Shock tube study of n-decane ignition at low pressures

Ignition delay times for n-decane/O2/Ar mixtures were measured behind reflected shock waves using endwall pressure and CH＊ emission measurements in a heated shock tube. The initial postshock conditions cover pressures of 0.09-0.26 MPa, temperatures of 1 227-1 536 K, and oxygen mole fractions of 3.9%-20.7% with an equivalence ratio of 1.0. The correlation formula of ignition delay dependence on pressure, temperature, and oxygen mole fraction was obtained. The current data are in good agreement with available low-pressure experimental data, and they are then compared with the prediction of a kinetic mechanism. The current measurements extend the kinetic modeling targets for the n-decane combustion at low pressures.

Development of efficient and accurate skeletal mechanisms for hydrocarbon fuels and kerosene surrogate

In this paper,the methodology of the directed relation graph with error propagation and sensitivity analysis（DRGEPSA）,proposed by Niemeyer et al.（Combust Flame 157：1760-1770.2010）.and its differences to the original directed relation graph method are described.Using DRGEPSA,the detailed mechanism of ethylene containing 71 species and 395 reaction steps is reduced to several skeletal mechanisms with different error thresholds.The 25-species and 131-step mechanism and the 24-species and115-step mechanism are found to be accurate for the predictions of ignition delay time and laminar flame speed.Although further reduction leads to a smaller skeletal mechanism with 19 species and 68 steps,it is no longer able to represent the correct reaction processes.With the DRGEPSA method,a detailed mechanism for n-dodecane considering low-temperature chemistry and containing 2115 species and8157 steps is reduced to a much smaller mechanism with249 species and 910 steps while retaining good accuracy.If considering only high-temperature（higher than 1000 K）applications,the detailed mechanism can be simplified to even smaller mechanisms with 65 species and 340 steps or48 species and 220 steps.Furthermore,a detailed mechanism for a kerosene surrogate having 207 species and 1592 steps is reduced with various error thresholds and the results show that the 72-species and 429-step mechanism and the66-species and 392-step mechanism are capable of predicting correct combustion properties compared to those of the detailed mechanism.It is well recognized that kinetic mechanisms can be effectively used in computations only after they are reduced to an acceptable size level for computation capacity and at the same time retaining accuracy.Thus,the skeletal mechanisms generated from the present work are expected to be useful for the application of kinetic mechanisms of hydrocarbons to numerical simulations of turbulent or supersonic combustion.

Effect of the high-power electromagnetic pulses on the reactivity of the coal-water slurry in hot environment

An effect of the high-power electromagnetic pulses onto the droplet of coal-water slurry inside the furnace was investigated.In contrary to the previously investigated laser-induced fuel atomization that occurs at the room temperature,the pre-heated(to 400 K)slurry becomes dry enough to prevent the explosion-like steam formation.Thus,fuel does not atomize and the ignition does not accelerate.Furthermore,the absorption of several laser pulses leads to evident sintering of irradiated surface with following increase of the ignition delay time for up to 24%.Variation of the pulse energy in range 48-118 mJ(corresponding intensity up to 2.4 J·cm^-2)leads to certain variation of the increase of ignition delay.The strong pulsed overheating of the coal water slurry which does not initiate the fine atomization of the fuel generally makes its ignition longer.

A Chemical Kinetics Perspective on the High-Temperature Oxidation of Methane and Propane through Experiments and Kinetic Analysis

In the conversion of methane and propane under high temperature and pressure,the ignition delay time(IDT)is a key parameter to consider for designing an inherently safe process.In this study,the IDT characteristics of methane and propane(700–1000 K,10–20 bar)were studied experimentally and using kinetic modeling tools at stoichiometric fuel-tooxygen ratios.All the experiments were conducted through insentropic compression.The reliable experimental data were obtained by using the adiabatic core hypothesis,which can be used to generate and validate the detailed chemical kinetics model.The IDTs of methane and propane were recorded by a rapid compression machine(RCM)and compared to the predicted values obtained by the NUIGMech 3.0 mechanism.To test the applicability of NUIGMech 3.0 under different reaction conditions,the influence of temperature in the range of 700–1000 K(and the influence of pressure in the range of 10–20 bar)on the IDT was studied.The results showed that NUIGMech 3.0 could reasonably reproduce the experimentally determined IDT under the wide range of conditions studied.The constant volume chemical kinetics model was used to reveal the effect of temperature on the elementary reaction,and the negative temperature coefficient(NTC)behavior of propane was also observed at 20 bar.The experimental data can serve as a reference for the correction and application of kinetic data,as well as provide a theoretical basis for the safe conversion of low-carbon hydrocarbon chemicals.

Effect of plasma on combustion characteristics of boron

As it is very difficult to release boron energy completely, kinetic mechanism of boron is not clear, which leads to the lack of theoretical guidance for studying how to accelerate boron combustion. A new semi-empirical boron combustion model is built on the King combustion model, which contains a chemical reaction path; two new methods of plasma-assisted boron combustion based on kinetic and thermal effects respectively are built on the ZDPLASKIN zero-dimensional plasma model. A plasma-supporting system is constructed based on the planar flame, discharge characteristics and the spectral characteristics of plasma and boron combustion are analyzed. The results show that discharge power does not change the sorts of excited-particles, but which can change the concentration of excited-particles. Under this experimental condition,plasma kinetic effect will become the strongest at the discharge power of 40 W; when the discharge power is less than 40 W,plasma mainly has kinetic effect, otherwise plasma has thermal effect. Numerical simulation result based on plasma kinetic effect is consistent with the experimental result at the discharge power of 40 W, and boron ignition delay time is shortened by 53.8% at the discharge power of 40 W, which indicates that plasma accelerates boron combustion has reaction kinetic paths, while the ability to accelerate boron combustion based on thermal effect is limited.

An experimental and modeling study of n-hexadecane autoignition under low-to-intermediate temperatures

N-hexadecane is a potential candidate of diesel surrogate fuels and is also the largest linear alkane(n-alkanes)with known chemical kinetic models.The objective of this study is to investigate the autoignition characteristics of n-hexadecane in the lowto-intermediate temperature region and to validate the existing kinetic models.In this study,the ignition delay times(IDTs)of nhexadecane were measured using a heated rapid compression machine(RCM)at two pressures of 7 and 10 bar,and over equivalence ratios ranging from 0.5 to 1.3.Two-stage ignition characteristic and the negative temperature coefficient(NTC)behavior of total ignition delay time were experimentally captured.This study paid special attention to the influence of pressure,equivalence ratio,and oxygen content on the IDTs of n-hexadecane.It is observed that both the total IDTs and the first-stage IDTs decrease with the rise of those parameters.It is worth noting that the first-stage IDT is found to show a greater dependence on temperature but a weaker dependence on other parameters compared to the total IDT.The observed IDT dependence in the lowtemperature region(LTR)were quantitatively described by ignition delay time correlations.The newly measured IDTs were then validated against two kinetic models(LLNL and CRECK).Simulation results show that both models underpredict the first-stage IDT but generally capture the temperature dependence.The CRECK model well predicts the total IDTs of n-hexadecane while the LLNL model significantly underpredicts the total IDTs at most investigated conditions.To the best of our knowledge,this study is the first investigation on n-hexadecane autoignition under low-to-intermediate temperatures,which deepens the understanding of large n-alkane oxidation and contributes to the improvement of the existing kinetic models.

Statistical characteristics of spray autoignition of transient kerosene jet in cross flow

To study statistical characteristics of the random spray autoignition,aviation kerosene was injected transiently into non-vitiated air crossflow in a flow reactor with optical accesses.The operating conditions were relevant to gas turbine combustor:the air crossflow pressure and temperature were in the range of 1.4-1.7 MPa and 830-947 K,respectively,and the jet-tocrossflow momentum flux ratios were 20,50 and 80.Statistical distributions of random ignition delay times with adequate convergence were estimated based on histograms.The dependences of the distributions on reactor pressure,temperature,and jet-to-crossflow momentum flux ratio were studied.The results show that the resulting distributions appear more concentrated with the increase of air temperature or jet-to-crossflow momentum flux ratio.And then the correlations for the mean and standard deviation of the ignition delay time sample data were developed based on the present results.Compared with the correlations of ignition delay time of homogeneous premixed gas-phase kerosene/air mixture reported in the literature,the results show a greater significance pressure dependence and lower temperature sensitivity of the ignition delay time of nonpremixed kerosene spray.

Implication of Sensitive Reactions to Ignition of Methyl Pentanoate:H-Abstraction Reactions by H and CH_(3) Radicals

Methyl pentanoate(MP)was identified as a potential candidate.To facilitate the application of MP with high efficiency in engines,a comprehensive understanding of combustion chemical kinetics of MP is necessary.In this work,the H-abstraction reactions from MP by H and CH_(3) radicals,critical in controlling the initial fuel consumption,are theoretically investigated at the DLPNO-CCSD(T)/CBS(T-Q)//M06-2X/cc-pVTZ level of theory.The multistructural torsional(MS-T)anharmonicity is characterized using the dual-level MS-T method;the HF/3-21G and M06-2X/cc-pVTZ methods are chosen as the low-and high-level methods,respectively.The conventional transition state theory(TST)is employed to calculate the high-pressure limit rate constants at 298-2000 K with the Eckart tunneling correction.Our calculations indicate that the hydrogen atoms of the methylene functional group are easier to be abstracted by H and CH_(3) radicals.The multistructural torsional anharmonicities of H-abstraction reactions MP+H/CH_(3) are significant within the temperature range investigated.The tunneling effects are more pronounced at low temperatures,and contribute considerably to the rate constants below 500 K.The model from the work of Diévart et al.is updated with our calculations,and the simulations of the updated model are in excellent agreement with the reported ignition delay time of MP/O2/Ar and MP/Air mixtures.The sensitivity analysis indicates that the H-abstraction reactions,MP+H-CH_(3)CH_(2)CHCH_(2)C(-O)OCH_(3)/CH_(3)CHCH_(2)CH_(2)C(-O)OCH_(3)+H2,are critical in controlling the initial fuel consumption and ignition delay time of MP.

Synthesis and Improved Properties of Hypergolic Boronium-Based Ionic Liquids

A series of asymmetric monoimidazolium dihydroboronium-based ionic liquids （ILs） were synthesized from amine-boranes. All the resulting ILs were fully characterized by 1H and 13C NMR, IR spectroscopy, elemental analysis or high resolution mass spectrum. Compared with the symmetric bisimidazolium dihydroboronium-based ILs, these new ILs exhibited improved properties with shorter ignition delay times （IDs）, higher densities, and lower phase transition temperature showing the promising application potential as green propellants. A series of asymmetric monoimidazolium dihydroboronium-based ionic liquids （ILs） were synthesized from amine-boranes. All the resulting ILs were fully characterized by 1H and 13C NMR, IR spectroscopy, elemental anal- ysis or high resolution mass spectrum. Compared with the symmetric bisimidazolium dihydroboronium-based ILs, these new ILs exhibited improved properties with shorter ignition delay times （IDs）, higher densities, and lower phase transition temperature showing the promising application potential as green propellants.