An experimental study of premixed laminar methane/oxygen/argon flames doped with hydrogen at low pressure with synchrotron photoionization

Laminar premixed stoichiometric methane/hydrogen/oxygen/argon flames were investigated with tunable synchrotron vacuum ultraviolet （VUV） photoionizaUon and molecular-beam sampling mass spectrometry techniques. The methane/hydrogen fuel blends with hydrogen volumetric fraction of 0, 20%, 40%, 60% and 80% were studied. All observed flame species, including stable intermediates and radicals in the flames, were detected by measuring photoionization mass spectra and photoionization efficiency （PIE） spectra. Mole fraction profiles of major species and intermediates were derived by scanning burner at some selected photon energies near ionization thresholds. The influence of hydrogen addition on mole fraction of major species and intermediates was analyzed. The results show that the major species mole fraction of CO, CO2 and CH4 decreases with the increase of hydrogen fraction. The mole fraction of intermediates measured in this experiment decreases remarkably with the increase of hydrogen fraction. This would be due to the increase of H and OH radicals by hydrogen addition and the high diffusivity and activity of H radical promoting the chemical reaction. In addition, the increase of H/C ratio with the increase of hydrogen fraction also leads to the decrease of the mole fraction of carbon-related intermediates and contributes to the decrease of unburned and incomplete combustion products.     

拉伸对甲烷/空气层流预混火焰影响的数值研究

对甲烷/空气对撞拉伸层流预混火焰进行了数值求解,所采用的化学反应机理为GRI_Mech3．0(包含53种物质和325个基元反应),讨论分析了火焰面的拉伸对层流火焰的结构、温度和组分分布的影响．结果显示,火焰面的拉伸降低了火焰的厚度和化学反应速率,高温区域的减小,是一些自由基如N0,0,H等的生成量减少的主要原因;0,H等活性自由基的减少会导致熄火．     

Study of low-pressure premixed laminar n-heptane+ propane/oxygen/nitrogen flames

Low-pressure premixed laminar n-heptane+propane/oxygen/nitrogen flames were investigated with tunable synchrotron vacuum ultraviolet (VUV) photoionization and molecular-beam sampling mass spectrometry. Three flames with different mass percentage of propane in the fuel blends of 0%, 10%, and 20% were studied. The combustion intermediates were identified by comparing the measured IEs with those values in literatures. Mole fraction profiles of the main species were compared among the three flames. The experime...     

N_2/CO_2/H_2O抑制甲烷燃烧数值分析

建立了CH4-O2预混气体等容绝热燃烧、爆炸的零维数学模型,并以此为基础对惰性气体抑制CH4点火、燃烧和爆炸的微观化学动力学过程进行数值模拟.数值计算结果表明,N2,CO2和H2O的加入,大大延长了CH4-O2预混气体的点火延迟时间,同时降低了燃烧反应系统温度.N2,CO2和H2O能有效抑制CH4点火、燃烧和爆炸,一方面源于CH4和O2在混合气体中的摩尔浓度被降低,致使离解出的H,O,OH和CH3自由基减少;另一方面则源于N2,CO2和H2O作为第三体稳定分子参与三元碰撞反应,使高活性的自由基转变成了低活性的稳定分子.相同条件下,CO2和H2O除了重点参与三元碰撞反应外,还不同程度地参与其他链式反应,而N2则是完全不参与其他链式反应.这就导致N2,CO2和H2O的抑燃、抑爆的能力和效果存在差异.     

Study of low-pressure premixed laminar n-heptane+propane/oxygen/nitrogen flames

Low-pressure premixed laminar n-heptane+propane/oxygen/nitrogen flames were investigated with tunable synchrotron vacuum ultraviolet (VUV) photoionization and molecular-beam sampling mass spectrometry. Three flames with different mass percentage of propane in the fuel blends of 0%, 10%, and 20% were studied. The combustion intermediates were identified by comparing the measured IEs with those values in literatures. Mole fraction profiles of the main species were compared among the three flames. The experimental results provide detailed data in understanding the combustion of n-heptane and n-heptane/propane blends in engine. They are also helpful in establishing and verifying the kinetic models. Supported by the National Natural Science Foundation of China (Grant Nos. 50636040 and 50521604)     

无声放电场作用下产生OH自由基的实验研究

用一种无声放电方法，使反应器中Ｎ２－Ｈ２Ｏ介质在高频高压电场作用下产生ＯＨ，以促进燃烧反应，抑制碳烟生成，并开发一种追踪化学反应的分子物理测量手段，用共振吸收光谱法测定ＯＨ浓度。     

窄通道中近可燃极限预混火焰的结构和稳定性

通过数值方法研究了窄通道中近可燃极限预混火焰的结构和稳定性. 窄通道由上、下两个圆形平行平板构成, 燃气和氧气组成的混合气体充满窄通道内部, 点燃后形成的预混火焰在一定条件下有可能稳定在窄通道内. 采用基于Arrhenius单步反应的反应-扩散火焰模型, 考察了平板间距、平板材料和平板半径对火焰的影响. 结果表明, 一定的平板间距下主要有两个火焰的稳态解: 一个对应较大的火焰半径, 另一个对应较小的火焰半径. 通过线性稳定性分析发现, 窄通道中存在一维稳定的火焰, 但不存在二维稳定的火焰. 对一维稳定但二维不稳定的火焰的失稳进行数值模拟可以发现, 失稳主要表现为火焰整体向边界漂移, 或者一个火焰分裂成两个新的火焰后分别沿相反方向向边界漂移.     

吡咯和吡啶火焰中含氮燃烧中间体的探测

利用同步辐射(SR)和分子束质谱(MBMS)研究了两种含氮燃料(吡咯和吡啶)分别在贫燃和富燃条件下的4个低压预混火焰.通过测量光电离质谱和扫描光电离效率谱(PIE),鉴别了火焰中的燃烧中间体的化学结构.结果表明在富燃火焰中容易产生乙炔(C2H2),而在贫燃火焰中则更容易形成一氧化氮(NO)/甲醛(HCHO).在4个火焰中同时观察到了HCN、C2H4、C3H4、C2H2O、HNCO、C3HN、C3H3N、C3H5N、C4H3N和C6H6等稳定中间体以及CH3、C3H3和C2H2N等自由基.     

CO2/N2稀释对H2/CH4层流火焰传播特性的影响

利用本生灯-纹影系统实验研究含有CO₂，N₂的掺氢天然气层流预混火焰传播速度，并应用GRI-3.0机理模拟计算不同组分预混燃气绝热火焰温度、敏感性系数及重要自由基浓度等，详细讨论CO₂，N₂的稀释效应.研究表明，GRI-3.0机理能较好地预测掺氢天然气层流预混火焰传播速度；CO₂，N₂稀释组分会显著抑制掺氢天然气层流预混火焰速度及其绝热火焰温度；与N₂相比，CO₂不仅具有较强的热力学效应，且随着CO₂稀释比的增加，火焰中重要自由基H浓度显著减少，抑制氧化反应H+O₂O+OH对燃烧的主导促进效应，使预混燃料的层流火焰传播速度显著降低.     

柴油机燃烧过程中多环芳香烃的生成机理

以正庚烷和甲苯作为柴油燃料替代混合物,构建了1个包含多环芳香烃（PAHs）的柴油燃料替代混合物燃烧化学动力学机理,PAHs的生成考虑到5个苯环。该机理包括153种组分,697个基元反应。在激波管、正庚烷预混火焰和均质充量压燃着火发动机条件下对该机理进行了验证,结果表明构建的机理在HCCI燃烧方面的预测性能是可靠的,可以进一步简化,进而为CFD多维模型与化学反应动力学模型相耦合计算燃烧和排放提供了可行的途径。     

A kinetic modeling study of pollutant formation in premixed hydrocarbon flames

A kinetic modeling of pollutant formation in hydrocarbon flames is presented through analysis of hierarchical structures. Based on the newly released GRI-Mech 3.0,it was mainly taken from Dean and Bozzelli (DB) and Wang mechanism respectively for the nitrogen chemistry, the formarion and growth of polycyclic aromatic hydrocarbons (PAH). The modeling was improved by considering C4 and Howard‘s PAH chemistry. The mechanism consists of 121 species in 731 reactions. Two premixed flame structures are predicted, and the computed results are compared with the experimental ones. It is shown that the mechanism predicts reasonably well the concentration profiles of major, key intermediate and minor species.     

基于文丘里的预混气体多孔介质燃烧特性

多孔介质燃烧因其燃烧稳定性好而具有广泛的应用前景。结合工业预混领域应用广泛的文丘里混合器,采用预混不均匀度（SMD）对经文丘里混合的CH4/air预混气体的非均匀性进行评估。在入口速度为0.8 m/s,过量空气系数1.4条件下,研究了预混不均匀度SMD对多孔介质燃烧稳定性的影响。结果表明： SMD小于2.5%对多孔介质燃烧火焰的稳定性影响较小;随着SMD的增大,燃烧高温区域面积进一步变大,最高温度随着SMD的增加呈线性增加;稳燃范围随着SMD的增大逐渐减小。     

低热值气体燃料掺氢火焰稳定性的研究

基于直接数值模拟方法和详细化学反应机理研究了流体动力学不稳定性和热-质扩散不稳定性共同作用下的低热值气体燃料掺氢胞状火焰的发展和演变过程.建立了多组分气体燃料燃烧控制方程,获得了不稳定性作用下的低热值气体燃料掺氢胞状火焰的多种演变形式:胞的分裂、局部熄灭、二次熄灭和再燃.研究结果表明随着燃料中H2的增加,胞状火焰出现的时间提前,火焰胞的幅值增加.随着燃料中CO2的增加,火焰的不稳定性受到抑制.低热值气体燃料掺氢火焰在不稳定时会出现火焰胞的分裂、局部熄灭和再燃等3种动力学形态.胞的二次熄灭只发生在热-质扩散不稳定性较强的稀燃H2/空气火焰中.     

垃圾焚烧过程中氯化氢对氮氧化物生成抑制机理

分别采用固定床和转式垃圾焚烧炉对广州市机模化有机垃圾进行焚烧实验，研究模化有机垃圾焚烧过程中NOx、HCl的生成特性，探讨氯对NOx生成的影响，研究结果表明，垃圾焚烧产生的HCl和NOx的生成起抑制作用，这是由于焚烧过程所产生的HCl与H、OH和O等自由基结合，从而抑制NCO、N、CN、HCN和NHi等氧化成NOx，同时HCl在其中起催化剂的作用，并且HCl影响NOx的能力随着焚烧温度的变化而变化。     

多孔陶瓷板城市燃气预混燃烧的数学模拟

对人工均布小孔的多孔陶瓷板内城市燃气的预混燃烧进行了研究．讨论了作为目前上海城市煤气的主要成分ＣＯ、Ｈ２、ＣＨ４的反应动力学及其参数——活化能、频率因子等,建立了反应动力学方程．通过理论分析推导出燃气－空气预混气体的连续性方程、组分方程、能量方程、状态方程及多孔陶瓷的能量方程,建立了多孔陶瓷板中城市煤气预混式燃烧的数学模型．由数值计算得到多孔陶瓷板的板内固体温度分布,并与实验数据进行比较     

Reaction zone characterization of counter-flow diffusion flame with diluted and preheated reactants

Reaction zone characteristics were studied using hydroxy radical planar laser-induced fluorescence (OH-PLIF) technique for a counter-flow preheated (CH₄+N₂)/(Air+N₂) diluted diffusion flames. The effects of preheat temperature and dilute ratio on the reaction zone characteristics were investigated by demonstrating the OH intensity distribution and reaction zone thickness from OH-PLIF images. Under the experimental conditions of constant cold flow velocity, the results show that the OH intensity and reaction zone thickness decrease with the increase of dilute ratio at constant preheat temperature and increase with preheat temperature at fixed dilute ratio. The OH maximum intensity shifts towards the "lean" side of counter flow at constant preheat temperature, and it shifts towards the fuel side with the increase of dilute ratio of fuel stream and towards the oxidizer side with the increase of dilute ratio of oxidizer stream respectively. The feasibility of OH as a reaction zone marker in this diluted combustion is verified further. The variation of diffusion and chemical reaction rate of reactants due to preheat and dilution contributes to the reaction zone characteristics simultaneously. The effect of strain on the flame reaction zone should be included in the future work.     

预混合燃烧系统中多孔介质作用数值研究

根据气固两相局部非热平衡假设,建立了混合气在惰性多孔介质中预混合燃烧的一维数学模型,研究了不同情况下甲烷-空气的预混合气在多孔介质中燃烧时的温度分布和燃烧速率,并与自由空间中相应的值进行比较．结果表明,多孔介质的存在可以扩展混合气的燃烧极限,明显改善了燃烧室的换热性能,强化了对新鲜混合气的预热,降低了热量损失;在多孔介质中混合气的燃烧温度和燃烧室的温度明显升高,反应区厚度和燃烧速率显著增大．数值结果与其他研究者的实验结果是一致的．     

预混火焰面附近的湍流特性测量

为考察预混火焰面附近的湍流特性,以及湍流与化学反应相互作用的机理,采用激光多普勒技术(laser Doppler anemometry,LDA)对本生火焰和V型火焰的流场进行了诊断。分别通过固体粉末和雾化硅油液滴进行无条件和条件示踪,研究了全场及反应物来流的流动特性。无条件示踪的测量结果表明,火焰区的流场存在湍流度迅速增大然后衰减的现象,而速度的测值呈现双峰分布。条件示踪测量结果表明,在火焰区内反应物来流的流动特性并没有发生明显的改变。在剪切流场中,火焰面的脉动和皱褶不显著影响上游反应物的流动特性。     

耦合详细反应动力学机理的碳氢燃料预混火焰结构数值预测

理论研究碳氢燃料、空气预混气流动燃烧过程数值计算方法 以碳氢类燃料中具有代表性的柴油为例 ,采用其最新研究的化学反应动力学机理 (包含 32 7个基元反应 ,涉及 71种组分 ) ,使用美国SANDIA国家实验室开发的CHEMKIN系列软件、PREMIX程序和LAWRENCE国家实验室开发的解刚性反应系统算法器 ,模拟了不同工况下预混火焰中温度、反应物、主产物和自由基浓度随火焰高度的变化关系 ,为反应设计提供依据     

CH3SH与简单自由基反应的研究现状

含硫有机化合物在对流层大气化学中起着重要的作用.目前在实验和理论上对CH3SH,CD3SH及CD3SD的反应进行了很多研究,主要集中在CH3SH与原子(O,H,F,Cl,Br等)、双原子分子和双原子自由基(NO,OH,OD,BrO,CN等)、三原子分子和自由基及多原子(O3,NO3等)的反应.本文中,笔者对CH3SH与原子和双原子自由基的反应进行了综述.