Efforts to reduce the United States’ dependence on foreign petroleum encourage the production of fuels from bioenergy crops. Recent energy mandates have therefore “opened doors” for alternative feedstock sources for ethanol production. Switchgrass is a candidate feedstock. Under the University of Tennessee’s Biofuels Initiative, the University of Tennessee, partnering with DuPont-Danisco Cellulosic Ethanol LLC, contracted for the production of switchgrass with local farmers to guarantee biomass feedstock supply for an ethanol conversion research facility. This study used methods borrowed from the social psychology literature in combination with economic theory to analyze factors influencing switchgrass farmers’ intentions to continue growing switchgrass after contracts with the granting agent expired. Understanding what motivates producers to make long term commitments to switchgrass production as an energy crop may be important information for private investors who will rely on a fixed supply of switchgrass. A probit model was used to determine the factors affecting producers’ intentions to continue producing switchgrass after their contract expires. Results suggest that community perceptions about the production of switchgrass as a dedicated energy crop may have an important impact on farmers’ intentions to make a long-term commitment to produce switchgrass. Therefore, educating and involving community and extension personnel may have a positive impact on farmers’ decisions to make long-term commitments to grow switchgrass as a dedicated energy crop.

Bioenergy will play an important role in reaching the EU targets for renewable energy. Sweden, with abundant forest resources and a well-established forest industry, has a key position regarding modern biomass use. Biomass gasification (BMG) offers several advantages compared to biomass combustion-based processes, the most prominent being the possibility for downstream conversion to motor fuels (biofuels), and the potential for higher electrical efficiency if used for electricity generation in a biomass integrated gasification combined cycle (BIGCC). BMG-based processes in general have a considerable surplus of heat, which facilitates integration with district heating or industrial processes. In this thesis integration of large-scale BMG, for biofuel or electricity production, with other parts of the energy system is analysed. Focus is on forest-based biomass, with the analysis including techno-economic aspects as well as considerations regarding effects on global fossil CO2 emissions. The analysis has been done using two approaches – bottom-up with detailed case studies of BMG integrated with local systems, and top-down with BMG studied on a European scale. The results show that BMG-based biofuel or electricity production can constitute economically interesting alternatives for integration with district heating or pulp and paper production. However, due to uncertainties concerning future energy market conditions and due to the large capital commitment of investment in BMG technology, forceful economic support policies will be needed if BMG is a desired route for the future energy system, unless oil and electricity prices are high enough to provide sufficient incentives for BMG-based biofuel or electricity production. While BMG-based biofuel production could make integration with either district heating or pulp and paper production economically attractive, BIGCC shows considerably more promise if integrated with pulp and paper production than with district heating. Bioenergy use is often considered CO2-neutral, because uptake in growing plants is assumed to fully balance the CO2 released when the biomass is combusted. As one of the alternatives in this thesis, biomass is viewed as limited. This means that increased use of bioenergy in one part of the energy system limits the amount of biomass available for other applications, thus increasing the CO2 emissions for those applications. The results show that when such marginal effects of increased biomass use are acknowledged, the CO2 mitigation potential for BMG-based biofuel production becomes highly uncertain. In fact, most of the BMG-based biofuel cases studied in this thesis would lead to an increase rather than the desired decrease of global CO2 emissions, when considering biomass as limited. / Bioenergi spelar en viktig roll för att nå EU:s mål för förnybar energi. Sverige har med sina goda skogstillgångar och sin väletablerade skogsindustri en nyckelposition vad gäller modern bioenergianvändning. Förgasning av biomassa har flera fördelar jämfört med förbränningsbaserade processer - i synnerhet möjligheten att konvertera lågvärdiga råvaror till exempelvis fordonsdrivmedel. Används gasen istället för elproduktion kan en högre verkningsgrad nås om gasen används i en kombicykel, jämfört med i en konventionell ångturbincykel. De förgasningsbaserade processerna har i allmänhet ett betydande överskott av värme, vilket möjliggör integrering med fjärrvärmesystem eller industriella processer. I denna avhandling analyseras integrering av storskalig biomassaförgasning för drivmedelseller elproduktion, med andra delar av energisystemet. Skogsbaserad biomassa är i fokus och analysen behandlar såväl teknoekonomiska aspekter, som effekter på globala fossila CO2-utsläpp. Forskningen har gjorts på två olika systemnivåer - dels i form av detaljerade fallstudier av biomassaförgasning integrerat med lokala svenska system, dels i form av systemstudier på europeisk nivå. Resultaten visar att förgasningsbaserad biodrivmedels- eller elproduktion kan komma att utgöra ekonomiskt intressanta alternativ för integrering med fjärrvärme eller massa- och papperstillverkning. På grund av osäkerheter i fråga om framtida energimarknadsförhållanden och på grund av de höga kapitalkostnaderna som investering i förgasningsanläggningar innebär, kommer kraftfulla ekonomiska styrmedel krävas om biomassaförgasning är en önskad utvecklingsväg för framtidens energisystem, såvida inte olje- och elpriserna är höga nog att i sig skapa tillräckliga incitament. Medan förgasningsbaserad drivmedelsproduktion kan vara ekonomiskt attraktivt att integrera med såväl fjärrvärme som med massa- och papperstillverkning, framstår förgasningsbaserad elproduktion som betydligt mer lovande vid integrering med massa- och papperstillverkning. Användning av bioenergi anses ofta vara CO2-neutralt, eftersom upptaget av CO2 i växande biomassa antas balansera den CO2 som frigörs när biomassan förbränns. Som ett av alternativen i denna avhandling ses biomassa som begränsad, vilket innebär att ökad användning av bioenergi i en del av energisystemet begränsar den tillgängliga mängden biomassa för andra användare, vilket leder till ökade CO2-utsläpp för dessa. Resultaten visar att när hänsyn tas till denna typ av marginella effekter av ökad biomassaanvändning, blir potentialen för minskade globala CO2-utsläpp med hjälp av förgasningsbaserade tillämpningar mycket osäker. I själva verket skulle de flesta av de förgasningsbaserade drivmedel som studerats i denna avhandling leda till en utsläppsökning, snarare än den önskade minskningen.

Biodrivmedel blev efter millennieskiftet en alltmer prioriterad energikälla för EU och ansågs kunna stävja både klimathot och energissäkerhetsproblem samtidigt som drivmedelsproduktionen skulle gynna sysselsättningen i jordbruket. EUkommissionen formulerade 2007 ett mål om att ersätta 10 % av transportenergin till biodrivmedel. Snabbt uppkom dock en strid mellan en grupp av aktörer (miljörörelse och livsmedelsindustri) som såg biodrivmedelssatsningen som ett hot mot både miljön och livsmedelssäkerheten medan en annan grupp bestående av företrädesvis biodrivmedelsintressenter såg det som viktigt att behålla och utveckla EU:s mål för att rädda både klimat och miljö. Motsättningarna som uppkommit väcker frågor kring vilka logiker som legat bakom detta. Avhandlingens syfte är att analysera EU:s biodrivmedelspolicy, vilka aktörer och nätverk som har format denna process, vilka problem och lösningar som dessa aktörer och nätverk argumenterat för i processen, samt hur de har agerat för att mobilisera stöd för sina ståndpunkter. Detta har kopplats till teorier om nätverksstyrning, förekomsten av utlösande händelser i policyprocessen, resursberoende i nätverksmodellen samt på vilket sätt managementteori utövat inflytande. Metoden har varit att utifrån dokumentstudier rekonstruera det historiska förloppet och de aktörer som medverkat i processen. Avhandlingens visar att en förhållandevis liten grupp aktörer har haft ett stort inflytande över policyprocessen från det att problemen som biodrivmedel var satta att lösa definierades i slutet av 80-talet till det att hållbarhetsstandarder utvecklades och implementerades. Dessa aktörer har funnits i policynätverkens kärna och har som ett av sina centrala mål velat utarbeta globala regelverk för råvaruhandeln. De miljöorganisationer som medverkat i processen har genom resursberoenden till stor del varit underordnade denna grupp. Processerna har innehållit ett stort inslag av strategisk planläggning men även utlösande händelser som klimat- och livsmedelskriser har varit viktiga för att motivera politiska beslut. / Biofuels became a prioritized energy source for the EU in the new millennium. It was believed that biofuels would suppress both climate change and problems with energy security, and would simultaneously benefit agricultural employment. The EU Commission decided in 2007 that 10 % of the energy used in transportation would be replaced by biofuels. This was, however, soon criticized by a group of actors (environmental associations and the food industry) that saw the biofuels initiative as a threat to both the environment and food security. The biofuels proponents, on the other hand, argued that it was important to maintain and develop the EU’s biofuels objectives to save both the climate and the environment. These contradictions raised my interest to understand and analyze the logics that lie behind these different perspectives on the same issue. The aim of this thesis is to analyze the EU's biofuels policy, which actors and networks shaped this process, which problems and solutions these actors and networks put forward in the process, and how they have acted to mobilize support for their positions. Theoretically, I have applied theories on policy networks, the occurrence of triggering events in the policy process, resource dependence between actors and networks, and how management theory can be used to understand how policy develops. The main results are that a relatively small group of actors has had a strong influence on the policy process. These actors have been at the core of the policy community. The environmental organizations involved in the process have been subordinate to this policy community through resource dependencies. One actor network was formed that wanted to increase the amount of biofuels, while another was formed to protect the forest and soil from heavy exploitation. It took over 20 years before these contradicting efforts collided. This thesis concludes that the process contained large elements of strategic planning and that triggering events such as climate and food crises have been important to justify political decisions.

Biofuels are of particular interest as they have the potential to reduce our dependence on petroleum-derived fuels for transportation. 1-Hexanol is a promising renewable long chain alcohol that can be used in conventional fuel blends or as a cosolvent for biodiesel mixtures. However, the fundamental combustion properties of 1-hexanol have not been fully characterized in the literature. Thus, new experimental results, consisting of temperature and concentration profiles of stable species were obtained for the oxidation of 1-hexanol generated in an opposed-flow diffusion flame at 0.101 MPa. The kinetic model consists of 361 chemical species and 2687 chemical reactions (most of them reversible). This experimental data were compared to the predicted values of a detailed chemical kinetic model proposed in literature to study the combustion of 1-hexanol. Reaction pathway and sensitivity analyses were performed to interpret the results. In addition, several improvements were investigated to optimize the proposed chemical kinetic mechanism.

Biofuels are of particular interest as they have the potential to reduce our dependence on petroleum-derived fuels for transportation. 1-Hexanol is a promising renewable long chain alcohol that can be used in conventional fuel blends or as a cosolvent for biodiesel mixtures. However, the fundamental combustion properties of 1-hexanol have not been fully characterized in the literature. Thus, new experimental results, consisting of temperature and concentration profiles of stable species were obtained for the oxidation of 1-hexanol generated in an opposed-flow diffusion flame at 0.101 MPa. The kinetic model consists of 361 chemical species and 2687 chemical reactions (most of them reversible). This experimental data were compared to the predicted values of a detailed chemical kinetic model proposed in literature to study the combustion of 1-hexanol. Reaction pathway and sensitivity analyses were performed to interpret the results. In addition, several improvements were investigated to optimize the proposed chemical kinetic mechanism.

Six ã-Al2O3 supported metallic nitride and carbide catalysts were chosen for a scouting test for the production of a diesel fuel cetane enhancer from canola oil. The six catalysts chosen for study were ã-Al2O3 supported molybdenum (Mo) carbide and nitride, tungsten (W) carbide and nitride, and vanadium (V) nitride and carbide. All six catalysts were prepared by the impregnation method and characterized using various techniques. The six catalysts were screened for their affinity for oxygen removal, fatty acid conversion, alkane/olefin selectivity, hydrogen consumption, and gas-by product production from oleic acid. The scouting test was carried out at a reaction temperature of 390°C, a LHSV of 0.46 hr-1, and elevated hydrogen partial pressures of greater than 7000 kPa, in a laboratory microreactor in an upflow configuration. The scouting test revealed that the two molybdenum catalysts performed the best with oxygen removal near 100% and alkane/olefin content of greater than 30%. <p>Next, the supported molybdenum carbide and nitride catalysts were compared against one another over a wider range of operating conditions. A temperature range of 380 390°C, a LHSV range of 0.64 1.28 hr-1, and a hydrogen partial pressure of 7100 kPa were used. Both catalysts had the same metal loading of 7.4 wt% molybdenum. The two catalysts were compared on the basis of oxygen removal, alkane/olefin selectivity, diesel fuel selectivity, and hydrogen consumption, while using both triolein and canola oil as the feed. It was found that the supported molybdenum nitride was the superior choice for this process, specifically when using the more complex canola oil feed. The supported molybdenum nitride catalyst delivered oxygen removal of greater than 85%, alkane/olefin selectivity of greater than 20%, and diesel fuel selectivity of greater than 40%, for all conditions studied. <p>Finally, a preliminary catalyst and process optimization was carried out on the chosen ã-Al2O3 supported molybdenum nitride catalyst. The catalyst optimization consisted of varying the metal loading of the catalyst from 7.4 wt% to 22.7 wt%. The catalysts were examined over a temperature range of 390 410°C, a LHSV range of 0.9 1.2 hr-1, and a hydrogen partial pressure of 8300 kPa, with canola oil as the chosen feed. It was found that the increase in molybdenum loading on the catalyst delivered an average increase in the alkane/olefin selectivity of 43.2% and an average increase in the diesel fuel selectivity of 5.3 %. The process optimization studied a temperature range of 390 410°C, a LHSV range of 0.6 1.2 hr-1, and a hydrogen partial pressure range of 7800 - 8900 kPa, with canola oil as the chosen feed. Within the limits of the design, it was found that the optimum operating conditions were 395°C, 1.05 hr-1, and 8270 kPa. At these conditions the predicted yields of alkane/olefin products and diesel fuel are 47.3 and 50.5 g/100g liquid fed, respectively.

Ion exchange resins, commonly used in water treatment, demonstrate promise for the production of biodiesel from biomass feedstocks. The goal of this presented PhD research is to investigate novel uses of ion exchange resins for processing biodiesel feedstocks. Specifically, this research explored using ion exchange resins to remove free fatty acids (FFA) from soybean and waste cooking oils, catalyze transesterification of soybean oil, and catalyze in-situ conversion of dried algal biomass to biodiesel and other recoverable organics. The effect of temperature, moisture content, mixing rate, and resin drying on deacidification of soybean oil with 5% oleic acid feedstock was explored using Dowex Monosphere MR-450 UPW within a batch reactor. The resins were observed to remove up to 83 +/- 1.3% of FFA from soybean oil with less than 5% moisture content while operated at a 20% resin loading at 50 degrees C while mixing at 550 rpm. Once operation characteristics impacting deacidification were evaluated, a series of experiments were carried out to demonstrate the use of mixed bed resin to remove FFA from waste cooking oils. An investigation of wash solutions capable of regenerating the resins was also carried out. Using methanol to regenerate the resins resulted in more than 40% FFA removal over three regeneration cycles, highlighting the utility of resin regeneration as a cost saving measure. Transesterification of soybean oil on Amberlyst A26-OH, a basic ion exchange resin, in the presence of excess methanol was carried out to determine the mechanism of the reaction occurring on the surface. A batch reactor approach was used and reactions were carried out with and without FFA present in the soybean oil feed stock at a 20% resin loading at 50 degrees C while mixing at 550 rpm. When FFA was present in the feedstock and methanol is present in excess, the rate constant for methanol consumption increased. Based upon model fitting, the rate constant of methanol consumption was determined to be 2.08 x 10^-7 /sec with FFA absent and 5.39 x 10^-4/sec when FFA is present when the Eley-Rideal model was used to fit the data. In-situ conversion of dried algal biomass to biodiesel and other recoverable organics was investigated using a batch reaction system with 1 gram of algae. The system was operated with 40:60 methanol:hexane as the solvent system operated at 50 degrees C while mixing at 550 rpm over a range of catalyst loadings. The highest observed ester yield, approximately 60% yield (37 mg_ester/g_algae), was observed when air dried algae was reacted with a 20% resin. An evaluation of the reaction products showed a mixture of esters, phytol, alcohols, and ketones; highlighting the complexity of the reactions occurring during in-situ biomass conversion.

The aviation industry represents approximately 3% of global greenhouse gas emissions, however with significant growth expected over the coming decades this proportion is expected to increase. Continued governmental and social pressure to reduce global emissions is posing a challenging question to the industry; how to improve environmental efficiency and reduce emissions with increasing industry growth. The environmental impact of aviation globally is discussed, examining the significant emissions and protocols that exist and their relative impacts both environmentally and economically. The viability of alternative biofuels is discussed, determining the life cycle environmental impact of future replacements to kerosene based jet fuel. This thesis therefore aims to provide an understanding of the fundamentals of aviation emissions but also most importantly provide possible solutions to assist the industry in reducing its emissions ‘footprint’. An important factor in determining efficiency improvements is to understand the impact of particular stages of an aircraft life and the impact they have individually. This was achieved using an established methodology called Life Cycle Assessment (LCA), which is an efficient tool for the analytical consideration of the environmental impact of manufacturing, operation and decommissioning. The results of a comprehensive LCA study of an Airbus A320 are documented considering all phases of the service life. The study draws useful conclusions, indicating the significance of special materials such as carbon fibre reinforced plastic (CFRP) on the total manufacturing emissions of the aircraft and indicating its operational phase as the one contributing most in its environmental performance breakdown. The thesis also examines short-term efficiencies for emissions reduction in commercial aviation, focussing on improvements in aircraft routing. The initiation of the EU emissions trading system (ETS) within European aviation willincentivise airlines to reduce their annual CO2 emissions. An alternative routing strategy is proposed for selected long haul routes, which introduces multiple stages into the route utilising two aircraft and is shown to reduce total CO2 emissions by up to 13.7%. Combined with blended biofuel, this reduction was estimated to increase to 16.6% with a reduction in ticket fares estimated to be as high as $19 per passenger per flight.

Volatility of oil prices along with major concerns about climate change, oil supply security and depleting reserves have sparked renewed interest in the production of biofuels and biochemicals. While the carbohydrate portion of edible crops is currently used as the primary feedstock in the biological production of fuels and chemicals, the availability of fatty acid (FA)-rich feedstocks and recent progress in the development of oil-accumulating organisms have drawn the attention to FAs as an attractive alternative. However, microbial platforms to enable this were nearly absent. To this end, we engineered native and heterologous fermentative pathways in E. coli to enable the efficient synthesis of fuels and chemicals from FAs. The current de facto strategy for the synthesis of non-native products in model organisms is He terologous M etabolic E ngineering (HeME), which consists of recruiting foreign genes from native producers. However, the relative incompatibility of the heterologous pathways with the host metabolism may be considered a drawback. As an alternative approach, the HoME ( Ho mologous M etabolic E ngineering) strategy that we propose overcomes this limitation by harnessing the metabolic potential of the host strain. HoME aims at reconstructing heterologous pathways to enable biosynthesis of non-natural products by identifying and assembling native functional surrogates. Implementation of both HeME and HoME strategies in the context of fuels and chemicals biosynthesis has usually been directed to the conversion of feedstocks constituents into a specific product. However, we demonstrated a novel metabolic platform based on a functional reversal of the fatty acid catabolic pathway (β-oxidation) as a means of synthesizing a wide array of products with various chain lengths and functionalities.

This thesis presents the mathematical modeling of two new Escherichia coli platforms with economical potential for the production of biofuels and chemicals, namely glycerol fermentation and the reversal of the β-oxidation cycle. With the increase in traditional fuel prices, alternative renewable energy sources are needed, and the efficient production of biofuels becomes imperative. So far studies have focused on using glucose as feedstock for the production of ethanol and other fuels, but a recent increase in glycerol availability and its consequent decrease in price make it an attractive feedstock. Furthermore, the reversed β-oxidation cycle is a highly efficient mechanism for the synthesis of long-chain products. These two platforms have been reported experimentally in E. coli but their mathematical modeling is presented for the first time here. Because mathematical models have proved to be useful in the optimization of microbial metabolism, two complementary models were used in this study: kinetic and stoichiometric. Kinetic models can identify the control structure within a specific pathway, but they require highly detailed information, making them applicable to small sets of reactions. In contrast, stoichiometric models require only mass balance information, making them suitable for genome-scale modeling to study the effect of adding or removing reactions for the optimization of the synthesis of desired products. To study glycerol fermentation, a kinetic model was implemented, allowing prediction of the limiting enzymes of this process: glycerol dehydrogenase and di-hydroxyacetone kinase. This prediction was experimentally validated by increasing their enzymatic activities, resulting in a two-fold increase in the rate of ethanol production. Additionally, a stoichiometric genome-scale model (GEM) was modified to represent the fermentative metabolism of glycerol, identifying key metabolic pathways for glycerol fermentation (including a new glycerol dissimilation pathway). The GEM was used to identify genetic modifications that would increase the synthesis of desired products, such as succinate and butanol. Finally, glucose metabolism using the reversal β-oxidation cycle was modeled using a GEM to simulate the synthesis of a variety of medium and long chain products (including advanced biofuels). The model was used to design strategies that can lead to increase the productivity of target products.