Thesis (MScEng)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: The purpose of this study was to develop modi ed tract-etched membranes using nanocomposite TiO2 for advanced water treatment processes. Photocatalytic oxidation and reduction reactions take place on TiO2 surfaces under UV light irradiation, therefore sunlight and even normal indoor lighting could be utilised to achieve this effect. In membrane ltration, caking is a major problem, by enhancing the anti-fouling properties of photocatalysts to mineralise organic compounds the membrane life and e ciency can be improved upon. In this study the rst approach in nanocomposite membrane development was to directly modify the surface of polyethylenetherephthalate (PET) track-etched membranes (TMs) with titanium dioxide (TiO2) using inverted cylindrical magnetron sputtering (ICMS) for TiO2 thin lm deposition. The second approach was rst to thermally evaporate silver (Ag) over the entire TM surface, followed by sputtering TiO2 over the silver-coated TM. As a result a noble metal-titania nanocomposite thin lm layer is produced on top of the TM surface with both self-cleaning and superhydrophilic properties. Reactive inverted cylindrical magnetron sputtering is a physical vapour deposition method, where material is separated from a target using high energy ions and then re-assimilated on a substrate to grow thin lms. Argon gas is introduced simultaneously into the deposition chamber along with O2 (the reactive gas) to form TiO2. The photocatalytic activity and other lm properties, such as crystallinity can be in uenced by changing the sputtering power, chamber pressure, target-to-substrate distance, substrate temperature, sputtering gas composition and ow rate. These characteristics make sputtering the perfect tool for the preparation of di erent kinds of TiO2 lms and nanostructures for photocatalysis. In this work, the utilisation of ICMS to prepare photocatalytic TiO2 thin lms deposited on track-etched membranes was studied in detail with emphasis on bandgap reduction and TM surface regeneration. Nanostructured TiO2 photocatalysts were prepared through template directed deposition on track-etched membrane substrates by exploiting the good qualities of ICMS. The TiO2-TM as well as Ag-TiO2-TM thin lms were thoroughly characterised. ICMS prepared TiO2 lms were shown to exhibit good photocatalytic activities. However, the nanocomposite Ag-TiO2 thin lms were identi ed to be a much better choice than TiO2 thin lms on their own. Finally a clear enhancement in the photocatalytic activity was achieved by forming the Ag-TiO2 nanocomposite TMs. This was evident from the band-gap improvement from 3.05 eV of the TiO2 thin lms to the 2.76 eV of the Ag-TiO2 thin lms as well as the superior surface regenerative properties of the Ag-TiO2-TMs. / AFRIKAANSE OPSOMMING: Die doel van hierdie studie was om verbeterde baan-ge etste membrane (BMe) met behulp van nano-saamgestelde titaandioksied (TiO2) vir gevorderde water behandeling prosesse te ontwikkel. Fotokatalitiese oksidasie- en reduksie reaksies vind plaas op die TiO2 oppervlaktes onder UV-lig bestraling, en dus kan sonlig en selfs gewone binnenshuise beligting gebruik word om die gewenste uitwerking te verkry. In membraan ltrasie is die aanpaksel van onsuiwerhede 'n groot probleem, maar die verbetering van die self-reinigende eienskappe van fotokatalisators deur organiese verbindings te mineraliseer, kan die membraan se leeftyd en doeltre endheid verbeter word. In hierdie studie was die eerste benadering om nano-saamgestelde membraan ontwikkeling direk te verander deur die oppervlak van polyethylenetherephthalate (PET) BMe met 'n dun lagie TiO2 te bedek, met behulp van reaktiewe omgekeerde silindriese magnetron verstuiwing (OSMV).Die tweede benadering was eers om silwer (Ag) termies te verdamp oor die hele BM oppervlak, gevolg deur TiO2 verstuiwing bo-oor die silwer bedekte BM. As gevolg hiervan is 'n edelmetaal-titanium nano-saamgestelde dun lm laag gevorm bo-op die oppervlak van die BM, met beide self-reinigende en verhoogde hidro liese eienskappe. OSMV is 'n siese damp neerslag metode, waar materiaal van 'n teiken, met behulp van ho e-energie-ione, geskei word, en dan weer opgeneem word op 'n substraat om dun lms te vorm. Argon gas word gelyktydig in die neerslag kamer, saam met O2 (die reaktiewe gas), vrygestel om TiO2 te vorm. Die fotokatalitiese aktiwiteit en ander lm eienskappe, soos kristalliniteit, kan be nvloed word deur die verandering van byvoorbeeld die verstuiwingskrag, die druk in die reaksiekamer, teiken-tot-substraat afstand, substraattemperatuur, verstuiwing gassamestelling en vloeitempo. Hierdie eienskappe maak verstuiwing die ideale hulpmiddel vir die voorbereiding van die verskillende soorte TiO2 lms en nanostrukture vir fotokatalisasie. In hierdie tesis word OSMV gebruik ter voorbereiding van fotokatalitiese TiO2 dun lms, wat gedeponeer is op BMe. Hierdie lms word dan in diepte bestudeer, met die klem op bandgaping vermindering en BM oppervlak hergenerasie. Nanogestruktureerde TiO2 fotokataliste is voorberei deur middel van sjabloongerigte neerslag op BM substrate deur die ontginning van die goeie eienskappe van OSMV. Die TiO2-BM dun lms, sowel as Ag-TiO2-BM dun lms, is deeglik gekarakteriseer. OSMV voorbereide TiO2 dun lms toon goeie fotokatalitiese aktiwiteite. Nano-saamgestelde Ag-TiO2 dun lms is egter ge denti seer as 'n veel beter keuse as TiO2 dun lms. Ten slotte is 'n duidelike verbetering in die fotokatalitiese aktiwiteit bereik deur die vorming van die Ag-TiO2 nano-saamgestelde BMe. Dit was duidelik uit die bandgapingverbetering van 3,05 eV van TiO2 dun lms in vergelyking met die 2,76 eV van Ag-TiO2 dun lms. 'n Duidelike verbetering is behaal in die fotokatalitiese aktiwiteit deur die vorming van die Ag-TiO2 nano-saamgestelde TMs.

Ce travail de thèse concerne l'étude et l'évaluation de l'extraction et de la séparation de molécules d'intérêt à partir des résidus de colza. L'impact des différents traitements (broyage, champs électriques pulsés, décharges électriques de hautes tensions et ultrasons) sur l'amélioration de l'extraction des polyphénols et des protéines à partir des tiges de colza a été comparé. Ces traitements permettent d'endommager les membranes et/ou parois cellulaires de manière mécanique, électrique ou acoustique, facilitant ainsi la libération des composés intracellulaires vers le milieu extérieur. La cinétique d'extraction, le rendement en polyphenols totaux et en protéines et la consommation énergétique sont principalement étudiés. De plus, l'efficacité des traitements étudiés pour l'extraction des polyphénols et protéines, en fonction du degré de maturité de la plante a été étudiée. Les méthodes testées pour la séparation des extractibles (polyphénols et protéines) concernent la coagulation, la filtration membranaire ainsi que le couplage de ces deux méthodes afin de réduire la consommation de solvants organiques et la rétention des polyphénols au cours de séparation. La séparation des extractibles a été évaluée par le biais de l'analyse de pureté et du taux de rétention. Enfin, des effets positifs du traitement électrique sur l'étape de séparation des extractibles tels que l'augmentation du flux du perméat et la diminution du colmatage ont été remarqués. / This thesis work concerns the study and the evaluation of the extraction and the separation of valuable compounds from rapeseed residues. The impact of different treatments (grinding, pulsed electric fields, high voltage electrical discharges and ultrasound) on the enhancement of the extraction of polyphenols and proteins from rapeseed stems was compared. These treatments can damage cell membranes and 1 or cell walls mechanically, electrically or acoustically, thus facilitating the release of intracellular compounds to the surroundings. The extraction kinetics, yield of total polyphenols and proteins and energy consumption were mainly studied. In addition, influences of plant maturity on the efficiency of studied treatments for the extraction of polyphenols and proteins have been studied. The methods tested for the separation of extractives (polyphenols and proteins) include coagulation, membrane filtration and the combination of these two methods in order to reduce the consumption of organic solvents and the retention ofpolyphenols during separation. The separation of extractives was evaluated by means of analysis of purity and relative removal. Finally, positive effects of electrical treatment on the extractive separation step such as the increase ofpermeate flux and the decrease of membrane fouling have been observed.

This diploma thesis explores treatment options of wastewater with a low presence of organic pollution produced by minor pollution sources. The research part describes objects with a low presence of organic pollution in wastewater and possible treatment methods in dependence of pollution source's size. The practical part contains the design of technological options of treatment of wastewater with a low presence of organic pollution for a specific object.

[ES] La problemática de los metales pesados en cuerpos de agua superficial se ha observado a nivel mundial y ha sido objeto de múltiples estudios. La presencia de metales en concentraciones por encima de los límites establecidos adquiere mayor relevancia cuando estos se encuentran en fuentes de agua para abastecimiento público. Esta investigación toma como área de estudio a la Microcuenca Milluni, la cual se encuentra cercana de actividades mineras pasadas e ilegales que afectan directamente sobre sus recursos hídricos. Milluni está ubicada en el departamento de La Paz y es una fuente natural de agua para dos ciudades importantes de Bolivia, La Paz y El Alto (540 000 habitantes aproximadamente). El objetivo de esta tesis doctoral es estudiar la implementación de la Ósmosis Inversa (OI) operada a bajas presiones como alternativa sostenible de tratamiento para eliminar la contaminación minera en las aguas de Milluni. Adicionalmente se busca contribuir a la gestión de recursos hídricos, con énfasis en el control de la de calidad de agua en la zona. Esta investigación doctoral se desarrolló en cuatro etapas. En la primera etapa se hizo la caracterización de los cuerpos de agua superficiales para identificar el metal pesado más peligroso presente en Milluni. Para ello, se diseñó un programa de monitoreo considerando las particulares características y limitaciones en la gestión del agua del área. En la segunda etapa del estudio se formularon dos mecanismos para fortalecer la gestión del agua de Milluni, planteando complementar el programa de monitoreo tradicional con la herramienta de teledetección de contaminantes e identificar las partes interesadas de Milluni, para contribuir a la toma de decisiones de la zona. En la tercera etapa de la investigación se diseñó, montó y puso en marcha una planta piloto de OI, tecnología seleccionada debido a su alta eficiencia en la separación de compuestos iónicos del agua. Además, se realizó un diseño de experimentos para estudiar el comportamiento y eficiencia de una membrana tipo ULP 2540 Marca Keensen. Finalmente, en la cuarta etapa se desarrolló un análisis estadístico de los resultados experimentales obtenidos, y la validación de los mismos por medio de un modelo matemático basado en el modelo de concentración de polarización de Spiegler-Kedem. El modelo incluyo un factor de ajuste de temperatura tipo Arrhenius, para obtener una predicción precisa del rendimiento del proceso. Esta tesis doctoral concluye que es posible remover el arsénico presente en aguas sintéticas utilizando la OI operada en condiciones sostenibles de presión (presiones bajas). Se ha demostrado que el uso de esta tecnología a baja presión no afecta a la eficiencia de separación del proceso y contribuye a disminuir el costo energético durante la operación. Este aporte es significativo en situaciones donde se cuenta con pocos recursos económicos y existen riesgos inminentes sobre la salud pública y los ecosistemas, como es el caso de la contaminación del agua por arsénico en Milluni, Bolivia. / [CA] La problemàtica dels metals pesats en cossos d'aigua superficial s'ha observat a nivell mundial i ha segut objecte de múltiples estudis. La presència de metals en concentracions per damunt dels llímits establits adquirix major rellevància quan estos es troben en fonts d'aigua per a abastiment públic. Esta investigació pren com a àrea d'estudi a la Microcuenca Milluni, la qual es troba propenca d'activitats mineres passades i illegals que afecten directament sobre els seus recursos hídrics. Milluni està ubicada en el departament de la Pau i és una font natural d'aigua per a dos ciutats importants de Bolívia, La Pau i L'Alt (540 000 habitants aproximadament). L'objectiu d'esta tesis doctoral és estudiar l'implementació de la Òsmosis Inversa (OI) operada a baixes pressions com a alternativa sostenible de tractament per a eliminar la contaminació minera en les aigües de Milluni. Adicionalment es busca contribuir a la gestió de recursos hídrics, en émfasis en el control de la de calitat d'aigua en la zona. Esta investigació doctoral es va desenrollar en quatre etapes. En la primera etapa es va fer la caracterisació dels cossos d'aigua superficials per a identificar el metal pesat més perillós present en Milluni. Per a això, es va dissenyar un programa de monitoreo considerant les particulars característiques i llimitacions en la gestió de l'aigua de l'àrea. En la segona etapa de l'estudi es varen formular dos mecanismes per a enfortir la gestió de l'aigua de *Milluni, plantejant complementar el programa de monitoreo tradicional en la ferramenta d' teledetección de contaminants i identificar les parts interessades de Milluni, per a contribuir a la presa de decisions de la zona. En la tercera etapa de l'investigació es va dissenyar, va montar i va posar en marcha una planta pilot de OI, tecnologia seleccionada per la seua alta eficiència en la separació de composts iònics de l'aigua. Ademés, es va realisar un disseny d'experiments per a estudiar el comportament i eficiència d'una membrana tipo ULP 2540 Marca Keensen. Finalment, en la quarta etapa es va desenrollar un anàlisis estadístic dels resultats experimentals obtinguts, i la validació dels mateixos per mig d'un model matemàtic basat en el model de concentració de polarisació de Spiegler-Kedem. El model incloc un factor d'ajust de temperatura tipo Arrhenius, per a obtindre una predicció precisa del rendiment del procés. Esta tesis doctoral conclou que és possible remoure l'arsènic present en aigües sintètiques utilisant la OI operada en condicions sostenibles de pressió (pressions baixes). S'ha demostrat que l'us d'esta tecnologia a baixa pressió no afecta a l'eficiència de separació del procés i contribuïx a disminuir el cost energètic durant l'operació. Este aporte és significatiu en situacions a on es conta en pocs recursos econòmics i existixen riscs imminents sobre la salut pública i els ecosistemes, com és el cas de la contaminació de l'aigua per arsènic en Milluni, Bolívia. / [EN] The problem of heavy metals in surface water bodies has been observed worldwide and has been the subject of multiple studies. The presence of metals in concentrations above the established limits becomes more relevant when they are found in water sources for public supply. This research takes the Milluni Micro-basin as a study area, which is close to past and illegal mining activities that directly affect its water resources. Milluni is located in the department of La Paz and is a natural source of water for two important cities in Bolivia, La Paz and El Alto (approximately 540,000 inhabitants). This doctoral thesis aims to study the implementation of Reverse Osmosis (RO) operated at low pressures as a sustainable treatment alternative to eliminate mining contamination in Milluni waters. Additionally, it seeks to contribute to the management of water resources, with an emphasis on the control of water quality in the area. This doctoral research was developed in four stages. In the first stage, surface water bodies were characterized to identify the most dangerous heavy metal present in Milluni. For this, a monitoring program was started considering the particular characteristics and limitations of water management in the area. In the second stage, two mechanisms were formulated to strengthen Milluni's water management, proposing to complement the traditional monitoring study program with the contaminant remote sensing tool and to identify the invited parties of Milluni to contribute to the decision-making of the area. In the third stage of the investigation, a RO pilot plant was worked on, assembled, and started up, a technology selected due to its high efficiency in separating ionic compounds from water. In addition, a design of experiments was carried out to study the behavior and efficiency of a ULP 2540 Keensen brand membrane. Finally, in the fourth stage, a statistical analysis of the experimental results obtained was presented, and their validation using a mathematical model based on the Spiegler-Kedem polarization concentration model. The model includes an Arrhenius-type temperature adjustment factor to accurately predict the process performance. This doctoral thesis concludes that it is possible to remove the arsenic present in synthetic waters using the RO operated under sustainable pressure conditions (low pressures). It has been shown that the use of this technology at low pressure does not affect the separation efficiency of the process and contributes to lower energy costs during operation. This contribution is significant in situations with few economic resources and imminent risks to public health and ecosystems, as is the case of water contamination by arsenic in Milluni, Bolivia. / Alvizuri Tintaya, PA. (2022). Estudio de la ósmosis inversa operada a baja presión como tratamiento de una fuente natural contaminada por actividad minera, en la micro cuenca Milluni en Bolivia, para el abastecimiento de agua segura a poblaciones [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/191428

Membrane filtration processes are widely utilized across different industrial sectors for biological and environmental separations. Examples of the former are sterile filtration and protein fractionation via microfiltration (MF) and ultrafiltration (UF) while drinking water treatment, tertiary treatment of wastewater, water reuse and desalination via MF, UF, nanofiltration (NF) and reverse-osmosis (RO) are examples of the latter. A common misconception is that the performance of membrane separation is solely dependent on the membrane pore size, whereas a multitude of parameters including solution conditions, solute concentration, presence of specific ions, hydrodynamic conditions, membrane structure and surface properties can significantly influence the separation performance and the membrane’s fouling propensity. The conventional approach for studying filtration performance is to use a single lab- or pilot-scale module and perform numerous experiments in a sequential manner which is both time-consuming and requires large amounts of material. Alternatively, high-throughput (HT) techniques, defined as the miniaturized version of conventional unit operations which allow for multiple experiments to be run in parallel and require a small amount of sample, can be employed. There is a growing interest in the use of HT techniques to speed up the testing and optimization of membrane-based separations. In this work, different HT screening approaches are developed and utilized for the evaluation and optimization of filtration performance using flat-sheet and hollow-fiber (HF) membranes used in biological and environmental separations. The effects of various process factors were evaluated on the separation of different biomolecules by combining a HT filtration method using flat-sheet UF membranes and design-of-experiments methods. Additionally, a novel HT platform was introduced for multi-modal (constant transmembrane pressure vs. constant flux) testing of flat-sheet membranes used in bio-separations. Furthermore, the first-ever HT modules for parallel testing of HF membranes were developed for rapid fouling tests as well as extended filtration evaluation experiments. The usefulness of the modules was demonstrated by evaluating the filtration performance of different foulants under various operating conditions as well as running surface modification experiments. The techniques described herein can be employed for rapid determination of the optimal combination of conditions that result in the best filtration performance for different membrane separation applications and thus eliminate the need to perform numerous conventional lab-scale tests. Overall, more than 250 filtration tests and 350 hydraulic permeability measurements were performed and analyzed using the HT platforms developed in this thesis. / Thesis / Doctor of Philosophy (PhD) / Membrane filtration is widely used as a key separation process in different industries. For example, microfiltration (MF) and ultrafiltration (UF) are used for sterilization and purification of bio-products. Furthermore, MF, UF and reverse-osmosis (RO) are used for drinking water and wastewater treatment. A common misconception is that membrane filtration is a process solely based on the pore size of the membrane whereas numerous factors can significantly affect the performance. Conventionally, a large number of lab- or full-scale experiments are performed to find the optimum operating conditions for each filtration process. High-throughput (HT) techniques are powerful methods to accelerate the pace of process optimization—they allow for multiple experiments to be run in parallel and require smaller amounts of sample. This thesis focuses on the development of different HT techniques that require a minimal amount of sample for parallel testing and optimization of membrane filtration processes with applications in environmental and biological separations. The introduced techniques can reduce the amount of sample used in each test between 10-50 times and accelerate process development and optimization by running parallel tests.