利用同步辐射研究汽油及其混合物的火焰成分特征

本文利用同步辐射和分子束取样技术并结合飞行时间质谱仪,分别检测了加入MTBE前后的汽油在氧气中的燃烧产物.通过比较标准汽油与MTBE/汽油在火焰中的成分差异,以及几种典型燃烧产物的空间分布曲线,分析了MTBE对汽油的微观影响机理,为建立燃烧反应动力学模型提供了参考.     

汽油/氧气预混火焰中烯丙基自由基的真空紫外光电离研究

分子束取样结合同步辐射光电离质谱技术研究了低压汽油／氧气／氩气预混火焰中的烯丙基自由基,测得了它的光电离效率曲线,通过光电离效率曲线得到烯丙基的电离阈值为(8.13±0.02)eV。另外,用从头算分子轨道理论得到了烯丙基及其阳离子的构型和能量,给出了烯丙基自由基的绝热电离能为8.18 eV。计算的电离能与实验得到的电离能符合得很好,这一结果有助于今后鉴别和分析其它火焰中的烯丙基自由基,且对研究火焰燃烧机理有十分重要的价值。     

利用同步辐射研究正庚烷火焰燃烧特性

利用同步辐射单光子电离和分子束取样技术并结合飞行时间质谱仪,在低压、预混、燃油当量比为1.0情况下研究正庚烷层流火焰的燃烧特性.共检测出24种中间产物,并计算出其摩尔分数.在燃烧反应前期,主要中间产物是酮、醚类物质.在燃烧反应后期,主要中间产物是碳氢化合物,燃烧反应前期的中间产物在燃烧反应后期继续氧化.乙烯在所有中间产物中摩尔分数最大的.另外,火焰中丙炔与苯有极大的相关性.     

基于光谱分析的油料池火内部传热特性研究

油料池火焰内部分为不同燃烧区域,目前对油池火内部传热特性研究较少。针对油池火内部传热特性研究不足的现状,构建了红外火焰光谱测试系统,研究分析了92#汽油、95#汽油及润滑油池火焰红外光谱特性,对油池火焰不同燃烧区域的光谱信息进行了提取分析,结果表明：三种油料池火焰光谱特征相似,存在多个CO₂,H₂O及炭黑颗粒等燃烧产物的特征发射波段,3.4 μm处C—H伸缩振动峰明显;火焰烟气区主要光谱特征为4～4.5 μm波段范围内高温CO₂发射峰,该区域火焰与空气换热剧烈,温度变化不稳定,火焰脉动频率较高;火焰间歇区的光谱特征是4～4.5 μm波段范围内高温CO₂发射峰,与烟气区相比,火焰间歇区脉动频率相对较低;与烟气区及间歇区相比,火焰连续区燃烧较为稳定,该区域的光谱特征明显,在2.5～3 μm波段范围内炭黑粒子发射光谱强度较高,且在3.4 μm处存在C—H伸缩振动峰,表明油料池火焰光谱3.4 μm处的特征峰由高温油蒸汽产生。油池火焰不同燃烧区域光谱特征分析表明,油池火焰液态油表面的“富燃料层”吸收火焰传热,引起3.4 μm附近油蒸汽分子能级的改变。油池火焰不同燃烧区域发射光谱强度计算表明,火焰连续区的强度最大,其次为间歇区,火焰烟气区与空气对流强烈,测得的发射光谱强度最低。研究结果为火焰—油料传热模型的修正提供了参考。     

汽油储罐火灾燃烧特性的实验研究

本文通过对直径为1 m、 1.5 m和2.7 m的汽油储罐进行火灾实验,分析了汽油罐燃烧时不同阶段的燃烧特 性。本文重点讨论了描述燃烧特性的几个重要参数的变化规律,包括火焰脉动频率、火焰高度、倾斜角度以及火焰的温度 分布等,并将结果拟合为相应的实验关联式,以揭示油罐火灾的内在规律和预测其发展趋势。     

同步辐射单光子电离技术研究乙醚富燃火焰

本文利用同步辐射单光子电离和分子束质谱技术研究了乙醚在富燃条件下的低压预混火焰.通过测量光电离质谱和扫描光电离效率谱,我们鉴别了该火焰中大部分的燃烧中间体及产物.此外,通过改变燃烧炉的位置测量光电离质谱,得到了各燃烧中间体及产物的摩尔分数曲线.实验结果为深入研究乙醚燃烧动力学并揭示含氧有机化合物在火焰中的反应机理提供了依据.     

油料池火焰红外光谱特性分析研究（英文）

油罐池火燃烧污染强度大、范围广,航天遥感可成为实时动态监测油罐池火灾污染的新途径。航天遥感监测以目标光谱特性分析为基础,针对油料池火焰光谱特性研究不足的现状,通过构建全火焰红外测试系统,在室外开放空间条件下对多种油料及混合油料池火焰光谱,其他可燃物火焰的发射光谱进行了测试分析研究,光谱范围1~14μm。结果表明:92#汽油、95#汽油、0#柴油、航空煤油、润滑油池火焰的光谱曲线特征相似,在特定的波长处存在特征发射峰,在1.1,2.4,2.8及6.3μm附近存在H2O特征发射峰,在4.2及4.5μm附近存在CO2发射峰,在3.4μm处存在C—H伸缩振动发射峰,6.3μm后各光谱曲线无明显特征峰。92#汽油与0#柴油以不同比例混合的池火焰光谱与各油料池火焰光谱相比也无明显差别。92#汽油池火焰光谱与木柴及纸张火焰光谱相比,在3.4μm处存在特征发射峰;酒精火焰光谱虽然在3.4μm附近也有类似辐射发射,但辐射强度与4.5μm处CO2的辐射强度之比远低于92#汽油池火焰光谱在此两波段处辐射强度之比;蜂窝煤火焰光谱近似灰体辐射光谱。各燃料火焰光谱的差异主要由燃料的化学组成及燃烧反应机理的差异决定的。对92#汽油池火焰连续区、间歇区及烟气区的光谱特性进行了比较分析,结果表明3.4μm处的C—H伸缩振动峰只存在于连续区,证明了该发射峰是参与燃烧化学反应的油气产生的,该结果与油料池火燃烧反应机理吻合。实验结论对基于光谱特性分析的油料池火焰遥感识别具有重要借鉴意义。     

着火油罐燃烧特性的理论分析

本文利用自行建立的油罐火灾燃烧特性通用模型,计算得到了燃烧速度、火焰高度,火焰跳动频率和平均温度等油罐燃烧特性的变化规律,并深入探讨了油品燃烧速度在油罐直径、风速、环境温度和油位等因素影响下的变化趋势。为了验证理论计算的准确性,将计算结果与汽油和柴油储罐的燃烧实验数据进行了对比,获得了较为满意的结果。     

油料池火焰红外光谱特性分析研究

油罐池火燃烧污染强度大、范围广,航天遥感可成为实时动态监测油罐池火灾污染的新途径。航天遥感监测以目标光谱特性分析为基础,针对油料池火焰光谱特性研究不足的现状,通过构建全火焰红外测试系统,在室外开放空间条件下对多种油料及混合油料池火焰光谱,其他可燃物火焰的发射光谱进行了测试分析研究,光谱范围1~14 μm。结果表明：92#汽油、95#汽油、0#柴油、航空煤油、润滑油池火焰的光谱曲线特征相似,在特定的波长处存在特征发射峰,在1.1,2.4,2.8及6.3 μm附近存在H₂O特征发射峰,在4.2及4.5 μm附近存在CO₂发射峰,在3.4 μm处存在C—H伸缩振动发射峰,6.3 μm后各光谱曲线无明显特征峰。92#汽油与0#柴油以不同比例混合的池火焰光谱与各油料池火焰光谱相比也无明显差别。92#汽油池火焰光谱与木柴及纸张火焰光谱相比,在3.4 μm处存在特征发射峰;酒精火焰光谱虽然在3.4 μm附近也有类似辐射发射,但辐射强度与4.5 μm处CO₂的辐射强度之比远低于92#汽油池火焰光谱在此两波段处辐射强度之比;蜂窝煤火焰光谱近似灰体辐射光谱。各燃料火焰光谱的差异主要由燃料的化学组成及燃烧反应机理的差异决定的。对92#汽油池火焰连续区、间歇区及烟气区的光谱特性进行了比较分析,结果表明3.4 μm处的C—H伸缩振动峰只存在于连续区,证明了该发射峰是参与燃烧化学反应的油气产生的,该结果与油料池火燃烧反应机理吻合。实验结论对基于光谱特性分析的油料池火焰遥感识别具有重要借鉴意义。     

同步辐射真空紫外光电离质谱研究乙烯扩散火焰

本文利用探针取样法结合同步辐射真空紫外光电离和分子束质谱技术研究了常压下的乙烯扩散火焰.通过测量光电离质谱和光电离效率谱分辨了该火焰中大部分的燃烧中间体及产物;通过改变探针取样位置以及半定量计算得到了其中部分燃烧中间体及产物的摩尔分数曲线.实验结果为探索多环芳烃和烟尘在扩散火焰中形成的最初阶段的反应机理提供了依据.     

二甲醚/氧气/氩气低压层流预混燃烧研究

利用同步辐射真空紫外单光子电离结合分子束质谱技术,对当量比φ=1.5的低压预混层流二甲醚火焰进行了实验研究。通过测量光电离质谱和光电离效率曲线,探测到了二甲醚/氧气/氩气的燃烧产物和火焰中间物,包括不稳定的分子和自由基。通过测量离子信号的空间分布曲线,计算了二甲醚/氧气/氩气火焰的主要物种C_2H_6O、O_2、Ar、H_2、H_2O、CO和CO_2的摩尔分数曲线,以及主要中间物种如CH_2O、C_2H_2、C_2H_4、CH_3OH、C_2H_2O、C_2H_4O、CH_3、CH_4、HCO、C_3H_3和C_3H_4的摩尔分数曲线,并分析了主要中间物种的产生和消耗过程。     

Photoionization mass spectrometry and modeling studies of the chemistry of fuel-rich dimethyl ether flames

Reaction paths are identified for dimethyl ether (DME) combustion using modeling of new data from fuel-rich DME flat flames. A molecular-beam flame-sampling photoionization mass spectrometer, employing VUV synchrotron radiation, is applied to the measurement of mole fractions for 21 flame species in low-pressure premixed fuel-rich (Φ = 1.2, 1.68) DME/oxygen/argon flat flames. This approach is capable of resolving and identifying isomers and other flame species of near equal masses with ionization thresholds that differ by as little as 0.1 eV. The measurements agree well with flame modeling predictions, using a recently revised high-temperature DME kinetic mechanism, which identify reaction paths quite analogous to alkane combustion. They further reveal the presence of ethyl methyl ether, a molecule previously unobserved in flames and not included in present flame models.     

Benzene precursors and formation routes in a stoichiometric cyclohexane flame

Benzene formation was found to be dominated by stepwise radical dehydrogenation of cyclohexane in a stoichiometric flat flame of cyclohexane/O₂/32.5% Ar, 30.00 Torr pressure, and 35.0 cm s⁻¹ feed velocity. This route, involving H-abstractions and β-scissions, is in contrast to conventional propargyl routes. Three types of analyses lead to this conclusion: identification of key flame species by mass and ionization energy; measurement and use of mole-fraction profiles in the flat flame; and mechanistic reactive-flow modeling of the flame, interpreted by analyzing the dominant reaction steps giving rise to the prediction. For relevant species, profiles of mole fraction were mapped by molecular-beam mass spectrometry in separate apparatuses with identical burners using electron ionization (UMass Amherst) and synchrotron VUV photoionization (LBNL ALS), respectively. In the latter, recently developed apparatus, ionization energies can be measured with greatly enhanced resolution, yielding improvements in species identification that include precise resolution of hydrocarbon isomers, crucial to the findings of this study.     

An experimental study of the rich premixed ethylbenzene flame at low pressure

A slightly sooting premixed ethylbenzene flame with an equivalence ratio of 1.90 was investigated at low pressure (4.0 kPa) using molecular-beam mass spectrometry (MBMS) and tunable synchrotron vacuum ultraviolet (VUV) photoionization. Basing on the ionization threshold measurements of photoionization efficiency (PIE) spectra, combustion intermediates up to C₁₉H₁₂ were identified, including a number of radicals and isomeric species. Mole fraction profiles of observed flame species were evaluated from the measurements of burner scan at the photon energies near ionization thresholds. Besides, the flame temperature profile was measured by a Pt/Pt-13%Rh thermocouple. From the intermediate identification and mole fraction measurements, the degradation of ethylbenzene, as well as the formation of some interested polycyclic aromatic hydrocarbons (PAHs), was discussed in detail. It is suggested that the formation of most typical PAHs observed in this work can be related to the H-abstraction/C₂H₂-addition (HACA) mechanism. Furthermore, the high concentration levels of intermediates in this flame is ascribed to the weak C-C bonds in the sidechain of ethylbenzene, which provides a potential explanation of the high sooting tendencies of ethylbenzene and other monocyclic aromatic fuels with complex sidechain structure. This study is anticipated to be constructive for combustion investigations of aromatic fuels, and the discussion is hoped to be helpful for further modeling studies concerning PAHs formation in combustion process.     

甲醇对正庚烷层流预混火焰影响的实验研究

利用低压层流预混火焰结合同步辐射真空紫外光电离技术和分子束取样质谱技术,探测到并计算了甲醇摩尔掺混比为0%、11%、28%和50%的甲醇/正庚烷/氧气/氩气火焰中62种燃烧中间产物和最终产物的摩尔分数.结果发现,甲醇的加入对正庚烷的消耗速率和大分子裂解没有影响,其主要作用表现在对C1和C2小分子摩尔分数的影响.甲醇的氧...     

An experimental and kinetic modeling study of a premixed nitromethane flame at low pressure

A premixed nitromethane/oxygen/argon flame at low pressure (4.67 kPa) has been investigated using tunable vacuum ultraviolet (VUV) photoionization and molecular-beam mass spectrometry. About 30 flame species including hydrocarbons, oxygenated and nitrogenous intermediates have been identified by measurements of photoionization efficiency spectra. Mole fraction profiles of the flame species have been determined by scanning burner position at some selected photon energies. The results indicate that N₂ and NO are the major nitrogenous products in the nitromethane flame. Compared with previous studies on nitromethane combustion, a number of unreported intermediates, including C₃H₄, C₄H₆, C₄H₈, C₂H₂O, C₂H₄O, CH₃CN, H₂CNHO, C₃H₃N and C₃H₇N, are observed in this work. Based on our experimental results and previous modeling studies, a detailed oxidation mechanism including 69 species and 314 reactions has been developed to simulate the flame structure. Despite some small discrepancies, the predictions by the modeling study are in reasonable agreement with the experimental results.     

An experimental and kinetic modeling study of premixed nitroethane flames at low pressure

An experimental and kinetic modeling study is reported on three premixed nitroethane/oxygen/argon flames at low pressure (4.655 kPa) with the equivalence ratios (Φ) of 1.0, 1.5 and 2.0. Over 30 flame species were identified with tunable synchrotron vacuum ultraviolet photoionization mass spectrometry, with their mole fractions quantified as the function of the height above burner. The flame temperature profiles were measured with a Pt–6%Rh/Pt–30%Rh thermocouple. A detailed kinetic mechanism with 115 species and 730 reactions was proposed and validated against experimental results. The computed predictions have shown satisfactory agreement with the experimental results. Basing on the rate-of-production analysis, the reaction pathways that feature the combustion of nitroethane were revealed, including the primary decomposition of C–N bond fission, the oxidation of C2 and C1 hydrocarbons and the formation of nitrogenous species. The presence of NO₂ and NO has been proved to be important for these processes.     

偶氮苯的同步辐射光电离研究

用同步辐射光电离质谱与符合技术的相结合测定了偶氮苯光电离效率谱，获得了该分子的电离势，导出了分子和分子离子中某些键的解离能以自由基Ｃ６Ｈ５Ｎ２的电离势。测得了不同光子能量激发下的质谱图，并对不同能量时偶氮苯的解离电离方式进行了分析。