An adsorbent suitable for adsorption desalination cycles is essentially characterized by a hydrophilic and porous structure with high surface area where water molecules are adsorbed via hydrogen bonding mechanism. Silica gel type A++ possesses the highest surface area and exhibits the highest equilibrium uptake from all the silica gels available in the market, therefore being suitable for water desalination cycles; where adsorbent’s adsorption characteristics and water vapor uptake capacity are key parameters in the compactness of the system; translated as feasibility of water desalination through adsorption technologies. The adsorption characteristics of water vapor onto silica gel type A++ over a temperature range of 30 oC to 60 oC are investigated in this research. This is done using water vapor adsorption analyzer utilizing a constant volume and variable pressure method, namely the Hydrosorb-1000 instrument by Quantachrome. The experimental uptake data is studied using numerous isotherm models, i. e. the Langmuir, Tóth, generalized Dubinin-Astakhov (D-A), Dubinin-Astakhov based on pore size distribution (PSD) and Dubinin-Serpinski (D-Se) isotherm for the whole pressure range, and for a pressure range below 10 kPa, proper for desalination cycles; isotherms type V of the International Union of Pure and Applied Chemistry (IUPAC) classification were exhibited. It is observed that the D-A based on PSD and the D-Se isotherm models describe the best fitting of the experimental uptake data for desalination cycles within a regression error of 2% and 6% respectively. All isotherm models, except the D-A based on PSD, have failed to describe the obtained experimental uptake data; an empirical isotherm model is proposed by observing the behavior of Tóth and D-A isotherm models. The new empirical model describes the water adsorption onto silica gel type A++ within a regression error of 3%. This will aid to describe the advantages of silica gel type A++ for the design of adsorption desalination processes where reducing capital cost and footprint area are highly important parameters to take into account.

Silica gels containing incorporated heteropolyacids (HPAs) were synthesized in acidic media by co-condensation of tetraethoxysilane (TEOS) with phosphotungstic or phosphomolybdic acids using the sol-gel technique. The effect of the synthesis conditions on their structure and morphology was studied. Yields of modified materials were somewhat lower compared to non-modified silica gels. All materials were mesoporous but contained micropores in their structures. Presence of bands of Keggin's structures in FT-IR spectra along with absence of XRD patterns of crystalline HPAs confirmed their fine incorporation into silica network. Particle sizes of modified materials were 500-1100 nm except for the W-containing sample obtained with trimethylstearylammonium chloride, which was significantly lower. This unusual effect was attributed to stabilization of primary silica nanoparticles by interactions between the surfactant and HPA. High ratio HPA/TEOS resulted in partial loss of porosity. Obtained results might be used for optimization of synthesis of effective catalysts and adsorbents containing HPAs in mesoporous structure.

Four ethylene bis-indenyl ligands containing tethers of various lengths were successfully immobilized on the surface of functionalized silica gel. The strategy of immobilization was based on catalytic thiol-ene coupling of terminal alkene groups in the tethers with surface thiol groups. Obtained materials have high BET surface area and pore volume. The method developed can be used for immobilization of catalytically active bis-indenyl metallocene complexes, thus preventing their dimerization and deactivation.

No description available.

[EN] This PhD study deals with the modelling of an adsorption system designed to provide air conditioning for vehicles, and is driven by the waste heat available from the water/glycol cooling circuit of the engine. The system is based on the sequential heating/cooling of two sorption beds containing a solid sorption material which desorbs or adsorbs water vapour. The condensation of the vapour is carried out by a cooling circuit while the subsequent evaporation of the condensed liquid is employed to produce the cooling effect, generating chilled water, which is then employed to cool down the air of the cabin. The developed model is fully dynamic and is based on zero-dimensional lumped parameter models for all the necessary components of the overall system including the engine, the beds, the heating circuit, the cooling circuit, the chilled water circuit and the vehicle cabin. The sorption bed model takes into account the non-equilibrium of the adsorption and desorption processes and is able to work with any kind of adsorbent materials, but the study has been restricted to silica gel and zeolite which are among the most appropriate materials for this application. The model is employed to simulate a standard driving cycle of a vehicle, evaluating the instantaneous available heat from the engine cooling system and the dynamic behaviour of the described sorption A/C system, resulting in the estimation of the evolution of the cabin temperature along the cycle. The model of the overall system has been developed under the MATLAB Simulink programming environment. The model of the adsorption system has been first validated against experimental results, showing its excellent capabilities to predict the dynamic behaviour of the system. The model was then used to analyse the influence of the main design parameters of the bed and the main operation parameters on the system's performance: cooling capacity and coefficient of performance (COP). This was done in order to provide rules for the optimal design and operation of this kind of systems. Finally, the model has been employed to analyse the overall system (engine, adsorption system, heating and cooling circuits, chilled water circuit and cabin) performance along a standard driving cycle, under various operation strategies with regards to the initial state of the adsorbent material in the beds, and operation conditions both for a car and a truck. The results show the difficulties of activating the system at the initial periods of the cycle, when the engine is warming up, and the difficulties to synchronise the operation of the system with the availability of waste energy. They also highlight the limitation in capacity of the designed system, showing that it would not able to fulfil the comfort requirements inside the cabin in hot days or after soaking conditions. Part of this PhD study was carried out in the frame of an R&D project called "Thermally Operated Mobile Air Conditioning Systems - TOPMACS", financially supported by the EU under the FP6 program, which was devoted to the evaluation of the feasibility and performance of potential sorption system solutions for the air conditioning of vehicles. / [ES] Esta tesis doctoral se centra en el modelado de un sistema de adsorción diseñado para proporcionar aire acondicionado de vehículos a partir del calor residual disponible en el circuito de refrigeración de agua/glicol del motor. El sistema se basa en el calentamiento/enfriamiento secuencial de dos reactores que contienen un material adsorbente sólido que desorbe o absorbe vapor de agua. La condensación del vapor se lleva a cabo mediante un circuito de refrigeración, mientras que la posterior evaporación del agua condensada se emplea para producir agua fría, que se emplea finalmente en enfriar el aire de la cabina. El modelo desarrollado es completamente dinámico y se basa en modelos cero dimensionales de parámetros concentrados, para todos y cada uno de los componentes del sistema global incluyendo el motor, los reactores, el circuito de calentamiento, el circuito de enfriamiento, el circuito de agua fría y la cabina del vehículo. El modelo del reactor contempla el no equilibrio de los procesos de adsorción o desorción y es capaz de trabajar con cualquier par de materiales adsorbentes. No obstante el estudio se ha restringido a gel de sílice y zeolita que se encuentran entre los materiales más adecuados para esta aplicación. El modelo se emplea para simular un ciclo de conducción estándar del vehículo, evaluando el calor disponible instantáneamente en el sistema de refrigeración del motor, y el comportamiento dinámico del sistema descrito adsorción-Aire Acondicionado, permitiendo como resultado principal la estimación de la evolución de la temperatura de la cabina a lo largo el ciclo. El modelo del sistema global se ha desarrollado en el marco del entorno de programación MATLAB Simulink. El modelo del sistema de adsorción se ha validado primero contra resultados experimentales demostrando las excelentes capacidades del modelo para predecir el comportamiento dinámico del sistema. A continuación, el modelo se ha aplicado para analizar la influencia de los principales parámetros de diseño del reactor, y de los principales parámetros de operación, sobre el rendimiento del sistema: la capacidad y coeficiente de operación (COP), con el fin de proporcionar directrices para el diseño y operación óptima de este tipo de sistemas. Por último, el modelo ha sido empleado para analizar el funcionamiento y prestaciones del sistema en su conjunto (motor, sistema de absorción, los circuitos de calefacción y refrigeración, circuito de agua fría, y la cabina) a lo largo de un ciclo de conducción estándar, bajo diferentes estrategias de operación en lo que se refiere al estado inicial del material adsorbente en los reactores, y las condiciones de operación, para el caso de un coche, y para el de un camión. Los resultados muestran las dificultades de la activación del sistema en los periodos iniciales del ciclo, cuando el motor se está calentando, y las dificultades para sincronizar el funcionamiento del sistema con la disponibilidad de energía térmica excedente del motor, así como la limitación en la capacidad de enfriamiento del sistema diseñado, que no resulta capaz de satisfacer los requerimientos mínimos de confort dentro de la cabina en los días calurosos o de enfriarlo con suficiente rapidez cuando el vehículo ha estado estacionado bajo el sol durante varias horas. Parte de este estudio de doctorado se ha llevado a cabo en el marco de un proyecto de I + D denominado " Thermally Operated Mobile Air Conditioning Systems - TOPMACS", financiado parcialmente por la UE en el marco del programa FP6, y que perseguía la evaluación de la viabilidad y el potencial de aplicación de soluciones de sistemas de adsorción activadas por el calor residual del motor para el aire acondicionado de vehículos. / [CA] Aquesta tesi doctoral es centra en el model d'un sistema d'adsorció dissenyat per a proporcionar aire acondicionat a vehicles a partir de la calor residual disponible al circuit de refrigeració d'aigua / glicol del motor. El sistema es basa en l'escalfament / refredament seqüencial de dos reactors que contenen un material adsorbent sòlid que desorbeix o absorbeix vapor d'aigua. La condensació del vapor es porta a terme mitjançant un circuit de refrigeració, mentre que la posterior evaporació de l'aigua condensada s'utilitza per a produir aigua freda, que s'empra finalment en refredar l'aire de la cabina. El model desenvolupat és completament dinàmic i es basa en models zero dimensionals de paràmetres concentrats, per a tots i cada un dels components del sistema global incloent el motor, els reactors, el circuit d'escalfament, el circuit de refredament, el circuit d'aigua freda i la cabina del vehicle. El model del reactor contempla el no equilibri dels processos d'adsorció o desorció i és capaç de treballar amb qualsevol parell de materials adsorbents. No obstant això, l'estudi s'ha restringit a gel de sílice i zeolita que es troben entre els materials més adequats per a aquesta aplicació. El model s'utilitza per a simular un cicle de conducció estàndard del vehicle, avaluant la calor disponible instantàniament en el sistema de refrigeració del motor, i el comportament dinàmic del sistema descrit Adsorció-Aire Acondicionat, permetent com a resultat principal l'estimació de l'evolució de la temperatura de la cabina al llarg del cicle. El model del sistema global s'ha desenvolupat en l'entorn de programació MATLAB Simulink. El model del sistema d'adsorció s'ha validat primer amb resultats experimentals demostrant les excel¿lents capacitats del model per a predir el comportament dinàmic del sistema. A continuació, el model s'ha aplicat per analitzar la influència dels principals paràmetres de disseny del reactor, i dels principals paràmetres d'operació, sobre el rendiment del sistema: la capacitat i coeficient d'operació (COP), amb la finalitat de proporcionar directrius per al disseny i operació òptima d'aquest tipus de sistemes. Finalment, el model ha estat utilitzat per analitzar el funcionament i prestacions del sistema en el seu conjunt (motor, sistema d'absorció, els circuits de calefacció i refrigeració, circuit d'aigua freda, i la cabina) al llarg d'un cicle de conducció estàndard, sota diferents estratègies d'operació pel que fa a l'estat inicial del material adsorbent en els reactors, i les condicions d'operació, per al cas d'un cotxe, i per al d'un camió. Els resultats mostren les dificultats de l'activació del sistema en els períodes inicials del cicle, quan el motor s'està escalfant, i les dificultats per sincronitzar el funcionament del sistema amb la disponibilitat d'energia tèrmica excedent del motor, així com la limitació en la capacitat de refredament del sistema dissenyat, que no resulta capaç de satisfer els requeriments mínims de confort dins de la cabina en els dies calorosos o de refredar amb suficient rapidesa quan el vehicle ha estat estacionat sota el sol durant diverses hores. Part d'aquest estudi de doctorat s'ha dut a terme en el marc d'un projecte d'I + D denominat "Thermally Operated Mobile Air Conditioning Systems - TOPMACS", finançat parcialment per la UE en el marc del programa FP6, i que perseguia l'avaluació de la viabilitat i el potencial d'aplicació de solucions de sistemes d'adsorció activats per la calor residual del motor per a l'aire condicionat de vehicles. / Verde Trindade, M. (2015). MODELLING AND OPTIMIZATION OF AN ADSORPTION COOLING SYSTEM FOR AUTOMOTIVE APPLICATIONS [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/54120

The focus of this research is on the optical measurement of uranyl in a solid matrix using fluorescence spectroscopy. Nanoporous silica-based materials were used to extract uranyl from contaminated soil and to enhance the fluorescence intensity and lifetime. The fluorescence lifetime and intensity of uranyl ions adsorbed on porous silica-based materials of varying pore size was measured as a function of pH and in the presence of fluoride. The feasibility of uranyl fluorescence detection on the top of soil by silica gel is carried out by four types of natural soil. The results show that the uranyl fluorescence intensity can be enhanced by approximately two orders of magnitude by the silica nanoporous matrix from pH 4-12 with the greatest enhancement occurring from pH 4-7. The enhanced fluorescence lifetime can be used in time-gated measurements to help minimize the influence of background environmental fluorophores. The pH and the fluoride variation causes different uranyl speciation and results in a peak shift in the fluorescence spectrum. The mechanism of the uranyl ion on the silica nanoporous matrix was studied through 15 different silica materials with different water content ratios and various concentrations of uranium on different silica structures. The result shows that the particle size, pore size, water content and uranyl concentration on silica surfaces are all important factors for optimizing the fluorescence intensity. The spacing between silica materials, either the pore inside materials or the space between particles, causes the variety of uranyl distribution on the material surface and changes the fluorescence performance. Also, X-Ray Photoelectron Spectroscopy (XPS) is used to identify the possible uranyl surface species on silica. The fluorescence emission spectra from silica materials and the XPS results are consistent with the presence of two different uranyl compounds. The specific surface area of silica materials plays an important role on uranyl adsorption mechanism. To further enhance the sensitivity, an optical ball lens was used to preferentially direct the fluorescence signal toward the excitation source in standoff measurements. The application of the ball lens was found to increase the detection distance up to 14 times.

Ce travail concerne l'étude des interactions bactéries /silicates grâce à de nouveaux matériaux ou gels de silice hybrides dopés en particules colloïdales de smectites (GSH). Les deux objectifs principaux sont la caractérisation physicochimique des GSH et l'amélioration des connaissances sur les mécanismes de l'altération minérale grâce aux GSH. Dans le premier volet de la thèse, nous avons ainsi pu mettre en évidence que le gel est constitué d'une matrice siliceuse particulaire de nature fractale dans laquelle les particules minérales sont dispersées. La structure des GSH est stabilisée par le traitement hydrothermal choisi (type autoclave). Dans le second volet de la thèse, l'altération minérale est étudiée pour des GSH à concentration variable en particules minérales, à teneur élevée (NAu-2) ou basse (SWy-2) en fer. Il est ainsi montré que la diffusion des acides organiques et des sidérophores dans le GSH, hors adhésion ou formation d'un biofilm en surface des minéraux, est suffisante pour altérer efficacement les particules minérales. La mise en évidence de gradients de protons locaux produits par la bactérie en interaction avec les GSH peut également expliquer l'efficacité biotique de la dissolution minérale par rapport à des conditions abiotiques. En conclusion, les points forts et les limites de l'utilisation d'un matériau hybride type GSH pour cibler les interactions minéral/microorganismes sont discutés / This work deals with the study of bacteria/silicate interactions by using new hybrid materials, i.e. hybrid silica gel dopped with colloidal smectite particles (HSG). The aims are (1) to characterize HSG physicochemical properties and (2) to get a better knowledge about mineral/bacteria interactions. In a first part of the thesis, it is shown that HSG is a fractal silica network containing well-dispersed mineral particles. Hydrothermal treatment is necessary to stabilize the HSG structure. In the second part, it is shown that diffusion of organic acids and siderophores is sufficient to explain the high efficiency of bacterial action compared to abiotic treatments. Preventing bacterial adhesion or biofilm formation at the mineral surface permits to enhance the influence of metabolites diffusion. To conclude, the advantages and limits of using HSG in environmental studies are discussed

Made available in DSpace on 2014-10-09T12:45:34Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:07:28Z (GMT). No. of bitstreams: 1 07179.pdf: 6113980 bytes, checksum: 1a969cfb7280cccf98f26594e185a2c2 (MD5) / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Made available in DSpace on 2015-05-14T13:21:48Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 1997340 bytes, checksum: d9de6932e705d57a480fc922a17f1ba4 (MD5) Previous issue date: 2009-11-01 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / In this work, modified silica gel with the group aminopropiletanoimina was used as retention capacity for the ions cadmium, lead and cromate. The tests were accomplished in aqueous solutions under different conditions of pH, in constant temperature of 298±1 K. The number of mol of the organic chain anchored to the matrix was 0,97mmol /g. The analysis of the curves TG, for the degradation interval between 0,12 and 0,4, shows certain constancy of the value of the activation energy with the increase of the value of the conversion degree, however, the comparison of the activation energies calculated by the method of FWO and by the method of Coats-Redfern shows different results for all the models of simple mechanisms, for that, it is believed that the process in such area conversion doesn't happen through a simple mechanism, but through a complex process where more than one mechanism is acting in the dynamics of the degradation reaction. Based in the number of mols of cadmium, lead and cromate adsorbed, it can settle down the following order: cadmium > cromate > lead. The analysis of the kinetics of the reaction for the three ions shows that the processes of adsorption follow a kinetic law of speed of pseudo-second order with the constants of speed cadmium > lead > cromate. The balance of the process of adsorption is not described by the same model of adsorption; the lead and the cromate are described reasonably well by Langmuir, but for the cadmium it was not found any model to describe the behavior of the process of adsorption satisfactorily. / Neste trabalho, sílica gel modificada com o grupo aminopropiletanoimina foi utilizada como adsorvente para os íons cádmio, chumbo e cromato. Os testes foram realizados em soluções aquosas sob diferentes condições de pH em temperatura constante de 298±1 K. O número de mol da cadeia orgânica ancorada à matriz foi de 0,97mmol /g. A análise das curvas TG, para o intervalo de degradação entre 0,12 e 0,4, mostra certa constância do valor da energia de ativação com o aumento do valor do grau de conversão, entretanto, a comparação das energias de ativação calculadas pelo método de FWO e pelo método de Coats-Redfern mostra resultados diferentes para todos os modelos de mecanismos simples, por isso, acredita-se que o processo em tal região de conversão não ocorre a través de um mecanismo simples, mas sim, através de um processo complexo onde mais de um mecanismo está atuando na dinâmica da reação de degradação. Com base no número de moles de cádmio, chumbo e cromato adsorvidos pode-se estabelecer a seguinte ordem: cádmio > cromato > chumbo. A análise da cinética da reação para os três íons mostra que os processos de adsorção seguem uma lei cinética de velocidade de pseudo-segunda ordem com as constantes de velocidade de cádmio > chumbo > cromato. O equilíbrio do processo de adsorção não é descrito pelo mesmo modelo de adsorção; o chumbo e o cromato são descritos razoavelmente bem pelo Langmuir, mas, para o cádmio não foi encontrado nenhum modelo que descrevesse o comportamento do processo de adsorção satisfatoriamente.

Made available in DSpace on 2014-10-09T12:45:34Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:07:28Z (GMT). No. of bitstreams: 1 07179.pdf: 6113980 bytes, checksum: 1a969cfb7280cccf98f26594e185a2c2 (MD5) / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP