Proton exchange membrane (PEM) fuel cells are considered one of the best potential alternative power sources for automobiles. For this application, high efficiency and high power density are required. Pressurizing the fuel cell system can give higher efficiency, higher power density and better water balance characteristics for the fuel cell, but pressurization uses a percentage of the fuel cell output power. The compressor used to elevate the pressure has a direct effect on the system efficiency and water balance characteristics. A variety of compressors are being developed for fuel cell applications. Two compressor and expander technologies are discussed in this paper: the Opcon 1050 positive displacement twin-screw compressor and expander, and a Honeywell turbocompressor and expander. The effect of these compressors and expanders on the system at maximum load, low load, and set minimum airflow are examined. The effects of ambient conditions, stack temperature, and increased twin-screw compressor pressure are also examined. The turbocompressor proves to be a superior machine in terms of efficiency, and therefore offers the most promising effect on system efficiency of the two compressors. The twin-screw compressor, on the other hand, offers more flexible pressure ratio and better water balance characteristics at low fuel cell loads, which is an important factor with PEM fuel cell systems. Increased ambient and stack temperature has a significant negative effect on the water balance and a small positive effect on efficiency. Increasing the pressure for the twin-screw compressor significantly improves the water balance characteristics with some loss in efficiency. These results show the importance of determining the system operating range and operating conditions in the choice of a compressor for a fuel cell system / Master of Science

Doctor of Philosophy / Department of Grain Science and Industry / Sajid Alavi / The Renewable Fuel Standard (RFS) in the Energy Independence and Security Act of 2007 has set the goal of 36 billion gallons of annual ethanol production in the U.S. by 2022, which is equivalent to 17.5% of the current gasoline consumption in the U.S. However, corn ethanol is expected to plateau at a level of 7.3% of current gasoline consumption on an energy-equivalent basis. Thus, it is essential to utilize a variety of substrates including lignocellulosic biomass from perennial energy crops such as switch grass, crop residues such as corn and sorghum stover, and agri-industrial co-products such as soybean hulls and wheat bran. Lignocellulosic substrates have a recalcitrant nature and require a pretreatment step that is critical for efficient enzymatic hydrolysis of cellulose and hemicellulose to fermentable sugars. In this study, soybean hulls were used as a model substrate for cellulosic ethanol. A novel thermo-mechanical pretreatment process using extrusion was investigated and compared with two traditional pretreatment methods, dilute acid and alkali hydrolysis, with regard to structural changes in the lignocellulosic substrate, and glucose and ethanol yields. The effect of extrusion parameters, such as barrel temperature, in-barrel moisture and screw speed, on glucose yield from soybean hulls was determined. Optimum processing conditions were screw speed of 350 rpm, maximum barrel temperature of 80C and 40% in-barrel moisture content, resulting in 95% cellulose conversion to glucose. Compared with untreated soybean hulls, the cellulose to glucose conversion of soybean hulls increased by 69.5, 128.4 and 132.2% for dilute acid, alkali and thermo-mechanical pretreatments, respectively. Glucose and other hexose sugars such as mannose and galactose were effectively fermented by Saccharomyces cerevisiae, resulting in ethanol yields of 13.04–15.44 g/L. Fermentation inhibitors glycerol, furfural, 5-(hydroxymethyl)-2-furaldehyde (HMF) and acetic acid were found in the thermo-mechanically pretreated substrate, ranging in concentrations from 0.072–0.431, 0–0.049, 0–0.023 and 0.181–0.278 g/L, respectively, which were lower than those reported from acid hydrolyzed substrates. The economic feasibility of commercial cellulosic ethanol production processes employing dilute acid hydrolysis and thermo-mechanical pretreatment were compared using a system dynamics modeling approach. It was concluded that low feedstock cost and high sugar conversion are important factors that can make cellulosic ethanol production commercially viable. Thermo-mechanical pretreatment was a more promising technology as compared to dilute acid hydrolysis because of the lower capital and operating costs, and higher sugar conversion.

This research addresses the manufacturing problems of the fuel cell in an applied industrial approach with the aim of investigating the technology of manufacturing of Proton Exchange Membrane (PEM) fuel cells, and using this technology in reducing the cost of manufacturing through simplifying the design and using less exotic materials. The first chapter of this thesis briefly discusses possible energy alternatives to fossil fuels, arriving at the importance of hydrogen energy and fuel cells. The chapter is concluded with the main aims of this study. A review of the relevant literature is presented in chapter 2 aiming to learn from the experience of previous researchers, and to avoid the duplication in the current work. Understanding the proper working principles and the mechanisms causing performance losses in fuel cells is very important in order to devise techniques for reducing these losses and their cost. This is covered in the third chapter of this thesis which discusses the theoretical background of the fuel cell science. The design of the fuel cell module is detailed in chapter 4, supported with detailed engineering drawings and a full description of the design methodology. So as to operate the fuel cell; the reactant gases had to be prepared and the performance and operating conditions of the fuel cell tested, this required a test facility and gas conditioning unit which has been designed and built for this research. The details of this unit are presented in chapter 5. In addition to the experimental testing of the fuel cell under various geometric arrangements, a three dimensional 3D fully coupled numerical model was used to model the performances of the fuel cell. A full analysis of the experimental and computational results is presented in chapter 6. Finally, the conclusions of this work and recommendations for further investigations are presented in chapter 7 of this thesis. In this work, an understanding of voltage loss mechanism in the fuel cell based on thermodynamic irreversibility is introduced for the first time and a comprehensive formula for efficiency based on the actual operating temperature is presented. Furthermore, a novel design of a 100W (PEMFC) module which is apt to reduce the cost of manufacturing and improve water and thermal management of the fuel cell is presented. The work also included the design and manufacturing of a test facility and gas conditioning unit for PEM fuel cells which will be useful in performing further experiments on fuel cells in future research work. Taking into consideration that fuel cell technology is not properly revealed in the open literature, where most of the work on fuel cells does not offer sufficient information on the design details and calculations, this thesis is expected to be useful in the manifestation of fuel cell technology. It is also hoped that the work achieved in this study is useful for the advancement of fuel cell science and technology.

<p>This dissertation shows the use of Constructal law to find the relation between the morphing of the system configuration and the improvements in the global performance of the complex flow system. It shows that the better features of both flow and heat transfer architecture can be found and predicted by using the constructal law in energy systems. Chapter 2 shows the effect of flow configuration on the heat transfer performance of a spiral shaped pipe embedded in a cylindrical conducting volume. Several configurations were considered. The optimal spacings between the spiral turns and spire planes exist, such that the volumetric heat transfer rate is maximal. The optimized features of the heat transfer architecture are robust. Chapter 3 shows the heat transfer performance of a helically shaped pipe embedded in a cylindrical conducting volume. It shows that the optimized features of the heat transfer architecture are robust with respect to changes in several physical parameters. Chapter 4 reports analytically the formulas for effective permeability in several configurations of fissured systems, using the closed-form description of tree networks designed to provide flow access. The permeability formulas do not vary much from one tree design to the next, suggesting that similar formulas may apply to naturally fissured porous media with unknown precise details, which occur in natural reservoirs. Chapter 5 illustrates a counterflow heat exchanger consists of two plenums with a core. The results show that the overall flow and thermal resistance are lowest when the core is absent. Overall, the constructal design governs the evolution of flow configuration in nature and energy systems.</p> / Dissertation

Currently, in the United States, on-road vehicles are primarily powered by petroleum fuels (gasoline and diesel). These vehicles have caused serious climate change effects from emissions of greenhouse gas (GHG) and health and environmental impacts from criteria air pollutant (CAP). The recent success of shale gas development has brought industry interest in using natural gas to power on-road vehicles. In addition to low costs and wide availability of this national fuel source, natural gas is a common feedstock to produce alternative fuels. The question arises of whether using natural gas for transportation could help or hinder the environment. In this dissertation, I study the economic and environmental effects of a wide range of natural gas fuel pathways for a selection of light duty (LDV) and medium and heavy duty (MHDV) vehicle types. I choose to focus on two environmental metrics: GHGs and CAPs emitted over the life cycle of each potential pathway for natural gas use. First in Chapters 2 and 3, I use life-cycle analysis to understand the emissions of GHGs from different natural gas pathway for LDVs and MHDVs. Then in Chapter 4 I focus on the CAP emissions from these vehicles. Overall, I find that none of the natural gas pathways eliminate life cycle air emissions. In fact, only a few pathways reduce life cycle GHG emissions and/or life cycle air pollution damages compared to baseline petroleum fuels (gasoline for light-duty vehicles (LDVs) and diesel for heavy-duty vehicles (HDVs)). For the cases of light duty vehicles (LDVs) and transit buses, battery electric vehicles (BEVs) powered by natural gas-based electricity provide significant reduction in life cycle GHG emissions and life cycle air pollution damages (for almost all counties) compared to the baseline petroleum fuels. However, the actual electricity that charges BEVs may not be natural gas-based electricity in most parts of the U.S. When powered by U.S. grid electricity (using average emission factors for 2010 and 2014), BEVs reduce life cycle GHG emissions to a lesser extent but increase life cycle air pollution damages significantly. Compressed natural gas (CNG), while reducing GHG emissions and CAP emissions (except CO) at tailpipe, are more likely to increase life cycle GHG emissions and increase life cycle air pollution damages in the majority of U.S. counties. For heavy-duty trucks, CNG sparking-ignition (SI) trucks and liquefied natural gas (LNG) high-pressure direct ignition (HPDI) trucks have mixed environmental impacts. While they are unlikely to reduce life cycle GHG emissions compared to diesel, they reduce life cycle air pollution damages in 76-99% of U.S. counties for local-haul tractor-trailers and in 32-71% of U.S. counties for long-haul tractor-trailers. In Chapters 5 and 6, I examine the economic impacts of natural gas fuel pathways for two vehicle types, tractor-trailers and transit buses. I study the economic feasibility of a national natural gas refueling infrastructure for long-haul trucks in U.S., which is a prerequisite for natural gas tractor-trailers. I find that a transition to natural gas fuels in long-haul trucks is more expensive when the shares of natural gas trucks are below 5% because of low refueling demands and over-capacity of the refueling infrastructure to ensure network coverage. At higher shares of natural gas trucks, both the total refueling capacity and the net economic benefits of the national refueling infrastructure increase almost linearly as adoption increases. Finally, in Chapter 6, I provide an economic-technology assessment for transit buses by considering both life cycle ownership costs and life cycle social costs due to GHG emissions and CAP emissions. Transit buses are early adopters of alternative fuel technologies because of funding supports and operation characteristics (such as high fuel consumption and private refueling infrastructure). I find that the availability of external funding is crucial for transit agencies to adopt any alternative fuel option. Without external funding, only rapid-charging battery electric buses (BEBs) have lower ownership & social costs than conventional diesel buses. When external funding is available to reduce bus purchase costs by 80%, BEBs become much more cost-effective. In this case, life cycle ownership and social costs of BEBs are 37-43% lower than conventional diesel buses. Including life cycle social costs does not change the ranking of alternative fuel options. The findings in this dissertation suggest different strategies of using natural gas for different vehicle markets. Natural gas is best used in electric power generation than to produce gaseous or liquid fuels for powering on-road LDVs. The use of CNG and LNG for heavy-duty trucks may continue as there are less alternative fuel options but issues such as methane leakage should be addressed to avoid important climate change effect. Finally, natural gas-based transportation fuels can at best partially mitigate climate change or air pollution damages, so other mitigation strategies in the transportation sector are ultimately needed to achieve sustainable transportation.

The United States leads the world in per capita production of Municipal Solid Waste (MSW), generating approximately 200 million tons per year. By 2000 A.D. the US EPA predicts a 20% rise in these numbers. Currently the major strategies of MSW disposal are (i) landfill and (ii) incineration. The amount of landfill space in the US is on a rapid decline. There are -10,000 landfill sites in the country, of which only 65-70% are still in use. The Office of Technology Assessment (OTA) predicts an 80% landfill closure rate in the next 20 years. The development of a viable energy resource from MSW, in the form of densified Refuse Derived Fuel (dRDF), provides solutions to the problems of MSW generation and fossil fuel depletions. Every 2 tons of MSW yields approximately 1 ton of dRDF. Each ton of dRDF has an energy equivalent of more than two barrels of oil. At current production rates the US is "throwing away" over 200,000,000 barrels of oil a year. In order to be considered a truly viable product dRDF must be extensively studied; in terms of it's cost of production, it's combustion properties, and it's potential for environmental pollution. In 1987 a research team from the University of North Texas, in conjunction with the US DOE and Argonne National Laboratory (ANL), cofired over 550 tons of dRDF and bdRDF with a high sulfur Kentucky coal in a boiler at ANL. This work examines the emission rates of polychlorinated dioxins (PCDDs) and furans (PCDFs) during the combustion of the dRDF, bdRDF, and coal. Even at levels of 50% by Btu content of dRDF in the fuel feedstock, emission rates of PCDDs and PCDFs were below detection limits. The dRDF is shown to be an environmentally acceptable product, which could help resolve one of the major social and environmental problems facing this country today.

Driven by the fact that the global oil market has become extremely volatile and the EU dependence on oil continues to grow, this paper argues that with more emphasis on renewable energy and by using domestically produced alternative energy sources instead of importing foreign oil the EU Member States would drastically improve their energy security and energy independence. The study investigates both past and present trends in the EU energy sources supply and consumption patterns. Additionally, the paper considers possibilities of the renewable and alternative energy both at the current stage and future development of this sector in the EU. The research findings confirm the initial hypothesis as to whether the share of alternative and renewable energy will be sufficiently large to contribute to solving a problem of the EU energy security and independency. The role of the renewables in national energy security strategies of three EU Member States is studied and government supporting policies that enhance renewable sources development are analyzed.

Doctor of Philosophy / Department of Chemistry / Stefan H. Bossmann / Porin A from Mycobacterial smegmatis (MspA) is an octameric trans-membrane channel protein and is one of the most stable porins known to date. MspA has been successfully isolated and purified to obtain liquid extracts and crystals using a modified extraction procedure. A full analytical assessment has been carried out to authenticate its’ structure, including gel electrophoresis, spectroscopy (fluorescence, UV, FTIR, NMR), HPLC, Bradford protein assay, dynamic light scattering and X-ray crystallography. Nanoscopic vesicle formation of MspA molecules in aqueous media has been thoughroughly investigated. Temperature dependent dynamic light scattering experiments reveal that size of such vesicles is dependent on temperature but is independent of ionic strength of the medium. Zeta potential measurements reveal a steady build up of positive charge on the vesicle surface with increasing temperature. For the first time, wild type (WT) MspA has been utilized as a channel forming agent. This phenomenon has future potential in DNA sequencing and the development of antimycobacterial drugs. Channel activity of WT MspA and mutant A96C MspA has been investigated and has shown to form stable channels across DPhPC lipid bilayers. Blocking of the channel current via external molecules (i.e. channel blocking) is an extremely important process, which helps to evaluate the biosensor ability of the pore. In this regard, two Ruthenium based compounds, Ru(QP-C2)38+ (i.e. RuC2) and Ru(bpy)32+have been successfully employed as channel blocking agents. Both compounds show evidence for channel blocking of WT MspA. However, these results are not reproducible. Three dimensional aggregation behavior of RuC2-MspA vesicles have been thoughroughly investigated. It is evident that addition of RuC2 significantly increases vesicle size and polydispersity of MspA aggregates in solution. The results provide explanations onto the lack of channel blocking ability of MspA by RuC2. Development of a ‘greener’ dye sensitized solar cell with the use of MspA as an electron carrier is investigated for the first time. A series of Ru(II)-phenanthroline-based dyes have been synthesized as non-toxic dyes in this regard. Chemical binding between the dyes and MspA has been achieved successfully. Two types of solar cell prototypes, i.e. TiO2-based (Grätzel type) and FTO-based have been developed and tested. Significant current generation and conversion efficiencies have been achieved for both cell types. This marks the first development of a protein-based photovoltaic device, which has the potential to be developed as a new class of “hybrid soft solar cells”.

Master of Science / Department of Biological and Agricultural Engineering / Donghai Wang / Biomass torrefaction is an important preprocessing step in improving biomass quality, specifically in terms of physical properties and chemical composition. The objective of this research was to study effects of torrefaction as a pretreatment method on chemical and elemental compositions and thermal properties of Conservation Reserve Program (CRP) biomass. Most CRP grasslands are a mixture of native grasses, and in the state of Kansas, species including indiangrass, big bluestem, little bluestem, sideoats grama, and switchgrass comprise a majority of CRP grounds. Pure forms of big bluestem biomass were analyzed and compared with a mixture of the species that make up CRP lands. Two strategies for torrefaction were tested: one with a pre-dry step and one without. After torrefaction, big bluestem and CRP biomass showed an increase in energy density, making the biomass more attractive as a biofuel source than raw biomass. Big bluestem also showed slightly higher calorific values than that of CRP biomass. The torrefaction process had a significant effect on chemical composition and elemental composition of the biomass. Carbon content increased and oxygen content decreased as torrefaction temperature increased. Glucan and xylose decreased and lignin increased as torrefaction temperature increased. Pre-drying biomass before torrefaction is beneficial to torrefaction of biomass with high moisture content because moisture removal leads to less dry matter loss while maintaining the same calorific value.

Master of Science / Department of Agricultural Economics / Jeffery Williams / Ethanol has become an important source of energy for transportation purposes in the U.S. The majority of the feedstock for this ethanol is corn grain. The use of crop residues and perennial grasses has been proposed as an alternative feedstock for ethanol production using cellulosic conversion processes. Commercial scale production of cellulosic ethanol is still on the horizon. In the meantime a wide variety of studies examining both the technical and economic feasibility of cellulosic ethanol production have been conducted. This is the first study that combines both county level cellulosic feedstock production and farmer participation rates to determine the feasibility of supplying it to cellulosic ethanol plants. This research determines the economic feasibility of supplying cellulosic feedstocks to seven potential add-on cellulosic ethanol plants of 25 million gallons per year at seven existing starch ethanol plants in Kansas. The feedstocks considered are corn stover, sorghum stalks, wheat straw, and perennial switchgrass. A mixed integer programing model determines the amount and mix of cellulosic feedstocks that can be delivered to these plants over a range of plant-gate feedstock prices given transportation costs and farm-gate production costs or breakeven prices. The variable costs of shipping are subtracted from the difference between plant-gate price and farm-gate price to find savings to the plant. The objective function of the model minimizes transportation costs which in turn maximizes savings to the plant. The role switchgrass may have as a feedstock given various switchgrass production subsidies is examined. The results indicate the minimum plant-gate price that must be paid to feedstock producers for all plants to have enough cellulosic feedstocks is $75 per dry ton. Switchgrass feedstocks were only a minor portion of biomass supplied and used without a production subsidy. A Biomass Crop Assistance Program payment increased the supply of switchgrass more than other production subsidies.