Doctor of Philosophy / Department of Industrial & Manufacturing Systems Engineering / Zhijian Pei and Donghai Wang / Currently, transportation is almost entirely dependent on petroleum-based fuels (e.g. gasoline, diesel fuel, and jet fuel). Increasing demands for sustainable sources of liquid transportation fuels make it imperative to develop alternatives to petroleum-based fuels. Biofuels derived from cellulosic biomass (forest and agricultural residues and dedicated energy crops) have been recognized as promising alternatives to petroleum-based liquid fuels. Cellulosic biofuels not only reduce the nation’s dependence on foreign petroleum but also improve the environment through reduction of greenhouse gas emissions. In order to convert cellulosic biomass into biofuels, cellulosic biomass must go through a size reduction step first, because large size cellulosic biomass (whole stems of herbaceous biomass or chunks of woody biomass) cannot be converted to biofuels efficiently with the current conversion technologies. Native cellulosic biomass has limited accessibility to enzyme due to its structural complexity. Size reduction can reduce particle size and disrupt cellulose crystallinity, rendering the substrate more amenable to enzymatic hydrolysis. The purpose of this research is to provide knowledge of how size reduction alters biomass structural features, and understand the relationships between these biomass structural features and enzymatic hydrolysis sugar yield. This research is also aimed to investigate the impacts of process parameters in biomass size reduction on the conversion of cellulosic biomass to biofuels to help realize cost-effective manufacturing of cellulosic biofuels. This dissertation consists of eleven chapters. Firstly, an introduction of this research is given in Chapter 1. Secondly, Chapters 2 presents a literature review on cellulosic biomass size reduction. Thirdly, a preliminary experimental study is included in Chapter 3. Chapters 4 to 6 present a three-phase study on confounding effects of two important biomass structural features: particle size and biomass crystallinity. Chapters 7 and 8 investigate effects of sieve size used in size reduction of woody and herbaceous biomass, respectively. Chapters 9 and 10 focus on the relationship between particle size and sugar yield. Chapter 11 studies effects of cutting orientation in size reduction of woody biomass. Finally, conclusions and contributions are given in Chapter 12.

Doctor of Philosophy / Department of Agricultural Economics / Jason S. Bergtold / The adoption of new technologies on-farm is affected by socio-economic, risk management behavior, and market factors. The adoption of cellulosic biofuel feedstock enterprises and conservation practices plays an important role in the future of Kansas agriculture. No set markets currently exist for bioenergy feedstocks and farmers may be reluctant to produce the feedstocks without contracts to mitigate uncertainty and risk. Adoption of conservation practices to improve soil productivity and health may be affected by risk considerations also. The purpose of this dissertation is to study how market mechanisms and risk influence Kansas farmers’ willingness to adopt cellulosic biofuel feedstock enterprises and conservation practices on-farm. The first essay examines farmers’ willingness to grow switchgrass under contract using a stated choice approach. Data were collected using an enumerated survey of Kansas farmers and analyzed using latent class logistic regression models. Farmers whose primary enterprise is livestock are less inclined to grow switchgrass. In addition, shorter contracts, greater harvest flexibility, crop insurance, and cost-share assistance increase the likelihood farmers will grow switchgrass. The second essay examines how farmers’ risk perceptions impact conservation practice adoption. Factor analysis of survey data was used to identify primary risk management behaviors of Kansas farmers. A multinomial logit model of conservation practice adoption incorporating these risk behaviors was developed. Estimation results indicate that different risk management factors may have no significant impact on practice adoption. Farmers may not consider certain aspects of risk significant in their adoption decision. The third essay examines the effect of different risk management behaviors on farmers’ willingness to produce alternative cellulosic bioenergy feedstocks under contract. Data were collected using a farmer survey with a set of stated choice experiments and analyzed using factor analysis and latent class logistic regression models. While farmers approach risk management differently, the risk management behaviors identified have no significant impact on farmers’ willingness to produce corn stover and switchgrass but have a negative impact on farmers’ willingness to produce sweet sorghum as a biofuel feedstock. These results may indicate that farmers are indifferent toward adopting new bioenergy cropping enterprises when traditional crop production is profitable and more certain.

In order to meet the energy needs of a growing world in a sustainable manner, new high efficiency, carbon-neutral fuels and chemical feedstocks are required. An emerging approach that shows promise for high efficiency production of renewable fuels and chemicals is the use of purified enzymes combined in one pot to catalyze complex conversions: synthetic pathway biotransformations (SyPaB). An exemplary technology in this burgeoning field is the production of hydrogen from biomass sugars. Lignocellulosic biomass, which includes agricultural residues, energy crops, and industrial waste streams, is an ideal substrate for SyPaB conversion, as it is abundant and cheap, second only to untaxed coal on a $/energy content basis. But the structure of biomass is highly recalcitrant, making high-yield biological conversion difficult to achieve. In order to increase susceptibility to enzymatic digestion, thermochemical pretreatments are applied, with the goals of removing of lignin, the simplest example being soaking in aqueous ammonia (SAA); hemicellulose removal, most often using dilute acid (DA); and increasing cellulose accessibility by cellulose solvent-based pretreatments, such as cellulose solvent- and organic solvent-based lignocellulose fractionation (COSLIF). In a comparison of the lignin removal (SAA) and accessibility increase (COSLIF) approaches, we found that certain levels of lignin removal (~15%) were important, but further lignin removal was less effective at achieving digestibility gains than increasing cellulose accessibility. Pretreated biomass forms an excellent substrate for SyPaB hydrogen generation, due to low cost and high sugar content. Following experiments demonstrating the high yield conversion of sucrose to hydrogen (97%) and SyPaB generation of hydrogen at a rate commensurate with the best biological rates achieved, 157 mmol/L/h. SyPaB was combined with enzymatic hydrolysis to enable the direct conversion of cellulosic biomass, including untreated, DA, and COSLIF corn stover. In addition, an updated kinetic model of the system was used to rationally increase the maximum hydrogen production rate by 70% while minimizing total enzyme loading and without increasing substrate concentration. Together, these results demonstrate the high level of engineering control in cell-free systems, which can enable conversion of a variety of substrates to hydrogen at the highest possible yield and rates as high as any biohydrogen production method. / Ph. D.