation. Finally, analytic BOP theory, is employed to identify the structural origins of the energetic differences between TCP structure-types that lead to the trends found within the two-dimensional structure map.

O presente trabalho teve como objetivo verificar a potencialidade do óleo de macaúba como matéria-prima para síntese de biodiesel pela rota enzimática. Utilizou-se como proposta a transesterificação do óleo de macaúba com etanol mediada pela enzima lipase em fluxo contínuo empregando reator de leito fixo, visando obter amostras de biodiesel com propriedades adequadas à sua utilização como biocombustível. A enzima selecionada para desenvolvimento experimental foi a lipase microbiana de Burkholderia cepacia imobilizada em suporte híbrido não comercial (SiO2-PVA). Foram testados reatores de leito fixo de um estágio e dois estágios. A primeira etapa do trabalho foi direcionada para testes visando avaliar a influência da razão entre a altura (l) e o diâmetro (d) do reator de leito fixo na etanólise do óleo de macaúba. As reações foram operadas continuamente por 20 dias, utilizando óleo: etanol numa razão molar de 1:12 na ausência de solvente e tempo espacial de 14h. Dois reatores foram testados: Reator A (l = 55 mm e d = 15 mm) e Reator B (l = 210 mm e d = 14 mm), apresentando relação geométrica (l/d) de 3,7 e 15, respectivamente. Os dados obtidos indicaram influência das dimensões da coluna empacotada na produção de biodiesel e nas condições testadas, a maior razão altura/ diâmetro não interferiu na transferência de massa do fluido através da coluna. O melhor desempenho foi obtido no sistema experimental que empregou o reator B, atingindo 89,7 ± 4,8% de rendimento e 40,4 ± 2,2 mgéster.gmeio -1.h--1 de produtividade. Na sequência o trabalho foi direcionado para a execução de testes empregando reatores de leito fixo (Reator B) duplo estágio incorporando uma coluna empacotada com resina catiônica (Lewatit® GF 202) para remover o glicerol formado e proporcionar um incremento na formação de ésteres de etila em relação ao primeiro estágio. O desempenho do reator foi avaliado para diferentes tempos espaciais (10 a 16h), mantendo fixas as demais condições operacionais (substrato constituído de óleo de macaúba e etanol na razão molar óleo: etanol de 1:12 e temperatura de 50 ºC). O funcionamento do sistema foi comprovado quantitativamente para tempos espaciais no sistema igual a 16h, resultando em valores médios de produtividade de 36,7 ??2,4 mgéster.gmeio -1.h-1com perdas mínimas de matéria-prima (rendimento de transesterificação = 96,3 ??2,1%), sem redução de eficiência durante 25 dias de operação. As amostras de biodiesel purificadas apresentaram baixos teores de monoacilgliceróis (3,8%) ausência de diacilgliceróis e viscosidade cinemática média de 5,8 ± 0,3 mm2.s-1, atendendo as normas vigentes pela resolução ANP n°14/2012, que estabelece viscosidade cinemática do B100 na faixa entre 3,0 - 6,0 mm2.s-1. O biocatalisador foi estável quanto suas características morfológicas e catalíticas, revelando tempo de meia-vida de 423 h. Desta forma, a configuração do sistema reacional constituído por reator de leito fixo duplo estágio com a remoção simultânea de glicerol tem grande potencial para atingir elevado rendimento de transesterificação, aumentando a produtividade de biodiesel e consequentemente diminuindo o custo do processo industrial. Em geral, os resultados foram promissores e mostraram o potencial do óleo de macaúba para ser usado como matéria-prima para a produção de biodiesel em fluxo contínuo. / The present study aimed at assessing the potential of macaw palm oil as a raw material for the synthesis of biodiesel by enzymatic route. The proposed experimental was to develop a process that was able to transesterify the macaw palm oil with ethanol by immobilized lipase in packed bed reactor under continuous flow, in order to obtain biodiesel having suitable properties to be used as a fuel. The enzyme chosen for the development of this work was the microbial lipase from Burkholderia cepacia immobilized on non-commercial hybrid matrix SiO2-PVA. Single and two stages packed bed reactors were tested. Initially the influence of the reactor dimensions and ratio between height (l) and diameter (d) in the performance of the ethanolysis of macaw palm oil was assessed. Tests were carried out using two reactors (A and B) having different geometric relations: Reactor A (l = 55 mm and d = 15 mm) and Reactor B (l = 210 mm and d = 14) which corresponded to height/diameter (l/d = 3.7 and l/d = 15), respectively. Runs were performed continuously for 20 days using substrate containing oil to ethanol molar ratio of 1:12 in a solvent-free system and fixed space time of 14h. Data suggested that the dimensions of the packed column had a slight influence on the biodiesel production and under the conditions tested, the highest relation (l/d = 15) did not affect the fluid mass transfer throughout the reactor column. Under these conditions runs carried out in the reactor B provided average yields of 89.7 ± 4.8% and productivities of 40.4 ± 2.2 mgester?g-1?h-1. Following this, a two-stage packed bed reactor incorporating a column with cationic resin (Lewatit® GF 202) to remove the glycerol formed as by-product was used. The reactor performance was quantified for four different flow rates corresponded to spatial times from 10 to 16 h. For each condition, the influence of spatial times in the ethyl esters formation, transesterification yields and productivities were determined. The reactor operation was demonstrated for spatial time igual to 16 h, attaining ethyl ester formation of 58.1?2.1 wt%, transesterification yields of 96.3 ??2.1% and productivities of 36.7 ??2.4 mgester?g-1?h-1 with no significant reduction in the efficiency during 25 days. The purified samples showed residual levels of monoglycerides (3.8 wt %), absence of diglycerides and average viscosity values of 5.8 mm2/s which can be considered appropriated according to Brazilian resolution ANP n° 14/2012. The immobilized lipase on SiO2-PVA was found to be stable regarding its morphological and catalytic characteristics, showing half-life time (t1/2) higher than 423 h. Therefore, the continuous packed-bed reactor connected in series with simultaneous glycerol removal has a great potential to attain high level of transesterification yields, raising biodiesel productivity, consequently decreasing industrial process cost. Overall, the results were promising and showed the potential of macaw palm oil to be used as feedstock for biodiesel production under continuous flow.

Este trabalho teve como objetivo a produção de hidrogênio em reator anaeróbio de leito fixo com fluxo ascendente utilizando-se efluente de indústria de refrigerantes. Os resultados obtidos demonstraram que a água residuária semi-sintética simulando efluente de indústria de refrigerantes tem um bom potencial de geração de hidrogênio. Dados da operação dos dois reatores utilizados mostraram que o maior rendimento foi alcançado pelo reator operado sem a adição de meio contendo nutrientes (R2), pois este foi capaz de atingir 4,2 mol \'H IND.2\'/mol de substrato em contraste com 2,5 mol \'H IND.2\'/mol de substrato, obtida pelo reator (R1), cujo afluente continha suplementação nutricional. Constatou-se que o reator operado sem adição de nutrientes (R2) apresentou continuidade na produção de hidrogênio, fato que não ocorreu com o reator R1, que exibiu uma produção efêmera e significativamente inferior. O melhor desempenho na velocidade de produção de hidrogênio e porcentagem do mesmo na composição do biogás também foi observado para o reator R2, que atingiu 0,52 L/h.L e 18,9% de \'H IND.2\' contra 0,28 L/h.L e 2,1% de \'H IND.2\' obtidos pelo reator com suplementação nutricional (R1). Após esta primeira etapa comparativa em que os reatores foram operados simultaneamente com TDH teórico de 0,5 h, prosseguiu-se apenas com a operação do reator R2, porém com tempo de detenção hidráulica teórico de 1 h, o que induziu uma maior conversão do substrato a ácidos e álcoois, mudou as características hidrodinâmicas do leito e afetou negativamente a produção de hidrogênio. / This work was aimed on hydrogen production in an upflow anaerobic packed-bed reactor fed with soft-drink wastewater. The results obtained show that the semisynthetic soft-drink wastewater has a good hydrogen generation potential. Data obtained from the operation of both reactors indicated that the reactor operated without the addition of medium containing macro and micronutrients (R2) provided higher hydrogen yield (4,2 mol \'H IND.2\'/mol of substrate) as compared to the reactor (R1) operated with the addition of nutrient medium, which achieved lower hydrogen production yield (2,5 mol \'H IND.2\'/mol of substrate). It was observed that the reactor operated without the addition of nutrients (R2) showed continuous hydrogen production, while the reactor R1 exhibited a short period of production and lower amounts of hydrogen. Better hydrogen production rate and percentage in the biogas were also observed for the reactor R2, which achieved 0,52 L/h.L and 18,9% of \'H IND.2\' against 0,28 L/h.L and 2,1% of \'H IND.2\' obtained by the reactor with nutrient addition (R1). After operation with HDT of 0,5 h, the reactor R2 was operated with theoretical HDT of 1 h. Under this condition, the substrate was mainly converted to acids and solvents, negatively affecting the hydrogen production and the hydrodynamic pattern of the reactor.

Objetivo deste trabalho foi o de caracterizar e estudar o processo de transferência de massa da absorção de CO2 em soluções aquosas de aminas em coluna recheada operando em pressão atmosférica. Com este objetivo, construíram-se dois equipamentos, sendo um constituído de coluna em escala laboratório com recheio estruturado e outro de uma coluna em escala piloto com recheio randômico. Empregou-se a absorção de CO2, diluído em ar, em solução de NaOH, para a determinação da área interfacial efetiva. Os coeficientes globais de transferência de massa foram determinados para a absorção de CO2, diluído em ar, em diferentes soluções aquosas absorvedoras a base de aminas, a saber: 25% em massa de MEA, MEA-MDEA nas concentrações mássicas 5% MDEA 25% MEA, 10% MDEA 20% MEA e 15% MDEA 15% MEA. Constatou-se uma forte correlação entre a proporção da solução MDEA-MEA e o coeficiente global de transferência de massa. O planejamento dos ensaios em coluna piloto foi realizado com o emprego de simulador de processos, para a verificação hidrodinâmica da coluna e especificação das vazões de gás e de solução absorvente. Compararam-se, também, os resultados obtidos experimentalmente com os previstos pela simulação, no caso da absorção em MEA. / The aim of the present work was to characterize and study the mass transfer process of the CO2 absorption into single and blended alkanolamines in a packed column under atmospheric pressure. For this purpose, two systems were built, one of the columns is a laboratory structure packed column and the other is a pilot random packed column. The absorption of CO2 into NaOH was performed to determine the effective mass-transfer area and the overall mass-transfer coefficient. The absorption performance was evaluated in terms of the overall mass-transfer coefficient for the absorption of CO2 in air into single and blended alkanolamines: MEA 25% wt, and MEA-MDEA mixtures, MEA-MDEA (25% /5% wt), MEA-MDEA (20% /10% wt) and MEA-MDEA (15% /15% wt). The CO2 absorption performance of MEA-MDEA mixture has a high correlation with the proportion MEA-MDEA. Experimental series were designed employing a process simulator for the hydrodynamic checking and determination of gas and liq flow rates. Comparison of the experimental data and simulation results was made for the absorption into MEA.

O lixiviado de aterros sanitários é um efluente líquido poluente devido, principalmente, à sua elevada concentração de amônia. Seu tratamento faz-se necessário para que sejam atendidas as exigências das legislações ambiental e trabalhista, além de minimizados os impactos ambientais de seu lançamento nos corpos d\'água. Esta pesquisa propõe a remoção da amônia presente no lixiviado por meio do processo físico-químico \"air stripping\", que promove a transferência da amônia da fase líquida para gasosa. Para que não se contribua com a poluição atmosférica, o efluente gasoso do \"air stripping\" deve ser tratado em solução de ácido sulfúrico ou água. A neutralização da amônia com solução de ácido sulfúrico gera o sulfato de amônio, e com água, a aquamônia. Tais subprodutos podem ser usados como fertilizantes. Nesta pesquisa, para remoção da amônia do lixiviado foi utilizada uma torre de PVC, com 2,24 m de altura e 15 cm de diâmetro, recheada com anéis do tipo Rashing de polietileno corrugados, com diâmetro de 1,5 cm e 5 cm de comprimento. As vazões de ar utilizadas foram 1200, 1600 e 3600 L/h e as vazões de lixiviado foram 18 e 30 L/h. Para ajuste no pH do lixiviado, utilizou-se hidróxido de cálcio (padrão analítico) e cal comercial. Os fluxos de líquido e ar eram em contracorrente. Para o recolhimento da amônia foram usados dois frascos de 6 L, preenchidos com 4 L de solução de ácido sulfúrico 0,4 mol/L ou água. Os resultados obtidos indicaram remoção praticamente completa de toda a amônia contida no lixiviado. Nas diferentes condições operacionais avaliadas, a concentração de amônia remanescente no lixiviado foi igual ou inferior aos 20 mg/L determinados pela Resolução 397/08 do CONAMA. Quanto ao recolhimento da amônia, a eficiência média obtida nos frascos lavadores próxima a 80%, tanto ) quando utilizada a solução de ácido sulfúrico 0,4 mol/L quanto quando utilizada água. / Sanitary landfill leachate is a pollutant liquid effluent mainly due to its high ammonia concentration. Its treatment is necessary due to environmental and labour legislation requirements, besides prevention of environmental impacts of leachate release in water bodies. This research proposes ammonia removal from leachate by air stripping process, which transfers ammonia from liquid to gaseous phase. In order to prevent atmospheric pollution, air stripping gaseous effluent must be treated with sulphuric acid solution or water. Ammonia neutralization by sulfuric generates ammonium sulfate and by water, aquammonia is generated. Such by-products may be used as fertilizer. In this research, in order to remove leachate ammonia it was used a PVC tower of 2.24 m high and 15 cm diameter, packed with Rashing rings of corrugated polyethylene of 1.5 cm diameter and 5 cm length. Air flows were 1200, 1600 and 3600 L/h and leachete flows were 18 e 30 L/h. Calcium carbonate (standard grade) and commercial hydrated lime were used for pH adjustments. Air and liquid flows were countercurrent. In order to recover ammonia, two flasks of 6 L were used and filled with 4 L of 0.4 mol/L sulfuric acid solution or water. Results showed that ammonia was almost completely removed from leachate. In all operational conditions evaluated, remaining ammonia concentration in leachate was equal or less than 20 mg/L, value established by Resolution 397/08 of Brazilian Council of the Environment. Ammonia recovery with water or a 0.4 mol/L sulfuric acid solution was about 80%.

Segundo a Organização Mundial da Saúde (OMS), a esquizofrenia é reconhecida como um transtorno neuropsiquiátrico grave que afeta mais de 21 milhões de pessoas em todo o mundo. Para diminuir os sintomas associados a esta doença, a maioria dos pacientes esquizofrênicos fazem uso concomitantemente de antipsicóticos, antidepressivos, ansiolíticos e anticonvulsivantes. O desenvolvimento de métodos analíticos para a determinação desses fármacos em fluidos biológicos é importante para ajustar as doses administradas, minimizar os efeitos adversos e verificar a anuência do paciente à terapia. A química analítica moderna tem se direcionado para a simplificação, através da miniaturização dos sistemas analíticos. Neste contexto, pode-se destacar a técnica de microextração em sorvente empacotado (MEPS). O desenvolvimento de novas fases extratoras para MEPS, como, os monolitos de sílica híbrida permitem pré-concentração seletiva dos analitos. Neste projeto monolitos de sílica híbrida funcionalizados com grupos aminopropil ou cianopropil foram sintetizados pelo processo sol-gel. Estes monolitos apresentaram estrutura contínua, uniforme e porosa, como evidenciado pelas imagens de microscopia eletrônica de varredura (MEV). As análises de espectroscopia vibracional na região do infravermelho por transformada de Fourier (FTIR) dos monolitos de sílica híbrida exibiram picos facilmente identificáveis, característicos dos grupos cianopropil e aminopropil. Estes monolitos foram avaliados como fase estacionária para a MEPS para a determinação de fármacos em amostras de plasma por cromatografia líquida acoplada a espectrometria de massa em Tandem (LC-MS/MS). As variáveis MEPS (influência do pH na sorção dos analitos, número de ciclos aspirar/dispensar, etapa de limpeza do sorvente e solvente de eluição) foram otimizadas para aumentar a eficiência da extração. Em comparação com a fase de sílica híbrida aminopropil, a fase de sílica híbrida cianopropil apresentou maior capacidade de sorção para os fármacos em estudo. O método desenvolvido, MEPS/LC-MS/MS, empregando a fase extratora de sílica híbrida cianopropil, apresentou linearidade adequada com concentrações que variaram desde o limite inferior de quantificação (0,05-1,00 ng.mL-1) até o limite superior de quantificação (40-10.500 ng.mL-1) com coeficientes de determinação (R2) maiores do que 0,9955. Este método apresentou precisão com coeficientes de variação (CV) inferiores a 14% e exatidão com erro padrão relativo (EPR) de -12 a 14%. O método MEPS/LC-MS/MS foi aplicado com êxito para análise simultânea de cinco antipsicóticos (olanzapina, quetiapina, clozapina, haloperidol e clorpromazina), em combinação com sete antidepressivos (mirtazapina, paroxetina, citalopram, sertralina, imipramina, clomipramina e fluoxetina), dois anticonvulsivantes (carbamazepina e lamotrigina) e dois ansiolíticos (diazepam e clonazepam) em amostras de plasma de pacientes esquizofrênicos para fins de monitorização terapêutica. / According to World Health Organization (WHO), schizophrenia is recognizably a devastating neuropsychiatric disorder that affects more than 21 million people worldwide. To lessen the symptoms associated with the disease, most schizophrenic patients use other classes of drugs such as antidepressants, anxiolytics, and anticonvulsants concomitantly with antipsychotics. Developing analytical methods to quantify these drugs in biological fluids is important in therapeutic drug monitoring (TDM) to adjust doses, minimize adverse effects, and check patient adherence to the therapy. Regarding miniaturization and automation, microextraction by packed sorbent (MEPS) is a promising sample preparation technique. Sample preparation of biological matrixes is an important step in analytical processes: it removes endogenous components from the sample and pre-concentrates trace-level analytes. The development of new phases for MEPS such as the hybrid silica monoliths allows selective pre-concentration of the analytes. The present study reports on the synthesis of two hybrid silica monoliths functionalized with aminopropyl or cyanopropyl groups by the solgel process; evaluates these monoliths as selective stationary phase for MEPS to determine drugs in plasma samples by liquid chromatography-tandem mass spectrometry (LC-MS/MS); and discusses important factors (influence of pH on the sorption of analytes, number of draw/eject cycles, washing step, and elution solvent) related to the optimization of MEPS efficiency. The prepared hybrid silica monoliths consisted of a uniform, porous, and continuous silica monolithic network, as shown by scanning electron microscopy (MEV) images. The Fourier-transform infrared spectroscopy (FTIR) spectra of the hybrid silica monoliths displayed readily identifiable peaks, characteristic of the cyanopropyl and aminopropyl groups. Compared with the aminopropyl hybrid silica phase, the cyanopropyl hybrid silica phase exhibited higher binding capacity for most of the target drugs. The developed method, MEPS/LC-MS/MS, afforded adequate linearity at concentrations ranging from the lower limit of quantification (0.05 to 1.00 ng.mL-1) to the upper limit of quantification (40 to 10500 ng.mL-1); the coefficients of determination (R2) were higher than 0.9955. The precision of the method presented coefficients of variation (CV) lower than 14%; the relative standard error (RSE) of the accuracy ranged from -12 to 14%. The developed MEPS/LC-MS/MS method allowed for simultaneous analysis of five antipsychotics (olanzapine, quetiapine, clozapine, haloperidol, and chlorpromazine) in combination with seven antidepressants (mirtazapine, paroxetine, citalopram, sertraline, imipramine, clomipramine, fluoxetine), two anticonvulsants (carbamazepine and lamotrigine), and two anxiolytics (diazepam and clonazepam) in plasma samples from schizophrenic patients, which should be valuable for TDM purposes.