Autoignition of surrogate fuels at elevated temperatures and pressures

Autoignition of Jet-A and mixtures of benzene, hexane, and decane in air has been studied using a heated shock tube at mean post-shock pressures of 8.5 ± 1 atm within the temperature range of 1000–1700 K with the objective of identifying surrogate fuels for aviation kerosene. The influence of each component on ignition delay time and on critical conditions required for strong ignition of the mixture has been deduced from experimental observations. Correlation equation for Jet-A ignition times has been derived from the measurements. It is found that within the scatter of experimental data dilution of n-decane with benzene and n-hexane leads to slight increase in ignition times at low temperatures and does not change critical temperatures required for direct initiation of detonations in comparison with pure n-decane/air mixtures. Ignition times in 20% hexane/80% decane (HD), 20% benzene/80% decane (BD) and 18.2% benzene/9.1% hexane/72.7% decane (BHD) mixtures at temperature range of T  1450–1750 K correlate well with induction time of Jet-A fuel suggesting that these mixtures could serve as surrogates for aviation kerosene. At the same time, HD, BD and BHD surrogate fuels demonstrate a stronger autoignition and peak velocities of reflected shock front in comparison with Jet-A and n-decane/air mixtures.     

Autoignition of propane–air mixtures behind reflected shock waves

Ignition times and autoignition modes for propane–air mixtures have been studied behind reflected shock waves. Experiments were performed over temperatures between 1000 and 1750 K, pressures between 2 and 20 atm, and equivalence ratios of = 0.5, 1.0, and 2.0. Ignition delay times were determined using pressure measurements, C₂ emission profiles, and luminosity measurements in the visible spectrum (380–680 nm). Empirical correlations for ignition time for low temperature (1000–1300 K) and high temperature (1300–1800 K) ranges have been deduced from the experimental data. Different autoignition modes of the mixture (strong, transient, and weak) were identified by comparing velocities of reflected shock wave at different distances from the reflecting wall.     

Combustion of nano-aluminum and liquid water

An experimental investigation on the combustion behavior of nano-aluminum (nAl) and liquid water has been conducted. In particular, linear and mass-burning rates of quasi-homogeneous mixtures of nAl and liquid water as a function of pressure, mixture composition, particle size, and oxide layer thickness were measured. This study is the first reported self-deflagration on nAl and liquid water without the use of any additional gelling agent. Steady-state burning rates were obtained at room temperature (25 °C) using a windowed vessel for a pressure range of 0.1–4.2 MPa in an argon atmosphere, particle diameters of 38–130 nm, and overall mixture equivalence ratios () from 0.5 to 1.25. At the highest pressure studied, the linear burning rate was found to be 8.6 ± 0.4 cm/s, corresponding to a mass-burning rate per unit area of 6.1 g/cm² s. The pressure exponent at room temperature was 0.47, which was independent of the overall mixture equivalence ratio for all of the cases considered. The mass-burning rate per unit area increased from 1.0 to 5.8 g/cm² s for an equivalence ratio range of 0.5–1.25. It varied inversely to particle diameter, increasing by 157% when the particle diameter was decreased from 130 to 50 nm at  = 1.0.     

Application of an aerosol shock tube to the measurement of diesel ignition delay times

Shock tube ignition delay times were measured for DF-2 diesel/21% O₂/argon mixtures at pressures from 2.3 to 8.0 atm, equivalence ratios from 0.3 to 1.35, and temperatures from 900 to 1300 K using a new experimental flow facility, an aerosol shock tube. The aerosol shock tube combines conventional shock tube methodology with aerosol loading of fuel-oxidizer mixtures. Significant efforts have been made to ensure that the aerosol mixtures were spatially uniform, that the incident shock wave was well-behaved, and that the post-shock conditions and mixture fractions were accurately determined. The nebulizer-generated, narrow, micron-sized aerosol size distribution permitted rapid evaporation of the fuel mixture and enabled separation of the diesel fuel evaporation and diffusion processes that occurred behind the incident shock wave from the chemical ignition processes that occurred behind the higher temperature and pressure reflected shock wave. This rapid evaporation technique enables the study of a wide range of low-vapor-pressure practical fuels and fuel surrogates without the complication of fuel cracking that can occur with heated experimental facilities. These diesel ignition delay measurements extend the temperature and pressure range of earlier flow reactor studies, provide evidence for NTC behavior in diesel fuel ignition delay times at lower temperatures, and provide an accurate data base for the development and comparison of kinetic mechanisms for diesel fuel and surrogate mixtures. Representative comparisons with several single-component diesel surrogate models are also given.     

The effect of stoichiometry on the combustion behavior of a nanoscale Al/MoO3 thermite

The effect of stoichiometry on the combustion behavior of the nanoscale aluminum molybdenum trioxide (nAl/MoO₃) thermite was studied in a burn tube experiment by characterizing the propagation velocity and pressure output of the reaction. Changing the stoichiometry affects the combustion through changes in the product temperature, phase, and composition. The mixture ratios of the composites were varied over an extremely wide range (5% nAl (95% MoO₃)–90% nAl (10% MoO₃)). Results revealed three separate combustion regimes: a steady high speed propagation (100 to 1000 m/s) from approximately 10% to 65% nAl, an oscillating and accelerating wave near 70% nAl, and a steady-slow speed propagation (0.1–1 m/s) from approximately 75% to 85% nAl. Propagation was observed to fail both <10% nAl and >85% nAl. This is the first known observation of such limits for a nanoscale thermite in a tube geometry. The instrumented tube tests revealed peak pressures over 8 MPa near stoichiometric conditions in the steady high speed propagation region, no measurable pressure rise at low speed propagation, and building pressures for accelerating waves. The results suggest the propagation mode to be a supersonic convective wave for near stoichiometric mixtures and a conductive deflagration for extremely fuel-rich mixtures. The implications of these results for microscale combustion applications are discussed.     

利用OH自由基特征发射谱测量正庚烷的点火延迟时间

在化学激波管中利用反射激波进行点火,采用OH自由基在306.4nm处特征发射谱线强度的急剧变化标志燃料的着火,由光谱单色仪、光电倍增管、压力传感器和示波器组成测量系统,测量了正庚烷/氧气的点火延迟时间,点火压力(1.0±0.1)和(0.75±0.05)atm,点火温度1 170～1 730K,当量比1.0,得到了在此实验条件下正庚烷/氧气点火延迟时间随温度变化的关系式。研究结果表明正庚烷/氧气点火延迟时间随温度的增加呈指数减小,点火压力为0.75atm时,随着点火温度的增加,点火延迟时间的变化率要小于1.0atm条件时。实验结果为建立正庚烷燃烧反应动力学模型,验证正庚烷燃烧反应机理提供了实验依据。     

Experimental and numerical investigation of the hetero-/homogeneous combustion of lean propane/air mixtures over platinum

The pure heterogeneous and the coupled hetero-/homogeneous combustion of fuel-lean propane/air mixtures over platinum have been investigated at pressures 1 bar  p  7 bar, fuel-to-air equivalence ratios 0.23  φ  0.43, and catalytic wall temperatures 723 K  T_w  1286 K. Experiments were performed in an optically accessible catalytic channel-flow reactor and involved 1-D Raman measurements of major gas-phase species concentrations across the reactor boundary layer for the assessment of catalytic fuel conversion and planar laser induced fluorescence (LIF) of the OH radical for the determination of homogeneous ignition. Numerical predictions were carried out with a 2-D elliptic CFD code that included a one-step catalytic reaction for the total oxidation of propane on Pt, an elementary C₃ gas-phase chemical reaction mechanism, and detailed transport. A global catalytic reaction step valid over the entire pressure–temperature-equivalence ratio parameter range has been established, which revealed a p^0.75 dependence of the catalytic reactivity on pressure. The aforementioned global catalytic step was further coupled to a detailed gas-phase reaction mechanism in order to simulate homogeneous ignition characteristics in the channel-flow reactor. The predictions reproduced within 10% the measured homogeneous ignition distances at pressures p  5 bar, while at p = 7 bar the simulations overpredicted the measurements by 19%. The overall model performance suggests that the employed hetero-/homogeneous chemical reaction schemes are suitable for the design of propane-fueled catalytic microreactors.     

Ignition delay times of methyl oleate and methyl linoleate behind reflected shock waves

Ignition delay times for methyl oleate (C₁₉H₃₆O₂, CAS: 112-62-9) and methyl linoleate (C₁₉H₃₄O₂, CAS: 112-63-0) were measured for the first time behind reflected shock waves, using an aerosol shock tube. The aerosol shock tube enabled study of these very-low-vapor-pressure fuels by introducing a spatially-uniform fuel aerosol/4% oxygen/argon mixture into the shock tube and employing the incident shock wave to produce complete fuel evaporation, diffusion, and mixing. Reflected shock conditions covered temperatures from 1100 to 1400 K, pressures of 3.5 and 7.0 atm, and equivalence ratios from 0.6 to 2.4. Ignition delay times for both fuels were found to be similar over a wide range of conditions. The most notable trend in the observed ignition delay times was that the pressure and equivalence ratio scaling were a strong function of temperature, and exhibited cross-over temperatures at which there was no sensitivity to either parameter. Data were also compared to the biodiesel kinetic mechanism of Westbrook et al. (2011) [10], which underpredicts ignition delay times by about 50%. Differences between experimental and computed ignition delay times were strongly related to existing errors and uncertainties in the thermochemistry of the large methyl ester species, and when these were corrected, the kinetic simulations agreed significantly better with the experimental measurements.     

Autoignition of gasoline surrogate mixtures at intermediate temperatures and high pressures: Experimental and numerical approaches

Ignition-delay times were measured in shock-heated gases for a surrogate gasoline fuel comprised of ethanol/iso-octane/n-heptane/toluene at a composition of 40%/37.8%/10.2%/12% by liquid volume with a calculated octane number of 98.8. The experiments were carried out in stoichiometric mixtures in air behind reflected shock waves in a heated high-pressure shock tube. Initial reflected shock conditions were as follows: Temperatures of 690-1200 K, and pressures of 10, 30 and 50 bar, respectively. Ignition delay times were determined from CH^∗ chemiluminescence at 431.5 nm measured at a sidewall location. The experimental results are compared to simulated ignition delay times based on detailed chemical kinetic mechanisms. The main mechanism is based on the primary reference fuels (PRF) model, and sub-mechanisms were incorporated to account for the effect of ethanol and/or toluene. The simulations are also compared to experimental ignition-delay data from the literature for ethanol/iso-octane/n-heptane (20%/62%/18% by liquid volume) and iso-octane/n-heptane/toluene (69%/17%/14% by liquid volume) surrogate fuels. The relative behavior of the ignition delay times of the different surrogates was well predicted, but the simulations overestimate the ignition delay, mostly at low temperatures.     

Experimental study and modeling of shock tube ignition delay times for hydrogen-oxygen-argon mixtures at low temperatures

Recent literature has indicated that experimental shock tube ignition delay times for hydrogen combustion at low-temperature conditions may deviate significantly from those predicted by current detailed kinetic models. The source of this difference is uncertain. In the current study, the effects of shock tube facility-dependent gasdynamics and localized pre-ignition energy release are explored by measuring and simulating hydrogen-oxygen ignition delay times. Shock tube hydrogen-oxygen ignition delay time data were taken behind reflected shock waves at temperatures between 908 to 1118 K and pressures between 3.0 and 3.7 atm for two test mixtures: 4% H₂, 2% O₂, balance Ar, and 15% H₂, 18% O₂, balance Ar. The experimental ignition delay times at temperatures below 980 K are found to be shorter than those predicted by current mechanisms when the normal idealized constant volume (V) and internal energy (E) assumptions are employed. However, if non-ideal effects associated with facility performance and energy release are included in the modeling (using CHEMSHOCK, a new model which couples the experimental pressure trace with the constant V, E assumptions), the predicted ignition times more closely follow the experimental data. Applying the new CHEMSHOCK model to current experimental data allows refinement of the reaction rate for H + O₂ + Ar ↔ HO₂ + Ar, a key reaction in determining the hydrogen-oxygen ignition delay time in the low-temperature region.     

Shock-tube study of the ignition of methane/ethane/hydrogen mixtures with hydrogen contents from 0% to 100% at different pressures

The ignition delay times of diluted hydrogen/reference gas (92% methane, 8% ethane)/O₂/Ar mixtures with hydrogen contents of 0%, 40%, 80% and 100% were determined in a high-pressure shock tube at equivalence ratios ? = 0.5 and 1.0 (dilution 1:5). The temperature range was 900 K ? T ? 1800 K at pressures of about 1, 4 and 16 bar.The reference gas and the 40% hydrogen/60% reference gas data showed typical characteristics of hydrocarbon systems and can be represented by:

     

Experimental determination of counterflow ignition temperatures and laminar flame speeds of C2–C3 hydrocarbons at atmospheric and elevated pressures

Experimental data were acquired for: (1) the ignition temperatures of nitrogen–diluted ethylene and propylene by counterflowing heated air for various strain rates and system pressures up to 7 atm; (2) the laminar flame speeds of mixtures of air with acetylene, ethylene, ethane, propylene, and propane, deduced from an outwardly propagating spherical flame in a constant-pressure chamber, for extensive ranges of lean-to-rich equivalence ratio and system pressure up to 5 atm. These data, respectively, relevant for low- to intermediate-temperature ignition chemistry and high-temperature flame chemistry, were subsequently compared with calculated results using a literature C₁–C₃ mechanism and an ethylene mechanism. Noticeable differences were observed in the comparison for both mechanisms, and sensitivity analyses were conducted to identify the reactions of importance.     

Ignition delay times of methane and hydrogen highly diluted in carbon dioxide at high pressures up to 300 atm

The need for more efficient power cycles has attracted interest in super-critical CO₂ (sCO₂) cycles. However, the effects of high CO₂ dilution on auto-ignition at extremely high pressures has not been studied in depth. As part of the effort to understand oxy-fuel combustion with massive CO₂ dilution, we have measured shock tube ignition delay times (IDT) for methane/O₂/CO₂ mixtures and hydrogen/O₂/CO₂ mixtures using sidewall pressure and OH* emission near 306?nm. Ignition delay time was measured in two different facilities behind reflected shock waves over a range of temperatures, 1045–1578?K, in different pressures and mixture regimes, i.e., CH₄/O₂/CO₂ mixtures at 27–286 atm and H₂/O₂/CO₂ mixtures at 37–311 atm. The measured data were compared with the predictions of two recent kinetics models. Fair agreement was found between model and experiment over most of the operating conditions studied. For those conditions where kinetic models fail, the current ignition delay time measurements provide useful target data for development and validation of the mechanisms.     

Autoignition of ethylene in shock waves

The delay time of ignition of various C₂H₄-O₂-Ar mixtures behind reflected shock waves were measured at temperatures of 1090–1520 K and a pressure of 0.65 ± 0.05 MPa. A kinetic scheme of the ignition of ethylene based on the known rate constants of the key elementary reactions was developed. The scheme satisfactorily describes our own and published data on the ignition of ethylene in shock waves over wide ranges of temperature (1100–2400 K), pressure (0.006–0.64 MPa) and ethylene (0.1–17.4 vol %) and oxygen (0.6–20.7 vol %) concentrations.     

An experimental and modeling study of the shock tube ignition of a mixture of n-heptane and n-propylbenzene as a surrogate for a large alkyl benzene

Alkyl aromatics are an important chemical class in gasoline, jet and diesel fuels. In the present work, an n-propylbenzene and n-heptane mixture is studied as a possible surrogate for large alkyl benzenes contained in diesel fuels. To evaluate it as a surrogate, ignition delay times have been measured in a heated high pressure shock tube (HPST) for a mixture of 57% n-propylbenzene/43% n-heptane in air (≈21% O₂, ≈79% N₂) at equivalence ratios of 0.29, 0.49, 0.98 and 1.95 and compressed pressures of 1, 10 and 30 atm over a temperature range of 1000–1600 K. The effects of reflected-shock pressure and equivalence ratio on ignition delay time were determined and common trends highlighted. A combined n-propylbenzene and n-heptane reaction mechanism was assembled and simulations of the shock tube experiments were carried out. The simulation results showed very good agreement with the experimental data for ignition delay times. Sensitivity and reaction pathway analyses have been performed to reveal the important reactions responsible for fuel oxidation under the shock tube conditions studied. It was found that at 1000 K, the main consumption pathways for n-propylbenzene are abstraction reactions on the alkyl chain, with particular selectivity to the allylic site. In comparison at 1500 K, the unimolecular decomposition of the fuel is the main consumption pathway.     

Dependence of flame propagation on pressure and pressurizing gas for an Al/CuO nanoscale thermite

The pressure dependence of flame propagation in an Al/CuO nanoscale thermite was studied. Experiments were performed by loosely packing the Al/CuO mixture in an instrumented burn tube, which was placed in a large volume, constant pressure chamber with optical windows. A high-speed camera was used to take photographic data, and six pressure transducers equally spaced along the length of the burn tube were used to measure the local transient pressure. Ambient pressures were varied between 0 and 15 MPa, and three different pressurizing gases were used: argon, helium, and nitrogen. Three modes of propagation were observed. The pressure at which the mode of propagation changed was similar for argon and nitrogen, however, when pressurized with helium, transition occurred at lower pressures. In the low-pressure regime (0–2 MPa) a constant velocity mode with speeds on the order of 1000 m/s was observed. In this region, a convective mode of propagation was dominant. An accelerating regime was observed for a pressure range of approximately 2–5 MPa in argon and nitrogen, with speeds ranging from 100 to 800 m/s. In helium, however, if an accelerating region existed it occurred over a narrow pressure range which was not observed in the present experiments. An oscillating regime was observed in all three gases, in a pressure range of 5–9 MPa for argon and nitrogen, and a range of 2–4 MPa for helium. Velocities in this region are bimodal, and differ by orders of magnitude, suggesting that the propagation mechanism was oscillating between convective and conductive. At relatively high ambient pressures, a constant velocity mode with speeds on the order of 1 m/s was observed for all three gases. The conductive mode of propagation was likely dominant in this region.     

An XeCl* Excimer Fluorescence Study on the Pulse Radiolysis of Xe–nCCl4 and Xe–SOCl2 Systems

The mechanism and kinetics of energy transfer from highly excited Xe states (E _ex > 9.5 eV), generated by a 12-ns electron beam, to chlorine donor molecules were deduced from time-resolved spectra of fluorescence in the region 240–340 nm. The emissions at 240–250 nm were assigned to Xe₂** excimers, and those at 308 and 340 nm to XeCl(B) and XeCl(C) states. Kinetic analysis of the recorded spectra for Xe–CCl₄ and Xe–SOCl₂ gas mixtures at constant xenon pressure and various pressures of molecular admixtures (0.1–1 Torr) allowed us to find the rate constants for the reactions (5) Xe** + RCI products, (6a) Xe** + RCl XeCl(B) + R*, and (6b) Xe** + RCl XeCl(C) + R*, where R is any radical.     

Effects of pressure on flame propagation in a premixture containing fine fuel droplets

Combustion experiments on fuel droplet–vapor–air mixtures have been performed with a rapid expansion apparatus which generates monodispersed droplet clouds with narrow diameter distribution using the condensation method. The effects of fine fuel droplets on flame propagation were investigated for ethanol droplet–vapor–air mixtures at various pressures from 0.2 to 1.0 MPa. A stagnant fuel droplet–vapor–air mixture, generated in a rapid expansion chamber, was ignited at the center of the chamber using an ignition wire. Spherical flame propagation under constant-pressure conditions was observed with a high-speed video camera and flame speed was measured. Total equivalence ratio, and the ratio of liquid fuel mass to total fuel mass, was varied from 0.6 to 1.4 and from zero to 56%, respectively. The mean droplet diameter of fuel droplet–vapor–air mixtures was set at 8.5 and 11 μm. It was found that the flame speed of droplet–vapor–air mixtures less than 0.9 in the total equivalence ratio exceeds that of premixed gases of the same total equivalence ratio at all pressures. The flame speed of fuel droplet–vapor–air mixtures decreases as the pressure increases in all total equivalence ratios. At large ratios of liquid fuel mass to total fuel mass, the normalized flame speed (the flame speed of droplet–vapor–air mixtures divided by the flame speed of the premixed gas with the same total equivalence ratio), increases with the increase in pressure for fuel-lean mixtures, and it decreases for fuel-rich mixtures. The outcome is reversed at small ratios of liquid fuel mass to total fuel mass; the normalized flame speed decreases with the increase in pressure for fuel-lean mixtures, and increases for fuel-rich mixtures. The results suggest that the increase in pressure promotes droplet evaporation in the preheat zone.     

Effect of pressure on soot formation in the pyrolysis of <Emphasis Type="Italic">n</Emphasis>-hexane and the oxidation of fuel-rich mixtures of <Emphasis Type="Italic">n</Emphasis>-heptane behind reflected shock waves

The results of detailed kinetic simulations of the formation of soot particles in the pyrolysis of n-hexane–argon mixtures and in the oxidation of fuel-rich (φ = 5) n-heptane–oxygen–argon mixtures behind reflected shock waves at pressures of 20–100 bar and a constant concentration of carbon atoms or a constant fraction of argon in the initial mixture within the framework of a modified reaction mechanism are reported. The choice of n-hexane and n-heptane for examining the effect of pressure on the process of soot formation was motivated by the availability for these hydrocarbons of experimental measurements in reflected shock waves at high pressures (up to ~100 bar). The temperature dependences of the yield of soot particles formed in the pyrolysis of n-hexane are found to be very weakly dependent on pressure and slightly shifting to lower temperatures with increasing pressure. In general, pressure produces a very weak effect on the soot formation in the pyrolysis of n-hexane. The effect of pressure and concentration of carbon atoms in the initial mixture on the process of soot formation during the oxidation of fuel-rich n-heptane mixtures behind reflected shock waves is studied. The results of our kinetic simulations show that, for both the pyrolysis of n-hexane and the oxidation of fuel-rich n-heptane–oxygen mixtures, the influence of pressure on the process of soot formation is negligible. By contrast, the concentration of carbon atoms in the initial reaction mixture produces a much more pronounced effect.