L’objectif de cette étude était d’améliorer les performances de séparation OSN de membranes commerciales en vue d’applications en métathèse dans laquelle des catalyseurs hautement dilués sont utilisés. Dans ce travail, des membranes polymères commerciales ont d'abord été étudiée pour caractériser leurs performances dans des milieux organiques en utilisant des mélanges binaires très dilués solute-solvant. Sur la base d'une revue de la littérature, il a été montré que la membrane PERVAP4060, dont le PDMS est la couche active dense était un candidat prometteur pour la nanofiltration milieu organique (OSN). En tant que membrane poreuse, les supports commerciaux AMS et PAN ont également été pris en compte. Dans cette étude, nous avons considéré la modification sur la surface pour conserver les propriétés de matrice polymère. Les multicouches de plasma Ar/O2 et/ou de polyélectrolytes ont été utilisées pour la préparation de membranes prototypes. Les membranes non modifiées et modifiées ont été testées dans des conditions OSN en utilisant des mélanges d'alimentation biniares. Plusieurs solutés très dilués, le ligand organophosphoré R-BINAP, un catalyseur de transfert de phase (ToABR) et des alcanes linéaires ont été étudiés. Le R-BINAP et le ToABR ont tous deux été utilisés dans la plage de 0,0001 à 0,5% en masse et la plupart des expériences ont été réalisées ensuite avec des concentrations de 0,05% en masse de soluté dans le toluène. Il a été montré que le PDMS était capable de retenir 80% de R-BINAP et environ 93% de ToABr dans du toluène. Après modification par les dépôt LBL, le taux de rejet est amélioré avec les membranes modifiées PERVAP4060, conduisant à une rétention de 88% du R-BINAP avec un dépôt de 10 bicouches de polyélectrolytes PAH / PSS en surface, ce taux de rejet pouvant atteindre 95% lorsque le nombre de bicouches est de 20. Le taux de rejet de ToABr augmente à 97%. Les performances de la membrane ont été étudiées sous différentes pressions comprises entre 1 et 40 bars; le haut rejet, encore observé dans ces conditions OSN, plaide résolument en faveur d'un mécanisme de transfert de type solution-diffusion à travers le PDMS. On a également étudié le traitement des mélanges ternaires mimant le mélange catalyseur / solutés / solvant, correspondant à l'hydroformylation ; aucun signe de couplage n’a été détectée et le taux rejet du soluté de masse molaire la plus forte est resté inchangé. D'autre part, l'amélioration du taux de rejet a également observée à partir des membranes poreuses après modification. Le taux de rétention du C44 dans l'AMS a été atteint 75% après modification par 10 bicouches de PDDA / PSS, alors qu’il n'était que de 25% avant modification. Dans le PAN modifié, le taux de rejet des solutés obtenus est dans la plage de 37 à 50%, alors qu’il n'était que de 3 à 7% en masse avant modification. L'inconvénient de la membrane poreuse est toutefois la forte diminution du flux après le dépôt des couches multiples. / The objective of this study was to improve the OSN separation performance of commercial membranes for metathesis applications in which highly diluted catalysts are used. In this work, commercial polymeric membranes were first studied to characterize their performance in organic media using very dilute solute-solvent binary mixtures. Based on a literature review, it was shown that the PERVAP4060 membrane, of which PDMS is the dense active layer, was a promising candidate for organic solvent nanofiltration (OSN). As a porous membrane, the AMS and PAN commercial supports have also been taken into account. In this study, we considered the modification on the surface to improve the separation properties of polymeric OSN membranes. Ar/O2 plasma and/or polyelectrolytes multilayers were used for the preparation of new prototype membranes. Unmodified and modified membranes were tested under OSN conditions using binary feed mixtures. Several highly dilute solutes, organophosphorus ligand R-BINAP, phase transfer catalyst ToABR, and linear alkanes have been studied. Both R-BINAP and ToABR were used in the range of 0.0001 to 0.5% by weight, and most experiments were subsequently performed with 0.05% solute concentrations in toluene. It has been shown that PDMS can retain 80% R-BINAP and about 93% ToABr in toluene. After modification by the LBL deposition, the rejection is improved with the modified PERVAP4060 membranes, leading to an 88% rejection of R-BINAP with a deposit of 10 PAH / PSS polyelectrolyte bilayers at the surface and this rejection being able to reach 95% when the number of bilayers is 20. ToABr rejection increases to 97% with the ten bilayered membranes. The performance of the membrane was studied under different pressures of between 1 and 40 bar; the high rejection, still observed in these OSN conditions, strongly supports a solution-diffusion transfer mechanism through the PDMS. The treatment of ternary mixtures mimicking the catalyst/solute/ solvent mixture corresponding to the hydroformylation has also been studied; no evidence of coupling was detected, and the highest retention remained unchanged. On the other hand, the improvement of the rejection also observed from the porous membranes after modification. The rejection of C44 in the AMS was reached 75% after modification by tention10 bilayers of PDDA / PSS, whereas it was only 25% before modification. In the modified PAN, the rejection of the solutes obtained is in the range of 37 to 50%, whereas it was only 3 to 7% by weight before modification. The disadvantage of the porous membrane, however, is the sharp decrease in flux after the deposition of the multiple layers.

Un des enjeux majeurs des procédés membranaires concerne le développement de nouveaux matériaux de filtration stables dont les propriétés texturales et structurales permettent d'orienter la sélectivité des membranes de nanofiltration. En particulier, l'utilisation de matériaux zéoliihiques comme couche filtrante a montré qu'après un traitement chimique adéquat, ces matériaux pouvaient acquérir des propriétés de sélectivité très particulières. Ce travail de thèse propose la synthèse, la caractérisation et l'optimisation de membranes de nanofiltration tubulaires en utilisant une zéolithe de type MFI. Plus particulièrement, des films mono et bicouches de zéolithes de type MFI ont été préparés sur un support tubulaire macroporeux asymétrique en alumine. La diffraction de rayons X et la microscopie électronique à balayage ont permis de déterminer la cristallinité, l'homogénéité et l'épaisseur des filins déposés (7 à 15 i_trn). La manométrie d'adsorption d'azote a été utilisée pour vérifier si la porosité après mise en forme restait accessible, ainsi qu'à déterminer la niasse de zéolithe déposée sur le support tubulaire en alumine. La perméabilité hydraulique, qui caractérise l'hydrodynamique d'une membrane, a été déterminée par filtration d'eau déminéralisée. Cette étape dite « de conditionnement » est nécessaire pour parvenir à un état de performance stable de la membrane (état d'équilibre), La perméabilité hydraulique de la membrane mono et bicouche MFI diminue rapidement au début de la phase de conditionnement, et finit par se stabiliser au bout de 15 heures de filtration pour atteindre une valeur minimale de 1,08 x tem-2 et 1,02 x 10-15 m3.ni-2 respectivement. La sélectivité et les performances de filtration de ces membranes vis-à-vis de différents types de solutés (ioniques, molécules organiques, mélanges) ont été analysées à l'issue de la phase de conditionnement. Les résultats obtenus sont très encourageants, ils ont fait l'objet de plusieurs articles de recherche. / Zeolites are very well-known materials especially for their controlled porosity, their crystalline structures, but also for the different applications where they can be used (catalysis, air treatment,...) . During the past ten years, a lot of developments have been done on the preparation of zeolite membranes for pervaporation applications. The present work explores new developments in the preparation zeolite membranes dedicated to the filtration of salty water. More particularly, we prepared MFI films on specific macroporous alumina tubular supports used for nanofiltration applications. There are different key steps which influence the formation of the MFI films: the cleaning procedure of the substrats, the hydrothermal synthesis conditions, the use of a secondary growth method for when preparing a bi-layered membrane. A complete characterization of the mono and the bi-layered membranes was carried out using various techniques, such as X-ray diffraction, scanning electron microscopy, X-ray fluorescence, energy dispersive X-ray spectroscopy, mercury porosimetry and nitrogen sorption measurements. Results show that a dense, continuous and highly crystallized thin film of MFI bas been obtained on the u-alumina support after the secondary growth experiment. The weight of zeolite deposited on the support was also estimated by nitrogen sorption measurement using the method of mass assessment. The MFI membrane was stabilized by pure water filtration tests until the hydraulic permeability reached a plateau. This conditioning step was necessary to reach an equilibrium state of the hydraulic membrane performances. Particularly, hydration of the MFI layer was a crucial step of the conditioning process, which leads to the modification of the MFI surface properties. The hydraulic permeability of the mono and bi-layer MFI membrane decreased rapidly at the beginning of the conditioning process, and stabilized alter 15 hours to reach 1.08 x 10.141113.m.2 and 1.02 x 10-15 m3.m-2 respectively. Filtration tests were then carried out with a neutral molecule (VB 12) in order to evaluate the mean pore radius of the mono and the bi-layered membranes. A rejection rate of 5% was obtained with the monolayer MFI membrane, while it reaches a value of 50% with the bi-layered one. These results lead to mean pore radius corresponding to 6.4 and 1.7 mn respectively. It menus that even alter the synthesis of the second MFI layer, the membrane porosity remains higher than the porous diameter of the zeolite. Filtration may occur at the interface of the MFI crystals.

Les procédés de réutilisation des eaux usées doivent être robustes, fiables et rentables pour que leur utilisation se démocratise et devienne complémentaire des traitements des eaux de surface. Le couplage d’un procédé biologique et de procédés membranaires représente une solution prometteuse pour répondre à ces challenges. Cette étude se focalise sur l’impact des conditions de fonctionnement du procédé secondaire (en particulier par bioréacteur à membrane BAM) sur le colmatage du procédé tertiaire de nanofiltration (NF) ou d’osmose inverse (OI) ainsi que sur le devenir des micropolluants et microorganismes tout au long de la chaine de traitement. Dans un premier temps, des expériences à court terme de filtration avec différentes membrane NF et d’OI ont été réalisées afin de caractériser les interactions entre effluents secondaires et membranes. Il a ainsi été observé de très fortes rétentions de tous les micropolluants ciblés par la Directive Cadre Européenne. En termes de colmatage, la chute de flux de l’OI, essentiellement liée pour ces essais de courte durée à une augmentation de pression osmotique puis à un dépôt de cristaux minéraux, peut être maîtrisée en contrôlant le pH et la concentration en carbonate et phosphate de l’effluent secondaire. Par ailleurs, des chutes de flux plus importantes sont observées lors des filtrations réalisées avec les membranes de NF qui sont plus sensibles au colmatage irréversible. Dans un second temps, l’optimisation de la filière de traitement des eaux usées urbaines couplant un bioréacteur à membranes à un procédé d’OI a été réalisée à partir d’une unité pilote fonctionnant en continu. La sélection de conditions opératoires adéquates a permis de faire fonctionner le procédé d’OI pendant plus de quatre mois sans qu’aucune maintenance ne soit réalisée. Une faible chute de flux de l’OI, linéaire sur toute la période de filtration, essentiellement dû à l’adsorption de molécules organiques à la surface de la membrane, a été observée. Sur l’ensemble de la période d’essais, la filière BAM/OI permet d’obtenir un abattement optimal en micropolluants présents. Lorsque des micropolluants sont injectés à des concentrations plus élevées (simulation d’une brusque dégradation de la qualité des eaux en entrée de filière) dans le bioréacteur, une chute de l’activité de la biomasse couplée à un relargage de produits microbiens solubles peut être observée. Néanmoins, ces pics de pollution n’ont eu aucun impact sur le colmatage de la membrane du BAM ni sur celle de l’OI. La filière BAM-OI permet donc de garantir un taux de rejet élevé et une productivité d’environ 15 L.h-1.m2 quelles que soient les fluctuations de la composition de l’eau usée urbaine à traiter. / In order to be competitive compare to surface water treatments, wastewater reuse needs robust, reliable and profitable combination of technologies. The combination of bioreactors and membrane processes seems to be a promising solution to these challenges. This study focus on the impact of the operating conditions of the secondary treatment (particularly the membrane bioreactor (MBR)) on the nanofiltration (NF) and reverse osmosis (RO) tertiary treatments as well as the fate of micropollutants and microorganisms along the treatment line. Firstly, short term filtration experiments with various NF and RO membranes were performed in order to characterize the interactions between secondary treatment effluents (STE) and membranes. High retentions of micropollutants listed by the European water framework directive were observed. During these short term experiments, RO flux decline is mainly due to an increase of osmotic pressure and then a precipitation of salts that can be solved by controlling the pH and thus the carbonate and phosphate concentration of the STE. In addition, higher flux declines are observed with NF because of a higher irreversible fouling behavior. Secondly, continuous long term tests were performed on a pilot unit combining a MBR and a RO processes. The appropriate selection of operating conditions allowed treating wastewater during more than four months without any maintenance. A linear low flux decline, mainly due to adsorption of organic molecules at the membrane surface was observed. During this filtration period, the MBR/RO process presented very high micropollutant retentions. When micropollutants are injected at higher concentration (simulation of sudden fluctuation of feed composition) into the MBR, a drop of biomass activity combined with soluble microbial products release can be observed. Nevertheless, these peaks of pollution did not cause any additional fouling of MBR as well as RO membranes. MBR/RO process is then a reliable technology that can guaranty high retention and productivity (around 15 L.h-1.m-2) whatever the fluctuations of the feed composition.

Les ressources de carbone primaires doivent être progressivement remplacées par des ressources renouvelables plus complexes comme les matières lignocellulosiques, pour produire des biocarburants ou des synthons (bioraffineries de 2ième génération). Cette évolution nécessite de modifications importantes à différentes étapes du procédé, au niveau de la fermentation elle-même ou dans les étapes ultérieures nécessaire pour l'obtention du produit cible. Dans ce travail, nous avons étudié un procédé de production de succinate à partir du xylose. La fermentation a été réalisée en utilisant une souche d' Escherichia coli modifiée par ingénierie métabolique. La purification du succinate a été réalisée par nanofiltration. Des travaux précédents ont permis, par ingénierie métabolique, de mettre au point une souche E. coli KJ122 permettant de produire du succinate par fermentation anaérobie de glucose dans un milieu contenant des sels minéraux. Cette souche ne permet cependant pas une fermentation performante lorsque le xylose est utilisé comme substrat. Afin de lever cette limitation, E. coli KJ122 a été modifiée. Le transporteur ABC codant pour les gènes xylFGH a été inactivé par une technique de suppression de gènes. La souche ainsi obtenue, baptisée KJ12201 (E. coli KJ122 ?xylFGH) a permis d'atteindre des vitesses de croissances rapides, des consommations de xylose et une production de succinate améliorées par rapport à la souche parente. Après modification génétique, E. coli KJ12201-14T permet de produire en mode une concentration élevée de succinate de 84 g/L, la concentration d'acétate accumulée étant de 11 g/L, à partir d'un milieu de composition adaptée (AM1) contenant 10% de xylose. En fermentation fed-batch, E. coli KJ12201-14T permet de produire du succinate à une concentration de 84 g/L, avec un rendement de 0.85 g/g et une productivité de 2 g/L/h. Ces résultats démontrent les potentialités de cette souche pour produire du succinate à partir de xylose ou d'hydrolysats riches en xylose issus de matières lignocellulosiques. La nanofiltration a ensuite été considérée afin de purifier le succinate obtenu par fermentation. Les expériences ont été réalisées avec une membrane NF45 et des milieux de fermentation synthétiques contenant le succinate et différentes impuretés, sels minéraux, glucose ou autres sels d'acides organiques, acétate en particulier. L'influence des conditions opératoires (pH, pression) sur les performances de la NF a été évaluée. Les mécanismes gouvernant le transfert des espèces à travers la membrane ont été étudiés afin d'expliquer la variation des rétentions en fonction de la composition du milieu. En solution simple, les résultats ont montré que la rétention du succinate augmente avec la pression appliquée et avec le pH et diminue lorsque la concentration augmente. Pour des concentrations faibles, de l'ordre de 0.1M, les rétentions du succinate et de l'acétate en mélange sont différentes et identiques à celles en solution simples. Une bonne purification du succinate est ainsi possible. Au contraire, pour des concentrations plus élevées en succinate, la rétention diminue par suite de l'écrantage des effets de charge. Les rétentions étant trop proches, la séparation acétate/succinate devient impossible. Considérant les mécanismes ainsi mis évidence, une méthodologie a été proposée afin de réaliser la purification du succinate obtenu par fermentation. La séparation acétate/succinate est effectuée en deux étapes. Une diafiltration du jus de fermentation, préalablement dilué, est d'abord réalisée en utilisant la membrane NF45. Le rétentat purifié est ensuite concentré, en utilisant une membrane d'osmose inverse. Grace à ce procédé, il est possible d'augmenter la pureté du succinate de 85 à plus de 99.5% avec un rendement global supérieur à 92%. L'intérêt de la nanofiltration pour purifier le succinate produit par fermentation est ainsi démontrée. / Current trend is to move from primary carbohydrate resources to more complex ones like lignocellulosic materials as a bio-renewable feedstock, to produce biofuels or chemical building blocks. This evolution requires significant modifications at different stages in the bioprocess engineering, including fermentation and downstream processes. In this work, the succinate production by a newly metabolically engineered Escherichia coli from xylose, and its purification from fermentative broth by nanofiltration were studied. Escherichia coli KJ122 strain was previously engineered to produce high titers and yields of succinate in mineral salts medium containing glucose under simple-batch anaerobic conditions. However, this strain does not efficiently utilize xylose due to catabolic repression. To improve the xylose uptake and its utilization of E. coli KJ122, xylFGH genes were inactivated by the gene deletion technique. The mutant strain named KJ12201 (E. coli KJ122 ?xylFGH) exhibited high abilities in fast growth, xylose consumption and succinate production compared to those of the parental strains. After performing metabolic evolution, E. coli KJ12201-14T efficiently consumed 10% xylose to produce a high succinate concentration at 84 g/L with an accumulated acetate concentration at 11 g/L in mineral salts medium (AM1) under batch fermentation. During fed-batch fermentation, E. coli KJ12201-14T produced succinate at a concentration, yield, and overall productivity of 84 g/L, 0.85 g/g, and 1.0 g/L/h, respectively. These results demonstrated that E. coli KJ12201 would be a potential strain for the economic bio-based succinate production from xylose and other xylose-rich hydrolysates derived from lignocellulosic materials. The succinate purification from fermentation broth by nanofiltration (NF) was also investigated. The experiment was carried out with a NF45 membrane and various synthetic fermentation broths containing succinate salt and different impurities such as inorganic salts, glucose, and other organic acid salts including acetate. The influence of the operating conditions (pH, pressure) as well as the broth composition on the NF performances was evaluated. The mechanisms governing the transfer of the solutes through the membrane were studied in order to explain the different solute retentions observed according to the fermentation broth composition. In single-solute solutions, the succinate retention increases with increasing pressure and feed pH and decreases with increasing feed concentration. For instance, at a low salts concentration at 0.1 M, it was observed that the retentions of succinate and acetate in the mixture are identical to those in single solutions. Thus, a good purification of succinate can be obtained. On the contrary, with higher succinate concentrations, the retention was decreased due to the screening effect. Retentions of those solutes were then too close to achieve a separation. Based on abovementioned mechanisms observed, a methodology was proposed to perform the succinate purification from fermentation broth. The succinate/acetate separation was carried out in two steps. A diafiltration of the diluted fermentation broth was initially performed, and the concentration step followed. With this process, it was possible to increase the succinate purity from 85% to more than 99.5% while maintaining a total yield higher than 92%. From this work, it was shown that NF could be effectively used for the succinate purification from fermentation broth.

The integration of organic solvent nanofiltration in processes of fine chemistry involving homogeneous metal catalysts has a great potentiel because this eco-friendly process, efficient at molecular scale, does not desactivate the catalyst contrary to conventionnal distillation. The aim of this study is to integrate organic solvent nanofiltration in the process of 10-undecenitrile hydroformylation in toluene. A one-step nanofiltration does not permit to fulfill the goals of the separation, which are to extract the product and to recycle the catalytic system (Rh, biphephos). Simulations of membrane cascades based on experimental data of flux and retention according to the concentration (acquired in the first part of the thesis) highlighted that a four stages cascades with recycling is realistic and competitive for an industrial plant. / L'intégration de la nanofiltration organique dans les procédés de chimie fine impliquant des catalyseurs organométalliques solubles a un fort potentiel car ce procédé éco-efficace de séparation à l'échelle moléculaire ne désactive pas les catalyseurs contrairement à la distillation classiquement utilisée. L'objectif de cette thèse est d'intégrer la nanofiltration organique dans le procédé d'hydroformylation du 10-undecenitrile dans le toluène. Un procédé en une étape de nanofiltration ne permet pas de remplir les objectifs de séparation qui sont l'extraction du produit et le recyclage du système catalytique (Rh, biphephos). Des simulations de cascades de membranes basées sur les données expérimentales de flux et de rétentions variables en fonction de la concentration, acquises en première partie de thèse, ont permis d'identifier un design de cascade à 4 étages avec recyclages réaliste et compétitif pour une conception industrielle.

Among the next generation materials being investigated for membrane development, partially reduced Graphene Oxide (rGO) has received increasing attention from the membrane community. rGO-based nanofiltration membranes have shown promising results in applications such as partial desalination, organic contaminant removal, gas-phase separations, and separations from solvent media. rGO offers a unique platform compared to common polymeric membranes since it can be used for separation applications in both aqueous and organic solvent media. An rGO-based platform could also be utilized to synthesize reactive membranes, giving rGO membranes the additional capability of reactively removing organic contaminants. This research focuses on the synthesis of rGO and nanocomposite membranes for applications including the separation of high-value phenolic compounds from a solvent-water mixture, removal of organic contaminants, and treatment of refinery wastewater. First, the behavior of a rGO membrane in water and isopropanol was investigated along with its ability to separate high-value, lignin-derived oligomeric compounds from a solvent-water mixture. This study revealed the formation of stable sorbates of water in the GO channels that resulted in declined membrane permeance and improved size-exclusion cutoff. Through controlled reduction of GO by heat treatment, it was demonstrated that physicochemical properties of the GO membrane could be modulated and separation performance tuned based on the extent of reduction. A varying degree of interlayer spacing was attained between the GO laminates by controlling the O/C ratio of GO. This allowed the rGO membrane to achieve tunable molecular separation of lignin-derived model oligomeric compounds from a solvent-water mixture. Second, the mechanism of ionic transport through the rGO membrane was studied as well as its application in partial desalination and removal of persistent organic contaminants from water. Through comprehensive experimental investigations and mathematical analysis, along with the aid of the extended Nernst Planck equation, the impacts of steric hindrance and charge interactions on the underlying ion transport mechanism were quantified. Charge interactions were observed to be the dominant exclusion mechanism for the rGO membranes. The application of rGO membranes for treatment of high TDS produced water was investigated with the goal of partial hardness and dissolved oil removal. In addition, this study demonstrated the removal of emerging organic contaminants, specifically perfluorooctanoic acid, by rGO membranes and elucidated a charge interaction-dominated exclusion mechanism for this contaminant, as well. Finally, rGO-based and microporous polyvinylidene fluoride (PVDF)-based catalytic membrane platforms were synthesized for removal of organic contaminants via an oxidative pathway. Herein, an advanced oxidation process was integrated with membrane technology by the in-situ synthesis of Fe-based nanoparticles. The unique capability to oxidatively remove contaminants in a continuous mode of operation was explored in addition to the separation performance of the membrane. The rGO-based platform achieved high oxidative removal of trichloroethylene via a sulfate-free, radical-mediated pathway, while simultaneously removing humic acids from water and potentially eliminating undesired side reactions. A PVDF-based microporous catalytic membrane platform was shown to effectively remove organic impurities, such as Naphthenic acids, from high TDS produced water by the same pathway. The enhancement of reaction extent for elevated temperatures and longer residence times was also quantified in this study. These studies benefit the membrane community in the following ways: 1) The work identifies the critical role of the physicochemical properties of GO, such as the O/C ratio and water sorption, for determining the permeability-selectivity of rGO membranes for solvent nanofiltration. 2) Investigations of ion transport through rGO membranes led to an understanding of a charge-dominated separation mechanism for ion retention. The Nernst-Planck equation-based approach employed in this study would enable further assessment and comparison of rGO membranes under a wide set of parameters. 3) Catalytic membrane platforms (rGO and microporous PVDF-based) were synthesized for conducting advanced oxidation reactions in the porous membrane domain, demonstrating potential applications in environmental remediation of organic contaminants.

Membrane technology has great potential to complement traditional energy-intensive molecular separation processes such as distillation, with the advantage of low footprint generation. However, this would only be achieved with the development of better membranes able to operate in challenging conditions, including combinations of organic solvents, high temperatures, extreme pHs, and oxidative environments. This dissertation aims to use high-performance polymeric materials that can withstand temperatures of 120 °C in polar aprotic solvents like N,N-dimethylformamide as separation membranes, using different crosslinking strategies and alternative routes for commercially available material processing. The thesis will be divided into two main approaches. The first approach will start from soluble polyimides as precursors, with designed functionalities that allow post-membrane modifications, such as chemical crosslinking, thermal crosslinking, and thermal rearrangement to enhance the material's chemical resistance. The focus will be on the polyimide synthesis by an alternative one-step room-temperature polyhydroxyalkylation reaction. The chemical and thermal crosslinking take place without involving the imide bond, by incorporating a highly tunable functional group (isatin) in the synthesis of the materials. Propargyl as a pendant group will be used for the thermal crosslinking, and hydroxyl group for the thermal rearrangement. In all cases, the obtained membranes were stable in common organic solvents at 120 °C. The second approach will start from intrinsically solvent-resistant and commercially available poly(aryl ether ketone)s, turned into membranes by a closed-loop modification-regeneration strategy, to address long-term separations in organic solvents at high temperatures. We present for the first time porous poly(aryl ether ketone) flat-sheet and hollow fiber membranes prepared without the use of strong acids or high temperatures. Two methodologies are proposed. The developed strategies shall contribute toward avoiding the regular consumption of new materials and waste generation since the polymer used does not require crosslinking for its stability under organic solvents.

Submitted in fulfillment of the academic requirements for the degree of Master of Technology in Engineering: Chemical Engineering, Durban University of Technology. Durban. South Africa, 2015. / The textile industry consumes large volumes of water and in turn produces substantial quantities of polluted effluents. Approximately 30% of reactive dyes used during the textile processing remain unfixed on fibres and are responsible for the colouration in effluents. Various conventional methods are being used to treat textile effluent. However, the disadvantage of these methods is that total colour removal is not achieved and chemical by-products are introduced from the use of chemicals. The water quality produced therefore does not meet the requirement for textile reuse. Membrane based processes provide interesting possibilities of separating hydrolysed dye stuff and dyeing auxiliaries, thereby reducing colouration and COD content. They can be employed to treat reactive dye bath effluent to recover the salts and water for the purpose of reuse. This study aimed at integrating membrane processes into the reactive dye bath of a textile industry. The objectives were to determine the quality of permeate produced in terms of removal of organics, ascertain its reusability for dyeing, investigate the production rate in terms of permeate fluxes and finally to investigate the cleanability and flux recovery of the membranes. Three effluent samples were chosen for this study based on the dyeing recipe; Light shade, Medium shade and Dark shade. Ultrafiltration (UF) and Nanofiltration (NF) membrane processes were employed to treat the reactive dye bath effluents to recover the salts and water. Investigations were conducted firstly with UF as a pre-treatment to NF. Secondly, evaluations were carried out on the performance of two types of NF membranes (SR90 and NF90) in terms of permeate quality and fluxes for the investigated samples. The effect of cleaning on membrane performance was done. A reusability test was carried out on the permeate samples for dyeing. It was found that the use of UF as a pre-treatment yielded an increase in permeate of 5–25% of the NF fluxes and 90% in organics reduction for all treated samples, hence increasing the water recovery. High rejection of ˃90% by NF90 for COD, TOC and colour were obtained for all the treated samples. SR90 rejection was 80–90% for colour and ˃90% for COD and TOC. Salt recovery for NF90 was 60–90% and for SR90 was 40–50%. The reusability tests carried out showed that permeate recycled from NF90 can be used for any section in the textile industry including the most critical such as dyeing on light shades, while that from SR90 can be used for dyeing dark shades only. It was then concluded that membrane based processes can be integrated into the dye bath of the textile process for the purpose of reuse, thereby saving on the cost of chemicals (salts), reducing fresh water usage and reducing the extent of final effluent treatment.

Este trabalho apresenta resultados de pesquisa realizada com objetivo de avaliar a qualidade das águas residuárias do branqueamento após aplicação de filtração por nanofiltração precedida de tratamento biológico e físico-químico para depuração inicial. Os tratamentos foram aplicados aos efluentes coletados nos estágios de extração alcalina e ácida da planta de branqueamento, sem diluição posterior. Obteve-se remoção de 83% da DQO, 95% da DBO, 80% do COT, remoção total de sólidos decantáveis, turbidez e fósforo, deixando apenas 63 mg/lPt de cor residual. Com relação aos sólidos totais, que englobam os íons cloreto e sulfato, além de outros componentes, consegui-se remoção de 70%. Não houve remoção significativa de cloretos. Comparando-se a qualidade do efluente final com os parâmetros requeridos para água fresca conclui-se que a qualidade atingida está próxima daquela requerida para preparo de produtos químicos na fabricação tanto de polpa química quanto de polpa mecânica. / This dissertation presents results from a research designed to assess kraft pulp bleaching wastewater after biological and physical-chemical treatment followed by nanofiltration filtration. The treatment was applied to effluents from the alkaline and acid extraction at the bleaching plant and were treated as collected, that is, without dilution. The overall removal efficiencies were 83% for the COD, 95% for the BOD, 80% for the TOC. The treatment system provide total removal of setteable solids, turbidity and phosphorus. The residual color was only 63 mg/lPt. Total solids removal, which encompases chloride and sulfate ions the removal efficiency reached 70%, however the removal of chloride ions was not significant. Comparing the final effluent quality with the fresh water requirements it is possible to conclude that the treatment provided a water quality close to the required for the preparation of chemicals used in chemical and mechanical pulping.

Este trabalho apresenta resultados de pesquisa realizada com objetivo de avaliar a qualidade das águas residuárias do branqueamento após aplicação de filtração por nanofiltração precedida de tratamento biológico e físico-químico para depuração inicial. Os tratamentos foram aplicados aos efluentes coletados nos estágios de extração alcalina e ácida da planta de branqueamento, sem diluição posterior. Obteve-se remoção de 83% da DQO, 95% da DBO, 80% do COT, remoção total de sólidos decantáveis, turbidez e fósforo, deixando apenas 63 mg/lPt de cor residual. Com relação aos sólidos totais, que englobam os íons cloreto e sulfato, além de outros componentes, consegui-se remoção de 70%. Não houve remoção significativa de cloretos. Comparando-se a qualidade do efluente final com os parâmetros requeridos para água fresca conclui-se que a qualidade atingida está próxima daquela requerida para preparo de produtos químicos na fabricação tanto de polpa química quanto de polpa mecânica. / This dissertation presents results from a research designed to assess kraft pulp bleaching wastewater after biological and physical-chemical treatment followed by nanofiltration filtration. The treatment was applied to effluents from the alkaline and acid extraction at the bleaching plant and were treated as collected, that is, without dilution. The overall removal efficiencies were 83% for the COD, 95% for the BOD, 80% for the TOC. The treatment system provide total removal of setteable solids, turbidity and phosphorus. The residual color was only 63 mg/lPt. Total solids removal, which encompases chloride and sulfate ions the removal efficiency reached 70%, however the removal of chloride ions was not significant. Comparing the final effluent quality with the fresh water requirements it is possible to conclude that the treatment provided a water quality close to the required for the preparation of chemicals used in chemical and mechanical pulping.