Thesis (Ph. D.)--University of Texas at Austin, 2005. / Vita. Includes bibliographical references.

Alkaline fuel cells (AFC's) using renewable fuels are a developing technology capable of meeting market niches in standby, standalone and distributed power generation. AFC's generate electricity, heat and water using hydrogen and oxygen as fuels. While AFC's have been known and the principles demonstrated for over sixty years, their use has been restricted primarily to space applications. Recent technological developments have seen the cost of AFC stacks fall considerably; this together with several other advantages over competing fuel cell technology, has rekindled interest in commercial systems. The main deterrent to wide spread commercialisation of AFC systems is susceptibility to carbon dioxide (CO2) in atmospheric air used as the oxygen supply. AFC's require a low cost, low energy, continuous scrubbing device to reduce CO2 in air from approximately 380 parts per million (ppm) atmospheric concentration to below 50 ppm. Current technology to overcome this problem, a solid expendable absorbent called soda lime, is not viable for commercial systems. The project scope included concept generation of a device to remove CO2 from air, the development of a CO2 measurement technique, investigation of chemistry and flow phenomena to determine design relations, and product design and embodiment. The scrubber system conceived specifically for AFC systems uses the temperature swing chemistry of a liquid chemical absorbent, monoethanolamine, and a packed bubble column apparatus to provide intimate gas-liquid interaction. Prototype development proved the Carbon Dioxide Continuous Scrubber (CDOCS) concept and a Patent Cooperation Treaty (PCT) patent was granted, followed by a full American patent. A gas chromatographic measurement technique was developed to measure low ppm concentration CO2 in air, enabling regular monitoring of scrubbed gas. Carbon dioxide was separated from a small sample of scrubbed air by chromatographic columns, and the gases analysed with a thermal conductivity detector. The GC system was capable of measuring to 10 ppm with good resolution and accuracy. Experimental studies were carried out to characterise the flow dynamics and absorption phenomena in the packed bubble column absorber. The relationship between absorption performance and gas-liquid contact time, an important operating parameter for use with AFC's, was theoretically determined and later confirmed by experiment. The regeneration process was studied and the optimal regenerator design determined to be second, smaller packed bubble column. Experiments were conducted to establish design relations for regeneration temperature, flush gas flow rate and the effect of multiple regeneration cycles. A prototype CDOCS system was built to enable experimental characterisation of scrubbing performance as a function of primary design and operating parameters including liquid depth, regenerator operating temperature and solution composition. This resulted in a good understanding of the system, and an optimised experimental run was performed for cost and performance comparison to existing scrubbing technology. The CDOCS was capable of reducing CO2 in air from 380 to 80 ppm for thirty days, providing low cost, low maintenance scrubbing compared to soda lime. The capital cost of the CDOCS is considerably more than for soda lime scrubbers, and the penalty for extended operation is parasitic power consumption by the CDOCS system totalling less than 7% of fuel cell output. It is suggested that a combination of the two technologies be used initially to provide effective, low cost scrubbing for AFC and CDOCS co-development. Future work on the CDOCS project should include reduction of chemical vapour carry over to the fuel cell, followed by integration with an AFC system. This would allow further development, refinement and design for production to reduce capital cost.

Removal of water vapor from humid streams is an energy-intensive process used widely in industry. Effective dehumidification has the potential to significantly reduce energy consumption and the overall cost of a process stream. Membrane-based separations, particularly dehumidification, are an emerging technology that can change the landscape of global energy usage because they have a small footprint, they are easy to scale up, to implement and to operate. The focus of this thesis is to evaluate new directions for the development and use of materials for membrane-based dehumidification processes. It will show advances in the synthesis of new copolymers, a surprising boost in performance with the addition of 2-D materials, propose the use of polybenzimidazole for challenging dehumidification applications, and show how by tuning the nanostructure of a commercially available block copolymer (BCP) it is possible to increase the performance. The design of novel amphiphilic ternary copolymers comprising P(AN-r-PEGMA-r-DMAEMA) allowed selective removal of water vapors from gaseous streams; the effect of varying PEGMA chain length on membrane performance was studied. The membranes showed an excellent performance when the content of the PEGMA segment was 2.9 mol% with a chain length of 950Da. In the mixed-matrix approach, the inclusion of graphene oxide (GO) nanosheets in a different copolymer enhanced the membrane performance by creating selective tortuous pathways for inert gases. The well-distributed GO nanosheets in the defect-free composite membranes resulted in an 8 fold increase in water vapor/N2 selectivity compared to neat membranes. Thirdly, dense polybenzimidazole membranes showed good water vapor permeability, and the addition of TiO2-based fillers with varying chemistry and geometry enhanced the performance of PBI membranes. Lastly, the effect of tuning the morphology of commercially available BCP on dehumidification was demonstrated successfully. The self-assembled morphology formed with cylindrical hydrophobic cores, and the hydrophilic coronas, formed ion-rich highways for fast water vapor transport. Water vapor permeability improved up to 6-fold with the nanostructure modulation more than any membrane reported in the literature. In summary, the work reported in this dissertation has the potential to lay a framework towards tailor-made next-generation membranes aimed for water vapor removal in various dehumidification applications.

This research was undertaken to develop state-of-the-art interfacially polymerized (IP) defect-free thin-film composite (TFC) membranes and understand their structure-function-performance relationships. Recent research showed the presence of defects in interfacially polymerized commercial membranes which potentially deter performance in liquid separations and render the membranes inadequate for gas separations. Firstly, a modified method (named KRO1) was developed to fabricate interfacially polymerized defect-free TFCs using m-phenylene diamine (MPD) and trimesoyl chloride (TMC). The systematic study revealed the ability to heal defects in-situ by tweaking the reaction time along with considerably improving the membrane crosslinking by controlling the organic solution temperature. The two discoveries were combined to produce highly crosslinked, defect-free MPD-TMC polyamide membranes which showed exceptional performance for separating H2 from CO2. Permeance and pure-gas selectivity of the membrane increased with temperature. H2 permeance of 350 GPU and H2/CO2 selectivity of ~100 at 140 °C were obtained, the highest reported performance for this application using polymeric materials to date. Secondly, the membranes produced using KRO1 were tested for reverse-osmosis (RO) performance which revealed significantly improved boron rejection compared to commercial membranes reaching a maximum of 99% at 15.5 bar feed pressure at pH 10. The study also unveiled direct correlations between membrane crosslinking and salt separation performance in addition to the membrane surface roughness. Thirdly, this was followed by replacing the conventional IP TMC monomer with a large, rigid and contorted tetra-acyl chloride (TripTaC) monomer to enhance the performance of IP TFCs. The fabricated TFCs showed considerable performance boosts especially for separating of small solutes from organic solvents such as methanol. A rise in H2 permeance was also observed compared to the conventional MPD-TMC TFCs while reaching a maximum H2/CO2 selectivity of 9 at 22 °C. Finally, the research was completed by showing the potential of KRO1 for fabrication of defect-free TFCs using a range of aqueous diamine monomers. KRO1 enabled defect-free gas properties for all monomers used showing exceptional performance for separating H2-CO2 and O2-N2 mixtures. It was further shown that the formulation could also improve the RO separation of interfacially polymerized polyamide TFCs beyond those shown by commercially available TFCs.

Distillation technology involves capital- and energy-intensive processes for light olefin/paraffin separation. Global demand for propylene has already exceeded 110 million tons per year. Therefore, distillation processes used for the separation of C3H6/C3H8 should be replaced or debottlenecked with more efficient and cost-effective technology. In the last three decades, membrane-based gas separation processes have successfully emerged, thus competing with conventional separation processes. Membranes potentially offer lower capital investment and operation cost than distillation columns. In this study, the use of advanced membrane materials for C3H6/C3H8 separation was investigated. Three novel triptycene-based polyimides were synthesized by Dr. Bader Ghanem from one diamine monomer, namely 2,6-dihydroxy-3,7-diaminotriptycene (DTA1-OH), and three dianhydride monomers, (i) non-substituted triptycene tetracarboxylic dianhydride (TDA), (ii) 9,10-dimethyltriptycene tetracarboxylic dianhydride (TDA1) and (iii) 9,10-iso-propyltriptycene tetracarboxylic dianhydride (TDAi3). It is important to note that polyimide membranes based on triptycene dianhydrides and triptycene diamines have never been reported in the literature before. Pure-gas permeability coefficients of He, H2, N2, O2, CO2, CH4, C3H6, and C3H8 were determined at 2 bar and 35 °C. Furthermore, C3H6 and C3H8 gas sorption isotherms were measured by gravimetric techniques, and experimental data were collected up to 7 bar at 35 °C. TDA-DAT1-OH, TDA1-DAT1-OH, TDAi3-DAT1-OH exhibited C3H6 permeability of 12.1, 16.6, and 5.64 Barrer with pure-gas C3H6/C3H8 selectivity of 35.7, 29.6, and 32.8 respectively. These properties exceeded the 2003 pure-gas upper bound for C3H6/C3H8. The BET surface area increased in the order of TDA-DAT1-OH (437 m2/g) < TDAi3-DAT1-OH (467 m2/g) < TDA1-DAT1-OH (557 m2/g). The frecational free volume (FFV) increased in the order of TDAi3-DAT1-OH (0.25) < TDA-DAT1-OH (0.28) < TDA1-DAT1-OH (0.30). TDA1-DAT1-OH (109 μm) showed less and slower physical aging than TDA-DAT1-OH (94 μm) after 60 days, where the O2 and CO2 permeability of both polyimides decreased by about 40% and 69%, respectively. After 30 days, TDAi3-DAT1-OH displayed the highest selectivity gain relative to its counterparts and exceeded the 2008 upper bound for CO2/CH4. TDA1-DAT1-OH exhibited 7-fold higher C3H6 permeability coupled with almost 3-fold higher C3H6/C3H8 selectivity relative to a previously reported commercial polyphenylene oxide (PPO) membrane.

The synthesis of highly porous organic polymers with predefined porosity has attracted considerable attention due to their potential in a wide range of applications. Porous organic polymers (POPs) offer novel properties such as permanent porosity, adjustable chemical nature, and noteworthy thermal and chemical stability. These remarkable properties of the POPs make them promising candidates for use in gas separation and storage. The emission of carbon dioxide (CO2) from fossil fuel combustion is a major cause of global warming. Finding an efficient separation and/or storage material is essential for creating a cleaner environment. Therefore, the importance of the POPs in the field is undeniable. Along these pursuits, several porous polymers have been synthesized with different specifications. The first class of porous polymers are called Covalent Organic Frameworks (COFs). They possess highly ordered structures with very high surface areas and contain light elements. COFs based on B-O, C-N, and B-N bonds have been reported so far. In particular, COFs based on B-O bond formation are well investigated due to the kinetically labile nature of this bond which is essential for overcoming the crystallization problem of covalent networks. Along this line, triptycene-derived covalent organic framework (TDCOF-5) has been synthesized through a condensation reaction between 1, 4-benzenediboronic acid and hexahydroxytriptycene which leads to the formation of boronate ester linkage. TDCOF-5 has the highest H2 uptake under 1 atm at 77K (1.6%) among all known 2D and 3D COFs derived from B–O bond formation and moderate CO2 uptake (2.1 mmol g-1) with Qst values of 6.6 kJ mol-1 and 21.8 kJ mol-1, respectively. The second class of porous structures discussed herein is diazaborole linked polymers (DBLPs). They are constructed based on B-N bond formation and possess amorphous structures due to the lack of the reversible bond formation processes. At this scope, 2, 3, 6, 7, 14, 15-hexaaminotriptycene (HATT) hexahydrocloride was synthesized and reacted with different boronic acid derivatives to produce three different porous polymers under condensation reaction conditions. DBLP-3, -4 and -5 have very high surface areas; 730, 904, and 986 m2 g-1, and offer high CO2 uptake (158.5, 198, and 171.5 mg g-1) at 1 bar and 273 K, respectively. DBLPs have much higher CO2 uptake capacity when compared to almost all reported B-N and B-O containing porous polymers in the field. In addition to high CO2 capacity, DBLPs showed remarkable CO2/N2 and CO2/CH4 selectivity, when the Henry`s law of initial slope selectivity calculations were applied. In general, DBILPs exhibit high selectivities for CO2/N2 (35-51) and CO2/CH4 (5-6) at 298 K which are comparable to those of most porous polymers.

The use of polymeric membranes for natural gas separation has rapidly increased during the past three decades, particularly for carbon dioxide separation from natural gas. Another valuable application is the separation of heavy hydrocarbons from methane (fuel gas conditioning), more importantly for remote area and off-shore applications. A new potential polymeric membrane that might be utilized for natural gas separations is a Tröger’s base ladder polymer (PIM-Trip-TB-2). This glassy polymeric membrane was synthesized by the polymerization reaction of 9, 10-dimethyl-2,6 (7) diaminotriptycene with dimethoxymethane. In this research, the polymer was selected due to its high surface area and highly interconnected microporous structure. Sorption isotherms of nitrogen (N2), oxygen (O¬2), methane (CH4), carbon dioxide (CO2), ethane (C2H6), propane (C3H8), and n-butane (n-C4H10) were measured at 35 °C over a range of pressures using a Hiden Intelligent Gravimetric Analyzer, IGA. The more condensable gases (C2H6, CO2, C3H8, and n-C4H10) showed high solubility due to their high affinity to the polymer matrix. The permeation coefficients were determined for various gases at 35 °C and pressure difference of 5 bar via the constant-pressure/variable-volume method. The PIM-Trip-TB-2 film exhibited high performance for several high-impact applications, such as O2/N2, H2/N2 and H2/CH4. Also, physical aging for several gases was examined by measuring the permeability coefficients at different periods of time. Moreover, a series of mixed-gas permeation tests was performed using 2 vol.% n-C4H10/98 vol.% CH4 and the results showed similar transport characteristics to other microporous polymers with pores of less than 2 nm. The work performed in this research suggested that PIM-Trip-TB-2 is suitable for the separation of: (i) higher hydrocarbons from methane and (ii) small, non-condensable gases such as O2/N2 and H2/CH4.