This dissertation describes the investigation of the fouling of a reverse osmosis membrane under different operating conditions. A mass transfer model to predict the permeate flux decline is defined. These studies used kaolin clay and bentonite clay as the fouling particles. As the membranes, thin film Low fouling Composite 1 polyamide reverse osmosis flat sheet membranes were used. Baseline experiments using only kaolin in D.I. water were conducted. At an operating pressure of approximately 1,380 kPa, no flux decline was observed. These results established the effects of a membrane-particle interaction. For the fouling experiments with kaolin clay, experiments show a linear relationship between the mass of the deposited foulant layer and total permeate flux decline. The increased concentration of scale forming salts such as calcium chloride and sodium carbonate combined with clay particles has been found to increase flux decline. It also leads to the formation of a less porous cake layer on the membrane surface, which may be due to the particle surface charge. The increase in transmembrane pressure leads to the formation of a well compacted, less porous, cake layer on the membrane surface. The reduced porosity results in the deterioration of the permeate quality, which is a direct result of reduced back diffusion of the salt solution.A fouling model that combines a resistance-in-series model and a simplified-mass-transport relationship were used to predict the transient stage permeate flux of a reverse osmosis membrane. This model contains a constant which is a function of the operating condition and the ionic species in the feed solution. It was found that the results from the model agreed with the experimental results.

Les recherches menées au cours de cette thèse constituent une première étape de développement de méthodes expérimentales de concentration de nanoparticules à l'aide de composants micro-nanofluidiques. L'objectif principal est donc d'explorer différentes architectures de systèmes micro-nanofluidiques où l'étape de concentration est effectuée par effet d'exclusion stérique et/ou ionique sous l'application d'un champ de pression et/ou électrique. Une attention toute particulière a été portée sur les méthodes de caractérisation, comprenant notamment les méthodes de particule Tracking Micro-PIV et de microscopie par fluorescence pour mesurer la répartition en nanoparticules et quantifier les facteurs de concentration. Le premier axe concerne la concentration de nanoparticules dans des architectures de type « Bypass ». Dans le cas de la filtration stérique, une modélisation par méthode de différence finie permet de prédire l'apparition d'une zone localisée où la concentration est d'une centaine à un millier de fois plus élevée que la concentration initiale après une heure d'opération. Des composants micro-nano fluidique en silicium ont été réalisés afin de mener une étude paramétrique. En accord avec le modèle proposé, cette étude montre que le nombre de Peclet est le paramètre déterminent dans le choix du design et des conditions d'expérimentations optimums. Concernant la préconcentration par effet électrocinétique, les expérimentations ont essentiellement consisté à explorer le phénomène d'ICP (Ion Concentration Polarisation) et d'appliquer cette technique pour la concentration de nanoparticules. Enfin le type de géométries « Bypass » a été testé sous différentes conditions. Ainsi, le couplage avantageux de phénomènes électro-hydrodynamiques tel que le « streaming potentiel » permet d'ouvrir la voie à des systèmes de préconcentration à actionnements manuels, rapides et très simples d'utilisation. Le deuxième axe d'étude est quant à lui dédié à la conception et l'utilisation de configuration micro-nanofluidique plus originales. Y sont notamment étudiés des systèmes à configuration radial offrant une meilleure stabilité lors des étapes de préconcentration électrocinétiques. Sur la base des performances et limitations des différents systèmes micro-nanofluidiques réalisés, le dernier chapitre est une mise en perspective des champs d'applications potentiels, notamment pour les laboratoires sur puces. / The researches conducted during this thesis consist in a first step for the development of experimental methods applied to the concentration of nanoparticles using micro-nanofluidic devices. The main aim is to explore different system architectures where the préconcentration step are achieved using steric and/or ion exclusion under the influence of a pressure and/or electric field. A special attention is directed toward the characterization methods including Micro-Particle Image Velocimetry micro-PIV and fluorescent microscopy to measure the nanoparticles repartition and to quantify the concentration folds. The first axis deals with the preconcentration of nanoparticles within « Bypass » like architectures. Concerning the steric filtration, a theoretical model using finite element method allows to predict the rising of a located preconcentration zone where the local concentration is enhanced 1000 fold as compared to the initial concentration after 1h of concentration operation. Silicon Micro-nanofluidic devices were fabricated in order to conduct a parametric study. According to the proposed theoretical model, this study shows that the Peclet number is a key parameter to choose the optimal design and experimental conditions. Concerning the electrokinetic preconcentration, the experiments mainly consisted in exploring the ICP phenomenon (Ion Concentration Polarization) and in using this technic to preconcentrate nanoparticles. Finally the Bypass geometry was tested in many conditions. Thus, the advantageous coupling of electro-hydrodynamic phenomena such as the so called “streaming potential” opens new ways to fast, simple and manual preconcentration systems suitable for LOC applications. The second axis is dedicated to the conception and utilization of original micro-nanofluidic configurations. Will also be studied radial micro-nanofluidic devices offering better stability during electrokinetic preconcentration. On the basis of the performances and limitations inherent to each systems, the last chapter will focus on the potential applications relative to LOC.

Currently, the most utilized desalination technology is reverse osmosis (RO), where a membrane is used as a physical barrier to separate the salts from the seawater, using high hydraulic pressure as driving force. A major problem in RO systems is biofouling, caused by severe growth of bacterial biofilms. Both, the need of an external energy input, as well as biofouling, impose a high cost on RO operation. Forward osmosis (FO) is an alternative membrane process that uses an osmotic pressure difference as driving force. FO uses a concentrated draw solution to generate high osmotic pressure, which extracts water across a semi permeable membrane from a feed solution. One of the main advantages of FO is the limited amount of external energy required to extract water from the feed solution. The objective of this research is the assessment of the impact of spacers, separating the membrane sheets, and biofouling on the FO system performance. This type of studies allow the optimization of membrane devices and operational conditions. For this, a two dimensional numerical model for FO systems was developed using computational fluid dynamics (CFD). This model allowed the evaluation of the impact of (i) spacers and (ii) biofilm, and (iii) the combined impact of spacers and biofilm on the performance of FO systems. The results obtained showed that the presence of spacers improved the performance of FO systems. Cavity configuration spacer gave the higher water flux across the membrane in clean systems; whereas for biofouled systems, the submerged configuration showed a better performance. In absence of spacers, the thickness or amount of biofilm is inversely proportional with the water flux. Furthermore, membrane surface coverage of the biofilm is more important than the amount of biofilm in terms of the impact on the performance. The numerical model can be adapted with other parameters (e.g. membrane and spacer thickness, feed and draw solution, solution concentration, etc.) to predict the impact of biofilm on FO systems under different experimental conditions. The use of numerical modeling may contribute to faster development of economic viable FO based desalination systems.

Submitted by Maria Medeiros (maria.dilva1@ufcg.edu.br) on 2018-10-17T14:32:29Z No. of bitstreams: 1 DANIEL SILVEIRA LIRA - DISSERTAÇÃO (PPGEQ) 2018.pdf: 2803681 bytes, checksum: 57ec3900710d6a6bdb50e2ac6a6a1f79 (MD5) / Made available in DSpace on 2018-10-17T14:32:29Z (GMT). No. of bitstreams: 1 DANIEL SILVEIRA LIRA - DISSERTAÇÃO (PPGEQ) 2018.pdf: 2803681 bytes, checksum: 57ec3900710d6a6bdb50e2ac6a6a1f79 (MD5) Previous issue date: 2018-04-25 / Capes / As indústrias têxteis são, em geral, grandes consumidoras de água, devido principalmente a seus processos de tingimento de tecidos, consequentemente, as indústrias têxteis se apresentam como grandes geradoras de efluentes. A esses efluentes, estão associadas grande número de produtos químicos, dentre estes produtos, podem-se destacar os corantes, que conferem à água cor indesejável, além de contribuir com o aumento da DBO e DQO do efluente. O índigo é um corante comumente utilizado nas indústrias têxteis, principalmente no tingimento de tecidos de jeans e brim. Dentre os processos de tratamento utilizados para realizar a separação do índigo da água, podem ser destacados os processos de separação por membrana, que são um processo físico de separação baseado na utilização de uma barreira semipermeável para separar os componentes. Um dos problemas mais comuns do processo de membranas é a formação de uma camada de polarização de concentração. Este trabalho teve o objetivo de estudar o processo de separação da água-índigo utilizando membranas. Para isto foi realizado um estudo de malha utilizando o método do Índice de convergência de malha, além de, definir um modelo fluidodinâmico baseado em uma abordagem de mistura multicomponente para estudar os fenômenos de transferência de massa. Além disso, foi utilizado o modelo das resistências-em-série para simular a formação da camada limite de polarização da concentração. As malhas foram geradas utilizando o software ICEM CFD 15.0, já as simulações foram feitas utilizando pacote computacional Ansys CFX 15.0, também foi desenvolvido código em VBA para determinação da espessura da camada limite de concentração. Tendo como base os resultados do ICM, foi escolhida uma malha com 87759 elementos para seguir o estudo fluidodinâmico da membrana. Já o estudo fluidodinâmico concluiu que as variáveis número de Reynolds e pressão influenciaram o comportamento da camada de polarização de concentração, já a variável concentração de soluto na alimentação não influenciou de forma significativa. / The textile industries are, in general, major water consumers, mainly due to their garment dyeing processes, consequently, the textile industries are presented as great effluent generators. These effluents are associated with a great quantity of chemical products, within these products, the dyes stand out, which confer to the water an undesirable color, besides contributing to the increase of BOD and COD of the effluent. The indigo dye is a commonly used dye in the textile industry, mainly for the coloring of jeans and denim garments. From the water treatment processes used to separate indigo from water, the membrane separation processes can be highlighted, these comprise physical separation process’ based on the use of a semipermeable barrier to separate the components. One of the major problems in the membrane separation processes is the formation of a concentration polarization layer. This work had the aim to study the indigo-water separation process using membranes. For so, a grid convergence study was realized, in addition to defining a fluid dynamical model based on a multicomponent mixture approach to study the mass transfer phenomena. Also, the resistance-in-series model was used to simulate the formation of the concentration polarization layer. The grids were generated using the software ICEM CFD 15.0, while the simulations were done using the computational package Ansys CFX 15.0, also, a VBA code was developed do determine the thickness of the concentration boundary layer. Results showed that, based on the Grid Convergence Index, a grid with 87759 elements was chosen to follow through with the study. While the fluid dynamics study concluded that the Reynolds number and outlet pressure variables influenced on the behavior of the concentration polarization layer, however, the inlet solute concentration variable did not influence in a significant manner.

Os efluentes contendo cádmio podem ser gerados dos por várias indústrias. A aplicação de ambas as tecnologias osmose inversa (OI) e nanofiltração (NF) para o tratamento de efluentes contendo o íon cádmio para reduzir a degradação ambiental foram estudadas no presente trabalho. Amostras sintéticas contendo o íon cádmio em várias concentrações foram preparadas e submetidas aos tratamentos por OI e NF em escala laboratorial. Assim, dividiu-se o processo de remoção em três etapas: 1- analisou-se os processos de osmose inversa e nanofiltração em termos da rejeição do íon cádmio, onde se correlacionou e avaliou os principais parâmetros de processos (concentração da solução alimentação, fluxo de permeado e pressão) e comparou-se os sistemas entre si. Nas etapas 2 e 3 avaliou-se os efeitos da salinidade utilizando os contra-íons zinco e sódio respectivamente, sobre a rejeição do íon cádmio no sistema de osmose inversa em soluções aquosas contendo misturas de sulfato de cádmio e sulfato de zinco, e sulfato de cádmio e sulfato de sódio. Mediu-se as concentrações de cádmio e zinco por espectroscopia de absorção atômica e as concentrações de sulfato e sódio por cromatografia de íons. Os resultados obtidos na primeira etapa dos experimentos mostram que a osmose inversa e nanofiltração são eficientes na remoção de cádmio, onde se obteve as taxas médias de rejeição de 92,4% e 96,6% respectivamente, sendo esses valores iguais em magnitude, tendo em vista os valores da incerteza padrão relativa associada a esses resultados. Em ambos os sitemas, os fluxos de permeado e as rejeições não sofreram influência do aumento da concentração de cádmio na solução alimentação.Na etapa 2, os resultados mostraram a diminuição da rejeição de cádmio com o aumento da concentração de sulfato de zinco na alimentação, sendo esse fenômeno atribuído a semelhança existente entre os íons Cd2+ e Zn2+ associados aos seus raios iônicos de hidratação e as energias de hidratação. Foram observadas as quedas do fluxo de permeado e das rejeições com o aumento da concentração de alimentação provavelmente devido ao efeito da polarização. Na etapa 3, a rejeição do íon cádmio não foi afetada pelo aumento da concentração de sulfato de sódio na alimentação, assim como os fluxos de permeado. Outro aspecto relacionado à rejeição é que a difusão do sódio através da membrana é favorecida frente à difusão do cádmio, sendo atribuído ao menor raio de hidratação do sódio / Effluents containing cadmium may be produced by a variety of industries. The application of the reverse osmosis and nanofiltration technologies for the treatment of effluents containing cadmium, in order to reduce environmental degradation, were studied in the present work. Synthetic samples containing the cadmium ion in different concentrations were prepared and treated by reverse osmosis and nanofiltration. The removal process was divided in three steps: 1- the reverse osmosis and nanofiltration processes were analyzed concerning the rejection of the cadmium ion, correlating and evaluating the main process parameters (feeding solution concentration, permeated flow and pressure), and comparing the systems between themselves. In steps 2 and 3, the effects of salinity in the elimination of the cadmium ion in aqueous solutions, containing a combination of cadmium sulfate and zinc sulfate, or a combination of cadmium sulfate and sodium sulfate, were assessed by the use of zinc and sodium counterions. The concentrations of cadmium and zinc were measured by atomic absorption spectroscopy, and the concentrations of sulfate and sodium were measured by ion chromatography. The results obtained in the first step of the experiments show that the reverse osmosis and the nanofiltration processes are efficient in removing cadmium, with an average rejection rate of 92,4% and 96,6%, respectively. Considering the standard relative incertitude associated to the results, the values obtained are considered of the same magnitude. In both systems, the permeated flow and the rejects were not influenced by a rise in cadmium concentration in the feeding solution. In step 2, the results showed a decrease in cadmium rejection related with a rise in the zinc sulfate concentration in the feeding solution. This phenomenon is due to the similarity between the Cd2+ and Zn2+ ions, associated to their hydration ionic radius and to their hydration energies. A decrease in the permeated flow and of the rejects related to a rise in the feeding concentration was observed and was probably due to the polarization effect. In step 3, the cadmium ion rejection was not affected by a sodium sulphate concentration rise in the feeding, as well as in the permeated flow. Another aspect related to the rejection is that, due to its smaller hydration radius, sodium has a better diffusion rate through the membrane than cadmium

Os efluentes contendo cádmio podem ser gerados dos por várias indústrias. A aplicação de ambas as tecnologias osmose inversa (OI) e nanofiltração (NF) para o tratamento de efluentes contendo o íon cádmio para reduzir a degradação ambiental foram estudadas no presente trabalho. Amostras sintéticas contendo o íon cádmio em várias concentrações foram preparadas e submetidas aos tratamentos por OI e NF em escala laboratorial. Assim, dividiu-se o processo de remoção em três etapas: 1- analisou-se os processos de osmose inversa e nanofiltração em termos da rejeição do íon cádmio, onde se correlacionou e avaliou os principais parâmetros de processos (concentração da solução alimentação, fluxo de permeado e pressão) e comparou-se os sistemas entre si. Nas etapas 2 e 3 avaliou-se os efeitos da salinidade utilizando os contra-íons zinco e sódio respectivamente, sobre a rejeição do íon cádmio no sistema de osmose inversa em soluções aquosas contendo misturas de sulfato de cádmio e sulfato de zinco, e sulfato de cádmio e sulfato de sódio. Mediu-se as concentrações de cádmio e zinco por espectroscopia de absorção atômica e as concentrações de sulfato e sódio por cromatografia de íons. Os resultados obtidos na primeira etapa dos experimentos mostram que a osmose inversa e nanofiltração são eficientes na remoção de cádmio, onde se obteve as taxas médias de rejeição de 92,4% e 96,6% respectivamente, sendo esses valores iguais em magnitude, tendo em vista os valores da incerteza padrão relativa associada a esses resultados. Em ambos os sitemas, os fluxos de permeado e as rejeições não sofreram influência do aumento da concentração de cádmio na solução alimentação.Na etapa 2, os resultados mostraram a diminuição da rejeição de cádmio com o aumento da concentração de sulfato de zinco na alimentação, sendo esse fenômeno atribuído a semelhança existente entre os íons Cd2+ e Zn2+ associados aos seus raios iônicos de hidratação e as energias de hidratação. Foram observadas as quedas do fluxo de permeado e das rejeições com o aumento da concentração de alimentação provavelmente devido ao efeito da polarização. Na etapa 3, a rejeição do íon cádmio não foi afetada pelo aumento da concentração de sulfato de sódio na alimentação, assim como os fluxos de permeado. Outro aspecto relacionado à rejeição é que a difusão do sódio através da membrana é favorecida frente à difusão do cádmio, sendo atribuído ao menor raio de hidratação do sódio / Effluents containing cadmium may be produced by a variety of industries. The application of the reverse osmosis and nanofiltration technologies for the treatment of effluents containing cadmium, in order to reduce environmental degradation, were studied in the present work. Synthetic samples containing the cadmium ion in different concentrations were prepared and treated by reverse osmosis and nanofiltration. The removal process was divided in three steps: 1- the reverse osmosis and nanofiltration processes were analyzed concerning the rejection of the cadmium ion, correlating and evaluating the main process parameters (feeding solution concentration, permeated flow and pressure), and comparing the systems between themselves. In steps 2 and 3, the effects of salinity in the elimination of the cadmium ion in aqueous solutions, containing a combination of cadmium sulfate and zinc sulfate, or a combination of cadmium sulfate and sodium sulfate, were assessed by the use of zinc and sodium counterions. The concentrations of cadmium and zinc were measured by atomic absorption spectroscopy, and the concentrations of sulfate and sodium were measured by ion chromatography. The results obtained in the first step of the experiments show that the reverse osmosis and the nanofiltration processes are efficient in removing cadmium, with an average rejection rate of 92,4% and 96,6%, respectively. Considering the standard relative incertitude associated to the results, the values obtained are considered of the same magnitude. In both systems, the permeated flow and the rejects were not influenced by a rise in cadmium concentration in the feeding solution. In step 2, the results showed a decrease in cadmium rejection related with a rise in the zinc sulfate concentration in the feeding solution. This phenomenon is due to the similarity between the Cd2+ and Zn2+ ions, associated to their hydration ionic radius and to their hydration energies. A decrease in the permeated flow and of the rejects related to a rise in the feeding concentration was observed and was probably due to the polarization effect. In step 3, the cadmium ion rejection was not affected by a sodium sulphate concentration rise in the feeding, as well as in the permeated flow. Another aspect related to the rejection is that, due to its smaller hydration radius, sodium has a better diffusion rate through the membrane than cadmium

La prédiction des performances des séparations membranaires barométriques, fortement affectées par la polarisation de concentration, serait une avancée importante pour le dimensionnement et l’optimisation des procédés. Dans ce contexte, les équations couplées de Navier-Stokes et de conservation du soluté adimensionnées sont résolues numériquement dans le cas d’un écoulement stationnaire laminaire en filtration tangentielle. Le canal plan bidimensionnel comporte des parois perméables soumises à des conditions aux limites du type solubilisation-diffusion. Le flux de perméat, le taux de rétention et le débit, la concentration et la chute de pression du rétentat sont déterminés localement. Les simulations soulignent l’influence des perméabilités membranaires au soluté et au solvant sur la polarisation de concentration et la dépendance non-asymptotique du taux de rétention avec la pression appliquée. Le modèle est validé pour des modules plans et spiralés d’osmose inverse et de nanofiltration dense en comparant les calculs à des résultats expérimentaux tirés de la littérature et de nos propres essais pilotes de dessalement. Aussi, une méthode à l’échelle de la paillasse permettant de déterminer les perméabilités au soluté et au solvant par des expériences d’osmose et diffusion est développée et appliquée à des membranes d’osmose inverse et de nanofiltration. La divergence des mécanismes de transfert engendrés sous l’influence de la pression ou sous l’influence d’un gradient osmotique est mise en évidence. Le modèle numérique et la méthode expérimentale sont des outils prometteurs d’applicabilité immédiate dans le domaine des membranes. / The prediction of the performance of pressure-driven membrane separations, deeply affected by concentration polarization, would be an important advance for process design and optimization. In this context, the dimensionless coupled Navier-Stokes and solute conservation equations are solved numerically for a steady laminar cross-flow filtration. The two-dimensional flat channel consists of permeable walls subject to solution-diffusion boundary conditions. The permeate flux, the rejection rate and the retentate’s flow rate, concentration and pressure drop are determined locally. The simulations highlight the influence of the membrane solute and solvent permeabilities on concentration polarization and the non-asymptotic dependence of the rejection rate on the applied pressure. The model is validated for reverse osmosis and tight-nanofiltration plate-and-frame and spiral-wound modules by comparison to experimental results from the literature and from our own pilot desalination tests. Furthermore, a bench-scale method enabling the determination of solute and solvent permeabilities from osmotic-diffusive experiments is developed and applied to reverse osmosis and nanofiltration membranes. The divergence between the transport mechanisms engendered by pressure and by an osmotic gradient is evidenced. The numerical model and the experimental method are new promising tools with immediate applicability in the membrane field.

Fouling in a nanofitration membrane module is usually a result of concentration polarization. The effect of permeate suction on the slightly negatively charged spiral wound nanofiltration membrane is investigated. According to the film theory, the mass transfer coefficient is inversely proportional to concentration polarization. The effect of permeate suction destabilizes the boundary layer. This will decrease the concentration polarization layer, and consequently will increase mass transfer through the membrane's surface. To validate the hypothesis, experiments were carried out on a NF membrane that can be described by the solution-diffusion model. This model has coefficients that can be measured experimentally. Using the membrane wall concentration in this model instead of the bulk feed concentration can help estimating the mass transfer coefficient more appropriately. Two experimental studies were carried out, one with a standard high pressure pump, and another one with the added effect of suction pressure applied to the permeate collector tube. Three different concentrations of binary dilute solutions of NaCl, MgSO4, and MgCl2, at three different pressures (low, medium, and high) were tested. For all tested solutions, permeate suction increased the diffusive Peclet number as a function of the feed concentration (x) according to the equation Pe = a1x²+b1x+c1, with R²>0.99, where x is the feed concentration in Mol/l, and a1, b1, and c1 are coefficients dependent on feed pressure for every salt solution. With the increase of the Peclet number, it was observed that the concentration polarization decreased, and both the product flow and the product quality were improved. Suction had the greatest impact at the range of 100 to 110 psi feed pressure, where the concentration polarization reduced approximately 14 to 20 %. ANOVA for the concentration polarization showed that suction was significant in reducing the calculated concentration polarization layer for all tested solutions. It was concluded that permeate suction reduced concentration polarization, increased product flow rate, and improved product quality. Thus, adding permeate suction has beneficial consequences because it reduces membrane fouling and extends its useful service life.

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