No description available.

The glassy copolyimide 6FDA-DAM:DABA was investigated as a polymer backbone for membranes used in aggressive sour gas separation applications. An esterification crosslinking mechanism enabled the synthesis of materials with augmented H₂S/CH₄ selectivity and plasticization resistance. These materials make use of polyethylene glycol (PEG) crosslinking agents and are referred to as PEGMC polymers. Rigorous dense film characterization of the novel crosslinkable materials indicates that excellent H₂S/CH₄ selectivity (24) is achievable while still maintaining high CO₂/CH₄ selectivity (29) under high pressure ternary mixed gas (CO₂/H₂S/CH₄) feeds. Defect-free asymmetric hollow fiber membranes were formed and appropriate crosslinking conditions were determined, allowing for the characterization of these fibers under realistic sour gas feed conditions. Also, a PDMS post-treatment was used to give ultra-high permselectivity for aggressive feeds. Using several mixed gas feeds containing high concentrations of CO₂ and H₂S at feed pressures up to 700 psig, it is shown that the crosslinked asymmetric hollow fiber membranes developed and manufactured through this work are capable of maintaining excellent separation performance even under exceedingly taxing operating conditions. For example, CO₂/CH₄ and H₂S/CH₄ permselectivity values of 47 and 29, respectively, were obtained for a 5% H₂S, 45% CO₂, 50% CH₄ feed at 35°C with 700 psig feed pressure. An extremely aggressive 20% H₂S, 20% CO₂, 60% CH₄ mixed gas feed with 500 psig feed pressure was also used; the maximum CO₂/CH4 and H₂S/CH₄ permselectivity values were found to be 38 and 22, respectively.

No description available.

Mixed matrix membranes (MMM) offer one potential path toward exceeding the Robeson upper bound of selectivity versus permeability for gas separation performance while maintaining the benefits of solution processing. Many inorganic materials, such as zeolites, metal-organic frameworks, or carbon nanotubes, can function as molecular sieves, but as stand-alone membranes are brittle and difficult to manufacture. Incorporating them into a more robust polymeric membrane matrix has the potential to mitigate this issue. In this work, phase inversion polymer solution processing for the fabrication and testing of asymmetric flat sheet mixed matrix membranes was employed with CVD-derived multiwall carbon nanotubes (MWCNTs) dispersed in a polyethersulfone (PES) matrix. The effect of MWCNT loading on membrane separation performance was examined. Notably, a distinct enhancement in selectivity was measured for several gas pairs (including O2/N2) at relatively low MWCNT loading, with a peak in selectivity observed at 0.1 wt% loading relative to PES. In addition, no post-treatment (e.g. PDMS caulking) was required to achieve selectivity in these membranes. In contrast, neat PES membranes and those containing greater than 0.5 wt.% MWCNT showed gas selectivity characteristic of Knudsen diffusion through pinhole defects. These results suggested that at low loading, the presence of MWCNTs suppressed the formation of surface defects in the selective layer in flat sheet mixed matrix membranes. Additionally, a bench-scale, single-filament hollow fiber membrane spinning line was designed and purpose-built at the University of Kentucky Center for Applied Energy Research (CAER). Hollow fiber membrane spinning capability was developed using polyethersulfone (PES) solution dopes, and the process was expanded to include polysulfone (PSf) as well as mixed matrix membranes. The effects of key processing parameters, including the ratio of bore to dope velocities, the spinning air gap length, and the draw-down ratio, were systematically investigated. Finally, direct hollow fiber analogues to flat sheet mixed matrix membranes were characterized. Consistent with the flat sheet experiments, the mixed matrix hollow fiber membranes showed a local maximum in selectivity at a nominal loading of 0.1 wt.% MWCNT relative to the polymer, suggesting that the pinhole suppression effect introduced by MWCNTs was not limited to flat sheet membrane casting. The development of asymmetric hollow fiber mixed matrix membrane processing and testing capability at the UK Center for Applied Energy Research provides a platform for the further development of gas separation membranes. Using the tools developed through this work, it is possible to further push the frontiers of mixed matrix gas separation by expanding the capability to include more polymers, inorganic fillers, and post treatment processes which previously have been focused primarily on the flat sheet membrane geometry.

No description available.

Electrically conductive membranes (ECMs) are of significant research interest for their ability to mitigate fouling, enhance separation capacity, and induce electrochemical degradation of contaminants. Most ECM development has been in flat sheet format suitable for laboratory studies; in industrial applications, formats such as hollow fiber (HF) are preferred for their high packing density. While ECMs in HF format are emerging in research, these techniques typically employ the same methods proven for flat sheet, often involving direct deposition of conductive material onto a support membrane with no further investigation into how the deposition process affects ECM properties. This is a significant challenge for long (~1 m) HF membranes where coating uniformity is essential to ensure consistent performance. The goal of this project was to fabricate conductive HF membranes, ensuring uniform performance along the fiber. In this work, we have developed a “crossflow deposition” technique to deposit a uniform layer of single walled/ double walled carbon nanotubes (SW/DWCNTs) onto the interior surface of commercial polyether sulfone HF membranes. In a design-of-experiments model, feed pressure and crossflow velocity were shown to directly impact composite membrane conductivity and permeability. The highest permeability (~2900 LMH/bar) and conductivity (~670 S/m) were both achieved at the high pressure (0.2 bar) and high crossflow velocity (1.06 cm/s) condition. An inverse relationship was identified between conductivity and permeability for 29 different HF membranes coated under various flow and particle loading conditions. Similar trends were evident in ECM literature when comparing 80 membranes across 38 papers, covering various conductive materials, separation types, configurations, and applications. Metallic-based ECMs outperformed graphitic nanomaterial or conductive polymer-based ECMs with conductivities three orders of magnitude higher. This review also revealed a wide variation in performance testing with 35 unique pollutants in 63 total tests, indicating a need for standardization to accurately compare ECMs and a need for testing with more realistic feed sources. Finally, electrochemical degradation of methyl orange using the CNT-coated HF membranes was evaluated in batch and continuous removal experiments. Although no significant MO removal was detected in either configuration, these modules can be used for further optimization in terms of targeted conductivity, contact time, and electrochemical parameters such as applied voltage. This work highlights the existence of a conductivity/ permeability trade-off in ECM development and how manipulation of flow parameters during deposition can impact this trade-off in HF membrane development. / Thesis / Master of Applied Science (MASc) / Membrane separation technologies are a common purification strategy in many fields due to their simplicity and low energy requirements. Membranes operate by rejecting particles from feed water based on their chemical or physical properties such as size or charge. Long-term membrane operations are limited by fouling, incurring large operating costs for frequent cleaning cycles and downtime. Furthermore, traditional membrane separations only physically remove particles, presenting a risk for contaminant re-introduction into the environment. Electrically conductive membranes are an emerging strategy for addressing these concerns due to their demonstrated antifouling, enhanced selectivity, and redox capabilities. To date, these membranes have almost exclusively been developed as flat sheets with limited research into other membrane formats. Hollow fiber membranes resemble thin tubes ~1 mm in diameter and up to ~1 m in length where filtration occurs through the tubular wall of the fiber; the small diameter allows for hundreds of fibers to pack into an individual module, thus maximizing throughput. In this thesis, several issues with hollow fiber conductive membrane fabrication are addressed to ensure consistent performance along the length of the fiber. A key trade-off between membrane surface conductivity and throughput was found to exist universally in the conductive membrane field. This knowledge can be used to select fabrication methods and parameters to target certain performance ranges.

No description available.

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.