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46 records · Page 3

Parametric Study of High Frequency Pulse Detonation Tubes

This paper describes development of high frequency pulse detonation tubes similar to a small pulse detonation engine (PDE). A high-speed valve injects a charge of a mixture of fuel and air at rates of up to 1000 Hz into a constant area tube closed at one end. The reactants detonate in the tube and the products exit as a pulsed jet. High frequency pressure transducers are used to monitor the pressure fluctuations in the device and thrust is measured with a balance. The effects of injection frequency, fuel and air flow rates, tube length, and injection location are considered. Both H2 and C2H4 fuels are considered. Optimum (maximum specific thrust) fuel-air compositions and resonant frequencies are identified. Results are compared to PDE calculations. Design rules are postulated and applications to aerodynamic flow control and propulsion are discussed.

Cutler, Anderw D.↗

Cosmic: Carbon Monoxide And Soot In Microgravity Inverse Combustion

Almost seventy percent of fire related deaths are caused by the inhalation of toxins such as CO and soot that are produced when fires become underventilated.(1) Although studies have established the importance of CO formation during underventilated burning,(2) the formation processes of CO (and soot) in underventilated fires are not well understood. The goal of the COSMIC project is to study the formation processes of CO and soot in underventilated flames. A potential way to study CO and soot production in underventilated flames is the use of inverse diffusion flames (IDFs). An IDF forms between a central air jet and a surrounding fuel jet. IDFs are related to underventilated flames because they may allow CO and soot to escape unoxidized. Experiments and numerical simulations of laminar IDFs of CH4 and C2H4 were conducted in 1-g and micro-g to study CO and soot formation. Laminar flames were studied because turbulent models of underventilated fires are uncertain. Microgravity was used to alter CO and soot pathways. A IDF literature survey, providing background and establishing motivation for this research, was presented at the 5th IWMC.(3) Experimental results from 1-g C2H4 IDFs and comparisons with simulations, demonstrating similarities between IDFs and underventilated fires, were presented at the 6th IWMC.(4) This paper will present experimental results from micro-g and 1-g IDFs of CH4 and C2H4 as well as comparisons with simulations, further supporting the relation between IDFs and underventilated flames.

Mikofski, M. A.↗

Experimental Measurements of Soot and Soot Precursors of Sustainable Aviation Fuels

Sustainable Aviation Fuels (SAFs) are promising for decarbonizing the challenging-to-electrify aerospace sector and reducing yearly greenhouse gas emissions by thousands of tons. Developing predictive detailed chemical kinetic models for SAF (and traditional) fuel mixtures necessitates a robust experimental database to elucidate the intricate pyrolysis and oxidation chemistry of SAF fuel blend components. Two critical components of SAF surrogate mixtures are iso-dodecane isomers and trans-decalin. This report characterizes the structure of three slightly sooting, laminar, non-premixed, nitrogen-diluted Planar Mixing Layer Flames (PMLFs) fueled by either pure ethylene, ethylene doped with 1500ppm of either 2,2,4,6,6-pentamethyl-heptane or trans-decalin. The flames have the same stoichiometric mixture fraction and total mole fraction of fuels in the fuel stream (X F,F = X C2H4,F + X Dopant,F = 0.26), resulting in approximately the same maximum temperature (T max ≈ 1800 K) to highlight the effect of doping on soot and its gaseous precursors. The PMLF is unconfined and established between adjacent planar jets of the fuel and oxidizer streams surrounded by annular shielding nitrogen. The flow is stabilized by exhausting the hot buoyant flame products through a slot in a downstream plate onto which the cold flow impinges. Importantly, any horizontal cross-section of the PMLF has a self-similar thermochemical structure of a reactive boundary layer that grows at increasing Height Above the Burner (HAB). Therefore, the horizontal cross-sections of a PMLF can be modeled as a One-Dimensional Counterflow Flame (1D-CF) with very low strain rates which are unachievable in traditional CFs and yield a structure that is several millimeters thick. In brief, the PMLF is ideal for performing spatially resolved measurements with minimal effects of the sampling-induced perturbations, to develop and validate detailed chemical kinetic models on time scales of a few tens of milliseconds that are relevant in aviation applications. The horizontal profiles of C0-C18 gaseous species at HAB = 50 mm and soot volume fraction at 25 and 50 mm are measured using capillary sampling followed by GC-MS analyses and Laser Induced Emission Spectroscopy (LIES), respectively. Additionally, the Elastic Laser Light Scattering (E-LLS) coefficient is measured at HAB = 50 mm and 25 mm to determine the strain rates of the 1D-CFs equivalent to the characterized PMLF horizontal cross sections and the profile of the E-LLS equivalent diameter of soot. The comparison of the results in the base PMLF fueled only by ethylene with those in either doped PMLF in which 1500 ppm of ethylene are replaced with 2,2,4,6,6-pentamethyl-heptane or trans-decalin, reveals that the doping increases the mole fraction of several Polycyclic Aromatic Hydrocarbons (PAHs) at both HABs by a factor of approximately 2.5, and the soot volume fraction at both HABs by factors of ~1.5 for 2,2,4,6,6-pentamethyl-heptane and ~1.25 for trans-decalin doping, respectively. Conversely, doping causes a near doubling of the soot equivalent diameter only at HAB = 50 mm, without significant effects at 25 mm. The experimental results partially validate the tested state-of-the-art detailed chemical kinetic model and also point toward the further improvement of its predictive capabilities.

10 SYNTHETIC FUELS↗

The Evolution of Hydrocarbons in Saturn's Northern Storm Region

The massive storm at 40N on Saturn that began in December 2010 has produced significant and lasting effects in the northern hemisphere on temperature and species abundances (Fletcher et aL 2011). The northern storm region was observed on several occasions between March 2011 and April 2012 by Cassini's Composite Infrared Spectrometer (CIRS) at a spectral resolution (0.5/cm) which permits the study of trace species in Saturn's stratosphere. During this time period, stratospheric temperatures in regions referred to as "beacons" (warm regions at specific longitudes at the latitude of the storm) became significantly warmer than pre-storm values of 140K, peaking near 220K, and subsequently cooling. These warm temperatures led to greatly enhanced infrared emission due to C4H2, C3H4, C2H2, and C2H6 in the stratosphere as well as the first detection of C2H4 on Saturn in the thermal infrared (Hesman et al. 2012). Using CH4 as a thermometer of Saturn's stratosphere in the beacon regions, we can derive the mixing ratios of each of these molecules. The most common hydrocarbons (C2H2 and C2H6) serve as dynamical tracers on Saturn and their abundances may constrain vertical motion in the stratosphere. All of these hydrocarbons are products of methane photolysis. Since many of the photochemical reactions that produce heavier hydrocarbons such as C4H2 and C3H4 are temperature sensitive, the beacon region provides a natural laboratory for studying these reactions on Saturn. We will discuss the time evolution of the abundances of each of these hydrocarbons from their pre-storm values, through the period of maximum heating , and during the period of cooling that is taking place in Saturn's stratosphere.

Bjoraker, Gordon↗

Elusive Ethylene Detected in Saturns Northern Storm Region

The massive eruption at 40 deg. N (planetographic latitude) on Saturn in 2010 December has produced significant and lasting effects in the northern hemisphere on temperature and species abundances. The northern storm region was observed on many occasions in 2011 by Cassini's Composite Infrared Spectrometer (CIRS). In 2011 May, temperatures in the stratosphere greater than 200 K were derived from CIRS spectra in the regions referred to as "beacons" (warm regions in the stratosphere). Ethylene has been detected in the beacon region in Saturn's northern storm region using CIRS. Ground-based observations using the high-resolution spectrometer Celeste on the McMath-Pierce Telescope on 2011 May 15 were used to confirm the detection and improve the altitude resolution in the retrieved profile. The derived ethylene profile from the CIRS data gives a C2H4 mole fraction of 5.9 +/- 4.5 x 10(exp -7) at 0.5 mbar, and from Celeste data it gives 2.7 +/- 0.45 x 10(exp -6) at 0.1 mbar. This is two orders of magnitude higher than the amount measured in the ultraviolet at other latitudes prior to the storm. It is also much higher than predicted by photochemical models, indicating that perhaps another production mechanism is required or a loss mechanism is being inhibited.

Hesman, B. E.↗

Circumventing thermodynamic limitations in converting carbon dioxide into carbon nanotubes via tandem catalysis

Carbon nanotubes (CNTs) are important materials for electronics and structural composites, but their production still relies on hydrocarbon-based chemical vapor deposition, an energy-intensive and fossil-dependent process, limited by rapid catalyst deactivation. Using CO2 as a carbon feedstock offers a sustainable route for CNT synthesis, yet direct CO2 conversion to CNTs is thermodynamically unfavorable and existing CO2-to-carbon pathways mainly yield amorphous or weakly graphitized solids. Here, we demonstrate a tandem electrochemical–thermochemical (EC-TC) strategy that overcomes these limitations. CO2 is first electrochemically reduced to a tunable mixture of C2H4 and CO, which is directly fed into a thermochemical reactor and converted into CNTs with controllable morphology and high CNT-to-metal mass ratios (~200) over NiFe catalysts at 750 °C. In situ synchrotron-based characterization and density functional theory calculations reveal that CO dissociation and C2H4 decomposition on NiFe alloys cooperatively promote CNT nucleation and sustained growth. This EC-TC strategy establishes a modular route for converting CO2 into value-added carbon nanomaterials.

03 NATURAL GAS↗

Reforming of glucose and wood at the critical conditions of water

Reforming of organics in aqueous solutions is being investigated as a potential waste treatment process. Earlier studies showed that glucose in water reacts to form a gaseous mixture of CO, H2, CH4, CO2, C2H6, and C2H4 in the vicinity of the critical conditions of water (374 C, 22 MPa). The earlier work has been extended to determine the effect of variations in temperature and feed concentration on the extent of gasification. The percent gasification decreases with increasing feed concentration, indicating an overall kinetic order less than unity. Surprisingly, the percent gasification decreases with increasing temperature. A number of preliminary experiments were conducted with maple sawdust feed, which was thought to be representative of complex organic wastes from paper and vegetable matter. Once again, no solid products were found under the critical conditions; the percent gasification ranged from 16 to 88 percent, depending on the feed composition and residence time.

Modell, M.↗

Development of a high temperature pyrolysis mechanism for cyclopentanone, a potential biofuel derived from biomass

Cyclopentanone (CPO) is a promising biofuel for spark-ignition engines due to its ring strain and high auto-ignition resistance. The Department of Energy has identified CPO as a potential biofuel candidate because of its unique chemical properties. Understanding CPO decomposition is crucial to building a high-temperature combustion model. In this study, we present a comprehensive kinetic model for high-temperature pyrolysis of CPO with verified results from high-pressure shock tube (HPST) measurements. The time histories of carbon monoxide (CO), ethylene (C2H4), and CPO absorbances over the temperature range of 1156-1416 K and 8.53-10.06 atm were measured. A corresponding kinetic model was generated using the Reaction Mechanism Generator (RMG) with the parameters of dominant pathways from either previous studies or quantum calculation within current work. The final model containing 821 species and 79,859 reactions exhibited a good agreement with the experimental results. In this study, the C2H4/CO ratio was used as an essential factor to validate the model and to prove that radical-involved bimolecular pathways were as significant as unimolecular decomposition of CPO. The rate of production (ROP) analysis showed that H radicals play major roles in both primary reactions and product pyrolysis. The insights from this work can be used to generate a better CPO combustion model and help evaluate CPO as a biofuel. Such understanding can also be helpful when proposing pyrolysis or combustion models for other biofuels.

cyclopentanone, reaction mechanism, pyrolysis, sho↗

Pressure and Temperature Dependence of the Reaction of Vinyl Radical with Ethylene

This work reports measurements of absolute rate coefficients and Rice-Ramsperger-Kassel-Marcus (RRKM) master equation simulations of the C2H3 + C2H4 reaction. Direct kinetic studies were performed over a temperature range of 300-700 K and pressures of 20 and 133 mbar. Vinyl radicals (H2C=CH) were generated by laser photolysis of vinyl iodide (C2H31) at 266 nm, and time-resolved absorption spectroscopy was used to probe vinyl radicals through absorption at 423.2 nm. Measurements at 20 mbar are in good agreement with previous determinations at higher temperature. A weighted three-parameter Arrhenius fit to the experimental rate constant at 133 mbar, with the temperature exponent fixed, gives k = (7 +/- 1) x 10(exp -l4) cu cm/molecule/s (T/298 K)(exp 2) exp[-(1430 +/- 70) K/T]. RRKM master equation simulations, based on G3 calculations of stationary points on the C4H7 potential energy surface, were carried out to predict rate coefficients and product branching fractions. The predicted branching to 1-methylallyl product is relatively small under the conditions of the present experiments but increases as the pressure is lowered. Analysis of end products of 248 nm photolysis of vinyl iodide/ethylene mixtures at total pressures between 27 and 933 mbar provides no direct evidence for participation of I -methylallyl.

Ismail, Huzeifa↗

Switching CO 2 Electroreduction Selectivity Between C 1 and C 2 Hydrocarbons on Cu Gas-Diffusion Electrodes

We report that regulating the selectivity toward a target hydrocarbon product is still the focus of CO 2 electroreduction. Here, we discover that the original surface Cu species in Cu gas-diffusion electrodes plays a more important role than the surface roughness, local pH, and facet in governing the selectivity toward C 1 or C 2 hydrocarbons. The selectivity toward C 2 H 4 progressively increases, while CH 4 decreases steadily upon lowering the Cu oxidation species fraction. At a relatively low electrodeposition voltage of 1.5 V, the Cu gas-diffusion electrode with the highest Cu δ+ /Cu 0 ratio favors the pathways of hydrogenation to form CH 4 with maximum Faradaic efficiency of 65.4% and partial current density of 228 mA cm -2 at -0.83 V vs RHE. At 2.0 V, the Cu gas-diffusion electrode with the lowest Cu δ+ /Cu 0 ratio prefers C–C coupling to form C 2+ products with Faradaic efficiency topping 80.1% at -0.75 V vs RHE, where the Faradaic efficiency of C 2 H 4 accounts for 46.4% and the partial current density of C 2 H 4 achieves 279 mA cm -2 . This work demonstrates that the selectivity from CH 4 to C 2 H 4 is switchable by tuning surface Cu species composition of Cu gas-diffusion electrodes.

36 MATERIALS SCIENCE↗