Diss. (sammanfattning) Stockholm : Karol. inst., 2004. / Härtill 7 uppsatser.

Diss. (sammanfattning) Stockholm : Karolinska institutet, 2005. / Härtill 5 uppsatser.

L'objectif de ces travaux vise à évaluer les performances d'un contacteur membranaire à fibres creuses utilisé pour réaliser l'absorption chimique du CO2 dans une solution ammoniacale ainsi que la régénération de cette dernière. Les membranes utilisées sont composites, c'est-à-dire composées d'une fine couche dense recouverte sur un support microporeux, la couche dense permettant d'éviter le mouillage par pénétration de liquide dans la membrane. Pour réaliser ces études, une approche combinant expérimentation et modélisation a été adoptée. Lors de la réalisation de l'absorption chimique avec un contacteur membranaire, des chutes importantes d’efficacité de captage du CO2 au cours du temps ont été observées et confirment les résultats obtenus lors de travaux ultérieurs. Cette baisse des performances est attribuée à la précipitation de sels d’ammonium en phase gaz. Lors de l'utilisation d’un gaz saturé en vapeur d'eau, comme le seraient les fumées industrielles, les performances du procédé se sont révélées stables. Un modèle 1D multi-composant adiabatique du contacteur a été développé sur Aspen Custom Modeler® et validé à partir des résultats expérimentaux. Les simulations réalisées avec ce modèle ont confirmé le potentiel d'intensification volumique de la technologie, toutefois, la réduction des pertes de NH3, grâce à l'utilisation d’une couche dense sélective moins perméable à NH3 qu’au CO2, n’a pas été satisfaisante. Les phénomènes de condensation dans les contacteurs membranaires ont été étudiés par expérimentation et modélisation. Il a ainsi été montré que le mouillage par condensation de la membrane ne devrait pas survenir, par contre, la condensation dans le lumen des fibres creuses entraîne une augmentation importante de la perte de charge pouvant conduire à des coûts de compression des gaz à traiter plus élevés. Des expériences et des simulations sur la régénération de solutions ammoniacales chargées avec des contacteurs membranaires ont été effectuées et des disparités importantes ont été trouvées entre les flux de CO2 mesurés et simulés. Une réduction volumique de trois par rapport à la colonne à garnissage a pu être calculée laissant entrevoir un potentiel intéressant de la technologie pour l’étape de régénération. En collaboration avec les partenaires du projet C2B, dans lequel s’intègre cette thèse, des essais d’absorption de CO2 ont été réalisés sur site avec un contacteur de taille industrielle. Les résultats de ce pilote sont conformes aux résultats obtenus au laboratoire et encourageants quant au transfert de la technologie vers l’échelle industrielle / This work aims to evaluate the performances of hollow fiber membrane contactors used for the CO2 absorption in aqueous ammonia and the regeneration of the latter within the frame of post-combustion CO2 capture. Fibers are made of a thin dense layer coated on a microporous support, the dense layer prevent membrane wetting by liquid penetration. Both experiment and modelling were done. During absorption experiments, important decrease of the CO2 capture efficiency was observed due to ammonium salts precipitation in the gas-side corroborating results from previous works. Experiments with CO2/N2 mixture saturated with water vapor, as would be the case for flue gas, interestingly, showed stable performances of the process. A one-dimensional multi-component adiabatic transfer model for CO2 absorption in NH3 has been implemented in Aspen Custom Modeler® and validated with experimental results. The simulations performed with the model confirmed the volumetric intensification potential of the technology, however, the NH3 slip reduction expected, because of the use of a dense layer more permeable to CO2 than NH3, wasn’t satisfying. Water condensation phenomenon in membrane contactors were studied with both experiments and simulations. It was thus showed that membrane pore wetting by condensation should not happened but gas-side condensation led to an important increase of the pressure drop with the potential of increasing compression costs. Experiments and simulations of the desorption of CO2 from a loaded aqueous ammonia solution with a membrane contactor were performed and important disparities were found between CO2 flux measured and simulated. A volumetric reduction of the membrane contactor when compared to the packed column was calculated highlighting the potential of the technology for the stripping step. In collaboration with the partners of the C2B project, in which this thesis is integrated, CO2 absorption essays were carried out on site with an industrial scale membrane contactor. The results of this pilot are consistent with laboratory results and encourages the transfer of the technology to the industrial scale

Les sites chimiques, pétrochimiques et pétroliers génèrent des effluents chargés en polluants soumis à une réglementation de plus en plus stricte. Le travail de thèse se focalise sur le traitement des effluents industriels et plus spécifiquement sur l'amortissement des pics de pollution via un procédé d'adsorption/désorption afin de minimiser les impacts négatifs sur l'épuration biologique. Pour cela, deux études complémentaires ont été menées en parallèle. La première étude concerne l'adsorption et la désorption de polluants en phase aqueuse avec notamment la sélection d’un adsorbant puis la détermination de ses capacités d'adsorption vis-à-vis de deux molécules modèles. Plusieurs cycles d'adsorption et de désorption ainsi que des pics de pollution ont été réalisés afin de (i) démontrer la faisabilité du procédé, (ii) d'identifier les phénomènes mis en jeu et les paramètres déterminants dans la capacité d'amortissement d'une colonne d'adsorbant et (iii) étudier les phénomènes de compétition entre molécules. Les données expérimentales ont pu être modélisées avec succès à l'aide d’un couplage du modèle Linear Driving Force (LDF) et de l'isotherme de Freundlich. D'autre part, l'impact d'une variation de charge sur les performances épuratoires du traitement biologique seul a été examiné et comparé aux effets observés lors d'un pic de pollution sur un procédé couplant une colonne d'adsorbant (en amont) et le traitement biologique. Un intérêt a également été porté aux foisonnements de bactéries filamenteuses, survenus à plusieurs reprises : une identification des filaments a été réalisée et un traitement de lutte efficace a été mis en place. Les résultats ont démontré qu'une colonne d'adsorbant placée en amont du bassin de biodégradation permet d'améliorer la qualité de l'effluent traité et ainsi de respecter les normes de rejet fixées par la législation. / Chemical, petrochemical and oil industries generate polluted effluents which are covered by increasingly stricter regulations. This PhD work focuses on the treatment of industrial effluents and more specifically on pollution peaks dampening through a process of adsorption/desorption so as to minimize the negative impacts on biological purification. Two complementary studies have been carried out simultaneously as part of this work. The first study concerns the adsorption and desorption of pollutants in aqueous phase including adsorbent selection and determination of its adsorption capacities, for two model molecules. Several cycles of adsorption and desorption, as well as peaks of pollution, have been carried out in order to (i) identify the phenomena involved and the determining parameters of the attenuation capacity of the adsorbent column, and (ii) to study competitive phenomenon between two molecules. Experimental data has been successfully modelled using both Linear Driving Force (LDF) and Freundlich isotherm models. For the second study, the impact of load variation on the biological treatment purifying performances has been investigated and compared to effects observed in response to a pollution peak on the process coupling an adsorption/desorption column and biological treatment. Concerning filamentous bacteria bulking, which occurs frequently, filament identification has been carried out and struggle treatments have been efficiently implemented. The results showed that an adsorbent column placed before the biological biodegradation improves treated effluent quality and so allows for the respect of discharge norms

The research presented in this thesis started with the idea to study alcohols as modifiers and dopants in differential ion mobility spectrometry (d-IMS) to produce complicated chemical signatures to explore a concept of chemical labels for product security application. D-IMS is a gas phase atmospheric pressure separation and detection technique which distinguishes compounds based on differences in their ions mobility as their travel under a low and high electric field. The hypothesis was that alcohols will form typical d-IMS products such as protonated monomers and proton bound cluster ions. However, the very first experiments revealed unexpected phenomena which included changes in the mobility of ions over a narrow range of concentrations that could not be explained by existing theory. Another observation was the apparent regeneration of reactant ions. It became evident that the observed phenomena had not been described in the open literature and that addressing the research-questions that were being raised would be essential for the determination of alcohols by d-IMS and its use in medical applications for toxicity screening and monitoring of alcohols. The above discovery shifted the research objective towards a fundamental and comprehensive study on the behaviour of alcohols in d-IMS. This thesis describes designed experiments and constructed systems allowing the efficient study of effect of concentration, electric field and temperature on the d-IMS responses of alcohols. The results of those studies demonstate: extensive fragmentation of alcohols, including previously undescribed fragmentation patterns with regeneration of the hydrated proton; new phenomena of adduct ion formation within the d-IMS drift tube, observed in the case of methanol within a narrow range of concentration; and self-modification of the alpha function of alcohols. This knowledge was exploited by developing an non-invasive analytical method for recovery, separation and detection of toxins from human saliva (including alcohols, diols and GHB) using TD-GC-d-IMS (thermal desorption - gas chromatography d-IMS) within a full range of toxicological concentration levels.

Made available in DSpace on 2016-12-12T20:15:50Z (GMT). No. of bitstreams: 1 Iara Maite Campestrini.pdf: 1744610 bytes, checksum: 71e01f191ae9fa061c877988b0114787 (MD5) Previous issue date: 2013-07-05 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / In order to increase the efficiency of magneto-optical traps, yielding a greater number of trapped atoms and long lifetimes, the effect of lightinduced desorption atom source emerges as an adjuvant and no thermal atoms. A prior experimental investigation (FRITSCH, 2011) showed that the number of rubidium atoms trapped increases when a light desorption focuses on the inner walls of the chamber imprisonment, whose material is stainless steel. The light desorption is applied from an incandescent lamp with power equal to 60 mW. The experimental data are adjusted and parameters are determined from the trap, in case of absence of light. Thus, the theoretical model proposed by Zhang et al. (2009) is applied, describing the increase of the number of atoms in the magneto-optical trap when the light desorption is triggered. In this setting, the rate of desorption and adsorption coefficient is estimated at 5x1017 atoms per second and 55 s-1. The combination of this model with that proposed by Monroe et al. (1990), in case of absence of light, perfectly describes the experimental curve generated when the mechanism for obtaining the magneto-optical trap and light desorption are actuated simultaneously. Furthermore, a theoretical prediction for the desorption rate, the rate of charging of magneto-optical trap and maximum number of atoms trapped on the basis of light desorption power is shown graphically. / Com o intuito de aumentar a eficiência das armadilhas magnéto-ópticas, obtendo-se um número maior de átomos aprisionados e longos tempos de vida, o efeito de dessorção atômica induzida por luz surge como uma fonte coadjuvante e não térmica de átomos. Uma investigação experimental prévia (FRITSCH, 2011) comprovou que o número de átomos de rubídio armadilhados aumenta quando uma luz de dessorção incide sobre as paredes internas da câmara de aprisionamento, cujo material é de aço inoxidável. A luz de dessorção aplicada é proveniente de uma lâmpada incandescente com potência igual a 60 mW. Os dados experimentais são fitados e os parâmetros da armadilha são determinados, para o caso sem luz. Com isso, o modelo teórico proposto por Zhang et al. (2009) é aplicado, descrevendo muito bem o incremento do número de átomos presentes na armadilha magnéto-óptica quando a luz de dessorção é acionada. Desse ajuste, a taxa de dessorção e o coeficiente de adsorção são estimados em 5x1017 átomos por segundo e 55 s-1. A união desse modelo com o proposto por Monroe et al. (1990), para o caso sem luz, descreve perfeitamente a curva experimental gerada quando o mecanismo para a obtenção da armadilha magnéto-óptica e a luz de dessorção são acionados simultaneamente. Além disso, uma previsão teórica para a taxa de dessorção, a taxa de carregamento da armadilha magnéto-óptica e o número máximo de átomos aprisionados em função da potência da luz de dessorção é mostrada graficamente.

nÃo hà / O presente trabalho tem como principal objetivo investigar as condiÃÃes mais adequadas para o estudo da difusividade de n-parafinas em um catalisador tÃpico para a sÃntese de Fischer-Tropsch (SFT), utilizando o mÃtodo cromatogrÃfico ZLC (coluna de comprimento zero), e avaliando-se a repetitividade e a reprodutibilidade desta metodologia. Objetiva, ainda, verificar o desempenho do catalisador em um reator de leito fixo, em escala piloto, e observar o efeito da difusÃo na seletividade a hidrocarbonetos de alta massa molar. O catalisador foi caracterizado, com Ãnfase nos ensaios de microscopia e anÃlise textural. Quanto à difusividade dos n-alcanos (n-C7, n-C9, n-C12, n-C16), foram utilizados dois sistemas ZLC, sendo um na Universidade Federal do Cearà (UFC) e o outro na Universidade de Edimburgo, empregando-se amostras de diferentes granulometrias (forma pà e pellet). Investigou-se, tambÃm, a influÃncia da temperatura, da vazÃo do gÃs de purga, da massa de catalisador e da concentraÃÃo do sorbato no gÃs de purga. Quanto à etapa reacional, esta ocorreu em uma unidade piloto para a SFT a 20 bar, nas temperaturas de 210 ÂC e 230 ÂC e em diferentes velocidades espaciais. O catalisador apresentou-se como mesoporoso, com um pouco de microporosidade, e com a fase ativa (Co) bem distribuÃda. Em relaÃÃo à difusividade efetiva, o diÃmetro de partÃcula mais adequado para o uso na coluna ZLC, dentre os testados, foi de 214 Âm para o catalisador na forma pÃ, com 5 mg de amostra. Comparando-se os experimentos realizados nas duas universidades, percebeu-se uma boa repetitividade, porÃm a reprodutibilidade, nÃo foi satisfatÃria. Observou-se ainda, a influÃncia da constante de Henry nos resultados obtidos para difusividade efetiva, em diferentes tamanhos de catalisador, entretanto, nÃo se perceberam mudanÃas significativas na difusividade efetiva em funÃÃo da variaÃÃo da temperatura e da concentraÃÃo de sorbato no gÃs de purga. Em se tratando da reaÃÃo, os resultados indicaram um forte efeito da temperatura na conversÃo de CO e na seletividade a C5+. O mecanismo difusivo à afetado pela difusividade de superfÃcie, e, a partir deste resultado, pode-se justificar o aumento da seletividade a metano com o incremento da relaÃÃo H2/CO. Com base nos resultados apresentados, o mÃtodo ZLC mostrou-se adequado para o estudo da difusividade efetiva de n-parafinas em um catalisador convencional para a SFT. / The main goal of the present research is to establish the most appropriate conditions for studying the diffusivity of n-paraffins in the presence of a typical catalyst for Fischer-Tropsch synthesis (FTS), by using the chromatographic method ZLC (zero length column) and evaluating the repeatability and reproducibility of this method. It also aims to verify the catalyst performance in a fixed bed reactor, at a pilot-scale, and observe the effect of diffusion in the selectivity of high molar mass hydrocarbons. At first, the catalyst characterization was done with emphasis on the microscopy studies and textural analysis with N2. Regarding the n-alkanes diffusivity (n-C7, n-C9, n-C12, n-C16), two ZLC equipments were used, one at the Federal University of Ceara (UFC) and the another one at the University of Edinburgh, with different particle size samples. This work has also evaluated the influence of temperature, the purge gas flow rate, the catalyst mass and sorbate concentration in the purge gas. The reaction step was done at a Fisher-Tropsch pilot-scale unit at 20 bar, with 210ÂC and 230ÂC in different space velocities. As a result, the catalyst was presented as mesoporous, with small microporosity, and with active phase (Co) well distributed. Concerning the effective diffusivity, the most appropriate particle diameter to be used at the ZLC column, among the tested diameters, is 214 Âm (dust form), with 5 mg of catalyst. Comparing the studies that were held at the two universities, it was noticed a good repeatability, however, the reproducibility was not satisfactory. It was observed a strong influence of the HenryÂs constant at the results of effective diffusivity, for different catalyst sizes; however, no significant changes at the effective diffusivity were noted due to temperature variation and sorbate concentration. Regarding the reaction, the results indicated a strong effect of temperature at the CO conversion and at the C5+ selectivity. The diffusive mechanism is strongly affected by the catalyst surface effects. Based on this result, the raise of methane selectivity by increasing H2/CO ratio can explained. As final result, the ZLC is found as a suitable method for surface diffusion estimation using typical Fischer-Tropsch catalyst.

[pt] O presente trabalho descreve o desenvolvimento de um sistema de dessorção térmica aplicável a remediação de solos contaminados por compostos orgânicos. O sistema consiste de um bastonete térmico capaz de aquecer o solo através de um fluxo radial e de um oxidador térmico destinado ao tratamento das emissões gasosas. Fazem parte do sistema, como equipamentos acessórios, controladores de temperatura do tipo rampa patamar, isolantes térmicos de fibra cerâmica, membranas plásticas e amostradores de água e de gases. Estes últimos são utilizados para averiguar a eficiência do oxidador térmico. O sistema desenvolvido atingiu aos objetivos de projeto. O bastonete térmico foi capaz de aplicar temperaturas de até 600 ºC seguindo trajetórias de temperatura programadas. O mesmo pode-se afirmar do sistema de tratamento das emissões gasosas. O programa experimental realizado em um solo residual de gnaisse, obtido de um talude rodoviário da Rodovia Washington Luís, contaminado por óleo queimado, revelou que o sistema desenvolvido é capaz de reduzir a concentração de compostos orgânicos a um valor mínimo, bem abaixo dos limites estabelecido pelos órgãos ambientais nacionais e estrangeiros. O programa expôs a importância da aeração da matriz porosa durante o tratamento para impedir a formação de coque. As determinações analíticas revelaram que as emissões gasosas resultantes do aquecimento do solo residual contaminado com óleo queimado tratam-se de parafinas de olefinas. A duração do ensaio bem como o projeto do arranjo espacial da distribuição dos bastonetes em um sistema in situ de remediação pode ser determinada através do emprego da formulação de propagação de calor formulada por Stegemeier (1998). / [en] This dissertation refers to the development of an in situ system devised to remediate soils contaminated with organic compounds. The system consists basically of a thermal probe capable of heating the soil matrix through radial flow and a thermal oxidizer that treats the resulting gases emissions. The system clearly reached the design aims. The thermal probe consistently programed temperatures up to 6000C to the soil matrix following applied thermal paths. The thermal oxidizer was capable to heat gases emissions up to 9000C under prolonged exposure. The experimental program was carried out using a residual soil from gnaiss taken from a slope at Washington Luiz Roadway. This soil was contaminated with used oil and submitted to a series of tests in order to assess the efficiency of the system developed herein. The results suggest that thermal desorption was able to reduce the degree of contamination to levels well below the limits established by National and International Environmental Agencies. The results also revealed the importance of aeration during the process to avoid the formation of coke. Fingerprinting tests carried out on gases emissions revealed that they were composed mainly by olefins and paraffins. The design of an in situ system as well as the termination criteria for in situ thermal desorption treatment might well be accomplished using the heat propagation theory developed by Stegemeier (1998).

L’objectif du travail est l’étude du processus d’adsorption-désorption d’un colorant azoïque sur l’argile naturelle provenant de deux gisements tunisiens. L’expérimentation en laboratoire a été menée en réacteur fermé et en colonne de percolation. Lors de la première étape, deux types d’argile ont été utilisées. L’étude cinétique montre que l’adsorption et la désorption suivent le modèle du pseudo premier ordre. L’isotherme d’adsorption est de type Langmuir alors que l’isotherme de désorption est de type hystérésis. La capacité d’adsorption de l’argile de Gafsa est plus prononcée que celle de l’argile de Borj Chekir. Les études en colonne de percolation ont été menées sur un mélange d’argile de Borj Chekir et du sable moyen H2F. Les paramètres hydrodynamiques ont été déterminés en utilisant un traceur inerte (fluorescéine). L’étude du transport réactif a montré que si le pourcentage d’argile augmente la rétention du colorant augmente alors que si on augmente le débit d’injection pour un pourcentage d’argile-sable constant la rétention du colorant diminue. Les courbes de sortie ont été ensuite comparées aux résultats numériques d’un modèle 1D de transport réactif, intégrant deux sites d’adsorption réversible et irréversible. / The aim of the work is to study the adsorption-desorption process of an azo dye on natural clay from two Tunisian deposits. The laboratory experiment was conducted in a closed reactor (batch) and percolation column. In the first step, two types of clay were used. The kinetic study shows that the adsorption and desorption follow the pattern of a pseudo first order phenomenon. A Langmuir isotherm is fitted to the adsorption process, while the desorption isotherm is characterised by hysteresis. The adsorption capacity of the Gafsa clay is more pronounced than that of the Borj Chekir clay. The percolation column studies were conducted on a mixture of of Borj Chekir clay and medium sand H2F. Hydrodynamic parameters were determined using an inert tracer (fluorescein). The reactive transport study showed that an increase in clay percentage will increase retention, but, on the other hand when using a constant percentage of the clay-sand mixture, increasing the injection rate will decrease the retention capacity of the mixture. The output curves were then compared with the numerical results of a 1D reactive transport model incorporating two reversible and irreversible adsorption sites.

Abstract The aim of the thesis is to expand the knowledge of the catalytic properties of platinum-loaded zeolite catalysts in the reduction of NOx by hydrocarbons. The work is divided into three parts. First the recent literature of zeolite catalysts has been introduced, secondly the adsorption capacity, activity, and acidity of the catalysts have been studied by TPD and IR techniques, and thirdly the derived reaction mechanisms based on the obtained data are presented. Parent and 1 wt-% Pt-loaded ZSM-5, Beta, Y, and Ferrierite zeolite catalysts have been studied in the C3H6-assisted reduction of NO. The Pd/Al2O3-based catalyst was used as a reference material for the reaction mechanistic studies. Several experimental techniques (in situ DRIFT, activity measurements, CO chemisorption, N2 physisorption, TPD, and TEM) have been used for the characterisation of the catalysts properties. The IR technique was used as the main technique for the determination of activities, surface species, and the acidic properties of the zeolite-based catalysts. The activity studies carried out by the gaseous FTIR technique provide information on the desired reaction products as well as the undesired by-products. The detection and identification of the surface species as well as the reaction intermediates formed were done by the DRIFT method. The activity experiments indicate the effectiveness of the Pt-loaded zeolite catalysts. The reduction of NO was found to decrease in the order: Pt/Beta > Pt/Y > Pt/Ferrierite > Pt/ZSM-5 in the conditions with excess O2. Platinum can be concluded to have an effect on O2 and NO dissociation. Oxidation reactions of NO to NO2 and propene to CO2 were observed to be more intense over the platinum-loaded zeolites than over the parent zeolites. In this work the reaction mechanisms for the C3H6-SCR of NO were derived over the Pt-loaded zeolite as well as the Pd/alumina catalysts based on the data obtained by DRIFT and activity experiments. The kinetics for the NO reduction by CO over Pd/Al2O3 was also derived. With the methods employed, the mechanistic steps over the Pt-loaded zeolites and Pd/Al2O3-based catalysts could be derived quite precisely and easily for C3H6-SCR of NO. Reaction routes were determined to go via different formations of intermediates over the two catalysts, i.e. via organonitrogen and isocyanate routes, respectively. The IR techniques were discovered to be effective tools in applied engineering studies.