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.     

n-Dodecane oxidation at high-pressures: Measurements of ignition delay times and OH concentration time-histories

Ignition delay times and OH concentration time-histories were measured during n-dodecane oxidation behind reflected shocks waves using a heated, high-pressure shock tube. Measurements were made over temperatures of 727-1422 K, pressures of 15-34 atm, and equivalence ratios of 0.5 and 1.0. Ignition delay times were measured using side-wall pressure and OH^∗ emission diagnostics, and OH concentration time-histories were measured using narrow-linewidth ring-dye laser absorption near the R-branchhead of the OH A-X (0, 0) system at 306.47 nm. Shock tube measurements were compared to model predictions of four current n-dodecane oxidation detailed mechanisms, and the differences, particularly in the low-temperature negative-temperature-coefficient (NTC) region where the influence of non-ideal facility effects can be significant, are discussed. To our knowledge, the current measurements provide the first gas-phase shock tube ignition delay times (at pressures above 13 atm) and quantitative OH concentration time-histories for n-dodecane oxidation under practical engine conditions, and hence provide benchmark validation targets for refinement of jet fuel detailed kinetic modeling, since n-dodecane is widely used as the principal representative for n-alkanes in jet fuel surrogates.     

Shock tube measurements of ignition delay times and OH time-histories in dimethyl ether oxidation

Ignition delay times and OH concentration time-histories were measured in DME/O₂/Ar mixtures behind reflected shock waves. Initial reflected shock conditions covered temperatures (T₅) from 1175 to 1900 K, pressures (P₅) from 1.6 to 6.6 bar, and equivalence ratios (?) from 0.5 to 3.0. Ignition delay times were measured by collecting OH^∗ emission near 307 nm, while OH time-histories were measured using laser absorption of the R₁(5) line of the A-X(0,0) transition at 306.7 nm. The ignition delay times extended the available experimental database of DME to a greater range of equivalence ratios and pressures. Measured ignition delay times were compared to simulations based on DME oxidation mechanisms by Fischer et al. [7] and Zhao et al. [9]. Both mechanisms predict the magnitude of ignition delay times well. OH time-histories were also compared to simulations based on both mechanisms. Despite predicting ignition delay times well, neither mechanism agrees with the measured OH time-histories. OH Sensitivity analysis was applied and the reactions DME ↔ CH₃O + CH₃ and H + O₂ ↔ OH + O were found to be most important. Previous measurements of DME ↔ CH₃O + CH₃ are not available above 1220 K, so the rate was directly measured in this work using the OH diagnostic. The rate expression k[1/s] =  1.61 × 10⁷⁹T^−18.4 exp(−58600/T), valid at pressures near 1.5 bar, was inferred based on previous pyrolysis measurements and the current study. This rate accurately describes a broad range of experimental work at temperatures from 680 to 1750 K, but is most accurate near the temperature range of the study, 1350-1750 K. When this rate is used in both the Fischer et al. and Zhao et al. mechanisms, agreement between measured OH and the model predictions is significantly improved at all temperatures.     

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。     

The development of a detailed chemical kinetic mechanism for diisobutylene and comparison to shock tube ignition times

Shock tube experiments and chemical kinetic modeling were carried out on 2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene, the two isomers of diisobutylene, a compound intended for use as an alkene component in a surrogate diesel. Ignition delay times were obtained behind reflected shock waves at 1 and 4 atm, and between temperatures of 1200 and 1550 K. Equivalence ratios ranging from 1.0 to 0.25 were examined for the 1-pentene isomer. A comparative study was carried out on the 2-pentene isomer and on the blend of the two isomers. It was found that the 2-pentene isomer ignited significantly faster under shock tube conditions than the 1-pentene isomer and that the ignition delay times for the blend were directly dependant on the proportions of each isomer. These characteristics were successfully predicted using a detailed chemical kinetic mechanism. It was found that reactions involving isobutene were important in the decomposition of the 1-pentene isomer. The 2-pentene isomer reacted through a different pathway involving resonantly stabilized radicals, highlighting the effect on the chemistry of a slight change in molecular structure.     

Experimental and modeling study of the autoignition characteristics of commercial diesel under engine-relevant conditions

Knowledge of the autoignition characteristics of diesel fuels is of great importance for understanding the combustion performance in engines and developing surrogate fuels. Here ignition delays of China's stage 6 diesel, a commercial fuel, were measured in a heated rapid compression machine (RCM) under engine-relevant conditions. Gas-phase autoignition experiments were carried out at equivalence ratios ranging from 0.37 to 1.0, under compressed pressures of 10, 15, and 20?bar, and within a temperature range of 685–865?K. In all investigated conditions, negative temperature coefficient (NTC) behavior of the total ignition delays is observed. The autoignition of the diesel fuel exhibits pronounced two-stage characteristics with strong low-temperature reactivity. Experimental results indicate that the total ignition delays shorten with increasing compressed pressure, oxygen mole fraction and fuel mole fraction. The first-stage ignition delays are mainly controlled by compressed temperature and also affected by oxygen mole fraction and compressed pressure but show a very weak dependence on fuel mole fraction. Correlations describing the first-stage ignition delay and the total ignition delay were proposed to further clarify the ignition delay dependence on the multiple factors. Additionally, it is found that the newly measured ignition delays well coincide with and complement the diesel ignition data in the literature. A recently developed diesel mechanism was used to simulate the diesel autoignition on the RCM. The simulation results are found to agree well the experimental measurements over the whole temperature ranges. Species concentration analysis and brute force sensitivity analysis were also conducted to identify the crucial species and reactions controlling the autoignition of the diesel fuel.     

Experiments and modeling of ignition delay times, flame structure and intermediate species of EHN-doped stoichiometric n-heptane/air combustion

The combustion of stoichiometric Ethyl-hexyl-nitrate (EHN)-doped n-heptane/oxygen/argon and (EHN)-doped n-heptane/air mixtures, respectively, was investigated in a low-pressure burner with a molecular-beam mass spectrometer and ignition delay-time (τ_ign) measurements were performed in a high-pressure shock tube. The experiments with the low-pressure flame were used for the determination of the flame structure including concentration profiles of reactants, products and important intermediates in the flame. The shock tube experiments provided τ_ign for a temperature range of 690 K ? T ? 1275 K at a pressure of 40 ± 2 bar for stoichiometric and lean mixtures under engine relevant conditions. A chemical mechanism for n-heptane/EHN mixtures was developed from an automatically generated mechanism for n-heptane by manually adding reactions to describe the influence of EHN. This mechanism was validated against the shock-tube data for various temperatures, levels of EHN-doping and equivalence ratios by homogeneous reactor calculations.The ignition delay times predicted by the model agree well with the shock tube results for a large range of temperatures, equivalence ratios and EHN concentrations. The influence of EHN onto ignition delay was largest in the low-temperature regime (770-1000 K).Numerical analysis suggests that the prevalent reason for the ignition-enhancing effect of EHN is the formation of highly reactive heptyl radicals by thermal decomposition of EHN. Due to this comparatively simple and generic mechanism, EHN is expected to have a similar ignition-enhancing effect also for other hydrocarbon fuels.     

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.     

A shock tube study of the auto-ignition of toluene/air mixtures at high pressures

The auto-ignition of toluene/air mixtures was studied in a shock tube at temperatures of 1021-1400 K, pressures of 10-61 atm, and equivalence ratios of Φ = 1.0, 0.5, and 0.25. Ignition times were measured using endwall OH∗ emission and sidewall piezoelectric pressure measurements. The measured pressure time-histories do not show significant pre-ignition energy release, in agreement with the rapid compression machine study of Mittal and Sung [G. Mittal, C.-J. Sung, Combust. Flame 150 (2007) 355-368] and disagreement with the shock tube study of Davidson et al. [D.F. Davidson, B.M. Gauthier, R.K. Hanson, Proc. Combust. Inst. 30 (2005) 1175-1182]. Kinetic modeling predictions from three detailed mechanisms are compared. Sensitivity analysis indicates that the reaction of toluene (C₆H₅CH₃) and the benzyl radical (C₆H₅CH₂) with molecular oxygen are important and examination of the rate coefficients for these reactions suggests that improved rate parameters for the multi-channel C₆H₅CH₂ + O₂ reaction may improve model predictions.     

Numerical simulations of the ignition of n-heptane droplets in the transition diameter range from heterogeneous to homogeneous ignition

Spontaneous ignition of single n-heptane droplets in a constant volume filled with air is numerically simulated with the spherical symmetry. The volume is closed against mass, species, and energy transfer. The numerical model is fully transient. It continues calculation even after the droplet has completely vaporized, and therefore can predict pre-vaporized ignition. Initial pressure and initial air temperature are fixed at 3 MPa and 773 K, respectively. The droplet is initially at room temperature, and its diameter is between 1 and 100 μm. When the overall equivalence ratio is fixed to be sufficiently large, there exists no ignition limit in terms of initial droplet diameter d₀, and the ignition delay takes a minimum value at certain d₀. In such a case, transition from the heterogeneous ignition to the homogeneous ignition with decreasing d₀ is observed. When d₀ is fixed to be so small that the ignition would not occur in an infinite volume of air, the ignition delay takes a minimum value at certain , which is less than unity. Two-stage ignition behavior is investigated with this model. Ignition delay of a cool flame has the dependence on d₀ that is similar to that of ignition delay of a hot flame when is unity. When is almost zero, the ignition limit for cool flame in terms of d₀ is not identified unlike that for hot flame.     

Effect of steam on the single particle ignition of solid fuels in a drop tube furnace under air and simulated oxy-fuel conditions

This article investigates the effect of steam on the ignition of single particles of solid fuels in a drop tube furnace under air and simulated oxy-fuel conditions. Three solid fuels, all in the size range 125–150 µm, were used in this study; specifically, a low rank sub-bituminous Colombian coal, a low-rank/high-ash sub-bituminous Brazilian coal and a charcoal residue from black acacia. For each solid fuel, particles were burned at a constant drop tube furnace wall temperature of 1475?K, in six different mixtures of O₂/N₂/CO₂/H₂O, which allowed simulating dry and wet conventional and oxy-fuel combustion conditions. A high-speed camera was used to record the ignition process and the collected images were treated to characterize the ignition mode (either gas-phase or surface mode) and to calculate the ignition delay times. The Colombian coal particles ignite predominately in the gas-phase for all test conditions, but under simulated oxy-fuel conditions there is a decrease in the occurrence of this ignition mode; the charcoal particles experience surface ignition regardless of the test condition; and the Brazilian coal particles ignite predominately in the gas-phase when combustion occurs in mixtures of O₂/N₂/H₂O, but under simulated oxy-fuel conditions the ignition occurs predominantly on the surface. The ignition delay times for particles that ignited in the gas-phase are smaller than those that ignited on the surface, and generally the simulated oxy-fuel conditions retard the onset of both gas-phase and surface ignition. The addition of steam decreases the gas-phase and surface ignition delay times of the particles of both coals under simulated oxy-fuel conditions, but has a small impact on the gas-phase ignition delay times when the combustion occurs in mixtures of O₂/N₂/H₂O. The steam gasification reaction is likely to be responsible for the steam effect on the ignition delay times through the production of highly flammable species that promote the onset of ignition.     

The internal propagation of fusion flame with the strong shock of a laser driven plasma block for advanced nuclear fuel ignition

An accelerated skin layer may be used to ignite solid state fuels. Detailed analyses were clarified by solving the hydrodynamic equations for nonlinear force driven plasma block ignition. In this paper, the complementary mechanisms are included for the advanced fuel ignition: external factors such as lasers, compression, shock waves, and sparks. The other category is created within the plasma fusion as reheating of an alpha particle, the Bremsstrahlung absorption, expansion, conduction, and shock waves generated by explosions. With the new condition for the control of shock waves, the spherical deuterium-tritium fuel density should be increased to 75 times that of the solid state. The threshold ignition energy flux density for advanced fuel ignition may be obtained using temperature equations, including the ones for the density profile obtained through the continuity equation and the expansion velocity for the r ≠ 0 layers. These thresholds are significantly reduced in comparison with the ignition thresholds at x = 0 for solid advanced fuels. The quantum correction for the collision frequency is applied in the case of the delay in ion heating. Under the shock wave condition, the spherical proton-boron and proton-lithium fuel densities should be increased to densities 120 and 180 times that of the solid state. These plasma compressions are achieved through a longer duration laser pulse or X-ray.     

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:

     

FTIR技术应用于香烟烟气的分析

文章采用傅里叶变换红外光谱(FTIR)结合气溶胶流管技术(AFT)和衰减全反射技术(ATR)分别得到香烟整体烟气和气溶胶的红外谱图。通过解析红外谱图可得到丰富的基团振动信息,1 230 cm-1处为酚类化合物的C—O伸缩振动峰,1 735 cm-1处的尖峰为羧酸中羰基的伸缩振动峰。由于烟气中气体占主要比例,所以CO在2 118和2 170 cm-1出现较强的双峰,2 343和2 362 cm-1为CO₂特征吸收峰,其强度远远高于其他峰的强度。而气溶胶谱图中最明显的不同就是CO峰消失,CO₂峰强度也大大减弱。因此将两种技术结合,特别是通过分析对比某些特征峰的变化,得到香烟烟气所发生的化学变化、组分挥发以及形态聚集等动态变化过程。为分析香烟燃烧产物提供了一个新思路,且不需对样品进行预处理,具有方便、快捷、无损等优点。     

Optimal design of shock ignition target in order to stop generated hot electrons within the cold fuel

Generation of hot electrons (HEs) within ignitor pulse interaction with pre-compressed fuel is an important challenge in the shock ignition approach. Target optimization in order to prevent the destructive effects of HE is the main goal of the present work. In the first stage, the spectrum of electron energy generated during the interaction of ignitor pulse at different widths with the HiPER pre-compressed target has been estimated by applying particle simulation tool. Then, by changing the thickness of the cold fuel in the range of 185–225 μm, the corresponding areal densities are calculated using 1D hydrodynamic simulations. Finally, in order to assess the energy fusion yield, the iso-gain curves are obtained for different ignitor time windows as well as target thicknesses. Simulation results indicate that by decreasing the baseline, target thickness leads to a 17–70% increase in the fuel areal density. Subsequently, it has been demonstrated that by properly adjusting the parameters of ignitor pulse launch time and its width and employing a target with areal density high enough to stop the HEs, energy gain above 140 can be achieved. Optimal areas for shell thickness and ignitor time window are identified.     

Measurement of laser-induced breakdown threshold intensities of high-pressure gasses and water droplets to determine the number density of an aerosol

The laser-induced breakdown threshold intensities of high-pressure gasses as a function of pressure were measured. The breakdown threshold intensity of N₂ gas was found to be much higher than those of He and Ar gasses at a gas pressure of 2.0 MPa. It was also 7 to 11 times higher than that of aerosol droplets, and is sufficiently high to allow the number density of droplets to be measured in a high-pressure aerosol by laser-induced breakdown.