Transforming carbon dioxide into jet fuel using an organic combustion-synthesized Fe-Mn-K catalyst.
ABSTRACT: 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: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: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: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: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:Combustion-derived black carbon (BC) aerosols accelerate glacier melting in the Himalayas and in Tibet (the Third Pole (TP)), thereby limiting the sustainable freshwater supplies for billions of people. However, the sources of BC reaching the TP remain uncertain, hindering both process understanding and efficient mitigation. Here we present the source-diagnostic ?(14)C/?(13)C compositions of BC isolated from aerosol and snowpit samples in the TP. For the Himalayas, we found equal contributions from fossil fuel (46±11%) and biomass (54±11%) combustion, consistent with BC source fingerprints from the Indo-Gangetic Plain, whereas BC in the remote northern TP predominantly derives from fossil fuel combustion (66±16%), consistent with Chinese sources. The fossil fuel contributions to BC in the snowpits of the inner TP are lower (30±10%), implying contributions from internal Tibetan sources (for example, yak dung combustion). Constraints on BC sources facilitate improved modelling of climatic patterns, hydrological effects and provide guidance for effective mitigation actions.
Project description:The Open-source Data Inventory for Anthropogenic CO2 (ODIAC) is a global high-spatial resolution gridded emission data product that distributes carbon dioxide (CO2) emissions from fossil fuel combustion. The emission spatial distributions are estimated at a 1×1 km spatial resolution over land using power plant profiles (emission intensity and geographical location) and satellite-observed nighttime lights. This paper describes the year 2016 version of the ODIAC emission data product (ODIAC2016) and presents analyses that help guiding data users, especially for atmospheric CO2 tracer transport simulations and flux inversion analysis. Since the original publication in 2011, we have made modifications to our emission modeling framework in order to deliver a comprehensive global gridded emission data product. Major changes from the 2011 publication are 1) the use of emissions estimates made by the Carbon Dioxide Information Analysis Center (CDIAC) at the Oak Ridge National Laboratory (ORNL) by fuel type (solid, liquid, gas, cement manufacturing, gas flaring and international aviation and marine bunkers), 2) the use of multiple spatial emission proxies by fuel type such as nightlight data specific to gas flaring and ship/aircraft fleet tracks and 3) the inclusion of emission temporal variations. Using global fuel consumption data, we extrapolated the CDIAC emissions estimates for the recent years and produced the ODIAC2016 emission data product that covers 2000-2015. Our emission data can be viewed as an extended version of CDIAC gridded emission data product, which should allow data users to impose global fossil fuel emissions in more comprehensive manner than original CDIAC product. Our new emission modeling framework allows us to produce future versions of ODIAC emission data product with a timely update. Such capability has become more significant given the CDIAC/ORNL's shutdown. ODIAC data product could play an important role to support carbon cycle science, especially modeling studies with space-based CO2 data collected near real time by ongoing carbon observing missions such as Japanese Greenhouse Observing SATellite (GOSAT), NASA's Orbiting Carbon Observatory 2 (OCO-2) and upcoming future missions. The ODIAC emission data product including the latest version of the ODIAC emission data (ODIAC2017, 2000-2016), is distributed from http://db.cger.nies.go.jp/dataset/ODIAC/ with a DOI.
Project description:There is strong evidence of an association between fine particulate matter less than 2.5 ?m (PM2.5) in aerodynamic diameter and adverse health outcomes. This study analyzes the global excess mortality attributable to the aviation sector in the present (2006) and in the future (three 2050 scenarios) using the integrated exposure response model that was also used in the 2010 Global Burden of Disease assessment. The PM2.5 concentrations for the present and future scenarios were calculated using aviation emission inventories developed by the Volpe National Transportation Systems Center and a global chemistry-climate model. We found that while excess mortality due to the aviation sector emissions is greater in 2050 compared to 2006, improved fuel policies (technology and operations improvements yielding smaller increases in fuel burn compared to 2006, and conversion to fully sustainable fuels) in 2050 could lead to 72% fewer deaths for adults 25 years and older than a 2050 scenario with no fuel improvements. Among the four health outcomes examined, ischemic heart disease was the greatest cause of death. Our results suggest that implementation of improved fuel policies can have substantial human health benefits.
Project description:Abstract In this “Grand Challenges” paper, we review how the carbon isotopic composition of atmospheric CO2 has changed since the Industrial Revolution due to human activities and their influence on the natural carbon cycle, and we provide new estimates of possible future changes for a range of scenarios. Emissions of CO2 from fossil fuel combustion and land use change reduce the ratio of 13C/12C in atmospheric CO2 (?13CO2). This is because 12C is preferentially assimilated during photosynthesis and ?13C in plant?derived carbon in terrestrial ecosystems and fossil fuels is lower than atmospheric ?13CO2. Emissions of CO2 from fossil fuel combustion also reduce the ratio of 14C/C in atmospheric CO2 (?14CO2) because 14C is absent in million?year?old fossil fuels, which have been stored for much longer than the radioactive decay time of 14C. Atmospheric ?14CO2 rapidly increased in the 1950s to 1960s because of 14C produced during nuclear bomb testing. The resulting trends in ?13C and ?14C in atmospheric CO2 are influenced not only by these human emissions but also by natural carbon exchanges that mix carbon between the atmosphere and ocean and terrestrial ecosystems. This mixing caused ?14CO2 to return toward preindustrial levels in the first few decades after the spike from nuclear testing. More recently, as the bomb 14C excess is now mostly well mixed with the decadally overturning carbon reservoirs, fossil fuel emissions have become the main factor driving further decreases in atmospheric ?14CO2. For ?13CO2, in addition to exchanges between reservoirs, the extent to which 12C is preferentially assimilated during photosynthesis appears to have increased, slowing down the recent ?13CO2 trend slightly. A new compilation of ice core and flask ?13CO2 observations indicates that the decline in ?13CO2 since the preindustrial period is less than some prior estimates, which may have incorporated artifacts owing to offsets from different laboratories' measurements. Atmospheric observations of ?13CO2 have been used to investigate carbon fluxes and the functioning of plants, and they are used for comparison with ?13C in other materials such as tree rings. Atmospheric observations of ?14CO2 have been used to quantify the rate of air?sea gas exchange and ocean circulation, and the rate of net primary production and the turnover time of carbon in plant material and soils. Atmospheric observations of ?14CO2 are also used for comparison with ?14C in other materials in many fields such as archaeology, forensics, and physiology. Another major application is the assessment of regional emissions of CO2 from fossil fuel combustion using ?14CO2 observations and models. In the future, ?13CO2 and ?14CO2 will continue to change. The sign and magnitude of the changes are mainly determined by global fossil fuel emissions. We present here simulations of future ?13CO2 and ?14CO2 for six scenarios based on the shared socioeconomic pathways (SSPs) from the 6th Coupled Model Intercomparison Project (CMIP6). Applications using atmospheric ?13CO2 and ?14CO2 observations in carbon cycle science and many other fields will be affected by these future changes. We recommend an increased effort toward making coordinated measurements of ?13C and ?14C across the Earth System and for further development of isotopic modeling and model?data analysis tools. Key Points Carbon isotopes, 14C and 13C, in atmospheric CO2 are changing in response to fossil fuel emissions and other human activities Future simulations using different SSPs show continued changes in isotopic ratios that depend on fossil fuel emissions and, for 13C, BECCS Applications using atmospheric 14C and 13C in studies of the carbon cycle or other fields will be affected by future changes
Project description:Abstract:Energy and the environment are intimately related and hotly debated issues. Today's crude oil-based economy for the manufacture of fuels, chemicals and materials will not have a sustainable future. The over-use of oil products has done a great damage to the environment. Faced with the twin challenges of sustaining socioeconomic development and shrinking the environmental footprint of chemicals and fuel manufacturing, a major emphasis is on either converting biomass into low-value, high-volume biofuels or refining it into a wide spectrum of products. Using carbon for fuel is a flawed approach and unlikely to achieve any nation's socioeconomic or environmental targets. Biomass is chemically and geographically incompatible with the existing refining and pipeline infrastructure, and biorefining and biofuels production in their current forms will not achieve economies of scale in most nations. Synergistic use of crude oil, biomass, and shale gas to produce fuels, value-added chemicals, and commodity chemicals, respectively, can continue for some time. However, carbon should not be used as a source of fuel or energy but be valorized to other products. In controlling CO2 emissions, hydrogen will play a critical role. Hydrogen is best suited for converting waste biomass and carbon dioxide emanated from different sources, whether it be fossil fuel-derived carbon or biomass-derived carbon, into fuels and chemicals as well as it will also lead, on its own as energy source, to the carbon negative scenario in conjunction with other renewable non-carbon sources. This new paradigm for production of fuels and chemicals not only offers the greatest monetization potential for biomass and shale gas, but it could also scale down output and improve the atom and energy economies of oil refineries. We have also highlighted the technology gaps with the intention to drive R&D in these directions. We believe this article will generate a considerable debate in energy sector and lead to better energy and material policy across the world. Graphic abstract: