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Climate change, industrial and agricultural activities, and population growth exacerbate global water stress. A variety of advanced technologies have been studied to alleviate water scarcity and water pollution. Membrane technology owing to its low footprints and ease of operation, has drawn intensive attention for water purification and wastewater treatment. Further, integrating membrane technology, electrochemistry and catalysis can improve separation and selectivity of the filtration process. This work aims to fabricate high-performance active and reactive ultrafiltration membranes involving electrically conductive membranes, catalytic membranes and electrocatalytic membranes. Their use in water treatment inspires the development of advanced functionalized membranes and further accelerates the transition to industrial applications. / Thesis / Doctor of Engineering (DEng)

Thesis (MTech (Chemical Engineering))--Cape Peninsula University of Technology, 2006 / A protocol already exists for fabrication of a capillary membrane having an internal ultrafiltration skin supported by a finger-like pore structure in the external capillary wall (Jacobs and Leukes, 1996; Jacobs and Sanderson, 1997). These membranes have been produced at the Institute of Polymer Science, University of Stellenbosch, South Africa. Two major applications emerged from the development of these internally skinned membranes. One application was in the production of potable water by Ultra-filtration (UF) from sources containing coloured water. A second application was in the immobilization of a white rot fungus in a ."gradostat" membrane bioreactor. Here a nutrient gradient through the membrane wall and fungal mat can be established and manipulated in order to stimulate continuous production of secondary metabolites (extra-cellular enzymes). These enzymes are useful in the degradation of polycyclic aromatic compounds, notably PCB species in contaminated water and soils (Jacobs and Sanderson, 1997). Two objectives emerged from experiences with the above applications. The first objective was to improve membrane performance in UF applications. In this case a reduction was sought in trans-membrane pressure differential required to attain a desired flux without sacrificing rejection. The pressure required for a given desired flux across a membrane depends on the resistance of the membrane skin layer and of its supporting sub-layer which together comprises the capillary wall and defmes its overall structure. If any of these resistances could be reduced, the overall resistance to transport of water would be reduced. Then it would be possible to operate the membrane at lower trans-membrane pressure differences. On the other hand, operation with higher pressure would also increase flux but require a thicker capillary wall to resist this pressure. In the attempt to optimise these properties of the capillary membrane, capillary membranes produced in the study reported here were tested to find the relationship of flux performance with the structures that resulted from varying key parameters affecting structure and integrity. The objective in the case of immobilizing fungi in membrane bioreactor applications was to attain thicker walls thus providing better support for the fungal mass. The internally skinned capillary membrane has finger-like microvoids that start next to the UF skin layer and extend across the capillary membrane wall and open at the external membrane periphery, giving an ideal structure for retaining the fungal biomass. The idea of a membrane with this type of morphology to immobilize white rot fungi was to anchor the growing fungus within these microvoids which imitate the natural environment in which these organisms live, that is, in the fibrous structure of decaying wood. The requirement to inoculate the microvoids with fungal spores (reproductive cells), implies that they need to be accessible from the outside, requiring a membrane wall that is externally unskinned. In the formation ofthe capillary membrane the processes of formation of the porous UP skin and the finger-like microvoids are mainly governed by diffusion of solvent out of a polymer dope (gel phase) and of non-solvent into the dope phase. Such exchanges are of primary importance between the bore fluid (containing non-solvent) and dope (containing solvent) or between the external spinning bath (high in solvent content) and dope. Diffusion effects also occur between the nascent pore voids and the precipitating polymer matrix. There are also expected to be some convection effects due to shear between the bore fluid and the moving dope gel phase and due to shrinkage ofthe gel phase. The variables selected for experimentation m the study reported here were: the dope extrusion rate (DER); dope composition (viscosity effects); bore fluid flow rate (BFF); bore fluid composition and wall thickness and diameter effects (determined largely by spinneret dimensions). Each of these has an expected effect on membrane structure and its resulting performance. Most were varied over narrow ranges indicated in the literature and by experience to be effective and critical. In addition, the effects of altering the walI thickness were investigated by using two different spinneret sizes. The external spinning bath composition (solvent content) was reported in the literature to be a particularly important parameter in the formation of externally unskinned membranes. Maintaining a high content of solvent in the external spinning bath could prevent skin formation. Too high a solvent content could, however, prevent phase transition and lead to later precipitation ofa dense skin on contact with the non-solvent in the later (humidification and rinsing) steps in the fmishing of the capillary membrane product. The external bath composition was therefore varied so as to find the bath composition that would match the cloud point for the polymer dope employed. As expected, the thickness of the membranes increased with DER increase. However, it was found that there is a critical wall thickness where an external skin layer is formed as a result of increasing the DER. A certain volumetric ratio ofDER to BFF (1,5:1 for this study) was therefore maintained in order to produce externally unskinned membranes. This shows that although the final membrane structure is detennined by the casting dope formulation, the fabrication protocol plays an equally important role in controlling structural properties and perfonnance. There was no significant change with the membrane thickness as a result of changing BFF but the voids became longer and more in number as the BFF was increased. Too high solvent content (99% NMP in this study) resulted in an external skin layer being formed. According to Smolders et.al. (1992), when the solvent content in the external spinning bath is too high, the polymer at the surface of the newly fonned membrane slowly dissolves in the external spinning bath re-forming a dope-like solution. When the newly formed membrane passes through the humidifier, the dope-like solution solidifies to form an external skin. At the same instance, too low solvent (93% for this study) resulted in external skin being fonned. Externally unskinned membranes were formed at 94 and 96% NMP bath composition. The use of a small spinneret resulted in very thin walled externally unskinned membranes.

A dry-jet wet-spinning process developed industrially for the preparation of hollow fibre membranes suitable for gas separation applications, has been reproduced on a laboratory scale. Polysulphone hollow fibres were spun from a variety of solvents and their gas transport properties were characterized using equipment built during the course of the research. The phase inversion process of membrane formation was studied in order that the best morphological structure could be produced. The spinning parameters were studied to establish their influence on the fibre dimensions. Further relationships were then sought between the gas transport properties and the fibre dimensions and spinning parameters. The behaviour of the membranes to both single gases and gas mixtures was studied. Both the permeation rate constants and the separation factors determined from the mixture permeation were found to be lower than the values predicted from the single gas permeation experiments. A model was developed to help understand the competitive nature of the adsorption-diffusion process and explain the differences in values recorded from the single gas and mixture studies. Experiments aimed at improving membrane performance were based on modification of the already established polysulphone hollow fibre. Modification of the selective surface layer of the hollow fibre membranes was considered to be the best approach. Coating of the fibres, other than to repair damage to the skin layer, was found to result in too large a decrease in permeability. Sulphonation of the surface layer was achieved using sulphur trioxide, although little improvement in the membrane performance was recorded. The sulphonation experiment results were, however, sufficiently encouraging to recommend future work.

There is a considerable volume of work available in literature which suggests that the performance of axial-flow hollow fibre membrane modules is limited by poorly distributed flow through the shell-side. This study was commissioned to examine the distribution of shell-side flow and its effect on mass transfer and to compare the performance measured by the axial-flow configuration to that obtained by a commonly used alternative known as the helically-wound module design. Laminar flow and mass transfer models have been developed to examine performance through axial-flow hollow fibre modules. These models also consider deviations from laminar flow in the form of turbulence and hydrodynamically undeveloped flow. Modelling analysis on four fibre bundle cross-sections quantify the extent to which channelling limits flow and mass transfer performance. Experimental flow and mass transfer work with locally fabricated hollow fibre modules demonstrated some inconsistencies with axial laminar flow modelling. Pressure drop and mass transfer results exceeded predictions from modelling. This thesis has hypothesised that fibres in axial-flow hollow fibre modules are not aligned as straight and parallel rods (as assumed in modelling) but interweave. Fibre interweaving results in flows between ducts. Such flows create mixing between ducts which results in more intimate contact between the flow and membrane surface, the consequence being higher pressure drop and higher mass transfer. The implication from this work was that axial flow and mass transfer modelling was limited in its use for characterisation of shell-side performance. The experience with helically-wound hollow fibre membrane modules (also fabricated locally) was that, by deliberately inducing flow between ducts, it was possible to considerably improve mass transfer performance. It was found that, whilst helically-wound modules could not be packed as tightly as axial-flow modules and required more sophisticated fabrication techniques, the benefit in their use arose from a substantial improvement in the level of shell-side mass transfer.

Sustainable energy supply and environmental protection are the major global scientific challenges in the 21st century, such as greenhouse gas capture, natural gas production, desalination of seawater for clean water production. Membrane separation technology offers attractive energy-efficient and environmental-friendly solutions to these challenges. This PhD thesis is focused on design and fabrication of membranes from novel molecularly defined polymers and understanding their physical properties, particularly the transport properties of gas molecules in polymer membranes. First, we demonstrate a simple approach of fabricating novel polymer nanocomposite membranes using established colloidal science. Crystalline microporous zeolitic imidazolate frameworks (ZIFs) nanocrystals are incorporated into a polyimide polymer matrix via solution mixing. The resulting nanocomposite membranes show excellent dispersion of nanoparticles, good adhesion at the interface, and enhanced gas permeability while the selectivity remain at high level. We then fabricated membranes from novel microporous polymers, polymers of intrinsic microporosity (PIMs). Using the PIM-1 polymer as a prototype, we discovered that ultraviolet irradiation of PIM-1 membranes in the presence of oxygen induces oxidative chain scission at the surface, resulting in local densification and structural transformation of free volume elements. Consequently, the membrane become asymmetric with a more gas-selective layer formed at the surface, while the overall permeability maintains at high level. Finally, we report a simple thermal oxidative crosslinking method to tailor the architecture of channels and free volume elements in PIM-1 polymer membrane by heat treatment in the presence of trace amounts of oxygen molecules. The resulting covalently crosslinked polymer networks offer superior thermal stability, chemical stability, reasonable mechanical strength, and enhanced rigidity. Most important of all, thermally crosslinked PIM-1 polymer membranes show significantly enhanced molecular sieving functions that yield remarkably high selectivity and high gas permeability, which surpass the upper bound that has been limiting the polymer membranes for decades. We also demonstrate that the thermal crosslinking method is effective for crosslinking of nanocomposite membranes with porous or nonporous fillers. These microporous molecular sieve membranes are promising for a wide range of molecular-level separation applications.

<p>Over the past 40 years, research pertaining to membrane technology has lead to the development of a wide range of applications including beverage production, water purification and the separation of dairy products. For the separation of gases, membrane technology is not as widely applied since the production of suitable gas separation membranes is far more challenging than the production of membranes for eg. water purification. Hydrogen is currently produced by recovery technologies incorporated in various chemical processes. Hydrogen is mainly sourced from fossil fuels via steam reformation and coal gasification. Special attention will be given to Underground Coal Gasification since it may be of great importance for the future of South Africa. The main aim of this study was to develop low temperature CsHSO4/SiO2 composite membranes that show significant Idea selectivity towards H2:CO2 and H2:CH4.</p>

Olefin/Paraffin separation, traditionally carried out by cryogenic distillation, is difficult to achieve due to the similar size and volatility of the components. Recently, many studies have explored membrane separation methods that utilize a metal ion to facilitate preferential olefin transport across the membrane. However, much of this work focuses on smaller molecules, C2-C3, which are gaseous at room temperature, while little work has been done studying separation of larger molecules, C5 and greater, which are generally liquid at room temperature. The processes developed to separate small molecules are not necessarily directly applicable to separate larger molecules. A polymer electrolyte membrane consisting of an active layer of polyethylene oxide (PEO) and silver tetrafluoroborate (AgBF4) has shown high selectivity for separating gaseous olefin/paraffin mixtures. The current project investigates the feasibility of applying this membrane to the separation of pentene and pentane (liquid C5 olefin and paraffin). Process variables investigated are the: pure component permeability ratio, equilibrium sorption uptakes, pure component diffusivities, and stable membrane lifetime. Permeation tests on individual species (n-pentane and 1-pentene) were performed in two operating modes with membranes of varying silver concentrations: direct liquid contact to the membrane, and vapour contact to the membrane. The vapour contact mode showed improved membrane stability in comparison to the liquid contact mode. The olefin/paraffin permeability ratio increases with increasing silver content in the membrane, however, the membrane selectivity is much lower than that achieved with smaller olefin/paraffin pairs. Selective chemical interactions between pentene and the membrane were observed, as the pentene sorption uptake is higher than that of pentane. In addition, a residual fraction is observed – a fraction of the pentene does not desorb from the membrane at ambient conditions – indicating a permanent or semi-permanent interaction. Desorption of pentane is determined to follow a Fickian diffusion model, while desorption of pentene appears to be governed by pseudo-second order kinetics.

Olefin/Paraffin separation, traditionally carried out by cryogenic distillation, is difficult to achieve due to the similar size and volatility of the components. Recently, many studies have explored membrane separation methods that utilize a metal ion to facilitate preferential olefin transport across the membrane. However, much of this work focuses on smaller molecules, C2-C3, which are gaseous at room temperature, while little work has been done studying separation of larger molecules, C5 and greater, which are generally liquid at room temperature. The processes developed to separate small molecules are not necessarily directly applicable to separate larger molecules. A polymer electrolyte membrane consisting of an active layer of polyethylene oxide (PEO) and silver tetrafluoroborate (AgBF4) has shown high selectivity for separating gaseous olefin/paraffin mixtures. The current project investigates the feasibility of applying this membrane to the separation of pentene and pentane (liquid C5 olefin and paraffin). Process variables investigated are the: pure component permeability ratio, equilibrium sorption uptakes, pure component diffusivities, and stable membrane lifetime. Permeation tests on individual species (n-pentane and 1-pentene) were performed in two operating modes with membranes of varying silver concentrations: direct liquid contact to the membrane, and vapour contact to the membrane. The vapour contact mode showed improved membrane stability in comparison to the liquid contact mode. The olefin/paraffin permeability ratio increases with increasing silver content in the membrane, however, the membrane selectivity is much lower than that achieved with smaller olefin/paraffin pairs. Selective chemical interactions between pentene and the membrane were observed, as the pentene sorption uptake is higher than that of pentane. In addition, a residual fraction is observed – a fraction of the pentene does not desorb from the membrane at ambient conditions – indicating a permanent or semi-permanent interaction. Desorption of pentane is determined to follow a Fickian diffusion model, while desorption of pentene appears to be governed by pseudo-second order kinetics.

<p>Over the past 40 years, research pertaining to membrane technology has lead to the development of a wide range of applications including beverage production, water purification and the separation of dairy products. For the separation of gases, membrane technology is not as widely applied since the production of suitable gas separation membranes is far more challenging than the production of membranes for eg. water purification. Hydrogen is currently produced by recovery technologies incorporated in various chemical processes. Hydrogen is mainly sourced from fossil fuels via steam reformation and coal gasification. Special attention will be given to Underground Coal Gasification since it may be of great importance for the future of South Africa. The main aim of this study was to develop low temperature CsHSO4/SiO2 composite membranes that show significant Idea selectivity towards H2:CO2 and H2:CH4.</p>