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Poly(arylene ether sulfone)s are high-performance engineering thermoplastics that have been investigated extensively over the past several decades due to their outstanding mechanical properties, high glass transition temperatures (Tg), solvent resistance and exceptional thermal, oxidative and hydrolytic stability. Their thermal and mechanical properties are highly suited to a variety of applications including membrane applications such as reverse osmosis, ultrafiltration, and gas separation. This dissertation covers structure-property-performance relationships of poly(arylene ether sulfone) and poly(ethylene oxide)-containing random and segmented copolymers for reverse osmosis and gas separation membranes. The second chapter of this dissertation describes synthesis of disulfonated poly(arylene ether sulfone) random copolymers with oligomeric molecular weights that contain hydrophilic and hydrophobic segments for thin film composite (TFC) reverse osmosis membranes. These copolymers were synthesized and chemically modified to obtain novel crosslinkable poly(arylene ether sulfone) oligomers with acrylamide groups on both ends. The acrylamide-terminated oligomers were crosslinked with UV radiation in the presence of a multifunctional acrylate and a UV initiator. Transparent, dense films were obtained with high gel fractions. Mechanically robust TFC membranes were prepared from either aqueous or water-methanol solutions cast onto a commercial UDEL® foam support. This was the first example that utilized a water or alcohol solvent system and UV radiation to obtain reverse osmosis TFC membranes. The membranes were characterized with regard to composition, surface properties, and water uptake. Water and salt transport properties were elucidated at the department of chemical engineering at the University of Texas at Austin. The gas separation membranes presented in chapter three were poly(arylene ether sulfone) and poly(ethylene oxide) (PEO)-containing polyurethanes. Poly(arylene ether sulfone) copolymers with controlled molecular weights were synthesized and chemically modified to obtain poly(arylene ether sulfone) polyols with aliphatic hydroxyethyl terminal functionality. The hydroxyethyl-terminated oligomers and α-ω-hydroxy-terminated PEO were chain extended with a diisocyanate to obtain polyurethanes. Compositions with high poly(arylene ether sulfone) content relative to the hydrophilic PEO blocks were of interest due to their mechanical integrity. The membranes were characterized to analyze their compositions, thermal and mechanical properties, water uptake, and molecular weights. These membranes were also evaluated by collaborators at the University of Texas at Austin to explore single gas transport properties. The results showed that both polymer and transport properties closely related to PEO-content. The CO2/CH4 gas selectivities of our membranes were improved from 25 to 34 and the CO2/N2 gas selectivity nearly doubled from 25 to 46 by increasing PEO-content from 0 to 30 wt.% in polyurethanes. Chapter four also focuses on polymers for gas separation membranes. Disulfonated poly(arylene ether sulfone) and poly(ethylene oxide)-containing polyurethanes were synthesized for potential applications as gas separation membranes. Disulfonated polyols containing 20 and 40 mole percent of disulfonated repeat units with controlled molecular weights were synthesized. Poly(arylene ether sulfone) polyols and α,ω-hydroxy-terminated poly(ethylene oxide) were subsequently chain extended with a diisocyanate to obtain polyurethanes. Thermal and mechanical characterization revealed that the polyurethanes had a phase-mixed complex morphology. / Ph. D.

Yes / In order to improve the performance of the reverse osmosis (RO) desalination plant powered by photovoltaic (PV), two cooling systems were proposed in this study to cool the PV and preheating the RO feed water as well. In the cooling design (1), the cooling fluid flows in direct contact with the back surface of the PV through channels of half circular cross-sections. While in the design (2), it flows through channels of squar cross-sections fixed on the PV back surface. Two nano-fluids were also tested as cooling fluid: H2O/CuO and H2O/Al2O3, in addition to distilled water for the purpose of comparison. The effect of changing the weight concentration of the nano-fluid (0.05, 0.1, and 0.15%) on the PV performance was also investigated. The results showed that the PV integrated with the cooling design (1) achieves better performance compared to design (2) at all studied cooling fluids. The improvements in the electric efficiency of the PV integrated with design (1) reached 39.5, 34.8 and 27.3 % when CuO and Al2O3 nano-fluids and distilled water were used as cooling fluid, respectively, compared to the uncooled PV. Based on the obtained experimental results, the PV integrated with design (1) was selected to power the RO with H2O/CuO nano-fluid of weight concentration 0.15% and flow rate 0.15 kg/s being used as the coolant. The RO powered by the improved PV was tested at different salinities of brackish water when the preheating technique was implemented. The results showed that the proposed PV-RO desalination system produces 366 l/day when brackish water of salinity 3000 ppm was used.

Sulfonated poly(arylene ether sulfone)s as ion conductive copolymers have numerous potential applications. Membranes cast from these copolymers are desirable due to their good chemical and thermal stability, excellent mechanical strength, satisfactory conductivity, and excellent transport properties of water and ions. These copolymers can be used in a variety of topologies. Structure-property-performance relationships of these membranes as candidates for electrolysis of water for hydrogen production and for purification of water from dissolved ions have been studied. Linear and multiblock sulfonated poly(arylene ether sulfone)s are potential alternative candidates to Nafion membranes for hydrogen gas production via electrolysis of water. In this investigation, these copolymers were prepared from the direct polymerization of di-sulfonated and non-sulfonated comonomers with bisphenol monomers. In systematic investigations, a series of copolymers with modified properties were synthesized and characterized by changing the ratio of the sulfonated/non-sulfonated comonomers in each reaction. These copolymers were investigated in terms of mechanical stability, proton conductivity and H2 gas permeability at a range of temperatures and under fully hydrated conditions. A multiblock copolymer was synthesized and evaluated for its potential as membranes for electrolysis of water and for fuel cell applications. The multiblock copolymer contained some fluorinated repeat units in the hydrophobic blocks, and these were coupled with a fully disulfonated hydrophilic block prepared from 3,3'-disulfonate-4,4'-dichlorodiphenyl sulfone and biphenol. After annealing, the multiblock copolymer showed enhanced proton conductivity and a more ordered morphology in comparison to the random copolymer counterparts. At 90 oC and under fully hydrated conditions, improved proton conductivity and controlled H2 gas permeability was observed. Finally, the performance of the multiblock copolymer, which was measured as the ratio of proton conductivity to H2 gas permeability, was improved when compared to the state-of-the-art membrane, Nafion 212, by a factor of 3. In another systematic study, two series of random copolymers were synthesized and characterized, and then cast into membranes to evaluate for electrolysis of water. One series contained solely hydroquinone as the phenolic monomer, while the second series contained a mixture of resorcinol and hydroquinone as phenolic comonomers. The polymers that contained only the hydroquinone monomer showed exceptionally good mechanical properties due to the para-substituted comonomer in the composition of the polymer. In the resorcinol-hydroquinone series, gas permeability was constrained due to the presence of 25% of the meta-substituted comonomer incorporated into its structure. Low gas permeability and high proton conductivity at elevated temperatures were obtained for both the linear random and multiblock copolymers. Performance of these copolymers was superior to Nafion at elevated temperatures (80-95°C). In order to enhance the durability of these materials in their hydrated states at elevated temperatures, the surfaces of these copolymer films were treated with fluorine gas. In comparison with pristine non-fluorinated membranes, the modified membranes showed decreased water uptake and longer durability in Fenton's reagent. A series of linear and crosslinked copolymers were investigated with respect to their potential for use as membranes for desalination of water by electrodialysis and reverse osmosis. The crosslinked membranes were prepared by reacting controlled molecular weight, disulfonated oligomers that were terminated with meta-aminophenol with an epoxy reagent. The oligomers had systematically varied degrees of disulfonation and either 5000 or 10,000 Da controlled molecular weights. Membrane casting conditions were established to fabricate highly crosslinked systems with greater than 90% gel fractions. At such a high gel fraction, the water uptake of the crosslinked membranes was lower than that of the linear biphenol-based, disulfonated random copolymer with a similar IEC. Among these series of copolymers, it was shown that the crosslinked membranes cast from the oligomers with 50% degree of disulfonation and a molecular weight of 10,000 Da had the lowest salt permeability of 10-8 cm2/sec. For desalination applications, a comonomer was synthesized with one sulfonate substituent on 4,4'-dichlorodiphenyl sulfone. This new monosulfonated comonomer allows for even distribution of the ions on the linear copolymer backbone, and this may be important for controlling ion transport. Mechanical tests were conducted on the membranes while they were submerged in a water bath. The ultimate strength of a fully hydrated copolymer with an IEC of 1.36 meq/g was approximately 60 MPa with an elongation at break of 160%. Moreover, in a monovalent/divalent mixed salt solution, the monosulfonated linear copolymer exhibited a constant Na+ passage of less than 1.0%. / Ph. D. / Purification systems have become an increasingly important scientific and technological need for millions around who face water shortages and/or impure sources of potable water. In response, water purification and hydrogen gas production have been widely used to produce pure products from a variety of water sources. In general, current state-of-the-art methods in separation technologies feature two major drawbacks: they are energy intensive and costly processes. In response to the growing need for purified water or pure hydrogen gas for energy generation, polymeric materials are increasingly used in the form of membranes to produce a purer product and overcome the hindrances associated with current energy intensive and inefficient methods. These membranes serve as a barrier for unwanted species, while at the same time allowing the desired species to pass through. Under proper conditions, these purification or chemical processes would generate pure materials that can be used on demand. The chemistry of candidate polymeric materials is extremely important to design a membrane with desired properties. Therefore, the principal goals of this investigation were to synthesize polymers for use as membranes in three areas: 1) Electrolysis of water for ultra-pure hydrogen gas generation 2) Fuel cells applications for electricity generation, and 3) Desalination of water to provide drinking water. For each technology, a series of sulfonated poly(arylene ether sulfone) copolymers were synthesized and characterized. By applying different monomers or chemistries, a range of appropriate copolymers were synthesized whose characteristics varied in topology and architecture, depending on the desired application. Once these copolymers were synthesized, they were cast into membranes under proper established conditions. In addition, the structure-property-performance relationship of these sulfonated polysulfone membranes were further investigated to provide a direction for future studies.

no / The optimal operation policy of flexible RO systems is studied in this work. The design and operation of RO process is optimized and controlled considering variations in water demands and changing seawater temperature throughout the day. A storage tank is added to the system layout to provide additional operational flexibility and to ensure the availability of freshwater to customer at all times. A steady state model for the RO process is developed and linked with a dynamic model for the storage tank. The membrane modules are divided into a number of groups to add flexibility in operation to RO network. The total operating cost of the RO process is minimized in order to find the optimal layout and operating variables at discreet time intervals for three design scenarios. (C) 2013 Elsevier Ltd. All rights reserved.

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This thesis deals with an agricultural wastewater treatment (liquid digestate) by membrane technology. There is a fundamental description of characteristics of membrane technology with regard to application of agricultural wastewater treatment in this thesis. Experimental device for treatment of liquid digestate is designed and it consists of three steps – microfiltration, ultrafiltration and reverse osmosis. The first step consists of four filters with different pore sizes (80, 25, 10 and 5 µm). The second step is ultrafiltration and the third and key step is reverse osmosis. In the final step monovalent ions such as NH4+ are separated. Reverse osmosis consists of two stage system which results in higher recovery. Three experiments were carried out in order to verify the efficiency of separation dissolved solids.

This master thesis aims to study the possibilities of eliminating, or separation of ammonium shares from technological water of plants, where is introduced a secondary method of flue gas denitrification (SCR, SNCR). The need for elimination of ammonium shares arose after introduction of emission cap, which have been tightened since January 2015. The denitrification technologies were installed on devices that did not comply with the new limits. The theoretical part of the thesis deals with the description of combustion processes, as a fluid, and high temperature combustion of solid fuels, mechanisms of emissions and their reduction options. At the conclusion of the theoretical part is discussed the contents of the ammoniacal nitrogen in waters used in electricity and heating facilities to transport, or from which are separated by solid products of some processes such as desulphurization. There are also discussed some options for removal of ammonium salts from technological waters. Experimental part deals with finding appropriate method of determination of ammoniacal nitrogen, and the possibilities of its elimination by conversion to insoluble compound. Last but not least, the work deals with the evaluation of the sustainability of the proposed solutions. And as well as the real possibilities of their application in practice.

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.