Thesis (M.Sc.)--Memorial University of Newfoundland, 2003. / Includes bibliographical references. Also available online.

Thesis (M.Sc.)--Memorial University of Newfoundland, 2003. / Includes bibliographical references. Also available online.

Thesis (Ph.D.)--Hong Kong University of Science and Technology, 2005. / Includes bibliographical references (leaves 137-145). Also available in electronic version.

Anthropogenic greenhouse gas emissions (GHG) contribute to global warming, and must be mitigated. With GHG mitigation as an overarching goal, this research aims to study the potential for newfound and abundant sources of natural gas to play a role as part of a GHG mitigation strategy. However, recent work suggests that methane leakage in the current natural gas system may inhibit end-use natural gas as a robust mitigation strategy, but that natural gas as a feedstock for other forms of energy, such as electricity generation or liquid fuels, may support natural-gas based mitigation efforts. Flaring of uneconomic natural gas, or outright loss of natural gas to the atmosphere results in greenhouse gas emissions that could be avoided and which today are very large in aggregate. A central part of this study is to look at a new technology for converting natural gas into methanol at a unit scale that is matched to the size of individual natural gas wells. The goal is to convert stranded or otherwise flared natural gas into a commercially valuable product and thereby avoid any unnecessary emission to the atmosphere. A major part of this study is to contribute to the development of a novel approach for converting natural gas into methanol and to assess the environmental impact (for better or for worse) of this new technology. This Ph.D. research contributes to the development of such a system and provides a comprehensive techno-economic and environmental assessment of this technology. Recognizing the distributed nature of methane leakage associated with the natural gas system, this work is also intended to advance previous research at the Lenfest Center for Sustainable Energy that aims to show that small, modular energy systems can be made economic. This thesis contributes to and analyzes the development of a small-scale gas-to-liquids (GTL) system aimed at addressing flared natural gas from gas and oil wells. This thesis includes system engineering around a design that converts natural gas to synthesis gas (syngas) in a reciprocating internal combustion engine and then converts the syngas into methanol in a small-scale reactor. With methanol as the product, this research aims to show that such a system can not only address current and future natural gas flaring regulation, but eventually can compete economically with historically large-scale, centralized methanol production infrastructure. If successful, such systems could contribute to a shift away from large, multi-billion dollar capital cost chemical plants towards smaller systems with shorter lifetimes that may decrease the time to transition to more sustainable forms of energy and chemical conversion technologies. This research also quantifies the potential for such a system to contribute to mitigating GHG emissions, not only by addressing flared gas in the near-term, but also supporting future natural gas infrastructure ideas that may help to redefine the way the current natural gas pipeline system is used. The introduction of new, small-scale, distributed energy and chemical conversion systems located closer to the point of extraction may contribute to reducing methane leakage throughout the natural gas distribution system by reducing the reliance and risks associated with the aging natural gas pipeline infrastructure. The outcome of this thesis will result in several areas for future work. From an economic perspective, factors that contribute to overall system cost, such as operation and maintenance (O&M) and capital cost multiplier (referred to as the Lang Factor for large-scale petro-chemical plants), are not yet known for novel systems such as the technology presented here. From a technical perspective, commercialization of small-scale, distributed chemical conversion systems may create a demand for economical compression and air-separation technologies at this scale that do not currently exist. Further, new business cases may arise aimed at utilizing small, remote sources of methane, such as biogas from agricultural and municipal waste. Finally, while methanol was selected as the end-product for this thesis, future applications of this technology may consider methane conversion to hydrogen, ammonia, and ethylene for example, challenging the orthodoxy in the chemical industry that “bigger is better.”

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Direct Methanol Fuel Cells (DMFCs) are a promising source of energy due to their potentially high energy density, facilitated fuel delivery and storage, and precluded fuel processing. However, DMFCs have several challenges which need to be resolved before they can replace existing energy sources. Some of the challenges include lower power density, relatively high cost, and uncertain reliability. These issues are all promoted, at least in part, by the methanol crossover phenomenon, wherein membrane permeability allows the undesirable species transport of methanol from anode to cathode. This phenomenon also causes the requirement of dilute fuel mixtures, which is undesirable from an energy density viewpoint. Steady flow polarization curves were first analyzed at various concentrations. An optimal concentration range was found wherein both methanol crossover and concentration losses were effectively minimized. During the study of transient phenomena, the fuel was first temporarily discontinued. It was found that a significant cell potential enhancement occurred due to anodic fuel concentration reduction and thus depleting the reactant crossover. The percentage voltage increase was considerably greater at higher concentrations. Based on the fuel discontinuation, a hydraulic pulsing operation was developed and tested. During some of these continuous pulsing schemes, fuel discontinuation did not result in an instantaneous cell potential enhancement mainly due to the internal inertia of the membrane. Nonetheless, a significant cell potential and fuel efficiency enhancement was observed. In addition, the pulse of both fuel and current density resulted in a significant power density increase.

The goal of this dissertation was to create a new class of DMFC targeted at high energy density and low loss for small electronic devices. In order for the DMFC to efficiently use all its fuel, with a minimum of balance of plant, a low-loss proton exchange membrane was required. Moderate conductivity and ultra low methanol permeability were needed. Fuel loss is the dominant loss mechanism for low power systems. By replacing the polymer membrane with an inorganic glass membrane, the methanol permeability was reduced, leading to low fuel loss. In order to achieve steady state performance, a compliant, chemically stable electrode structure was investigated. An anode electrode structure to minimize the fuel loss was studied, so as to further increase the fuel cell efficiency. Inorganic proton conducting membranes and electrodes have been made through a sol-gel process. To achieve higher voltage and power, multiple fuel cells can be connected in series in a stack. For the limited volume allowed for the small electronic devices, a noble, compact DMFC stack was designed. Using an ADMFC with a traditional DMFC including PEM, twice higher voltage was achieved by sharing one methanol fuel tank. Since the current ADMFC technology is not as mature as the traditional DMFCs with PEM, the improvement was accomplished to achieve higher performance from ADMFC. The ultimate goal of this study was to develop a DMFC system with high energy density, high energy efficiency, longer-life and lower-cost for low power systems.

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In this work, a hybrid power module comprising of a direct methanol fuel cell (DMFC) and a Li-ion battery has been proposed for low power applications. The challenges associated with low power and small DMFCs were investigated and the performance of commercial Li-ion batteries was evaluated. At low current demand (or low power), methanol leakage through the proton exchange membrane (PEM) reduces the efficiency of a DMFC. Consequently, a proton conducting methanol barrier layer made from phospho-silica glass(PSG) was developed. At optimized deposition conditions, the PSG layers had low methanol permeability and moderate conductivity. The accumulation of CO2 inside the fuel tank was addressed by fabricating CO2 vents. Poly (dimethyl siloxane) (PDMS) and poly (1-trimethyl silyl propyne) (PTMSP) base polymers were used as the backbone material for these vents. The selectivity of CO2 transport through the vent was further enhanced by using additives like 1, 6-divinylperfluorohexane. Finally, the effects of self-discharge and voltage loss were evaluated for Panasonic coin cells and thin film LiPON cells. It was observed that the thin film battery outperformed the others in terms of low energy loss. Nonetheless, the performance of small Panasonic coin cells with vanadium oxide cathode was comparable at low discharge rates of less than 0.01% depth of discharge. Lastly, it was also observed that the batteries have stable cycles at low discharge rates.

Includes bibliographical references (p. 115-129).