Comprehensive Assessment of Composition and Thermochemical Variability by High Resolution GC/QToF-MS and the Advanced Distillation-Curve Method as a Basis of Comparison for Reference Fuel Development.
ABSTRACT: Commercial and military aviation is faced with challenges that include high fuel costs, undesirable emissions, and supply chain insecurity that result from the reliance on petroleum-based feedstocks. The development of alternative gas turbine fuels from renewable resources will likely be part of addressing these issues. The United States has established a target for one billion gallons of renewable fuels to enter the supply chain by 2018. These alternative fuels will have to be very similar in properties, chemistry, and composition to existing fuels. To further this goal, the National Jet Fuel Combustion Program (a collaboration of multiple U.S. agencies under the auspices of the Federal Aviation Administration, FAA) is coordinating measurements on three reference gas turbine fuels to be used as a basis of comparison. These fuels are reference fuels with certain properties that are at the limits of experience. These fuels include a low viscosity, low flash point, high hydrogen content "best case" JP-8 (POSF 10264) fuel, a relatively high viscosity, high flash point, low hydrogen content "worst case" JP-5 (POSF 10259) fuel, and a Jet-A (POSF 10325) fuel with relatively average properties. A comprehensive speciation of these fuels is provided in this paper by use of high resolution gas chromatography/quadrupole time-of-flight - mass spectrometry (GC/QToF-MS), which affords unprecedented resolution and exact molecular formula capabilities. The volatility information as derived from the measurement of the advanced distillation curve temperatures, Tk and Th, provides an approximation of the vapor liquid equilibrium and examination of the composition channels provides detailed insight into thermochemical data. A comprehensive understanding of the compositional and thermophysical data of gas turbine fuels is required not only for comparison but also for modeling of such complex mixtures, which will, in turn, aid in the development of new fuels with the goals of diversified feedstocks, decreased pollution, and increased efficiency.
Project description:Background:Aviation fuels are an important target of biofuels research due to their high market demand and competitive price. Isoprenoids have been demonstrated as good feedstocks for advanced renewable jet fuels with high energy density, high heat of combustion, and excellent cold-weather performance. In particular, sesquiterpene compounds (C15), such as farnesene and bisabolene, have been identified as promising jet fuel candidates. Results:In this study, we explored three sesquiterpenes-epi-isozizaene, pentalenene and ?-isocomene-as novel jet fuel precursors. We performed a computational analysis to calculate the energy of combustion of these sesquiterpenes and found that their specific energies are comparable to commercial jet fuel A-1. Through heterologous MVA pathway expression and promoter engineering, we produced 727.9 mg/L epi-isozizaene, 780.3 mg/L pentalenene and 77.5 mg/L ?-isocomene in Escherichia coli and 344 mg/L pentalenene in Saccharomyces cerevisiae. We also introduced a dynamic autoinduction system using previously identified FPP-responsive promoters for inducer-free production and managed to achieve comparable amounts of each compound. Conclusion:We produced tricyclic sesquiterpenes epi-isozizaene, pentalenene and ?-isocomene, promising jet fuel feedstocks at high production titers, providing novel, sustainable alternatives to petroleum-based jet fuels.
Project description:<h4>Background</h4>In an effort to ensure future energy security, reduce greenhouse gas emissions and create domestic jobs, the US has invested in technologies to develop sustainable biofuels and bioproducts from renewable carbon sources such as lignocellulosic biomass. Bio-derived jet fuel is of particular interest as aviation is less amenable to electrification compared to other modes of transportation and synthetic biology provides the ability to tailor fuel properties to enhance performance. Specific energy and energy density are important properties in determining the attractiveness of potential bio-derived jet fuels. For example, increased energy content can give the industry options such as longer range, higher load or reduced takeoff weight. Energy-dense sesquiterpenes have been identified as potential next-generation jet fuels that can be renewably produced from lignocellulosic biomass.<h4>Results</h4>We developed a biomass deconstruction and conversion process that enabled the production of two tricyclic sesquiterpenes, epi-isozizaene and prespatane, from the woody biomass poplar using the versatile basidiomycete Rhodosporidium toruloides. We demonstrated terpene production at both bench and bioreactor scales, with prespatane titers reaching 1173.6 mg/L when grown in poplar hydrolysate in a 2 L bioreactor. Additionally, we examined the theoretical fuel properties of prespatane and epi-isozizaene in their hydrogenated states as blending options for jet fuel, and compared them to aviation fuel, Jet A.<h4>Conclusion</h4>Our findings indicate that prespatane and epi-isozizaene in their hydrogenated states would be attractive blending options in Jet A or other lower density renewable jet fuels as they would improve viscosity and increase their energy density. Saturated epi-isozizaene and saturated prespatane have energy densities that are 16.6 and 18.8% higher than Jet A, respectively. These results highlight the potential of R. toruloides as a production host for the sustainable and scalable production of bio-derived jet fuel blends, and this is the first report of prespatane as an alternative jet fuel.
Project description:With mounting concerns over climate change, the utilisation or conversion of carbon dioxide into sustainable, synthetic hydrocarbons fuels, most notably for transportation purposes, continues to attract worldwide interest. This is particularly true in the search for sustainable or renewable aviation fuels. These offer considerable potential since, instead of consuming fossil crude oil, the fuels are produced from carbon dioxide using sustainable renewable hydrogen and energy. We report here a synthetic protocol to the fixation of carbon dioxide by converting it directly into aviation jet fuel using novel, inexpensive iron-based catalysts. We prepare the Fe-Mn-K catalyst by the so-called Organic Combustion Method, and the catalyst shows a carbon dioxide conversion through hydrogenation to hydrocarbons in the aviation jet fuel range of 38.2%, with a yield of 17.2%, and a selectivity of 47.8%, and with an attendant low carbon monoxide (5.6%) and methane selectivity (10.4%). The conversion reaction also produces light olefins ethylene, propylene, and butenes, totalling a yield of 8.7%, which are important raw materials for the petrochemical industry and are presently also only obtained from fossil crude oil. As this carbon dioxide is extracted from air, and re-emitted from jet fuels when combusted in flight, the overall effect is a carbon-neutral fuel. This contrasts with jet fuels produced from hydrocarbon fossil sources where the combustion process unlocks the fossil carbon and places it into the atmosphere, in longevity, as aerial carbon - carbon dioxide.
Project description:Decarbonizing the transportation sector is critical to achieving global climate change mitigation. Although biofuels will play an important role in conventional gasoline and diesel applications, bioderived solutions are particularly important in jet fuels and lubricants, for which no other viable renewable alternatives exist. Producing compounds for jet fuel and lubricant base oil applications often requires upgrading fermentation products, such as alcohols and ketones, to reach the appropriate molecular-weight range. Ketones possess both electrophilic and nucleophilic functionality, which allows them to be used as building blocks similar to alkenes and aromatics in a petroleum refining complex. Here, we develop a method for selectively upgrading biomass-derived alkyl methyl ketones with >95% yields into trimer condensates, which can then be hydrodeoxygenated in near-quantitative yields to give a new class of cycloalkane compounds. The basic chemistry developed here can be tailored for aviation fuels as well as lubricants by changing the production strategy. We also demonstrate that a sugarcane biorefinery could use natural synergies between various routes to produce a mixture of lubricant base oils and jet fuels that achieve net life-cycle greenhouse gas savings of up to 80%.
Project description:Safety is of utmost essence in the aviation sector, both on-ground and in the air. Aviation Turbine Kerosene (ATK) commonly referred to as jet fuel is one of the major resources of the aviation sector, contributing significantly to the operating cost of an airline. Flight safety is a top-notch requirement in air transportation management. Jet fuel quality affects flight safety, and this makes it mandatory to ensure that, at all points in the jet A-1 aviation fuel supply chain, the jet fuel is contamination free and on-spec. Jet fuel quality is determined via various mandatory Joint Inspection Group (JIG) based quality analysis test procedures; both baseline and extensive lab tests by third party labs. Acceptable parameter range has been established for each jet fuel property, the electrical conductivity of jet A-1 fuel must be between 50 and 600?pS/m and the density at 15?°C must be between 0.775 and 0.840?g/cm3. Beyond this range, the fuel is deemed off-spec and unsafe for into-plane fuelling operations. This data article presents daily jet fuel test records for jet-A1 fuel. The dataset contains the date of the test, the conductivity, the specific gravity at ambient temperature, the converted specific gravity at 15?°C, and the temperature of the jet fuel sample under study. All the tests were performed at standard laboratory conditions using approved and certified equipment. The dataset provides an opportunity for developing a predictive model that can be used for jet fuel properties prediction on a given day, based on previous data trends and analysis using data pattern recognition, as an indication of the variation of jet fuel properties with daily weather variation.
Project description:For the first time, renewable high density aviation fuels were synthesized at high overall yield (95.6%) by the Guerbet reaction of cyclopentanol which can be derived from lignocellulose, followed by the hydrodeoxygenation (HDO). The solvent-free Guerbet reaction of cyclopentanol was carried out under the co-catalysis of solid bases and Raney metals. Among the investigated catalyst systems, the combinations of magnesium-aluminium hydrotalcite (MgAl-HT) and Raney Ni (or Raney Co) exhibited the best performances. Over them, high carbon yield (96.7%) of C10 and C15 oxygenates was achieved. The Guerbet reaction products were further hydrodeoxygenated to bi(cyclopentane) and tri(cyclopentane) over a series of Ni catalysts. These alkanes have high densities (0.86?g mL(-1) and 0.91?g mL(-1)) and can be used as high density aviation fuels or additives to bio-jet fuel. Among the investigated HDO catalysts, the 35?wt.% Ni-SiO2-DP prepared by deposition-precipitation method exhibited the highest activity.
Project description:BackgroundThe hydrotreatment of oleochemical/lipid feedstocks is currently the only technology that provides significant volumes (millions of litres per year) of “conventional” biojet/sustainable aviation fuels (SAF). However, if biojet fuels are to be produced in sustainably sourced volumes (billions of litres per year) at a price comparable with fossil jet fuel, biomass-derived “advanced” biojet fuels will be needed. Three direct thermochemical liquefaction technologies, fast pyrolysis, catalytic fast pyrolysis and hydrothermal liquefaction were assessed for their potential to produce “biocrudes” which were subsequently upgraded to drop-in biofuels by either dedicated hydrotreatment or co-processed hydrotreatment.ResultsA significant biojet fraction (between 20.8 and 36.6% of total upgraded fuel volume) was produced by all of the processes. When the fractions were assessed against general ASTM D7566 specifications they showed significant compliance, despite a lack of optimization in any of the process steps. When the life cycle analysis GHGenius model was used to assess the carbon intensity of the various products, significant emission reductions (up to 74%) could be achieved.ConclusionsIt was apparent that the production of biojet fuels based on direct thermochemical liquefaction of biocrudes, followed by hydrotreating, has considerable potential.
Project description:The economic viability of hydrodeoxygenation process using Camelina, Carinata and Jatropha feedstocks for aviation biofuel production was evaluated for two product profiles: (i) maximum diesel production and (ii) maximum jet fuel production (HRJ).Deterministic analysis of Camelina and Carinata diesel facilities returned positive NPVs and IRRs of 25 and 18%, respectively. Stochastic analysis suggested that the probabilities of positive NPVs were 75, 59 and 15%, respectively, for Camelina, Carinata and Jatropha diesel plants. Jet fuel facilities presented probabilities of loss of 98, 99 and 100% for Camelina, Carinata and Jatropha scenarios, respectively. Sensitivity analysis determined that financial performance was majorly influenced by feedstock and fuel prices. Categories of subsidies to enhance the attractiveness of the projects were studied.Camelina, Carinata and Jatropha plants targeting HRJ required incentives of 0.31, 0.39 and 0.61 US$/L of biofuel produced, respectively, to reduce the probabilities of loss to approximately 30%.
Project description:Alka(e)nes are ideal fuel components for aviation, long-distance transport, and shipping. They are typically derived from fossil fuels and accounting for 24% of difficult-to-eliminate greenhouse gas emissions. The synthesis of alka(e)nes in Yarrowia lipolytica from CO<sub>2</sub>-neutral feedstocks represents an attractive alternative. Here we report that the high-titer synthesis of alka(e)nes in Yarrowia lipolytica harboring a fatty acid photodecarboxylase (CvFAP) is enabled by a discovered pathway. We find that acyl-CoAs, rather than free fatty acids (FFAs), are the preferred substrate for CvFAP. This finding allows us to debottleneck the pathway and optimize fermentation conditions so that we are able to redirect 89% of acyl-CoAs from the synthesis of neutral lipids to alka(e)nes and reach titers of 1.47?g/L from glucose. Two other CO<sub>2</sub>-derived substrates, wheat straw and acetate, are also demonstrated to be effective in producing alka(e)nes. Overall, our technology could advance net-zero emissions by providing CO<sub>2</sub>-neutral and energy-dense liquid biofuels.
Project description:The effect of accidental fires are simulated to understand the response of items such as vehicles, fuel tanks, and military ordnance and to remediate the effects through re-design of the items or changes in operational procedures. The comparative combustion emissions of using jet propellant (JP-5) liquid fuel pools or a propane manifold grid to simulate the effects of accidental fires was investigated. A helium-filled tethered aerostat was used to maneuver an instrument package into the open fire plumes to measure CO, CO2, fine particulate matter (PM2.5), polycyclic aromatic hydrocarbons (PAHs), volatile organic compounds (VOCs), and elemental/organic/total carbon (EC/OC/TC). The results showed that all emissions except CO2 were significantly higher from JP-5 burns than from propane. The major portion of the PM mass from fires of both fuels was less than 1 ?m in diameter and differed in carbon content. The PM2.5 emission factor from JP-5 burns (129 ± 23 g/kg Fuelc) was approximately 150 times higher than the PM2.5 emission factor from propane burns (0.89 ± 0.21 g/kg Fuelc). The PAH emissions as well as some VOCs were more than one hundred times higher for the JP-5 burns than the propane burns. Using the propane test method to study flammability responses, the environmental impact of PM2.5, PAHs, and VOCs would be reduced by 2300, 700, and 100 times per test, respectively.