<p>Today, a majority of the world’s energy need is supplied through sources that are finite and, at the current usage rates, will be consumed shortly. The high energy demand and pollution problems caused by the widespread use of fossil fuels make it increasingly necessary to develop renewable energy sources of limitless duration with smaller environmental impact than the traditional energy sources.</p><p>Three fuels – rapeseed methyl ester (RME), Fischer-Tropsch (FT) diesel and FT jet fuel – derived from biomass, coal or gas were evaluated in this project. The fuel properties evaluated are in most cases listed in standards, often with recommendations, developed for biodiesel, petroleum diesel and jet fuel.</p><p>Biodiesel is monoalkyl esters, e.g. RME, produced by transesterification of triglycerides in vegetable oil and an alcohol to esters and glycerin. This produce a fuel that is suitable as a direct substitution for petroleum diesel. Biodiesel may be used in pure form or in a blend with petrodiesel. Oxidative degradation and weak low temperature performance of biodiesel are properties of concern when substituting petrodiesel with biodiesel, as was shown in this project. The experiments show that oxidative stability can be improved with a synthetic antioxidant, e.g. butylated hydroxytoluene (BHT).</p><p>The FT process converts syngas (a mixture of hydrogen and carbon monoxide) to a range of hydrocarbons. Syngas can be generated from a variety of carbon sources, e.g. coal, natural gas and biomass. The high-temperature (300-350 °C) FT process with iron-based catalysts is used for the production of gasoline and linear low molecular mass olefins (alkenes). The lowtemperature (200-240 °C) FT process with either iron or cobalt catalysts is used for the production of high molecular mass linear waxes. By applying various downstream processes, fuels suitable for substitution of petrodiesel and conventional jet fuel can be obtained. The FT fuels have lower densities than the conventional fuels. However, conclusions from this project are that most of the properties of FT fuels are better, or equal, than conventional petroleum fuels.</p>

Thesis (M.Sc.)--Victoria University of Wellington, [2008] / Includes bibliographical references.

Thesis (M.S.)--Mississippi State University. Department of Chemistry. / Title from title screen. Includes bibliographical references.

Drastic reductions of greenhouse gas emissions are required to limit the severe risks associated with a changing climate. One measure is to disrupt the fossil-fuel dependency in the transport sector, but it appears difficult and costly in comparison to other measures. Vehicles and fuels are available, but no single alternative can replace petrol and diesel in all parts of the transport system. None of them are ideal regarding all of the following aspects: vehicle performance, fuel production potential, sustainability, infrastructure, technology development and economy. Instead, several fuels are needed. In this thesis, the aim is to investigate the role of methane and hydrogen in a fossil- free vehicle fleet in Sweden, and compare them with other fuels in terms of well-to-wheel energy efficiency and economy. Processes for producing methane from biomass, waste streams from pulp mills and electricity are studied with techno-economic methods. Furthermore, well-to-wheel studies and scenarios are used to investigate the fuel chains and the interaction with the energy and transport systems. Effects of policy instruments on the development of biogas in the Swedish transport sector are also analysed and policy instruments are suggested to increase the use of methane and to introduce hydrogen and fuel cell electric vehicles. The results reveal that tax exemptions and investment support have been and will continue to be important policy instruments, but that effective policy instruments are needed to develop fuelling infrastructure and to support alternative vehicles. Electricity will be an important transport fuel for several reasons; the electric powertrain enables high energy efficiency and electricity can be produced from various renewable energy sources. Nevertheless, other fuels will be needed as complements to electricity. The results reveal that methane and hydrogen and associated vehicles may be necessary to reach a fossil-free vehicle fleet in Sweden. These fuels have several advantages: -        The function of the vehicles resembles conventional vehicles but with lower local and global emissions. -        Methane is a well proven as a transport fuel and hydrogen infrastructure and FCEVs, are commercial or close to commercialisation. -        They enable high well-to-wheel energy efficiency. -        They can be produced from renewable electricity and act as energy storage. / <p>QC 20150929</p>

The first chapter of this dissertation examines welfare impacts of a combination of subsidies to alternative fuels (AFs) and alternative fuel vehicles (AFVs), and how they compare to gasoline taxes. The particular AF examined here is ethanol that is produced from agricultural products in a small open economy. The model in this paper characterizes a country or state where gasoline is the major source of fuel for automobiles, but that also produces and consumes ethanol as an AF. Gasoline combustion is polluting and its use equals the total amount of emissions produced. Thus, a gasoline tax here is the same as an emissions tax and is the most direct environmental instrument. However, increasing gasoline taxes for pollution purposes is often politically not feasible. Thus, this paper studies how closely subsidies to alternative fuels (AFs) and alternative fuel vehicles (AFVs) emulate abatement behavior from a unit gasoline tax in a simple three sector general equilibrium model, and in the presence of pre-existing labor taxes. The model can also be used to track the effects of each policy on outputs, exports, and fuel use. The analytical results of the model are then calibrated to data from the largest ethanol producing state in the U.S., namely Illinois. The paper finds that subsidies can achieve up to 64 percent of the welfare gains from the gasoline tax, if the uncompensated wage elasticity is low enough or the elasticities of substitution between the transportation goods is high enough. The second chapter estimates behavior of households who jointly make discrete decisions about vehicle ownership and continuous decisions about miles driven. The paper uses seven years of data from 1995-2001 for the 35 states and union territories of India. The estimated parameters will be used to calculate elasticities of each different type of vehicle for percentage changes in petrol price per unit distance travelled and in vehicle taxes. The paper also computes income and price elasticities for petrol consumption. Two types of vehicles predominant in India are cars and two-wheelers such as motorcycles, mopeds, and scooters. The latter type of vehicle is more fuel efficient than the former. However, patterns of vehicle ownership across the country reflect a growing number of cars relative to motorcycles. This paper investigates the impact alternative policies such as taxes on petrol or on cars have on efficient methods of vehicle emission abatement in India. In particular, the chapter estimates the effect of each such policy on vehicle choice and driving behavior, and how they in turn affect emissions. The main results are summarized as follows: First, continuous choice own-price elasticities are higher for 4w relative to 2w, given age, and for older vehicles relative to newer ones, within each category. Second, discrete choice own-price elasticities with respect to capital cost are higher for 2w relative to 4w. Moreover, older vehicles of each type are more sensitive to higher vehicle prices relative to their newer counterparts. Third, income elasticities for discrete vehicle choices are all positive and greater than unity. Thus, higher income encourages purchase of newer vehicles of each type. Moreover, usage of vehicles rises with income, conditional on the particular vehicle choice. Finally, the paper conducts simulations that alter the price per kilometer by adding either an additional gas tax, a distance tax or an emissions tax. Results show that a distance tax reduces vehicle kilometers traveled the most, followed by an emissions tax and lastly by the gas tax. However, local emissions are reduced the most by an emissions tax, followed by a distance tax and then by a gasoline tax. Even though it would be ideal to compare the results obtained in this paper to results generated using a micro-level data set, the estimates presented here are indicative of whether a distance tax or a gasoline tax is more effective for emissions abatement in India. The third chapter of this dissertation evaluates how information asymmetry in private automobile markets affects programs to accelerate vehicle retirement, also known as scrappage programs. We use a dynamic framework where agents have heterogenous preference for car quality. Cars can either be new, or used. While all new cars have the same quality, used cars can be of high- or low-quality. The quality of a car is perfectly correlated with emissions. The goal of a scrappage program is to induce car owners to voluntarily scrap low-quality used cars. One key result is that in the presence of adverse selection a subsidy that maintains an active resale market unambiguously makes all types of consumers better off. However, if this option of implementing the subsidy does not exist, then the only other way to induce effective scrappage in our framework is to shut down the used car market. Welfare implications suggest that it might be better not to do anything rather than have a scrappage program such as the latter. / text

M. Tech. Mechanical Engineering. / Biodiesel, produced from the transesterification of vegetable oils or animal fats with simple alcohol in the presence of a catalyst, is well positioned to replace petroleum-based diesel. Biodiesel is a non-toxic, biodegradable and renewable fuel. Despite its advantages, the chemical nature of biodiesel makes it more susceptible to oxidation compared to mineral diesel during long-term storage. The production of Croton Oil Methyl Ester (COME), Moringa Oil Methyl Ester (MOME) and Jatropha Oil Methyl Ester (JOME) was therefore carried out. Also, a determination of the fuel related properties and investigation of oxidation stability of the methyl esters produced without and with antioxidants and its blends with mineral diesel were conducted. The results showed that most of the measured fuel related properties of produced methyl esters fulfilled the minimum requirements of EN 14214 and ASTM 6751 biodiesel standards. However, COME and MOME did not meet EN 14214 oxidation stability standards (6 h) while JOME displayed very high oxidation stability (10.43 h) well within specified oxidation stability standards. Overall, the biodiesel derived from non-edible oils of African origin such as COME, MOME and JOME can be utilized as a partial substitute for mineral diesel. This study recommends that PY and PG antioxidants be used for safeguarding biodiesel fuel from the effects of autoxidation during storage.

Inexpensive petroleum is the cornerstone of the modern global economy despite its huge environmental costs and its nature as a non-renewable resource. While ninety percent of petroleum is ultimately used as fuel and can in principle be replaced by sources of renewable electricity, ten percent is used as a feedstock to produce societally important chemicals that cannot currently be made at a reasonable cost through alternative processes. In this dissertation, I will discuss my efforts, together with several colleagues, to apply synthetic biology approaches to the challenge of producing renewable petrochemical replacements. In Chapter 2, I discuss our efforts to engineer E. coli to produce fatty acids with a wide range of chain lengths at high yield, thereby providing an alternative platform for the production of diverse petrochemicals. In Chapter 3, I describe a novel method of DNA assembly that we developed to facilitate synthetic biology efforts such as those in Chapter 2. This method is capable of simultaneously assembling multiple DNA pieces with substantial sequence homology, a common challenge in synthetic biology. In Chapter 4, I discuss the development of a "bionic leaf": a hybrid microbial-inorganic catalyst that marries the advantages of photovoltaic-based light capture and microbial carbon fixation to achieve solar biomass yields greater than those observed in terrestrial plants. This technology offers a potentially low-cost alternative to photosynthesis as a source of biomass and derived chemicals and fuels. The work described in this dissertation demonstrates the capacity of synthetic biology to address the problem of renewable chemical production, and offers proof of principle demonstrations that both the scope and efficiency of biological chemical production may be improved.

Project I: [Ru(OH2)3(4'-phenyl-2,2':6',2''-terpyridine)](OTf)2 as a Homogeneous Hydrogenation Catalyst for Biomass Derived Substrates. The complex [Ru(OH2)3(4'-phenyl-2,2':6',2''-terpyridine)](OTf)2 has been shown to be an active ionic hydrogenation catalyst for selected carbonyls, diols and glycerol by the Schlaf group. It was postulated to also be active for other biomass derived substrates such as levulinic acid (LA), furfural and 5-hydroxymethyl furfural (HMF). Synthesis of the complex was optimized and full characterization carried out by 1H/13C –NMR. The complex was tested against LA in aqueous sulfolane medium and the furfural/HMF model system 2,5-hexanedione in water. Activity of the complex was compared to the analogous metal-ligand bifunctional (MLB) system described in Project II. The complex exhibited good thermal stability up to 200 oC in 90/10 wt% sulfolane/water mixtures and was capable of hydrogenation of LA to γ-valerolactone in 95% yield. Addition of protic acids to the reaction mixture and increasing proportions of water decreased the activity of the complex towards the hydrogenation of LA. Project II: [Ru(OH2)3(di(picolyl)amine)](OTf)2 as an acid-, water- stable, metal-ligand bifunctional deoxygenation catalyst. The complex [Ru(OH2)3(di(picolyl)amine)](OTf)2 was postulated to be an active MLB ionic hydrogenation catalyst under acidic aqueous conditions. Using the substantially labile [Ru(DMF)6](OTF)3 ruthenium complex as the precursor, the desired complex was prepared insitu by coordination of the DPA ligand and concomitant reduction of Ru3+ to Ru2+. The complex was characterized by 1H/13C-NMR and tested for the hydrogenation of LA, 2,5-hexanedione, furfural and HMF under acidic aqueous conditions. The complex exhibited thermal stability up to 150 oC and was active for the hydrogenation of carbonyls, as demonstrated by the conversion of 2,5-hexanedione to 2,5-hexanediol in 94% yield in water. Addition of H3PO4 as an acid cocatalyst resulted in nearly complete conversion to dimethyltetrahydrofuran (DMTHF) but further deoxygenation could not be achieved. Direct comparision of [Ru(OH2)3(di(picolyl)amine)](OTf)2 and [Ru(OH2)3(4'-phenyl-2,2':6',2''-terpyridine)](OTf)2 under identical conditions against LA and 2,5-hexanedione demonstrated that the[Ru(OH2)3(di(picolyl)amine)](OTf)2 catalyst is more active than the [Ru(OH2)3(4'-phenyl-2,2':6',2''-terpyridine)](OTf)2 complex in all cases, suggesting that the di(picolyl)amine complex operates through a MLB ionic hydrogenation mechanism. / NSERC

Surrogate fuels are mixtures of pure hydrocarbons that mimic specific properties of a real fuel. The use of a small number of pure compounds in their formulation ensures that chemical composition is well controlled, helping increase reproducibility of experiments and reduce the computational cost associated with numerical modeling. In this work, surrogate mixtures were developed for Jet A fuel based on correlations between fuel properties (cetane number, smoke point, threshold sooting index (TSI), density, viscosity, boiling point and freezing point) and the nuclear magnetic resonance (NMR) spectra of the fuel as a measure of the fuel's chemical composition. Comparison of the chemical composition and target fuel properties of the surrogate fuels developed in this work to a Jet A fuel sample and other surrogate fuels proposed in the literature revealed the superiority of these surrogate fuels in mimicking the fuel properties of interest.

Characterization of jet fuels obtained from sources other than crude oil is a modern area of research that is developing continuously to replace available petroleum-based fuels with ‘drop-in’ alternative fuels. Therefore, reliable composition-property relations are developed to correlate the hydrocarbon compositions of formulated synthetic fuels with their properties to be certified for aviation commercial use. Intensive studies have been initiated at Texas A&M University Qatar in collaboration with industry and academia to study synthetic jet fuels derived from natural gas. These studies are being implemented at its Fuel Characterization Lab where the most advanced testing equipment is used and strict Quality Management and safety systems are followed. This study is divided into two tracks. The first track is focused on conducting experimental investigations using in-house formulated synthetic jet fuels derived from natural gas via Gas-to-Liquid technology and Fischer-Tropsch chemistry. Throughout this research work, these fuels will be referred to as Synthetic Paraffinic Kerosene (SPK). These experimental investigations activities are composed of three phases: the first phase focuses on the influence of SPK building blocks (paraffinic hydrocarbons) on fuels’ properties, the second phase concerns evaluating the role of aromatics and cyclo-paraffins on properties, and the third phase studies the influence of mixing SPK with conventional Jet A-1 derived from crude oil. All of the aforementioned experimental investigations are aimed at building an experimental data bank to assist the efforts of the formulation of new generations of SPKs that meet aviation industry standards. On the other hand, the second track is directed towards the development of mathematical correlations for four properties of high importance to SPK certification. These correlations aim at optimizing fuel composition whereby major physical/chemical properties of ASTM D1655 are met at the lowest cost of composed fuel. The primary findings of this study showed that GTL derived SPK paraffinic constituents can improve certain properties while affecting others negatively, and emphasizing the necessity of aromatics in improving specific properties. Further studies compensating the absence of aromatics and sulfur through blended Jet A-1 revealed a practical solution through jet fuels optimization based on cost and technical effective manners.