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NASA NTRS1991

Fuel-rich, catalytic reaction experimental results

Future aeropropulsion gas turbine combustion requirements call for operating at very high inlet temperatures, pressures, and large temperature rises. At the same time, the combustion process is to have minimum pollution effects on the environment. Aircraft gas turbine engines utilize liquid hydrocarbon fuels which are difficult to uniformly atomize and mix with combustion air. An approach for minimizing fuel related problems is to transform the liquid fuel into gaseous form prior to the completion of the combustion process. Experimentally obtained results are presented for vaporizing and partially oxidizing a liquid hydrocarbon fuel into burnable gaseous components. The presented experimental data show that 1200 to 1300 K reaction product gas, rich in hydrogen, carbon monoxide, and light-end hydrocarbons, is formed when flowing 0.3 to 0.6 fuel to air mixes through a catalyst reactor. The reaction temperatures are kept low enough that nitrogen oxides and carbon particles (soot) do not form. Results are reported for tests using different catalyst types and configurations, mass flowrates, input temperatures, and fuel to air ratios.

Rollbuhler, Jim↗

NASA NTRS2017

Personal Rotorcraft Design and Performance with Electric Hybridization

Recent and projected improvements for more or all-electric aviation propulsion systems can enable greater personal mobility, while also reducing environmental impact (noise and emissions). However, all-electric energy storage capability is significantly less than present, hydrocarbon-fueled systems. A system study was performed exploring design and performance assuming hybrid propulsion ranging from traditional hydrocarbon-fueled cycles (gasoline Otto and diesel) to all-electric systems using electric motors generators, with batteries for energy storage and load leveling. Study vehicles were a conventional, single-main rotor (SMR) helicopter and an advanced vertical takeoff and landing (VTOL) aircraft. Vehicle capability was limited to two or three people (including pilot or crew); the design range for the VTOL aircraft was set to 150 miles (about one hour total flight). Search and rescue (SAR), loiter, and cruise-dominated missions were chosen to illustrate each vehicle and degree of hybrid propulsion strengths and weaknesses. The traditional, SMR helicopter is a hover-optimized design; electric hybridization was performed assuming a parallel hybrid approach by varying degree of hybridization. Many of the helicopter hybrid propulsion combinations have some mission capabilities that might be effective for short range or on-demand mobility missions. However, even for 30 year technology electrical components, all hybrid propulsion systems studied result in less available fuel, lower maximum range, and reduced hover and loiter duration than the baseline vehicle. Results for the VTOL aircraft were more encouraging. Series hybrid combinations reflective of near-term systems could improve range and loiter duration by 30. Advanced, higher performing series hybrid combinations could double or almost triple the VTOL aircrafts range and loiter duration. Additional details on the study assumptions and work performed are given, as well as suggestions for future study effort.

electric motors↗

NASA NTRS2007

Opposed Jet Burner Extinction Limits: Simple Mixed Hydrocarbon Scramjet Fuels vs Air

Opposed Jet Burner tools have been used extensively by the authors to measure Flame Strength (FS) of laminar non-premixed H2 air and simple hydrocarbon (HC) air counterflow diffusion flames at 1-atm. FS represents a strain-induced extinction limit based on air jet velocity. This paper follows AIAA-2006-5223, and provides new HC air FSs for global testing of chemical kinetics, and for characterizing idealized flameholding potentials during early scramjet-like combustion. Previous FS data included six HCs, pure and N2-diluted; and three HC-diluted H2 fuels, where FS decayed very nonlinearly as HC was added to H2, due to H-atom scavenging. This study presents FSs on mixtures of (candidate surrogate) HCs, some with very high FS ethylene. Included are four binary gaseous systems at 300 K, and a hot ternary system at approx. 600 K. The binaries are methane + ethylene, ethane + ethylene, methane + ethane, and methane + propylene. The first three also form two ternary systems. The hot ternary includes both 10.8 and 21.3 mole % vaporized n-heptane and full ranges of methane + ethylene. Normalized FS data provide accurate means of (1) validating, globally, chemical kinetics for extinction of non-premixed flames, and (2) estimating (scaling by HC) the loss of incipient flameholding in scramjet combustors. The n-heptane is part of a proposed baseline simulant (10 mole % with 30% methane + 60% ethylene) that mimics the ignition of endothermically cracked JP-7 like kerosene fuel, as suggested by Colket and Spadaccini in 2001 in their shock tube Scramjet Fuels Autoignition Study. Presently, we use FS to gauge idealized flameholding, and define HC surrogates. First, FS was characterized for hot nheptane + methane + ethylene; then a hot 36 mole % methane + 64% ethylene surrogate was defined that mimics FS of the baseline simulant system. A similar hot ethane + ethylene surrogate can also be defined, but it has lower vapor pressure at 300 K, and thus exhibits reduced gaseous capacity. The new FS results refine our earlier idealized reactivity scale that shows wide ranging (50 x) diameter-normalized FSs for various HCs. These range from JP-10 and methane to H2 air, which produces an exceptionally strong flame that agrees within approx. 1% of recent 2-D numerically simulations. Finally, we continue advocating the FS approach as more direct and fundamental, for assessing idealized scramjet flameholding potentials, than measurements of unstrained laminar burning velocity or blowout in a Perfectly Stirred Reactor.

Pellett, Gerald L.↗

NASA NTRS1997

The Effects of Sooting and Radiation on Droplet Combustion

The burning of liquid hydrocarbon fuels accounts for a significant portion of global energy production. With predicted future increases in demand and limited reserves of hydrocarbon fuel, it is important to maximize the efficiency of all processes that involve conversion of fuel. With the exception of unwanted fires, most applications involve introduction of liquid fuels into an oxidizing environment in the form of sprays which are comprised of groups of individual droplets. Therefore, tremendous benefits can result from a better understanding of spray combustion processes. Yet, theoretical developments and experimental measurements of spray combustion remains a daunting task due to the complex coupling of a turbulent, two-phase flow with phase change and chemical reactions. However, it is recognized that individual droplet behavior (including ignition, evaporation and combustion) is a necessary component for laying the foundation for a better understanding of spray processes. Droplet combustion is also an ideal problem for gaining a better understanding of non-premixed flames. Under the idealized situation producing spherically-symmetric flames (produced under conditions of reduced natural and forced convection), it represents the simplest geometry in which to formulate and solve the governing equations of mass, species and heat transfer for a chemically reacting two phase flow with phase change. The importance of this topic has promoted extensive theoretical investigations for more than 40 years.

Lee, Kyeong-Ook↗

NASA NTRS1983

Catalytic oxidation of very fuel rich mixtures

The objective of this research is to demonstrate the feasibility of using a catalytic reactor as a tool to study soot formation from the fuel rich side of the soot limit (null set = 3 - 6). The experimental approach to be taken in the first phase of the research is to document that a hydrocarbon fuel can be burnt at very rich equivalence ratios without forming soot. A simple mono-component fuel, iso-octane, will be used as the test fuel. To insure that combustion is uniform across the catalyst bed, measurements will be made of the fuel-air equivalence ratio profile across the inlet and the temperature and product distribution across the outlet. Phase Two will be to use this environment as a testing ground for determining the effect the structure of a hydrocarbon fuel has on its tendency to form soot. Various amounts of organic compounds such as benzene will be added to the iso-octane and the reaction products studied. Other compounds to be tested will xylene, toluene, and naphthalene.

Brabbs, T. A.↗

DOE OSTI2020

Mechanistic understanding of catalytic conversion of ethanol to 1-butene over 2D-pillared MFI zeolite

Ethanol is an important C2 platform molecule for producing value-added chemicals and distillate hydrocarbon fuels (e.g., jet and diesel). Among these, catalytic upgrading of ethanol to butenes can generate valuable commodity chemicals (e.g., 1-butene) and provide C4 olefin intermediates that can be further upgraded to jet/diesel fuels. 2D zeolites offer hierarchical mesoporous structures, leading to improved mass transport and reduced diffusion length, which can help to address the coking challenges faced by ethanol conversion to hydrocarbons over 3D zeolites. In this study, we investigate the acid-catalyzed conversion of ethanol to 1-butene over the Brønsted acid sites (BAS) in 2D-pillared MFI zeolite (2D-PMFI) using ab initio molecular dynamics (AIMD) simulations, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and calorimetric measurements. A detailed thermodynamic analysis, using quasi-harmonic approximation (QHA), on the Gibbs free energy pathway of ethanol conversion shows that the consideration of entropy is critical to accurately capture the detailed thermodynamic profiles. The formation of bulky ethoxy-ethene complex is found to be a potential rate-determining step (RDS), proceeding via stepwise mechanism. The reactivity of 2D-PMFI can be further tuned by manipulating RDS through a careful control of number of BAS and operating temperatures. The accuracy of computational model is confirmed through the comparison of calculated vibrational density of states (VDOS) against the experimental DRIFTS measurements. Overall, our study provides mechanistic insights into ethanol upgrading over the 2D-PMFI and shows the importance of evaluating entropic effects in such confined system.

Ethanol conversion, 2D-pillared zeolite, MFI, Anha↗

NASA NTRS2007

Methane Hydrates: More Than a Viable Aviation Fuel Feedstock Option

Demand for hydrocarbon fuels is steadily increasing, and greenhouse gas emissions continue to rise unabated with the energy demand. Alternate fuels will be coming on line to meet that demand. This report examines the recovering of methane from methane hydrates for fuel to meet this demand rather than permitting its natural release into the environment, which will be detrimental to the planet. Some background on the nature, vast sizes, and stability of sedimentary and permafrost formations of hydrates are discussed. A few examples of the severe problems associated with methane recovery from these hydrates are presented along with the potential impact on the environment and coastal waters. Future availability of methane from hydrates may become an attractive option for aviation fueling, and so future aircraft design associated with methane fueling is considered.

Hendricks, Robert C.↗

DOE OSTI2020

Production and Fuel properties of Iso-Olefins with Controlled Molecular Structure and Obtained from Butene Oligomerization

The ability to control the molecular structure (e.g., degree of branching) of iso-olefins produced from oligomerizing light olefins is a valuable tool for tuning the final compositions of hydrocarbon fuels and targeting specific fuel properties. In this study, we demonstrated that the degree of branching of iso-olefins obtained from butene(s) oligomerization can be controlled by tuning process conditions (i.e., temperature, weight hourly space velocity [WHSV], and nature of butene feedstock) and by choosing the proper catalyst (i.e., Amberlyst-36 vs. Y/ZSM-22). In this study, we produced three types of iso-olefin mixtures: 1) a methyl-heptenes rich (74 wt.%) mixture, 2) dimethyl-hexenes rich (80–96 wt.%) mixtures, and 3) highly branched (i.e., more than three methyl substitutions) iso-olefins rich (>50 wt.%) mixtures. While dimethyl-hexenes are preferentially formed at lower temperatures (60–100°C) and WHSV (i.e., 2 hr-1), methyl-heptenes are favorably produced at higher temperatures (>100°C) and WHSVs (i.e., 7 hr-1) over Amberlyst-36. The use of either 1-butene or 2-butene as feedstock resulted in liquid products with similar branching because facile intramolecular isomerization occurs prior to oligomerization. However, the use of isobutylene feedstock forms a significantly more branched olefin product. The formation of highly branched iso-olefins also is favored at higher temperature (140°C) over Amberlyst-36. Using Y/ZSM-22 instead of Amberlyst-36 allowed preferential formation of less-branched methyl-heptenes. For each type of iso-olefins mixture, we determined fuel properties including research octane number (RON), motor octane number (MON), and octane sensitivity (S), which is the difference between RON and MON. We found that not only RON and MON but also S values increased with the degree of branching of these complex mixtures of iso-olefins. The highest RON of 99.7 and S value of 9.3 were obtained for a mixture of highly branched iso-olefins.

Dagle, Vanessa↗

DOE OSTI2023

A systematic multicriteria-based approach to support product portfolio selection in microalgae biorefineries

Here this work proposes and applies a sequential approach of objective methods to aid the decision-making process for the deployment of microalgae biorefineries. The strategy combines Multicriteria Decision Analysis (MCDA) and weight assignment methods to simultaneously consider technical, economic, and environmental criteria to (1) outrank the best bioproduct options from different biomass fractions present in microalgae biomass at different ratios (namely carbohydrates, lipids, and protein) and (2) define the most suitable biorefining pathways associated with specific pairings of microalgae strains and cultivation conditions. The first part of the assessment identified succinic acid, acrylic acid, and citric acid as the top-ranked bioproducts from carbohydrates, polyurethane from lipids, and thermoplastic extrusion co-feed from protein. The second step of the analysis determined that, when production of a hydrocarbon fuel is desired, the compositional profile of a strain is paramount in defining the biorefining setup that should be pursued. In summary, microalgae lipids should be sent to the production of hydrocarbon fuels if the ratio between neutral lipids and fermentable carbohydrates is higher than roughly 1, with carbohydrates and protein being converted to the higher-value products noted above. Finally, this result was corroborated through process simulations, which indicated superior economic and environmental metrics when strains are paired with suitable conversion pathways identified through MCDA based on their compositional profiles. The outcomes of this work provide clear, objective, guidelines for establishing the best biorefining approach for a large suite of biochemical compositions as a screening method prior to employing detailed process simulations alongside rigorous techno-economic and life-cycle assessments.

09 BIOMASS FUELS↗

NASA NTRS1986

Advances in high chamber pressure propulsion

NASA has been involved in the development of improved high thrust booster rocket engines to meet the propulsion requirements of launch vehicles such as the Space Shuttle. Solutions that NASA/Marshall Space Flight Center pursued to accomplish the high performance, long life goals set for SSME are discussed. In addition, currently projected requirements for liquid rocket engines have identified liquid oxygen/hydrocarbon-fueled engines for booster application in the near future. These advanced hydrocarbon-fueled engines will require improvements in performance and life to be suitable for their projected missions. Raising chamber pressure to increase performance and reduce engine envelope are the key objectives in hydrocarbon-fueled engine technology. This paper traces the history of advances in high pressure rocket engine systems and the challenges it presents.

Mccool, A. A.↗

DOE OSTI2022

Feedstock and Catalyst Impact on Bio-Oil Production and FCC Co-Processing to Fuels

NREL's thermochemical biomass conversion research is focused on ex-situ upgrading of biomass fast-pyrolysis (FP) vapors as an efficient route to completely biogenic pyrolysis-based fuel precursors, fuels, and value-added chemicals depending on catalyst and process conditions. A near term pathway being developed uses these liquids for co-processing with petroleum feedstocks to assess biogenic carbon incorporation in hydrocarbon fuel feedstocks for potential refinery use. In this work, the impact of feedstock and catalyst on catalytic fast pyrolysis oil (CFPO) composition was determined with the oils then assessed for biogenic fuel production via FCC (fluidized catalytic cracking) co-processing. Biomass vapors were generated via fast pyrolysis with destabilizing vapor components (char, inorganics, tar aerosols) removed by hot gas filtration to produce clean vapors more responsive to catalytic upgrading. A Davison Circulating Riser (DCR), a petroleum industry standard for fluidized catalytic cracking (FCC) catalyst evaluation, was coupled to a custom pyrolyzer system designed to produce consistent-composition pyrolysis vapors as feed to the DCR. Pyrolysis vapors, derived from pure hardwood and softwood, were upgraded using commercially available modified zeolite-based catalysts to produce CFPOs. These upgraded oils were analyzed via 31P and 13C NMR spectroscopy, GCxGC-TOF/MS, carbonyl and ultimate analysis (CHNO), and simulated distillation (SIMDIS) to assess both oil chemistry and distillation behavior as they relate to catalyst and feedstock type for producing fungible hydrocarbon product liquids. These exploratory vapor-phase-upgrading results demonstrated the feasibility of producing refinery-compatible hydrocarbon fuel intermediates entirely from biomass-derived fast-pyrolysis vapors using an industry-accepted DCR system for catalytic upgrading. The FCC co-processing results demonstrated the feasibility of using CFPOs with VGO feeds in FCC refinery operations to produce biogenic carbon containing fuels.

biogenic carbon↗

NASA NTRS1974

Emissions of nitrogen oxides from an experimental hydrogen-fueled gas turbine combustor

The effect of operating variables of a hydrogen fueled combustor on exhaust concentrations of total oxides of nitrogen was determined at inlet-air temperature levels up to 810 K, pressure of 414,000N/sa m, and reference velocity of 21.3 m/sec. The combustor, which was originally designed for hydrocarbon fuel produced a NO(x) concentration of 380 ppm with hydrogen at 810 K inlet-air temperature. A reduction in NO(x) of about 30 % was obtained by modification to a lean or rich primary zone. The lowest NO(x) levels obtained with hydrogen were equivalent to those of the reference combustor burning hydrocarbon fuels.

Norgren, C. T.↗

NASA NTRS2016

Range and Endurance Tradeoffs on Personal Rotorcraft Design

Rotorcraft design has always been a challenging tradeoff among overall size, capabilities, complexity, and other factors based on available technology and customer requirements. Advancements in propulsion, energy systems and other technologies have enabled new vehicles and missions; complementary advances in analysis methods and tools enable exploration of these enhanced vehicles and the evolving mission design space. A system study was performed to better understand the interdependency between vehicle design and propulsion system capabilities versus hover / loiter requirements and range capability. Three representative vertical lift vehicles were developed to explore the tradeoff in capability between hover efficiency versus range and endurance capability. The vehicles were a single-main rotor helicopter, a tilt rotor, and a vertical take-off and landing (VTOL) aircraft. Vehicle capability was limited to two or three people (including pilot or crew) and maximum range within one hour of flight (100-200 miles, depending on vehicle). Two types of propulsion and energy storage systems were used in this study. First was traditional hydrocarbon-fueled cycles (such as Otto, diesel or gas turbine cycles). Second was an all-electric system using electric motors, power management and distribution, assuming batteries for energy storage, with the possibility of hydrocarbon-fueled range extenders. The high power requirements for hover significantly reduced mission radius capability. Loiter was less power intensive, resulting in about 1/2 the equivalent mission radius penalty. With so many design variables, the VTOL aircraft has the potential to perform well for a variety of missions. This vehicle is a good candidate for additional study; component model development is also required to adequately assess performance over the design space of interest.

systems analysis↗

NASA NTRS2016

Range and Endurance Tradeoffs on Personal Rotorcraft Design

Rotorcraft design has always been a challenging tradeoff among overall size, capabilities, complexity, and other factors based on available technology and customer requirements. Advancements in propulsion, energy systems and other technologies have enabled new vehicles and missions; complementary advances in analysis methods and tools enable exploration of these enhanced vehicles and the evolving mission design space. A system study was performed to better understand the interdependency between vehicle design and propulsion system capabilities versus hover loiter requirements and range capability. Three representative vertical lift vehicles were developed to explore the tradeoff in capability between hover efficiency versus range and endurance capability. The vehicles were a single-main rotor helicopter, a tilt rotor, and a vertical take-off and landing (VTOL) aircraft. Vehicle capability was limited to two or three people (including pilot or crew) and maximum range within one hour of flight (100-200 miles, depending on vehicle). Two types of propulsion and energy storage systems were used in this study. First was traditional hydrocarbon-fueled cycles (such as Otto, diesel or gas turbine cycles). Second was an all-electric system using electric motors, power management and distribution, assuming batteries for energy storage, with the possibility of hydrocarbon-fueled range extenders. The high power requirements for hover significantly reduced mission radius capability. Loiter was less power intensive, resulting in about 12 the equivalent mission radius penalty. With so many design variables, the VTOL aircraft has the potential to perform well for a variety of missions. This vehicle is a good candidate for additional study; component model development is also required to adequately assess performance over the design space of interest.

systems analysis↗

NASA NTRS1976

Hydrogen rich gas generator

A process and apparatus is described for producing a hydrogen rich gas by introducing a liquid hydrocarbon fuel in the form of a spray into a partial oxidation region and mixing with a mixture of steam and air that is preheated by indirect heat exchange with the formed hydrogen rich gas, igniting the hydrocarbon fuel spray mixed with the preheated mixture of steam and air within the partial oxidation region to form a hydrogen rich gas.

Houseman, J.↗

DOE OSTI2025

A Synchrotron-Based Vacuum Ultraviolet Photoionization Mass Spectrometer-Coupled Microreactor To Probe Thermocatalysis

Vacuum ultraviolet photoionization (VUV-PI) mass spectrometry offers an isomer-selective and universal ionization with minimal fragmentation detection of organics in complex chemical systems such as pyrolysis and combustion. Here, in this study, we report a state-of-the-art experimental setup of a universal catalytic microreactor combined with a molecular beam to investigate the thermocatalytic oxidation of a heterogeneous system relevant for probing reactions at gas–solid interfaces. In strong contrast to traditional off-line analytical methods, this technique is capable of identifying and quantifying short-lived species (radicals) as well as stable products to decipher initial reaction steps via the detection of nascent products. The thermocatalytic oxidative degradation of exo-tetrahydrodicyclopentadiene (JP-10), a high energy-density hydrocarbon fuel, over solid titanium–aluminum–boron reactive mixed metal nanopowder (Ti-Al-B RMNP) is exploited to showcase potential applications. Overall, some 59 nascent gas-phase products are identified via photoionization efficiency (PIE) curves, including oxygenated species and hydrocarbons comprising closed-shell molecules and radicals. The critical temperature for complete oxidative decomposition of JP-10 was lowered by 450 K from 1400 K to 950 K, indicating an efficient thermocatalytic action of Ti-Al-B nanoparticles on JP-10. The enabling of a universal chemical microreactor along with VUV-PI mass spectrometry broadens the applicability of this technique to hydrocarbon fuel oxidation and pyrolysis characterization. This isomer-selective sensitive probing along with the detection of radical transients makes the aforementioned technique superior to other conventional analytical techniques such as microflow tube and pyrolysis-gas chromatography coupled with mass spectrometry for investigating similar pyrolysis reactions and comprehensive quantification.

Paul, Dababrata [Univ. of Hawaii at Manoa, Honolul↗

NASA NTRS1986

Evaluation of a storable fluorine based pilot for scramjets

An ignitor/pilot device for scramjet engines has been tested with C2H4, C2H6, and CH4 gaseous hydrocarbon fuels at Mach 2. The pilot was designed to operate with storable nontoxic propellants rather than hazardous pyrophorics; the pilot fluid is a mixture of ethylene, oxygen, and sulfur hexafluoride. The pilot reduced the minimum temperature at which all three hydrocarbon fuels ignited; a comparison was then conducted between combustion efficiency calculations for these test results and those of pilots using nitrogen in place of sulfur hexafluoride, and using silane-hydrogen (yielding equivalent energy). The nitrogen-substituted pilot exhibited the highest efficiency.

Diskin, G. S.↗

NASA NTRS2005

The Synthesis and Testing of Highly Strained Cyclic and Polycyclic Molecules as Hypergolic Fuels

Increasing fuel efficiency has been a goal for chemists for several decades. Particularly, a more efficient fuel can increase the range of liquid-hydrocarbon-fueled ram-jets and cruise missiles. A storable high-energy fuel that spontaneously ignites upon addition of an oxidizer is defined as a hypergolic fuel. Hypergolic storable fuels provide an increase in energy per unit volume of fuel and eliminate the need for an external ignition system. Several classes of functionalized hydrocarbons such as amines, boranes, and phosphines are known to be hypergolic with nitric acid oxidizers, but only hydrazine and its simple derivatives5 have been found to exhibit true hypergolic behavior with H2O2. Hydrogen peroxide is a good candidate for an oxidizer due to its reduced toxicity and improved storage capability. Hydrazine-based fuels are expensive, highly corrosive, and toxic, thus providing the need for investigation of other fuels that may be hypergolic with H2O2. Strained hydrocarbons have been studied as high-density fuels. Some examples including benzvalene and cubane, exhibit an increase in heat of combustion as the density of the fuel increases. Many conventional hydrocarbon fuels, such as JP-5 and JP-10, show a decrease in heat of combustion as density of the fuel increases. Strained hydrocarbons can therefore increase the range of the missile by increasing the combustion efficiency per volume of fuel. The goal of this research is to investigate hypergolic behavior of strained hydrocarbons by adding an amine functional group which has been found to hypergolic with nitric acid oxidizers. N,N-Dimethyl-[3]-triangulane-7-methylamine (l), cyclopropylamines (2), cyclobutylamines (3), propylamines (4), and butylamines (5) were synthesized and investigated. The amino group should react with oxygen, providing the initiation step for ring decomposition. The highly exothermic reactions will accumulate energy and potentially lead to spontaneous ignition of the fuel. Triangulanes possess high strain energy, while the less strained cyclopropane and cyclobutanes are more volatile and may show shorter ignition times.

Eccles, Wendy↗