A high-temperature study of 2-pentanone oxidation: experiment and kinetic modeling

Small methyl ketones are known to have high octane numbers, impressive knock resistance, and show low emissions of soot, NO_x, and unburnt hydrocarbons. However, previous studies have focused on the analysis of smaller ketones and 3-pentanone, while the asymmetric 2-pentanone (methyl propyl ketone) has not gained much attention before. Considering ketones as possible fuels or additives, it is of particular importance to fully understand the combustion kinetics and the effect of the functional carbonyl group. Due to the higher energy density in a C₅-ketone compared to the potential biofuel 2-butanone, the flame structure and the mole fraction profiles of species formed in 2-pentanone combustion are of high interest, especially to evaluate harmful species formations. In this study, a laminar premixed low-pressure (p?=?40 mbar) fuel-rich (??=?1.6) flat flame of 2-pentanone has been analyzed by vacuum-ultraviolet photoionization molecular-beam mass-spectrometry (VUV-PI-MBMS) enabling isomer separation. Quantitative mole fraction profiles of 47 species were obtained and compared to a model consisting of an existing base mechanism and a newly developed high-temperature sub-mechanism for 2-pentanone. High-temperature reactions for 2-pentanone were adapted in analogy to 2-butanone and n-pentane, and the thermochemistry for 2-pentanone and the respective fuel radicals was derived by ab initio calculations. Good agreement was found between experiment and simulation for the first decomposition products, supporting the initial branching reactions of the 2-pentanone sub-mechanism. Also, species indicating low-temperature chemistry in the preheating zone of the flame have been observed. The present measurements of a 2-pentanone flame provide useful validation targets for further kinetic model development.     

Probing fuel-specific reaction intermediates from laminar premixed flames fueled by two C5 ketones and model interpretations

The flame chemistry was explored for two C₅ ketones with distinct structural features, cyclopentanone (CPO) and diethyl ketone (DEK). Quantitative information for numerous species, including some reactive intermediates, was probed from fuel-rich (?= 1.5) laminar premixed flames fueled by the ketones with a photoionization molecular-beam mass spectrometer (PI-MBMS). Furthermore, a new kinetic model was proposed aimed at interpreting the high-temperature combustion chemistry for both ketones, which could satisfactorily predict the current flame speciation measurements. Experimental observations in combination with modeling analyses were used to reveal the similarities and differences between the compositions of the species pools of the two flames, with emphasis on the effects of the carbonyl functionality on pollutants formations. Besides some primary species which preserve fuel-specific features produced from initial steps of fuel consumptions, basic C₁C₄ intermediates also differ much between the two flames. More abundant intermediates were observed in the CPO flame because the cyclic fuel structure enables ring-opening processes followed by formations of C₃ and C₄ hydrocarbons which cannot be easily produced from the two isolated ethyl moieties in DEK under flame conditions. The consumptions of C₃C₄ hydrocarbons in the CPO flame further lead to larger C₅C₆ species which were under the detection limit in the DEK flame. In both flames, the tightly bonded carbonyl groups in the fuels tend to be preserved, leading to carbon monoxide through α-scissions of fuel-related acyl radicals. The carbonyl moieties in most detected C₁C₃ aldehydes and ketones form through oxidations of hydrocarbon species rather than directly originating from the fuels.     

Formation and destruction of nitric oxide in methane flames doped with NO at atmospheric pressure

A study of formation and destruction of NO in adiabatic laminar premixed flames of CH₄ + O₂ mixtures diluted with N₂ or Ar (with various dilution ratios) in a range of equivalence ratios at atmospheric pressure is presented. Nitric oxide was seeded into the flames using mixtures of diluent gas + 100 ppm of NO. The heat flux method was employed to measure adiabatic burning velocities of these flames. Nitric oxide concentrations in the post-flame zone at 10, 15 and 20 mm above the burner surface were measured using probe sampling. Burning velocities and NO concentrations simulated using a previously developed chemical kinetic mechanism were compared with the experimental results. The conversion ratio of NO seeded into the flames was determined. The kinetic mechanism accurately predicts burning velocities over the range of equivalence ratios and NO conversion in the rich flames. Significant discrepancies between measured and calculated NO conversion in the lean and near-stoichiometric flames were observed and discussed.     

近贫燃极限甲烷/空气火焰的层流燃烧速度研究

利用微重力条件下向外传播的球形火焰,对贫燃极限附近甲烷/空气预混火焰的层流燃烧速度进行了测量,得到当量比从0.512(本文微重力实验中测定的可燃极限)到0.601范围内的零拉伸层流燃烧速度,并与前人实验数据和使用3种化学反应动力学模型的计算结果进行了比较.本文实验结果与已有的微重力实验数据非常接近,而其他研究者在常重力...     

On laminar premixed flame propagating into autoigniting mixtures under engine-relevant conditions

Usually premixed flame propagation and laminar burning velocity are studied for mixtures at normal or elevated temperatures and pressures, under which the ignition delay time of the premixture is much larger than the flame resistance time. However, in spark-ignition engines and spark-assisted compression ignition engines, the end-gas in the front of premixed flame is at the state that autoignition might happen before the mixture is consumed by the premixed flame. In this study, laminar premixed flames propagating into an autoigniting dimethyl ether/air mixture are simulated considering detailed chemistry and transport. The emphasis is on the laminar burning velocity of autoigniting mixtures under engine-relevant conditions. Two types of premixed flames are considered: one is the premixed planar flame propagating into an autoigniting DME/air without confinement; and the other is premixed spherical flame propagating inside a closed chamber, for which four stages are identified. Due to the confinement, the unburned mixture is compressed to high temperature and pressure close to or under engine-relevant conditions. The laminar burning velocity is determined from the constant-volume propagating spherical flame method as well as PREMIX. The laminar burning velocities of autoigniting DME/air mixture at different temperatures, pressures, and autoignition progresses are obtained. It is shown that the first-stage and second-stage autoignition can significantly accelerate the flame propagation and thereby greatly increase the laminar burning velocity. When the first-stage autoignition occurs in the unburned mixture, the isentropic compression assumption does not hold and thereby the traditional method cannot be used to calculate the laminar burning velocity. A modified method without using the isentropic compression assumption is proposed. It is shown to work well for autoigniting mixtures. Besides, a power law correlation is obtained based on all the laminar burning velocity data. It works well for mixtures before autoignition while improvement is still needed for mixtures after autoignition.     

富燃料丙烷/空气预混火焰特性的微重力实验研究

地面常重力(1g)条件下,丙烷/空气预混火焰向上传播的富燃极限为9.2%C_3H_8,而向下传播时的富燃极限仅为6.3%C_3H_8,二者之间存在明显差距。利用微重力条件下的实验,对燃料浓度从6.5%到8.6%(微重力实验中测定的可燃极限)范围内的丙烷/空气预混火焰特性进行了研究。实验发现,重力对近极限丙烷/空气火焰的传播有显著影响,影响程度随着当量比的增加而增大。微重力下丙烷/空气的富燃极限为8.6%C_3H_8(φ=2.24),明显高于1g条件下向下传播火焰的可燃极限,略低于向上传播火焰的可燃极限。随着当量比的增大,根据压力变化曲线计算的火焰层流燃烧速度从8.5cm/s逐渐减小到2.7 cm/s,可燃极限处的层流燃烧速度与前人实验数据一致。     

A theoretical study of premixed turbulent flame development

Flame development in a statistically stationary and uniform, planar, one-dimensional turbulent flow is theoretically studied. A generalized balance equation for the mean combustion progress variable, which includes turbulent diffusion and pressure-driven transport terms, as well as the mean rate of product creation, is introduced and analyzed by invoking the sole assumption of a self-similar flame structure, well-supported by numerous experiments. The assumption offers the opportunity to simplify the problem by splitting the aforementioned partial differential equation into two ordinary differential equations, which separately model spatial variations of the progress variable and time variations of flame speed and thickness. The self-similar profile of the progress variable, obtained in numerous experiments, is theoretically predicted. Closures of the normalized pressure-driven transport term and mean rate of product creation are obtained. The closed balance equation shows that turbulent diffusion dominates during the initial stage of flame development, followed by the transition to counter-gradient transport in a sufficiently developed flame. A criterion of the transition is derived. The transition is promoted by the heat release and pressure-driven transport. Fully developed mean flame brush thickness and speed are shown to decrease when either density ratio or pressure-driven transport increases. Solutions for the development of the thickness are obtained. The development is accelerated by the pressure-driven transport and heat release.     

预混气体燃烧火焰闪烁现象分析

在低速射流的预混火焰和扩散火焰中都存在火焰闪烁现象。对扩散火焰,其机理已比较明确,是由于浮力诱导引起的一种水力学不稳定性。而对预混火焰闪烁现象则存在水力学不稳定性和热驱动不稳定性两种观点。本文根据水力学不不稳定性观点,把预混火焰的闪烁现象看成是包围火焰锋面的已燃混气层中内、外区间在垂直方向上的相对脉动,应用Ｋｅｌｖｉｎ－Ｈｅｌｍｈｏｌｔｚ不稳定性机理进行了分析,获得了火焰闪烁频率与重力和压力的关系式,并与已有的结果作了对比。     

层流预混气体多棱火焰燃烧现象的分析

在一定条件下,层流预混气体燃烧过程中可清晰地观察到多棱火焰现象。本文从燃料浓度、温度对燃烧速度、气流速度的影响出发,推导出了火焰面变化随空气消耗系数的关系式,并得出了形成多棱火焰现象的条件为:Kx<0。用该式判断的丁烷层流预混气体燃烧的多棱火焰区与实验结果基本吻合。     

Nitrous oxide conversion in laminar premixed flames of CH4 + O2 + Ar

Experimental measurements of the adiabatic burning velocity in neat and NO formation in CH₄ + O₂ + Ar flames doped with small amounts of N₂O are presented. The oxygen content in the oxidizer was varied from 15 to 17%. Non-stretched flames were stabilized on a perforated plate burner at 1 atm. The Heat Flux method was used to determine burning velocities under conditions when the net heat loss of the flame is zero. Adiabatic burning velocities of methane + oxygen + argon mixtures were found in satisfactory agreement with the modeling. The NO concentrations in the flames doped with N₂O (100 ppm in the argon stream before mixing) were measured in the burnt gases at a fixed distance from the burner using probe sampling. Axial profiles of [NO] were found insensitive to the downstream heat losses. Experimental dependencies of [NO] versus equivalence ratio had a maximum between φ = 1.1 and 1.2. Calculated concentrations of NO were in good agreement with the measurements. In lean flames calculated concentrations of NO strongly depends on the rate constant of reaction N₂O + O=NO + NO if too high values proposed in the literature are employed. These new experimental data thus allowed for validation of the key reactions of the nitrous oxide mechanism of NO formation in flames.     

Hydrodynamic instability of premixed flame propagating in narrow planar channel in the presence of gas flow

The paper analyses the hydrodynamic instability of a flame propagating in the space between two parallel plates in the presence of gas flow. The linear analysis was performed in the framework of a two-dimensional model that describes the averaged gas flow in the space between the plates and the perturbations development of two-dimensional combustion wave. The model includes the parametric dependences of the flame front propagation velocity on its local curvature and on the combustible gas velocity averaged along the height of the channel. It is assumed that the viscous gas flow changes the surface area of the flame front and thereby affects the propagation velocity of the two-dimensional combustion wave. In the absence of the influence of the channel walls on the gas flow, the model transforms into the Darrieus–Landau model of flame hydrodynamic instability. The dependences of the instability growth rate on the wave vector of disturbances, the velocity of the unperturbed gas flow, the viscous friction coefficients and other parameters of the problem are obtained. It is shown that the viscous gas flow in the channel can lead, in some cases, to a significant increase in instability compared with a flame propagating in free space. In particular, the instability increment depends on the direction of the gas flow with respect direction of the flame propagation. In the case when the gas flow moves in the opposite direction to the direction of the flame propagation, the pulsating instability can appear.     

Effect of the reversibility of the chemical reaction on triple flames

We examine a new aspect of triple flames, namely the effect of the reversibility of the chemical reaction on flame propagation. The study is carried out in the configuration of the two-dimensional strained mixing layer formed between two opposing streams of fuel and oxidiser. The chemical reaction is modelled as a single reversible reaction following an Arrhenius law in the forward and backward directions. The problem is formulated within the constant-density (thermo-diffusive) approximation, the main non-dimensional parameters relevant to this study being a reversibility parameter R (equal to zero in the irreversible case), a non-dimensional measure of the strain rate ? and a stoichiometric parameter S. We provide analytical (asymptotic) expressions for the local burning speed of the triple flame in terms of ?, S, and R. In particular we describe how the propagation speed of the front is decreased by an increase in R and how the location of its leading edge is affected by reversibility. For example, it is found that the leading edge shifts towards the fuel stream for S > 1 and towards the oxidiser if S < 1, as R is increased. A detailed numerical study is conducted covering all propagation regimes ranging from weakly stretched positively propagating (ignition) fronts to thick negatively propagating (extinction) fronts. In the weakly stretched cases we show that the numerics are in good agreement with the asymptotic findings. Furthermore, the results allow the determination of the domains of the distinct propagation regimes, mainly in the terms of R and ?. In line with our physical intuition, it is found that reversibility reduces the domain of ignition fronts and promotes extinction. The results provide a systematic investigation which can be considered as a first step when considering a more realistic chemistry, or poorly explored aspects (such as the existence of a temperature gradient in the unburnt mixture), when analyzing triple flames.     

C-Br bond fission mechanism of 1-bromo-3-chloropropane at 234 and 265 nm

The photodissociation of 1-bromo-3-chloropropane was studied at 234 and 265 nm using ion velocity imaging technique. Bromine fragments in this study were produced via direct dissociation of C-Br bond. The speed and angular distributions of Br^∗ and Br were measured. The appearance of chlorine fragments at 234 nm was assigned to a secondary dissociation process. The contributions of three excited states: ¹Q₁, ³Q₀ and ³Q₁ were estimated at each wavelength. Comparing with previous results, the study reveals more details about the dynamics of molecules with multichromophores.     

湍流和预混火焰相互作用的实验研究

建立了湍流预混火焰实验系统并实现了驻定火焰。无条件示踪条件下的研究结果表明,火焰区的速度分布呈现 双峰分布,初步证实火焰区湍流度峰值的存在是由于火焰脉动导致速度测值分散,最终由统计得到表观湍流度的增大。条 件示踪测量结果表明,在火焰区反应物来流的湍流度与上游的测值并没有明显的变化,进一步证实了这一结论。     

HNCO在201 nm的离子成像光解动力学:CO(X1Σ+)与NH(a1Δ)

本文通过时间切片离子速度成像技术在201 nm附近研究了HNCO分子在S₁电子激发态的光解动力学. CO产物通过共振增强多光子电离的方法进行了选态探测,获得了CO产物的振动基态和激发态切片影像. 从CO的影像得到了解离产物的能量分布和空间角分布,确定了NH(a¹Δ)产物的振转态分布信息. 研究发现¹NH的振动分支比(v=1/v=0)随CO(v=0)转动能的增大先增大后下降,展现了¹NH与CO之间特殊的态态相关性. 大约一半的可资用能分配给解离产物的平动自由度. 负的各向异性参数表明HNCO的光解是个快速的直接解离过程.     

Measurement and simulation of partially-premixed cellular tubular flames

Experimental and numerical simulation results are reported of partially-premixed cellular tubular flames. Parametric measurements across stretch rate and equivalence ratio are taken by chemiluminescent imaging and are presented for the first time. Select hybrid cases with both cellular and non-cellular flame structures are examined with laser-induced spontaneous Raman scattering. Results are spatially resolved in two dimensions and radial interpolations of reaction and extinction zones are compared to numerical simulations using multicomponent transport and detailed chemical kinetics. Experimental cell structures and extinction zones are well predicted by numerical simulation, with discrepancies of temperature and H₂O and temperature primarily observed in locations with moderate and high mole fractions of CO₂. A novel cellular structure, denoted as a “split-cell” flame, is reported for the first time with both chemiluminescent imaging and Raman scattering. Results indicate that partially-premixed flames are valuable as experimental and numerical benchmarks to advance fundamental combustion research.     

Numerical simulations of soot aggregation in premixed laminar flames

In this paper we make use of a detailed particle model and stochastic numerical methods to simulate the particle size distributions of soot particles formed in laminar premixed flames. The model is able to capture the evolution of mass and surface area along with the full structural detail of the particles. The model is validated against previous models for consistency and then used to simulate flames with bimodal and unimodal soot particle distributions. The change in morphology between the particles from these two types of flames provides further evidence of the interplay among nucleation, coagulation, and surface rates. The results confirm the previously proposed role of the strength of the particle nucleation source in defining the instant of transition from coalescent to fractal growth of soot particles.     

铬在氢/空气预混火焰中氧化分析

用实验方法研究了铬在层流氢/空气预混火焰中的氧化行为。首先把铬以蒸汽状态添加到火焰中,就保证了铬完全没有被氧化。在燃烧过程中产生了Cr_2O_3颗粒和其它气态铬的金属氧化物。对预混火焰中样本的分析表明,起初随着与燃烧器的距离增加,六价铬的数量也增加;当与燃烧器的距离增大到一定值时,六价铬的数量就开始减少,直至5％。