Submitted by Marcia Silva (marcia@latec.uff.br) on 2015-10-29T16:05:33Z No. of bitstreams: 1 Dissert Jefferson Fernandes do Amaral Silva.pdf: 25102387 bytes, checksum: edad0b0e6d5f6991523db2537c6c1061 (MD5) / Made available in DSpace on 2015-10-29T16:05:33Z (GMT). No. of bitstreams: 1 Dissert Jefferson Fernandes do Amaral Silva.pdf: 25102387 bytes, checksum: edad0b0e6d5f6991523db2537c6c1061 (MD5) Previous issue date: 2015-03-20 / A água é vital para os seres humanos. Projeções sobre o futuro indicam que o atual cenário de escassez de recursos hídricos pode se agravar e provocar consequências dramáticas para a própria sobrevivência da humanidade. O Brasil, que possui a maior fonte renovável de água doce do mundo, apresenta regiões de elevada escassez hídrica, como é o caso do semiárido e das regiões metropolitanas das grandes cidades. Esta pesquisa refere-se a um estudo sobre o panorama global da distribuição e uso de água doce e uma análise de custos da utilização de um sistema de dessalinização da água do mar por osmose reversa alimentada com energia gerada por painéis fotovoltaicos, por um motor gerador a biodiesel e pela rede elétrica, em uma organização com acesso à água do mar da Baía de Guanabara. Foram analisados os principais documentos publicados pela Organização das Nações Unidas e pelos órgãos no Brasil responsáveis pelo gerenciamento dos recursos hídricos e realizada uma vasta revisão bibliográfica para identificar os modelos utilizados para avaliação econômica de plantas de osmose reversa alimentadas por energia elétrica de fontes renováveis de energia, solar e biodiesel, e da própria rede elétrica. A análise econômica, focada no levantamento de custos, utilizou a combinação de taxas de juros nominais ao ano, 5%, 10% e 15%, com períodos de vida útil de 10, 15 e 20 anos. Os custos de produção de água doce obtidos variaram entre R$ 6,22/m3 a R$ 7,71/m3 para a configuração do dessalinizador de osmose reversa alimentado com energia da rede elétrica (Rede-OR), entre R$ 12,47/m3 e 25,67/m3 para a configuração do dessalinizador de osmose reversa alimentado com a energia elétrica gerada pelos painéis fotovoltaicos (FV-OR), e entre R$ 16,79/m3 e 18,51/m3 para a configuração do dessalinizador alimentado com energia elétrica gerada pelo motor gerador movido a biodiesel (Biodiesel-OR). Os resultados apresentaram valores competitivos e indicam que organizações com fácil acesso à água do mar e que possuem demandas elevadas de água, com custos também expressivos, devem investigar a produção autônoma de água doce por meio da dessalinização por osmose reversa, combinadas com energias renováveis, caso disponíveis / Water is vital for human beings. Projections on the future indicate that the current scenario of scarcity of freshwater resources may worsen and cause dramatic consequences for the mankind survival. Although it has the largest renewable source of freshwater in the world, Brazil presents high freshwater scarcity regions, like semi-arid and the metropolitan areas of major cities. This research aim to study about the global picture of the distribution and use of freshwater and to analyze the costs of the use of a system of seawater desalination by reverse osmosis powered by energy generated from photovoltaic panels, biodiesel stationary engine and power grids, in an organization with access to seawater of Guanabara Bay. Publications of United Nations and Brazil were analyzed about the conditions of freshwater resources and extensive literature to identify the models used to carry out the economic evaluation of reverse osmosis plants powered by electricity from renewable energy sources, solar and biodiesel, and the electrical power grid. The economic analysis, focused on cost survey, used a combination of nominal interest rates per annum 5%, 10% and 15%, with useful life of 10, 15 and 20 years. Freshwater production costs obtained ranged from BRL$ 6.22/m3 to BRL$ 7.71/m3 for the configuration with reverse osmosis desalination unit powered by energy from the electric power grid (Grid-RO), from BRL$ 12.47/m3 to BRL$ 25.67/m3 for the configuration with reverse osmosis desalination unit powered by electricity generated from the photovoltaic panels (PV-OR), and from BRL$ 16.79/m3 to BRL$ 18.51/m3 for the configuration with reverse osmosis desalination unit powered by electricity generated from the biodiesel stationary engine (Biodiesel-RO). The results showed competitive values and indicate that organizations with easy access to seawater and have high water demands, with also significant costs, should investigate the autonomous production of fresh water through desalination by reverse osmosis, combined with renewable energies, if available

Forward osmosis (FO) is a membrane technology that uses the osmotic pressure difference to treat two fluids at a time giving the opportunity for an energy-efficient water and wastewater treatment. Various applications are possible; one of them is the application in industrial water management. In this review paper, the basic principle of FO is explained and the state-of-the-art regarding FO application in manufacturing industries is described. Examples of FO application were found for food and beverage industry, chemical industry, pharmaceutical industry, coal processing, micro algae cultivation, textile industry, pulp and paper industry, electronic industry, and car manufacturing. FO publications were also found about heavy metal elimination and cooling water treatment. However, so far FO was applied in lab-scale experiments only. The up-scaling on pilot- or full-scale will be the essential next step. Long-term fouling behavior, membrane cleaning methods, and operation procedures are essential points that need to be further investigated. Moreover, energetic and economic evaluations need to be performed before full-scale FO can be implemented in industries.

Cette étude s’intéresse à la conception systémique intégrant simultanément les questions de dimensionnement et de gestion optimale de l'énergie. Le système étudié concerne un procédé de pompage intégrant un processus de dessalement d’eaux saumâtres alimenté par des sources de puissance hybrides renouvelable incluant un minimum de stockage électrochimique. Ce cas d’étude appartient à une classe typique de systèmes autonomes alimentés par des sources intermittentes dont profil de puissance a une forme "donnée" : « selon les conditions climatiques (ensoleillement, vent), avec un minimum de stockage d’électricité, la puissance offerte doit être convertie ou stockée hydrauliquement sous peine d’être gaspillée ». L'influence des conditions d'environnement et la robustesse du processus d’optimisation est enfin aussi discutée dans cette thèse. Deux types de modèles mathématiques, dynamiques et quasi-statiques, sont mis en œuvre pour décrire l'ensemble du dispositif. Le système est tout d’abord modélisé dynamiquement par Bond Graphs. Pour une simulation plus rapide, plus adaptée à l’optimisation globale du système, un modèle quasi-statique est créé pour être simulé dans l'environnement Matlab. Pour de tels dispositifs, étant donné une certaine puissance offerte au fil du vent et du soleil, trouver le point optimal de fonctionnement à chaque période consiste en un partage de puissance entre les sous systèmes de pompage et de traitement de l’eau : ce processus est plutôt complexe compte tenu des non linéarités (courbes rendement – puissance) et de la présence de nombreuses contraintes relatives aux limitations de puissance des pompes, aux conditions de niveau des réservoirs, ainsi qu’aux limitations de pression et de débit dans les processus hydrauliques (pompes osmoseur). Nous montrerons qu’il n’est pas si trivial de choisir une fonction objectif qui assure simultanément la performance et la robuste du système vis-à-vis des conditions d’environnement : une fonction objectif robuste quel que soit le profil de puissance des sources est ainsi proposée pour mettre en œuvre une gestion optimale de l’énergie. Le problème d’optimisation étant posé sous forme standard, consistant en la maximisation d’une fonction objectif sous contraintes, des approches d’optimisation efficaces par programmation non linéaire sont employées. La question du dimensionnement et son couplage à la gestion énergétique est finalement étudiée. En particulier, l’intérêt de la modularité des systèmes, considérant plusieurs pompes connectées en parallèle pour la même fonction, est investigué. / This study focuses on systemic design, integrating simultaneously issues of sizing and optimal energy management. The system under study consists of a pumping process including a brackish water desalination system fed by hybrid renewable power sources with minimum electrochemical storage. Such a device belongs to the class of “autonomous systems” supplied by intermittent sources whose power profile has a “given” waveform: “with minimum electrical storage, power has to be converted, stored in water tanks, or wasted following climatic (sun, wind) conditions”. Influence of environment conditions and robustness of the optimization process is then also discussed in this thesis. Both dynamic and quasi static models are implemented for representing the whole system. The device is firstly modeled dynamically by Bond Graph methodology. For faster simulations, which are more suitable for system optimization, a quasi static model is created to be simulated in the Matlab environment. For such systems, given a certain source power, finding optimal operation point at each period consists of a power sharing between all pumping devices: it is a complex process with huge nonlinearities (efficiency vs power curves) and with many constraints as for the limitation of pump powers, tank level conditions, or pressure and flow limitations in hydraulic network and pumping devices. It is not so trivial to define an objective function which ensures system performance and robustness versus environment conditions: a convenient objective function, whatever the input power profile, is then proposed to implement the optimal management. The optimization problem being mathematically expressed, consisting of objective function maximization under constraints, efficient optimization methods by non linear programming are implemented. The issue of sizing and its coupling with system management efficiency is finally studied. In particular, the interest of modular operation with several pumps connected in parallel is also concerned in this research.

La dégradation des ressources en eaux par la présence de matières organiques (MO) et de micropolluants nécessite la mise en œuvre de procédés de production d’eau potable robustes. Dans ce contexte, de nombreuses municipalités françaises comme Saint Cloud et Angers ont décidé d’implanter un procédé d’adsorption sur charbon actif en poudre couplé à l’ultrafiltration (CAP/UF). Le CAP est utilisé en amont des membranes afin d’éliminer les traces de micropolluants tandis que les membranes d’UF assurent une qualité d’eau produite excellente et constante au cours du temps. Cependant, les retours d’expérience montrent une dégradation des performances de séparation liée notamment à un vieillissement des matériaux membranaires ainsi qu’une vulnérabilité du procédé vis-à-vis de certains micropolluants émergents tels que les composés organiques polaires (PMOCs). Les travaux réalisés au cours de cette thèse visent à mieux comprendre les conséquences du vieillissement chimique des membranes utilisées dans ces procédés et d’évaluer l’efficacité d’élimination de micropolluants afin de proposer des voies d’optimisation. Plus particulièrement il a été montré que la cause principale de vieillissement est l’exposition au chlore des membranes durant les phases de lavage modifiant les propriétés des matériaux. En effet, les nombreux outils de caractérisation utilisés ont permis de mettre en évidence une corrélation entre la dégradation de l’agent hydrophile des membranes et l'augmentation de la perméabilité lors de l'exposition au chlore. L’étude des performances membranaires a mis en évidence une altération de la résistance au colmatage vis-à-vis de la MO pour les membranes exposées au chlore. Cependant les résultats obtenus pour évaluer les performances de sélectivité des membranes vis-à-vis de virus n’ont pas souligné d’altérations majeures. Les essais d’adsorption ont démontré l’efficacité limitée du CAP pour la rétention des PMOCs. En effet, parmi les molécules testées, les molécules aromatiques les plus hydrophobes sont efficacement adsorbées par le CAP tandis que les plus polaires sont peu éliminées. Finalement, l’utilisation de la nanofiltration ou l’osmose basse pression, présentant des taux de rétention en moyenne supérieurs à 90%, en font des solutions techniques de choix pour l’élimination des PMOCs. / The degradation of water resources by the presence of organic matter (OM) and micropollutants requires the implementation of robust drinking water production processes. In this context, many French municipalities such as Saint Cloud and Angers have decided to set up a powdered activated carbon adsorption process coupled to ultrafiltration (PAC/UF). PAC is used upstream of membranes to remove traces of micropollutants while UF membranes provide excellent and constant water quality over time. However, the feedback reveals a degradation of the separation performances related in particular to an aging of the membrane materials and a vulnerability of the process towards some emerging micropollutants such as polar organic compounds (PMOCs).The work carried out during this thesis aims to better understand the consequences of the chemical aging of the membranes used in these processes and to evaluate the micropollutants removal efficiency in order to propose optimization ways. More particularly it has been shown that the main cause of aging is the chlorine exposure of the membranes during washing phases modifying the properties of the materials. In fact, the numerous characterization tools used have made it possible to demonstrate a correlation between the degradation of the hydrophilic agent of the membranes and the increase in the permeability during exposure to chlorine. The study of the membrane performances revealed an alteration of the resistance to fouling towards OM for membranes exposed to chlorine. However, the results obtained to evaluate the selectivity performance of the membranes with respect to viruses have not underlined any major alterations. Adsorption tests have demonstrated the limited efficiency of PAC for PMOCs removal. Indeed, among the molecules tested, the most hydrophobic and aromatic molecules are effectively adsorbed on PAC while the more polar ones are slightly adsorbed. Finally, the use of nanofiltration or low-pressure reverse osmosis, with average rejection rates over 90%, makes them the technological solutions of choice for the removal of PMOCs.

[pt] A escassez de recursos de água doce está ameaçando nossa sociedade. A urbanização, a industrialização, o crescimento populacional e as alterações climáticas estão a representar um grande desafio para a segurança dos recursos hídricos humanos. Com base nessa situação crítica, os cientistas estão prestando cada vez mais atenção à dessalinização. Os métodos tradicionais de dessalinização empregam o processo de destilação. Esses métodos desempenham um papel importante no serviço de abastecimento de água em alguns locais carentes de água. No entanto, devido ao alto consumo de energia desses métodos, o preço da água produzida é elevado. Portanto, desenvolver novas tecnologias de dessalinização com baixo consumo de energia é de grande interesse e uma delas tem atraído a atenção dos pesquisadores, que é a osmose reversa (OR). O RO utiliza a membrana semipermeável como filtro, o que permite que a água ou moléculas relativamente pequenas passem por si mesmas, mas impede que as grandes moléculas ou íons penetrem. Esta tecnologia reduziu significativamente o consumo de energia em comparação com os métodos de destilação e rapidamente ocupa mais de 60 por cento da capacidade total de dessalinização instalada. O desempenho da tecnologia RO depende fortemente do material das membranas desempenha um papel importante. Nas últimas décadas, polímeros, por exemplo, poliamida e acetato de celulose, dominaram a indústria de RO de membrana semipermeável por sua boa eficiência de rejeição de sal e baixo custo de consumo de energia. No entanto, mesmo com as vantagens das membranas poliméricas, o custo final da água produzida ainda é alto. É por isso que os recursos de água doce ainda continuam sendo a preocupação. Desde a primeira vez que o grafeno foi produzido a partir do grafite, chamou a atenção de pesquisadores em todo o mundo por sua estrutura 2D ultrafina, excelente condutividade e transparência etc. Logo depois, o grafeno e seus derivados, como óxido de grafeno e óxido de grafeno reduzido, exibem potencial na dessalinização devido à sua estrutura 2D fina e expansibilidade. Este trabalho explora a possibilidade de aplicação de derivados de grafeno em um processo de dessalinização relativamente prático. No prsente projeto foram produzidos tanto GO (pelo método de Hammer) e RGO (a partir de aquecimento em atmosfera inerte) e de membranas a partir de acetato de celulose com GO e RGO. Ensaios de dessalinação também foram realizados para amostras produzidas variando de modo sistemático diferentes parâmetros de síntese de GO e RGO e de fabricação das membranas de acetato de celulose. / [en] Fresh-water resource scarcity is threatening our society. Urbanization, industrialization, population growth and climate change are making big challenge to human s water resource security. Based on this critical situation, scientists are paying more and more attention to desalination. Traditional desalination methods employ distillation process. These methods play an important role in water supply service in some water-lacked places. However, due to high energy consumption of these methods, the price of produced water is very high. Therefore, developing new desalination technologies with low energy consumption is of high interest and one of them has attracted researchers attention, which is reverse osmosis (RO).(1) RO utilizes the semi-permeable membrane as a filter, which allows the water or relatively small molecules pass through itself, but prevents the large molecules or ions from penetrate. This technology significantly reduced the energy consumption compared to the distillation methods and quickly takes more than 60 percent of the total installed desalination capacity.(2) The performance of RO technology strongly depends on the material of membranes plays an important role. In the past decades, polymers, for instance polyamide and cellulose acetate, dominate the semi-permeable membrane RO industry for their good salt rejection efficiency and low cost of energy consumption. However, even with the advantages of polymer membranes, the final cost of produced water is still high. That s why fresh-water resource still remain the concern. Since the first time that graphene was produced from graphite, it caught researcher’s attention all over the world for its ultra-thin 2D structure, excellent conductivity and transparency, etc. Soon after, graphene and its derivatives, such as graphene oxide and reduced graphene oxide, exhibit potential in desalination due to their thin 2D structure and expandability.(3) This work explores the possibility of application of graphene derivatives in a relatively practical desalination process. In the present project, GO (by the Hammer method), RGO (from heating in air atmosphere) and cellulose acetate membranes with GO and RGO were produced. Desalination tests were also performed for samples produced by systematically varying different parameters of GO, RGO and fabrication of cellulose acetate membranes.

Cette thèse porte sur le développement d’un capteur plasmonique intégrant une fonction d’actuation des objets visés. L’objectif est de passer outre la limite de diffusion rencontrée à basse concentration en piégeant les particules sur la surface de détection. La stratégie adoptée est de structurer le film d’or servant à la détection de manière à pouvoir l’utiliser pour mettre en mouvement le fluide et les molécules par le biais de champs électriques. Le transfert de masse est réalisé par diélectrophorèse et électroosmose, deux effets électrocinétiques mis en oeuvre par des électrodes servant à la fois d’actuateur et de capteur plasmonique. Un état de l’art exhaustif et des simulations multiphysiques ont permis de concevoir un prototype de capteur intégré constitué d’électrodes interdigitées en or permettant la détection plasmonique. Le dispositif proposé a été obtenu par microfabrication en salle blanche puis caractérisé avant l’étude de ses performances. Une première phase de tests sur un système modèle, des billes de polystyrène dans de l’eau, a permis d’apporter la preuve de concept du fonctionnement du capteur, qui est effectivement capable de piéger rapidement les objets visés à sa surface afin de les détecter. Les mécanismes de transfert de masse ont été expliqués et la preuve de l’amélioration de la limite de détection par un facteur supérieur à 100 a été apportée. Dans un second temps, les performances du capteur appliqué à des objets biologiques ont été évaluées. Celui-ci piège efficacement des levures et des protéines, mais aucune amélioration n’a été observée dans le cas de la détection spécifique de l’hybridation entre deux brins d’acide désoxyribonucléique (ADN). Les causes de ce résultat ont été discutées et comprises et deux solutions différentes ont été explorées : l’adaptation de la fréquence d’opération et l’optimisation de la géométrie des électrodes. Ainsi, cette étude a permis de souligner la problématique de la mise en oeuvre d’effets électrocinétiques dans des milieux biologiques et de réfléchir aux pistes pertinentes pour sa résolution. / This thesis focuses on the development of an integrated plasmonic sensor capable to perform mass transport on targeted objects. The goal is to overcome the diffusion limit by trapping particules directly on the sensing surface. The adopted strategy was to structure the gold layer used for plasmonic detection in order to use the sofabricated structures to set the fluid and the molecules in motion by applying electric fields in the fluid. The mass transfer is realized through dielectrophoresis and electroosmosis, those two electrokinetic effects being operated by electrodes acting as sensor and actuator at the same time. An exhaustive state of the art as well as multiphysical simulations allowed us for designing a prototype for an integrated sensor consisting in gold interdigitated electrodes enabling plasmoninc sensing. The proposed device was obtained through microfabrication in clean room facilities and was characterized before the study of its performances. A first sequence of tests on a model system – polystyrene microbeads in water – brought the proof of concept we needed to validate the correct operation of the sensor, which is indeed capable of quickly trapping targeted objects on its surface and detecting them. The mass transfer mechanisms were explained and we showed the enhancement of the limit of detection by a factor greater than 100. In a second phase, performances of the sensor applied to biological objects were evaluated. It can effectively trap yeasts and proteins but no enhancement has been observed while detecting DNA hybridization events. Causes for this result were discussed and understood and two different solutions were explored: the adaptation of the operating frequency and the optimization of the electrodes geometry. Thus, this study highlighted the problematic of operating electrokinetic effects in biological media and suggested relevant leads towards its resolution.

L'objectif de cette recherche est l'étude du transfert d'eau en phase liquide dans les parois du bâtiment et de définir une nouvelle métrologie pour déterminer le coefficient de perméabilité liquide des matériaux du bâtiment. Une partie théorique fait l'état des connaissances en matière de modélisation du transfert d'eau en phase liquide. Elle est suivie par une partie qui relate les méthodes utilisées pour mesurer ou imposer des pressions capillaires (ou succions) avec un intérêt particulier à la méthode osmotique qui est utilisée plus tard pour imposer des conditions aux limites en terme de succion. Cette dernière partie s'ouvre sur une revue des méthodes de mesure de la perméabilité liquide et sera conclue par la définition et la mise au point d'une nouvelle méthode de mesure de la perméabilité liquide, qui a fait l'objet d'un dépôt de brevet d'invention, s'appuyant sur la méthode osmotique et qui fonctionne en régime permanent, mesurant les débits entrant et sortant de l'échantillon. Une campagne d'essais est menée sur du béton cellulaire autoclave avec différents couples de conditions aux limites. Il s'ensuit une recherche d'identification d'une relation entre la perméabilité liquide et la succion, démarche qui mérite plus d'approfondissement. Finalement cette nouvelle méthode de mesure mérite d'être diffusée, et son caractère opérationnel est manifeste.