In this study, membranes were made from three polyvinylidene fluoride (PVDF) polymers individually and the blend systems of high (H) and low (L) molecular weight PVDF by phase inversion process. After investigating membrane casting solutions’ viscous and thermodynamic properties, the membranes so fabricated were characterized by scanning electron microscopy, gas permeation tests, porosity measurement, contact angle (CA) and liquid entry pressure of water (LEPw) measurement, and further subjected to vacuum membrane distillation (VMD) in a scenario that was applicable for cooling processes, where the feed water temperature was maintained at 27℃. It was found that PVDF solutions’ viscosities and thermodynamic instabilities were determined by the types of PVDF employed in single polymer systems and the mixing ratios of two PVDF polymers in blend systems. Thus the membrane properties and performances were influenced by the aforesaid factors as well. In single polymer systems, it was found that the membrane surface roughness and porosity increased with an increase in molecular weight. Among all the membranes casted in this study, the water vapor flux of VMD was found to be the highest at the intermediate range of H:L ratio, i.e., 4:6, at which the thickness of the sponge-like layer showed a minimum, the finger-like macro-voids formed a more orderly single-layer structure, and the LEPw showed a minimum. A conclusion can be made that blend systems of high molecular weight PVDF polymers and low molecular weight PVDF polymers could be used to optimize membrane performance in vacuum membrane distillation.

In this research, a heat localizing solar thermal membrane distillation system has been developed for producing potable water from untreated surface water, wastewater, and seawater, using solely solar thermal energy. Unlike most other membrane technologies, this system requires no electrical power or equipment for its operation. The high production rate was achieved through the effective evaporation of water molecules within the pores of the membrane without dissipating much heat to the bulk feed water. It can remove suspending particles, microorganisms, inorganic salts, as well as organic contaminants from the feed water. The system can produce potable water for 32, 18, and 10 days on average under simulated sunlight when distilling seawater, canal water, and municipal wastewater, respectively, without cleaning the membrane. Low cost, high energy efficiency (i.e., 55%), and good water quality make the new system feasible for undeveloped areas where basic water treatment is lacking. / Includes bibliography. / Thesis (M.S.)--Florida Atlantic University, 2019. / FAU Electronic Theses and Dissertations Collection

Water scarcity is among the most serious, long-term challenges in the world. To an ever increasing degree, sustainable water supply depends on the utilization of water of impaired initial quality. This is particularly true in developing nations and in water-stressed areas such as the American Southwest. Water of impaired quality could be water of high salinity such as brackish groundwater. Traditionally, reverse osmosis (RO) would be chosen to desalinate the brackish groundwater, since RO costs are competitive with those of thermal desalination, even for seawater applications. However, both conventional thermal distillation and RO are energy intensive, complex processes that discourage decentralized or rural implementation. In addition, both technologies require enhanced expertise for operation and maintenance, and are susceptible to scaling and fouling unless extensive feed pretreatment is employed. Membrane distillation (MD), driven by vapor pressure gradients, can potentially overcome many of these drawbacks. MD can operate using low-grade, sub-boiling temperature heat sources. When it is driven by solar energy it does not require highly concentrating collection devices, non-aqueous working fluids, or complex temperature control systems, nor does it require extensive operational expertise. Membrane Distillation (MD) applications, background and modeling efforts are discussed in the first part of this dissertation. Two main studies are presented in this document: Firstly, Sweeping Gas Membrane Distillation (SGMD) through a hollow fiber membrane was studied both experimentally and modeled mathematically to describe performance of SGMD and extend results to predict membrane module efficiency and secondly, SGMD through a flat sheet MD module to study the effect of membrane characteristics in combination with operational variables. A final study was conducted to examine the effect of mesh spacer insertion in flat sheet membrane module on the permeate water production.

Water scarcity is one of the biggest issues we have to face as population and water consumption levels increase despite a fixed supply of renewable fresh water. Meeting the challenges that water scarcity poses to food production, ecosystem health, and political and social stability will require new approaches to using and managing water. Desalination already plays an essential role in water management. It constitutes a secure source of safe drinking water supply once demand management measures are fully implemented. Overcoming problems related to brine minimization and disposal is key to sustainable, efficient inland water desalination. The main focus of this was the investigation of technical limits and improvements for application in inland desalination. The first part of the dissertation covers the study of Membrane Distillation (MD) for desalination of water. The second part provides a broad perspective of Reverse Osmosis (RO), pretreatments -comparison of slow sand filtration and microfiltration-, post-mortem study of membranes to determining fouling and scaling causes, and RO brine minimization via Vibratory Shear Enhance Processing (VSEP®) for use in RO brine minimization. The study of Vacuum Membrane Distillation in a hollow fiber membrane was studied. Experimental work is supported by an original mathematical model to expose the physics of VMD and support predictions that extend VMD results beyond these generated in the laboratory. The advantages and disadvantages of each pretreatment, including their effects the effect on the performance of RO, a post-mortem membrane study and an economic analysis. The post-mortem study of membranes used during Yuma Desalting Plant operation. This work was used to identify the best pretreatment and more suitable membrane to treat saline water in the lower Colorado River. The work performed during the brine minimization study using VSEP®. This study included experimental data and an extensive economic analysis comparing Ion Exchange (IX) as pretreatment and VSEP® as post-treatment for RO.

In this study, membranes were made from three polyvinylidene fluoride (PVDF) polymers individually and the blend systems of high (H) and low (L) molecular weight PVDF by phase inversion process. After investigating membrane casting solutions’ viscous and thermodynamic properties, the membranes so fabricated were characterized by scanning electron microscopy, gas permeation tests, porosity measurement, contact angle (CA) and liquid entry pressure of water (LEPw) measurement, and further subjected to vacuum membrane distillation (VMD) in a scenario that was applicable for cooling processes, where the feed water temperature was maintained at 27℃. It was found that PVDF solutions’ viscosities and thermodynamic instabilities were determined by the types of PVDF employed in single polymer systems and the mixing ratios of two PVDF polymers in blend systems. Thus the membrane properties and performances were influenced by the aforesaid factors as well. In single polymer systems, it was found that the membrane surface roughness and porosity increased with an increase in molecular weight. Among all the membranes casted in this study, the water vapor flux of VMD was found to be the highest at the intermediate range of H:L ratio, i.e., 4:6, at which the thickness of the sponge-like layer showed a minimum, the finger-like macro-voids formed a more orderly single-layer structure, and the LEPw showed a minimum. A conclusion can be made that blend systems of high molecular weight PVDF polymers and low molecular weight PVDF polymers could be used to optimize membrane performance in vacuum membrane distillation.

Desalination has been increasingly adopted over the last decades as an option, and sometimes as a necessity to overcome water shortages in many areas around the world. Today, several thermal and physical separation technologies are well established in large scale production for domestic and industrial purposes.  Membrane distillation is a novel thermally-driven process that can be adapted effectively for water desalination or water treatment in industrial applications, due to its potential lower energy consumption and simplicity. The general objective of this thesis is to contribute to the technical understanding of membrane distillation as a new technology in water treatment for both industrial and drinking water purposes, as a starting point for further improvement. The thesis includes experimental and numerical investigations that highlight some aspects of the technology application and fundamental aspects. In the field of industrial application, an experimental and numerical assessment has been carried out on an Air Gap Membrane Distillation (AGMD) prototype to assess the utilization of the technology in thermal cogeneration plants; in particular, demineralization of water boiler feed water and treating flue gas condensate. The main assessment parameters were water quality and energy consumption. The results from full-scale simulations of a system of 10 m3/hr production capacity,  connected to the district heating network were as follows: 5 to 12 kWh/m3 specific thermal energy consumption, and  0,6 to 1,5 kWh/m3 specific electricity consumption, depending upon the heat source (district heat supply line or low-grade steam). For desalination applications, experimental and simulation work was conducted on an AGMD semi-commercial system as part of the EU MEDESOL project. The aim was to evaluate AGMD performance with saline water of 35 g/l NaCl in order to establish an operation data base for simulation of a three-stage AGMD desalination system. Specific thermal energy consumption was calculated as 950 kWht/m3 for a layout without heat recovery, and 850 kWht/m3 for a layout with one stage heat recovery.  The lack of internal heat recovery in the current MD module means that most of the heat supplied to MD system was not utilized efficiently, so the thermal energy consumption is high. This would mean that a large solar field is needed. In order to analyze the flow conditions in feed flow and cooling channels, CFD was used as tool to analyze a spacer-obstructed flow channel for different types of spacer geometrical characteristics: flow of attack angle, spacer to channel thickness ratio, and void ratio. Velocity profiles, shear stress, and pressure drop were the main assessment criteria. Results show the flow of attack angle has a very minimum effect on the performance of spacers. The effect of spacer to channel thickness ratio was significant in all assessment parameters. Higher void ratios were found advantageous in promoting flow mixing, but resulted in lower sheer stress and hence reduced heat transfer. Physical modifications were implemented on a semi-commercial AGMD prototype to assess experimentally any improvement in its performance. These modifications were mainly focused on reducing the conductive heat transfer losses by modifying the physical support in the air gap that separates the membrane from the condensation surface. In addition, several feed channel spacers were tested and assessed based on their effect in increasing the mass transfer while maintaining or reducing pressure drop. The modifications yielded a two-fold augmentation: slight increase in the distillate mass flow rate (9-11%), and increased thermal efficiency (6%). The pressure drop in the module was reduced by 50% through selecting the appropriate spacer that would achieve the above mass flow rate increase. / QC 20111021

Le présent travail de thèse met l'accent sur divers aspects de la distillation membranaire dans l'objectif de concevoir des procédés de dessalement proches du " zéro effluent liquide ". De manière générale, deux sujets sont discutés en détail: (i) la corrélation entre les caractéristiques de la membrane et les performances du procédé de distillation membranaire (ii) la compréhension et le contrôle de la polarisation thermique en DM. L'analyse de l'état de l'art en distillation membranaire porte notamment sur les progrès dans le développement des membranes, dans la compréhension des phénomènes de transport, les récents développements dans la conception des modules et le colmatage. Des phénomènes annexes et les applications innovantes sont également discutés dans la partie introductive de la thèse. L'effet des conditions de fabrication et de la composition des collodions sur les caractéristiques des membranes et la corrélation entre ces dernières et leurs performances a été discuté dans la section suivante. Il est établi que la morphologie de la membrane joue un rôle crucial dans ses performances pour des applications sur des fluides réels. En outre, on met en évidence que l'impact de la morphologie de la membrane est différente selon que la procédé fonctionne avec une phase liquide froide du côté distillat (Direct Contact Membrane Distillation - DCMD)) ou avec un courant d'air sec ou le vide (Air Gap ou Vacuum Membrane Distillation). Dans une deuxième partie, les aspects théoriques et expérimentaux de la polarisation thermique en distillation membranaire (DCMD) ont également été étudiés. Les phénomènes de polarisation thermique sur une membrane plane ont été étudiés en utilisant une cellule spécialement conçue. L'effet des conditions de fonctionnement et de la concentration de la solution sur la polarisation thermique a été étudié expérimentalement. Nous avons observé que l'augmentation de concentration de la solution favorise la polarisation thermique à cause d'une détérioration de l'hydrodynamique résultante à la surface de la membrane. Certaines techniques actives et passives pour réduire la polarisation thermique et le colmatage en distillation membranaire ont également été examinées dans l'étude cette étude. Nous avons montré que la polarisation thermique peut être considérablement réduite en générant des écoulements secondaires dans le fluide circulant à l'intérieur du canal d'alimentation, donc à l'intérieur de la fibre creuse si c'est cette configuration qui est retenue. Dans la présente étude, l'induction d'un écoulement secondaire a été réalisée en utilisant les fibres torsadées en hélice et une configuration ondulée. En raison de l'amélioration du niveau de polarisation thermique du côté de l'alimentation et du distillat, les géométries de fibres ondulées fournissent des flux et des taux de rendement supérieurs à ceux des autres configurations. La mise en œuvre d'un écoulement pulsé et intermittent pour contrôler la polarisation en distillation membranaire a également été examinée. Notre étude permet de conclure que ces types d'écoulements ont un impact positif sur les taux de rendement et le facteur d'amélioration volumique (gain en flux ramené par rapport à l'augmentation du volume de l'équipement) sans compromis sur le taux de remplissage des carters de fibres creuses. / The current PhD work emphasizes on various aspects of membrane distillation for approaching zero liquid discharge in seawater desalination. In broader sense, two themes have been discussed in detail: (i) correlation between membrane features and their performance in MD (ii) understanding and control of thermal polarization in MD. Introduction and state-of-the-art studies of MD including progress in membrane development, understanding the transport phenomenon, recent developments in module fabrication, fouling and related phenomenon and innovative applications have been discussed in introductory part of the thesis. The effect of operating conditions and dope compositions on membrane characteristics and correlation between membrane features and their performance has been discussed in subsequent section. It has been established that membrane morphology plays a crucial role in performance of the membrane for real applications. Furthermore, it has been demonstrated that the effect of membrane morphology is different for direct contact and vacuum configurations. Theoretical and experimental aspects of thermal polarization in direct contact membrane distillation have also been investigated. Thermal polarization phenomenon in a flat sheet membrane has been studied by using a specifically designed cell. The effect of operating conditions and solution concentration on thermal polarization has been explored experimentally. It has been observed that increased solution concentration favors the thermal polarization due to resulting poor hydrodynamic at the membrane surface and increase in diffusion resistance to the water vapors migrating from bulk feed phase to the membrane surface. Some active and passive techniques to decrease thermal polarization and possible fouling in membrane distillation have also been discussed in the current study. Thermal polarization can be greatly reduced by inducing secondary flows in the fluid flowing inside the fiber. The induction of secondary flows in the current study has been realized by using the fibers twisted in helical and wavy configurations. Due to improvement of thermal polarization coefficient on up and downstream, the undulating fiber geometries provide high flux and superior performance ratio. Application of intermittent and pulsatile flow to control thermal polarization in MD has also been discussed. It has been inferred that these flows have positive impact on performance ratio and volume based enhancement factors without compromising on packing density of the system. The application of MD for treatment of produced water has also been studied.

Nous nous intéressons au traitement tertiaire d'eaux issues de stations d'épuration traitant des eaux usées domestiques, en vue de leur réutilisation en particulier pour l'irrigation. Les opérations de séparation membranaires sont aujourd'hui les plus souvent considérées pour ce type de traitement, avec par exemple l'osmose inverse couplée à de l'ultrafiltration en pré traitement. Ces solutions présentent les inconvénients propres à ces technologies, inconvénients qui restent à lever au plan scientifique mais aussi au plan technologique. Notre objectif initial était de reconstruire totalement le schéma de procédé de réutilisation des eaux, à partir de son analyse globale. Nous avons pu réaliser seulement trois des étapes de ce travail : L'analyse de l'efficacité de techniques de modification de surface de membranes d'ultrafiltration en vue de rendre le colmatage réversible. L'analyse de la faisabilité d'utiliser la distillation membranaire pour traiter des eaux usées en sortie de station d'épuration traditionnelles ou par bio réacteurs à membranes, dont nous avons fait une évaluation expérimentale à partir d'eaux de complexité croissante, allant jusqu'au traitement d'eaux prélevées directement en sortie de station. Les résultats prometteurs de ces essais ont été complété par une recherche de points de fonctionnement de la distillation membranaire, par une analyse classique de bilans matière et d'énergie, dont l'originalité est la prise en compte du facteur de conversion comme paramètre opératoire. / We are interested in polishing steps of waters from sewage treatment plants dealing with domestic wastewater, with a view to their re-use, in particular for irrigation. Membrane separation operations are today most often considered for this type of treatment, with, for example, reverse osmosis coupled with ultrafiltration as a pretreatment. These options present the disadvantages peculiar to these technologies, disadvantages which still need to be sorted out scientifically but also at the technological level. Our initial objective was to completely reconstruct the water reuse flow sheet, based on its overall analysis. We were able to achieve only three of the stages of this work: Analysis of the efficiency of surface modification techniques of ultrafiltration membranes in order to make them fouling resistant. The analysis of the feasibility of using membrane distillation to treat wastewater discharged from traditional sewage treatment plants or by bio-membrane reactors, of which we have made an experimental evaluation based on waters of increasing complexity, up to the treatment of water taken directly from the treatment plant. The promising results of these tests lead us to define operating points for membrane distillation, by a classical analysis of material and energy balances, in which the stage cut-off was considered as an operational parameter.

No que diz respeito às águas residuais industriais, além da elevada frequência direta de efluentes salinos, o tratamento convencional de efluentes aquosos de diferentes tipos de indústria quase sempre resulta em uma solução contendo sais solúveis e insolúveis que podem ter qualidade suficiente para serem descartados em corpos aquosos, mas qualidade insuficiente para permitir a reutilização da água em processos industriais. Para reutilizar a água, visando o descarte zero de líquido, a cristalização se mostrou tecnicamente viável e tem sido utilizada nesta separação. Simultaneamente com a evaporação da água, os sais dissolvidos tornam-se materiais particulados que são subsequentemente separados por filtração ou centrifugação. Contudo, para atender às necessidades modernas da indústria em relação aos tratamentos com efluentes salinos, o processo de cristalização deve mostrar melhorias, especialmente devido à sua importância para atingir as metas de descarga de líquidos. Neste sentido, a cristalização simultânea representa a possibilidade de remover vários compostos em uma única operação de cristalização a partir de uma solução multicomponente. Isso significa que além da purificação da água, essa operação também pode permitir a recuperação dos compostos nos efluentes, que podem ser considerados como matéria-prima, eliminando resíduos - ou dando-lhes a destinação mais adequada. Para isso, é necessário projetar processos para separar os diferentes componentes que compõem as correntes de efluentes salinos e produzir produtos cristalinos com características morfológicas conhecidas. Dessa forma, o presente trabalho visou investigar o comportamento de sistemas ternários em cristalização, utilizando como modelo o sistema NaCl-KCl-H2O no processo de cristalização evaporativa em batelada, no intuito de avaliar a influência dos parâmetros de processo nos cristais formados e de traçar estratégias que possibilitassem o aproveitamento dos sais contidos nos efluentes. Três diferentes rotas de operação foram testadas para avaliar o comportamento dos cristais: uma inicialmente saturada apenas em NaCl, uma inicialmente saturada apenas em KCl e uma já de início saturada em ambos sais. Diferentes taxas de evaporação, tamanhos e teores de sementes foram testados. Verificou-se, de maneira geral, que o controle de dois fenômenos elementares é a chave para contornar os principais obstáculos desse processo: crescimento epitaxial e nucleação secundária. Em determinadas condições foi possível obter o produto das bateladas em distribuições bimodais, com cada pico rico em um dos sais, com purezas superiores a 90 %. Estes produtos, passíveis de separação simultânea dos cristais por composição e tamanho, foram obtidos em condições de supersaturações mais baixas e semeadura de cristais grandes de KCl e pequenos de NaCl. A partir destes resultados, considerando-se a necessidade de desenvolver técnicas de purificação de água menos intensivas em energia e mais favoráveis ao meio ambiente, um sistema de cristalização por membranas (MC) foi testado, utilizando-se o mesmo sistema modelo. O design proposto para MC possibilitou operar com este sistema por tempos superiores a 6 horas, com decaimento do fluxo em torno de 20 %. Contudo, o produto da cristalização simultânea por membranas não apresentou melhorias quanto à segregação. / In the industrial wastewater treatment, besides high direct frequency of saline effluents, conventional treatment of aqueous effluents of different types of industry usually results in a solution containing soluble and insoluble salts that may be of sufficient quality to be disposed in aqueous bodies, but insufficient quality for water reuse in industrial processes. In order to reuse the water, aiming at zero liquid discharge, crystallization has proved to be technically feasible and has been used in this separation. At the same time, with the evaporation of the water, the dissolved salts become particulate materials which are subsequently separated by filtration or centrifugation. However, to meet the industry\'s modern needs for saline effluent treatments, the crystallization process should show improvements, especially because of its importance in achieving liquid discharge goals. In this sense, simultaneous crystallization represents the possibility of removing several compounds in a single crystallization step from a multicomponent solution. This means that in addition to the purification of the water, this operation can also allow the recovery of the compounds in the effluents. In addition, particulate materials can be considered as raw material, eliminating waste - or disposing the residues appropriately. To this end, research is still needed to design processes to separate the different components that compose saline effluent streams and produce crystalline products with known morphological characteristics. Thus, the present work aimed to investigate the behaviour of ternary systems in crystallization, using as model the NaCl-KCl-H2O system in the batch evaporative crystallization process, in order to evaluate the influence of the process parameters on the crystals formed and to trace strategies to enable the use of the salts contained in the effluents. Three different routes of operation were tested to evaluate the behaviour of the crystals: one initially saturated only in NaCl, one initially saturated only in KCl and one initially saturated in both salts. Different evaporation rates, seed sizes and contents were tested. It was generally verified that control of two elementary phenomena is the key to overcome the main obstacles of this process: epitaxial growth and secondary nucleation. Some experimental conditions enablesd the obtaining of the batch product in bimodal distributions, where each peak was rich in one salt, with purities higher than 90 %. These fractions of the yield, that can be simultaneously separated by composition and size, were achieve mainly at lower supersaturations and using big KCl and small NaCl seeds. From these results, considering the need to develop energy-less and more environmentally friendly water purification techniques, a membrane crystallization (MC) system was tested using the same model system. The proposed design for the MC enable the operation for over 6 hours with a flux decay around 20 %. Yet, the proposed the yield of simultaneous membrane crystallization has not shown improvements in composition segregation.

The objective of this PhD project is to develop novel membranes and desiccants that would help develop a second generation vacuum desiccant cooling (VDC) garment that is efficient, robust, durable and wearer-friendly. It was found that properly chosen support material could improve both mechanical strength and vapor flux for flat sheet polyvinylidene fluoride (PVDF), due to improved membrane structure and structure integrity that enhanced vapour mass transfer. Super solid desiccants were developed using a super absorbent polymer (SAP), which are sodium polyacrylate granules, as the host matrices to harbour LiCl. Furthermore, a novel desiccant based on loading LiCl in to hydrophobic hollow fibre membranes and therefore called membrane based desiccant fiber (MDF), was developed and demonstrated to be suitable for VDC. Heat and mass transfer for vapor absorption in MDF were analyzed. These membranes and desiccants, although developed for application in VDC, may also found applications in other fields such as water treatment, air conditioning, and natural gas dehumidification. Finally, based on the newly developed membranes and desiccants, three conceptual designs of second generation VDC garments are proposed.